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Work on the cutting edge: metallographic investigation of Late Bronze Age tools in southeastern Lower Austria

Work on the cutting edge: metallographic investigation of Late Bronze Age tools in southeastern... This paper analyses 20 Late Bronze Age (ca 1080–800 BC) copper alloy objects to discern their manufacture and the skills of local craftsmen. Several tools and jewellery were studied that originated from a bronze workshop located immediately next to the Prigglitz-Gasteil copper ore mining site and several contemporaneous sites in the surrounding area. The samples were studied with optical microscopy (microstructurally), and SEM-EDXS and XRF (chemical analyses). Our analyses are part of a larger study and suggest that the Prigglitz region’s bronze production was not standardized. Particular alloys do not seem to have been chosen for object types or due to their intended use-function. Notably, approximately 20% of the objects contain unalloyed copper inclusions, which are most likely a result of the incomplete mixing of scrap metals and alloys during their production. Keywords Late Bronze Age · Eastern Alps · Austria · Mining site · Metallographic analysis · XRF analyses · Production of copper alloy objects · Chaîne opératoire Introduction Schneeberg (Mühlhofer, 1952; Trebsche et al., 2019, and Rauheneck near Baden (Calliano, 1894, 90). The raw metal Numerous bronze casting workshops have been found that that supplied these workshops is disputed; however recent belong to the Middle Danubian Urnfield Culture dating to archaeometallurgical investigations of copper alloys from the Late Bronze Age (ca 1300–800 BC) in eastern Austria, the region suggest that there were likely several ore min- southern Moravia, southwestern Slovakia, and western Hun- ing sites that supplied Late Bronze Age metalworkers in the gary (Lochner, 2013). Evidence of archaeological and metal- Middle Danube region (Czajlik, 2013; Zachar and Salaš, lurgical remains in these regions (e.g. casting moulds and 2018, 2019; Mödlinger and Trebsche, 2020). debris and semi-finished products) shows that metalworking During recent excavations at the Prigglitz-Gasteil site, in was concentrated in central hillforts at sites such as Szentvid the Neunkirchen district, an extraordinary Late Bronze Age near Velem (comitate of Vas), and Gór-Kápolnadomb (comi- casting workshop was discovered. The site is not located at a tate of Vas) and Várvölgy (comitate of Zala) in western Hun- hillfort but immediately next to a contemporaneously dated gary (Ilon, 1992, 1996, 2018; Müller, 2006; Czajlik, 2014). copper ore mine at the slopes of the Gahns mountain in In adjacent Lower Austria, metal workshops are assumed the Schneeberg-Rax region of southeastern Lower Austria. to have existed at the hillforts Schanzberg near Thunau am Excavations at the site from 2010 to 2014, and subsequent Kamp (Lochner, 2004, 2017), ‘Gelände’ near Grünbach am geophysical surveys and core drillings from 2017 to 2018 (Trebsche, 2013, 2015b, 2015a; Trebsche and Pucher, 2013; Haubner, et al., 2019), have shown that copper ore, mainly * Marianne Mödlinger chalcopyrite and pyrite mineralization, were extracted from marianne.moedlinger@gmail.com opencast mines at the site during the Late Urnfield Period Peter Trebsche (Ha B, ca 1080 to 800 BC). The dwellings and workshops peter.trebsche@uibk.ac.at of Late Bronze Age miners and craftsmen at the site were Dipartimento di Chimica e Chimica Industriale (DCCI), constructed on artificial terraces cut into the heaps of mining Università degli Studi di Genova, Genoa, Italy debris. During the excavations, two terrain terraces, T3 and Institut für Archäologien, Leopold-Franzens-Universität T4, were investigated in detail, yielding evidence for bronze Innsbruck, 6020 Innsbruck, Austria Vol.:(0123456789) 1 3 125 Page 2 of 19 Archaeological and Anthropological Sciences (2021) 13:125 casting activities. The evidence consists of numerous casting hilltop, and hoards, located within a radius of ca 15 km, drops and fine platy slags that predominantly belong to three were selected for metallographic investigation. The 20 met- occupation phases: T3-10, T3-08F, and T3-08A. allographic analyses presented in this paper are compared On the upper terrain terrace of T3, which according to to objects from the Mahrerdorf Late Bronze Age hoard a series of radiocarbon dates, was in use from the end of (Mödlinger and Trebsche 2020). the tenth century BC to the end of the ninth century BC (Trebsche, 2015b; Trebsche, in preparation), only casting waste and fragments of casting tools were found so that the Materials and methods spectrum of production is unknown. However, four finds from the  site are important as they indicate the produc- Selected objects and their site context tion of at least three categories of bronze objects: first, one fragment of a sandstone casting mould for a knife with a From the numerous copper alloy fragments found at, and in tang hilt (Griffdornmesser, probably type Baumgarten after one instance near, Prigglitz-Gasteil, almost all of the pre- Říhovský, 1972, 64–71; Trebsche, 2015b, 49, Fig.  2/7); served tools with cutting edges or points were selected for second, one sandstone casting cone for the production of metallographic analysis. These tools include a tanged Still- a socketed axe; third, a bronze casting cone that fits into fried-type knife (Fig. 2: 10; cf. Říhovský, 1972, 55–58; Jiráň the socket of small arrowheads, indicating on-site weapon 2002, 59–60; Veliačik 2012, 305–306), a tanged knife that production; fourth, a casting sprue that cannot be precisely had been reworked from a fragment (Fig. 2: 9; Říhovský, attributed to an artefact type but is the size appropriate for 1972, 76), and three double-pointed awls (Fig. 2: 1–3). One casting an object like a knife, razor, or sickle (Trebsche and socketed axe with curved decoration (Fig. 2: 4; cf. Mayer, Pucher, 2013, 127–128, Fig. 14/2). Hence, the workshop at 1977, 192–198) was found ca 500 m away at Klausgraben. Prigglitz-Gasteil seems to have produced a range of artefacts The jewellery selected for analysis included two belt clips that indisputably included arrowheads, knives (Griffdorn- (Fig. 2: 5–6), one fragment of a bracelet with a flat cross- messer), and socketed axes. section (Fig. 2: 7), and a rod or wand of unknown function No heavy tools, such as hammers, axes and pickaxes, (Fig. 2: 11). All the objects are copper-tin alloys except for a or weapons like swords, were found at the site; only small casting cake of unalloyed copper (Fig. 2: 8). Strictly speak- objects such as rings, belt clips, double-pointed tools, two ing, the local production of the bronze artefacts cannot be completely preserved knives, and two dress pins were dis- proven, as chemical and lead isotope analyses have shown covered during the excavations. Nevertheless, the number that mixing of different copper alloys and recycling played a of copper alloy artefacts found on terraces T3 and T4, in an significant role at the Prigglitz-Gasteil site (Mödlinger et al. area of ca 210 m , is high at about 250 weighing a total of ca 2021). 663 g. Most of the artefacts are remnants of the metalwork- For comparison to these alloys, objects from sev- ing processes with ca 200 casting drops and small bronze eral nearby sites were selected. The first is a gravesite fragments, and 23 other pieces from casting or recycling. In at Pottschach located 5 km away from Prigglitz-Gasteil a recent study of the chemistry and isotopic makeup of the (Kerchler, 1960). It was chosen because the same types Prigglitz-Gasteil metal finds and copper ores, we investi- and decoration of dress pins are found there (Trebsche and gated the chaîne opératoire of local copper production and Pucher, 2013, 122, Fig. 7/1–2). From the grave goods, two bronze working, as well as the regional distribution networks decorated tanged knives, a Velem-St. Vid type (Fig. 2: 15; of metal artefacts. In that study, we concluded that Prig- cf. Říhovský, 1972, 51–53) and a Baumgarten type (Fig. 2: glitz-Gasteil was an active copper mining, metal-making, 16; cf. Říhovský, 1972, 67–71), and one pin with a small and importation and recycling site, especially in the late vase head (Fig. 2: 17; cf. Říhovský, 1979, 198–207) were tenth/ninth centuries BC. Prigglitz-Gasteil sourced metal studied. The second site, the Kammerwandgrotte cave, or raw materials were exchanged at least in the Schwarza located 7 km from the Prigglitz mine at Reichenau an der Valley’s micro-region. However, additional investigations Rax where there is evidence for Early and LBA activities, of more distant LBA sites will be necessary to fully explore including metallurgy (Hottwagner and Lang, 1999), was the extent of exchange and the Prigglitz-Gasteil mining site’s selected. One chisel fragment (Fig.  2: 13) and one wire role (Mödlinger et al. 2021). fragment (Fig. 2: 14) from the cave were analysed due to The aim of this paper is to investigate the post-casting their compositional similarity to the copper produced at treatment of select bronze objects to gain insight into post- Prigglitz-Gasteil. These artefacts cannot be precisely dated casting manufacturing processes and the skills of regional by find contexts. In the third site, from the LBA mining craftsmen (Fig. 1). For this work, a series of 20 copper and region of Prein an der Rax, ca 13 km from Prigglitz, a bronze objects from the Prigglitz-Gasteil copper mining site, double-pointed bronze tool (Fig.  2: 18) was chosen for and the surrounding Late Bronze Age dated cemetery, cave, study. Smelting activities in this region have been dated by 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 3 of 19 125 Fig. 1 Location of Prigglitz-Gasteil and the surrounding find spots of the analysed finds in this paper (Cartography: © BEV (Bundesamt für Eich- und Vermessungswesen), 2021) radiocarbon to the Late Urnfield period (ninth century BC; In sum, the objects studied in this paper include four axes, Trebsche, 2015b, 43–47). Fourth, from the metalworking four knives, four awls, one casting cake, two belt clips, one centre likely located at the Gelände near Grünbach hillfort chisel,  two pieces of jewellery (bracelet, pin),  one wire in Schneeberg, one end-winged Haidach type axe (Mayer, fragment, and a bronze rod/wand (Table 1). X-ray fluores- 1977, 152–158; Fig. 2: 12) was selected. It belongs to a cence and Pb-isotope analyses of ca 125 finds from Prigglitz hoard dating to phase Ha A (ca 1200 to 1080 BC; Trebsche and the surrounding area, including the objects presented in et  al.,  2019). Fifth, almost all cutting tools (a pickaxe, this paper, are published elsewhere (Mödlinger et al. 2021). a chisel, an adze, two winged axes, and three socketed axes) from the Mahrersdorf hoard (Lauermann and Ram- Methodology mer, 2013, pl. 44–47) were sampled. Archaeometallurgi- cal analyses of this hoard have already been published in Microstructural characterization of the objects and chemi- a separate article (Mödlinger and Trebsche, 2020). And cal analyses using energy-dispersive X-ray spectroscopy finally, two LBA socketed axes found without context from (EDXS) were performed on freshly polished cross-sections Sieding (Fig. 2: 19) and at the mountain Gfieder in Ternitz taken at the edges of the blades for axes, chisels, and knives; (Fig. 2: 20), respectively, were chosen for comparison to tip for awls; centre of wires and bracelets; and end of belt the samples from Prigglitz. The specimen from Ternitz clips and pins (Fig. 2). Further, X-ray fluorescence (XRF) belongs to the type ‘mit bogenumrandetem Lappendekor chemical and high-resolution multi-collector inductively und abgesetzter Klinge’ (Mayer, 1977, 198–199), whereas coupled mass spectrometry (HR-MC-ICP-MS) Pb isotope the other has unique decoration and was classified as a analyses were later carried out on the same and on freshly special type (Mayer 1977, 204 no. 1175). polished samples (see Mödlinger et al. 2021). The EDXS 1 3 125 Page 4 of 19 Archaeological and Anthropological Sciences (2021) 13:125 1 3 Table 1 Metal objects sampled for metallographic analysis from Prigglitz and the surrounding area. Objects in ‘[]’ do not have inventory numbers and are instead labelled with the sampling number. ‘NHM’ corresponds to the Natural History Museum Vienna; ‘LNÖ’, State Collections of Lower Austria; and ‘SL’, Reinhard Lang’s private collection, Gloggnitz. The absolute chronol- ogy follows Sperber (2017) No Find spot Context Object Museum Inv. no Sampling Relative chronol- Absolute chronol- Type Reference ogy ogy 1 Prigglitz-Gasteil Mining site Double-pointed LNÖ UF-22692.1272 Tip Ha B2-3 960–800 BC - Unpublished ‘awl’ 2 Prigglitz-Gasteil Mining site Double-pointed LNÖ UF-22692.1140A Tip Ha B2-3 960–800 BC - Trebsche / Pucher, ‘awl’ 2013, Fig. 19/10 3 Prigglitz-Gasteil Mining site Double-pointed LNÖ UF-22692.1672 Tip Ha B2-3 960–800 BC - Unpublished ‘awl’ 4 Prigglitz-Gasteil, Isolated find near Axe (socketed) SL [S001] Edge Ha B 1080–800 BC With curved deco- Trebsche, 2015b, 47 Klausgraben mining site ration Fig. 2/3 5 Prigglitz-Gasteil Mining site Belt clip LNÖ UF-22692.1652 End Ha B2-3 960–800 BC - Unpublished 6 Prigglitz-Gasteil Mining site Belt clip LNÖ UF-22692.1673 End Ha B2-3 960–800 BC - Unpublished 7 Prigglitz-Gasteil Mining site Bracelet LNÖ UF-22692.1780 End Ha B2-3 960–800 BC - Unpublished 8 Prigglitz-Gasteil Mining site Casting cake LNÖ UF-22692.675 Border Ha B2-3 960–800 BC - Unpublished 9 Prigglitz-Gasteil Mining site Knife LNÖ UF-10,964 Edge Ha B2-3 960–800 BC (Reworked from a Říhovský, 1972, 76 fragment) no. 303 pl. 29/303 10 Prigglitz-Gasteil Mining site Knife LNÖ UF-22692.2188 Edge Ha B2-3 960–800 BC Type Stillfried Trebsche, 2015b, Fig. 2/6 11 Prigglitz-Gasteil Mining site Rod/wand LNÖ UF-22692.912 End Ha B2-3 960–800 BC - Trebsche / Pucher, 2013, Fig. 19/6 12 Grünbach, Hilltop settlement Axe (end-winged) LNÖ UF-19,452 Edge Ha A 1200–1080 BC Type Haidach Trebsche et al., Gelände 2019, 561 Fig. 5 13 Reichenau, Kam- Cave Chisel LNÖ [S041] Edge LBA? 1330–800 BC? - Hottwagner / Lang, merwandgrotte 1999, 779 Fig. 749 14 Reichenau, Kam- Cave Wire (bent) LNÖ [S013] End LBA? 1330–800 BC? - Hottwagner and merwandgrotte Lang, 1999, 779 Fig. 748 15 Pottschach Cemetery Knife NHM 72.485 Edge LBA 1330–800 BC ‘Griffdornmesser Říhovský, 1972, 52 vom Typ Velem no. 179 pl. 17/179 St. Vid’ 16 Pottschach Cemetery Knife NHM 72.484 Edge Ha B2-3 960–800 BC ‘Griffdornmesser Říhovský, 1972, 68 vom Typ Baum- no. 274 pl. 26/274 garten’ 17 Pottschach Cemetery Pin NHM 72.488 Shaft Ha B2-3 960–800 BC ‘Nadel mit kleinem Říhovský, 1979, Vasenkopf’ 203 no. 1706 pl. 62/1706 18 Prein an der Rax Smelting site Double-pointed LNÖ UF-9958 Tip Ha B2-3 960–800 BC - Hampl and May- ‘awl’ rhofer, 1963, 52 (Prein V) Archaeological and Anthropological Sciences (2021) 13:125 Page 5 of 19 125 analyses were performed using a JEOL JSM-6460LV SEM with an Oxford Instruments SDD XMax 20 under high vac- uum at IRAMAT-CRP2A, Bordeaux, France. The SEM was calibrated using the internally provided software database standards, as well as certified pure Si and Co standards for quantification. The results shown are the mathematical aver - age of 5–8 spectra of approximately 200 × 600 μm taken for 60 s each. The presence of minor and trace elements was supported by their detection in higher amount in the cor- rosion layers. The SEM-EDXS analyses were used to iden- tify different intermetallic compounds, inclusions, and the absence or presence (qualitative) of sulphur (S), which was not detected by XRF. The qualitative presence of each alloy- ing element was classified as major with wt.% > 1, minor between 1 and 0.3, and trace at < 0.3; their presence was normalized and is given in wt.% in Table 2. Chemical analysis was carried out on drilling samples using an ARL Quant’X (Thermo Fisher Scientific) XRF (bulk analyses) at 28 kV (with Pd filter) and 50 kV (with Cu filter), and on the surfaces of the samples polished for metallographic study using a Fischerscope X-ray XAN 150 (W-band) (point measurements) at 50 kV (Al-filter) using a 1 mm collimator SD-detector for 50 s. The measuring time/ spot of 1–2 measurements/sample depended on the sample size for both instruments. Each analysis was performed at the CEZA-laboratory in Mannheim, Germany, for the bulk and points, respectively. Quantification of the resultant analyses closely followed the procedure described in Lutz and Per- nicka (1996). Manganese, Co, Zn, Se, Cd, Te, and Bi were below the detection limit of the Fischerscope, and, since S was only measured with EDXS, the results shown in Table 2 should be considered qualitative. There are notable differ - ences between the ARL Quant’X and Fischerscope results (e.g. sample nos. 19a and b), which are due to all-inclusive bulk versus point measurements, the nature of the sample (drilling vs. metallographic cross-section), and the presence of inhomogeneities and corrosion. The error rate for both techniques is 5–10% for the major elements, and even lower for Cu, and 20–50% for minor and trace elements. Characterization of the sample’s microstructure was per- formed on prepared cross-sections. Each sample was mounted in cold acrylic resin and polished using 400–1200 SiC papers, followed by a diamond suspension paste of up to 0.25 μm granulometry. The samples were characterized using optical microscopy in both bright and dark fields, chemically analysed using EDXS, and then etched for metallographic examination using aqueous ferric chloride and Klemm II to show greater detail. While aqueous ferric chloride produces a grain contrast, Klemm II is a colour etchant, which colours grains depend- ing on their orientation; segregation also becomes visible and intermetallics are not etched. The total amount of deformation applied to each sample was calculated by measuring the shape factor (SF) of the CuS or CuFeS inclusions (see Mödlinger and 1 3 Table 1 (continued) No Find spot Context Object Museum Inv. no Sampling Relative chronol- Absolute chronol- Type Reference ogy ogy 19 Sieding Isolated find Axe (socketed) LNÖ UF-5098 Edge Ha B 1080–800 BC (Special type) Mayer, 1977, 204 no. 1175 pl. 84/1175 20 Ternitz, Gfieder Isolated find from Axe (socketed) SL [S042] Edge Ha B2-3 960–800 BC ‘mit bogenum- Lang, 2000, 599 hilltop settlement randetem Fig. 474 Lappendekor und abgesetzter Klinge’ 125 Page 6 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Fig. 2 Late Bronze Age objects from southeastern Lower Aus- tria. Numbers 1–3 and 5–11 are from Prigglitz-Gasteil; 4 from Prigglitz-Gasteil, Klausgraben; 12 Grünbach, Gelände; 13–14 Reichenau, Kammerwandgrotte; 15–17 Pottschach; 18 Prein an der Rax; 19 Sieding; and 20 Ternitz, Gfieder The drawings; nos. 1–3, 5–8, 10–12, 18 were done by Daniela Fehlmann and Ulrike Weinberger; 4, 13–14, 20 by Franz Drost; 9, 15–17, 19 are from unknown artist(s). The numbers correspond to those listed in Tables 1, 2, and 3 Piccardo 2013). Vickers hardness measurements were carried chemical compositions of the finds discussed in this paper out using a Leitz Durimet 72-1b instrument at 100 g load over are provided in Table 2. 10 s. An FT-9929195 test block from Future-Tech-Corporation was used as a standard. Axes and chisel Prigglitz‑Gasteil, ID S001, socketed axe Results A sample was taken on the edge of the axe’s blade. Analy- In the following, the results are focused on the metallo- sis of the sample showed 8.5 wt.% Sn and 0.6% S. Nickel graphic analyses. The chemical analyses are thoroughly was also present at about 0.1% with Fe, As, Sb, Ag, and discussed elsewhere (Mödlinger et al. 2021). However, the Pb in trace amounts. The unetched sample shows CuS- inclusions with about 60–70% deformation. Etching with 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 7 of 19 125 Table 2 The elemental percentages of each sample are given in isque (*) indicates drilling samples analysed by ARL Quant’X XRF. wt.%. Manganese, Co, Zn, Se, Cd, Te, and Bi were not detected in Noteworthy are the differing amounts of Sn in the socketed axe from the samples analysed with the Fischerscope (FS). All other sam- Sieding that appear with different analytical methods (see ‘Sieding, ples show ≤ 0.005 Mn, Se, and Te, 0.01 Co, < 0.1 Zn, < 0.01 Cd, inv. no. UF-5098, socketed axe’) and < 0.06 Bi. Use of the Fischerscope is indicated by FS. An aster- No Site Object Inv.no Cu Fe Ni As Ag Sn Sb Pb FS 1 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1272 89 n.d n.d n.d n.d 11.0 n.d n.d x 2 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1140A 90 n.d n.d n.d n.d 9.5 0.12 n.d x 3 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1672 86 n.d 0.07 n.d n.d 13.7 0.10 0.08 x 4 Prigglitz-Gasteil, Axe (socketed) [S001]* 91 < 0.05 0.12 0.021 0.008 8.5 0.092 0.011 Klausgraben 5 Prigglitz-Gasteil Belt clip UF-22692.1652 91 0.22 0.07 0.03 n.d 8.3 0.24 n.d x 6 Prigglitz-Gasteil Belt clip UF-22692.1673 88 0.06 0.28 0.32 0.28 10.3 0.37 0.34 x 7 Prigglitz-Gasteil Bracelet UF-22692.1780 87 0.13 0.04 n.d n.d 12.8 0.13 n.d x 8 Prigglitz-Gasteil Casting cake UF-22692.675* 100 0.11 0.06 0.012 0.010 0.017 0.095 0.012 9 Prigglitz-Gasteil Knife UF-10,964 84 0.73 0.05 n.d n.d 15.3 n.d 0.14 x 10 Prigglitz-Gasteil Knife UF-22692.2188 89 0.19 0.14 0.14 n.d 9.9 0.41 n.d x 11 Prigglitz-Gasteil Rod / wand UF-22692.912 87 n.d 0.03 n.d n.d 11.9 0.06 0.61 x 12 Grünbach, Gelände Axe (end-winged) UF-19,452 89 0.09 0.40 0.51 0.15 9.1 0.52 0.19 x 13 Reichenau, Kam- Chisel [S041] 91 n.d 0.15 0.19 0.08 7.5 0.25 0.39 x merwandgrotte 14 Reichenau, Kam- Wire (bent) [S013] 88 0.14 0.06 0.06 n.d 12.0 0.20 0.05 x merwandgrotte 15 Pottschach Knife 72,485* 89 0.36 0.06 0.132 0.087 9.2 1.24 0.019 16 Pottschach Knife 72,484* 89 0.05 0.07 0.021 0.016 10.6 0.214 0.020 17 Pottschach Pin 72,488* 90 0.10 0.07 0.015 0.020 9.2 0.130 0.007 18 Prein an der Rax Double-pointed ‘awl’ UF-9958 94 0.08 0.05 n.d n.d 5.2 0.10 0.69 x 19a Sieding Axe (socketed) UF-5089 [S022]* 92 0.11 0.13 0.051 0.011 7.7 0.095 0.102 19b Sieding Axe (socketed) UF-5089 [S039] 89 0.11 0.11 0.06 n.d 10.3 0.14 0.09 x 20 Ternitz, Gfieder Axe (socketed) [S003]* 91 0.16 0.06 0.01 0.005 8.7 0.02 0.005 ferric chloride reveals coring (zones with 9 to 15% Sn are Grünbach am Schneeberg, inv. no. UF‑19.452, clearly distinguishable) and small, equiaxed polyhedric median‑winged axe grains. The grains are deformed and show strain lines and annealing twins. In the matrix, (α + δ) eutectoid is present; The median-winged axe-type Freudenberg from Grün- due to its brittleness and the applied deformation, there are bach am Schneeberg was sampled on the edge and found many cracks (Fig. 3a). Their presence in the axe indicates to contain 9% Sn, 0.5% of As and Sb each, as well as 0.1% that annealing took place at relatively low temperatures Ag, 0.4% Ni, and 0.2% Pb. Iron is present in traces. The (i.e. < 520 °C), which counterintuitively still permitted the unetched sample shows ca 30–40% deformed, light grey formation of new grains. Corrosion in the sample mainly CuS-inclusions. Etching with ferric chloride reveals cor- consists of copper oxide inclusions (cuprite) and copper ing (indicating a non-complete homogenization) as well as carbonates. There are also corrosion layers of tin oxides on slightly deformed polyhedric grains with twins and strain the object’s surface, which are typical for bronze. Hardness lines. Some eutectoid is present. Corrosion can be found measurements give up to 297 HV values in tin-richer zones inter- and intracrystalline. On the edge of the sample, corro- and 245 HV in zones with less tin. In the more homogenous sion follows the dendritic structure. Also, bacterial-induced zone at the very edge, hardness reaches 254 HV, while the corrosion was noted (see Piccardo et al., 2013) (Fig. 3b). sample’s core is between 206 and 245 HV. Copper oxide (mainly cuprite) and copper carbonate layers cover the surface of the sample. Hardness measurements give about 151–221 HV values, with a harder edge than in the sample’s core. 1 3 125 Page 8 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Fig. 3 Microstructures. Axe ID S001 from Prigglitz-Gasteil: a SEM image showing coring, CuS-inclusions (dark grey), and broken (α + δ) eutectoid (light grey). Winged axe inv. no. UF-19.452 from Grünbach: b Unetched, in polarized light. Bacterial induced corrosion is visible. Chisel ID S041 from Kammerwandgrotte: c Unetched. Coring is visible as massively elongated CuS-inclu- sions. The corrosion follows the microstructural features inter- and intracrystallinearly. Socketed axe ID S042 from Ternitz: d Unetched. Coring is visible. At the centre, one can see (α + δ) eutectoid (light grey) with surrounding inter- and intracrystalline corrosion, under which are cuprite (dark grey, below the eutectoid) and a copper inclusion. The CuFeS- inclusions (dark grey) are not significantly deformed. e Etched with ferric chloride. Note the deformed grains of α-solid solu- tion with deformed twins and strain lines. Socketed axe inv.no. UF-5098 from Sieding: f Etched with ferric chloride. Note the deformed grains of α-solid solu- tion with deformed twins and strain lines Hardness measurements give about 202–237 HV values, Kammerwandgrotte, ID S041, chisel with a harder edge than in the core of the sample. The chisel was sampled on its edge and found to contain 7.1–8% Sn (depending on the analytical method used), 0.2% Ternitz (Gfieder), ID S042, socketed axe As, 0.1% Ni, 0.2% Sb, 0.4% Pb, and some S. The S was under the detection limit of the EDXS for bulk analyses but The socketed axe was sampled on its edge and found to contain 10.8% Sn using EDXS and 8.7% with XRF, and was detected in the CuS-inclusions. Iron and Ag are present in traces, and the unetched sample shows ca 90% deformed 0.7% S and about 0.16% Fe. Sulphur and Fe are mainly present in the CuFeS-inclusions. Nickel, As, Ag, Sb, and light grey CuS- and globular Pb-inclusions (Fig. 3c). Etch- ing with ferric chloride revealed slight coring, indicating Pb are present in trace amounts. The unetched sample shows slightly deformed CuFeS-inclusions, which indi- incomplete homogenization, and fine, slightly deformed, polyhedric grains with strain lines and twins. There is also cate a total deformation of about 10–20% in the sampled area (Fig.  3d). Etching the sample with ferric chloride (α + δ) eutectic, and corrosion is present both inter- and intracrystallinearly. Copper oxide crystals (cuprite; dark revealed an inhomogeneous microstructure — tin-rich areas contain up to 15% Sn, tin poor areas up to 6% — red in polarized light) and alternating copper oxides and carbonate layers cover the surface of the sample. Tin oxides and severely deformed equiaxed grains of α-solid solution (Fig. 3e). The grains show deformed annealing twins as are present, as are P, Si, and Ca, which derive from the soil. well as strain lines, and (α + δ) eutectoid is present. The 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 9 of 19 125 deformation and presence of eutectoid indicate annealing ferric chloride revealed equiaxed grains of α-solid solution at low temperature (< 520 °C) or short annealing at higher with twins (Fig. 4a). Only at the very edge, congruent with temperatures with a final heavy deformation. Some cop- the significantly more deformed CuFeS-inclusions in this per drops are also visible in the matrix, and the corrosion area did the grains show deformation and show strain lines follows both the original dendritic structure and, in small with slight coring. areas, the grain boundaries and the intracrystalline struc- As the final working step, the edge of the chisel was cold tures of the α-solid solution equiaxed grains. Both copper deformed. The corrosion follows both the deformed α-solid oxides (cuprite) and copper carbonates (mainly azurite and solution equiaxed grains’ grain boundaries and the intra- malachite) are visible in polarized light, as is cuprite as granular annealing twins. Under polarized light, the sample inclusions. The hardness values are 206–242 HV on the showed both copper oxides (cuprite) and carbonates (mainly very edge and slightly lower (193–221 HV) 3 mm inward, azurite and malachite). The hardness values of 206–228 HV corresponding to high final deformation. on the very edge correspond with microstructural observa- tions (higher levels of total deformation of CuFeS-inclusions Sieding, inv. no. UF‑5098, socketed axe and grain deformation and strain lines) and the relatively high amount of Sn. The core of the sample dissimilarly The socketed axe was sampled on its edge and contained showed 132–151 HV. 7.7–11.4% Sn, 0.5% S, and about 0.1% Fe, Ni, Sb, and Pb. Sulphur and Fe are mainly present in the CuFeS-inclusions, Pottschach, inv. no. 72.485, knife and As and Ag are in trace amounts. The Sn composition varied by sample type, with XRF of the drilling samples The knife was sampled on its edge and found to be a tin- showing 7.7% and surface analyses of the metallographic antimony bronze containing mean values of 9% Sn, 1.2% Sb, sample at about 10.3%, similar to the 11.4% result from 0.1% As, 0.7% S, and 0.4% Fe. Sulphur and Fe are mainly the EDXS. The unetched sample shows slightly deformed present in CuFeS-inclusions, and Ni, Ag, and Pb are present CuFeS-inclusions, which indicate a total deformation of in trace amounts. The sample was taken from the edge at about 10–20%. Lead is present in small inclusions. Etching the centre of the blade. The unetched sample shows slightly the sample with ferric chloride revealed coring and a very elongated CuFeS-inclusions, which indicate a total amount fine grain structure (grain sizes smaller than 10, according of deformation of 20–30% at the very edge in the sampled to ASTM) (Fig. 3f). The equiaxed grains of α-solid solu- area, and about 10–20% in the core. Etching the sample with tion showed twins and strain lines. While the grains show ferric chloride revealed heavy coring and large equiaxed slight deformation on the very edge, they are slightly more grains (ca 30–60 μm in diameter) of α-solid solution with deformed in the sample’s core. The corrosion follows the twins (Fig. 4c). As the final working step, the knife’s edge inter- and intracrystalline structures of the grains. Calcium, was annealed. Some copper drops are visible in the matrix Cl, Si, and tin oxides were present in the corrosion, with (Fig. 4b). The corrosion follows the grain boundaries of the the former three deriving from the surrounding burial soil. α-solid solution equiaxed grains. According to their colour The most significant part of the corrosion is copper oxides under polarized light, copper carbonates (mainly azurite and (cuprite) and carbonates of mainly azurite and malachite. malachite) are the main corrosion products. The hardness The hardness values of 213–216 HV in the sample’s core are values of 128–143 HV confirm the microstructural obser - higher than on the very edge (166–170 HV). These hardness vations; though the edge received a higher amount of total values also correspond with the more deformed grains in the deformation, the annealing following the cold deformation sample’s core. resulted in an equally low hardness throughout the sample. Knives Prigglitz, inv. no. 10.964, knife Pottschach, inv. no. 72.484, knife X-ray fluorescence analyses could not be carried out with accuracy due to the presence of corrosion; however, it is The knife was sampled on its edge and found to contain worth pointing out that traces of Ni and Pb were detected. 11% Sn, 0.2% Sb, and 0.4% S. Sulphur and small amounts The following compositional percentages derive from the of Fe are mainly present in CuFeS-inclusions. Iron, Ni, As, SEM-EDXS analyses carried out on the polished metal- Ag, and Pb are present in trace amounts. The sample was lographic sample’s surface. The knife was formed from a taken from the centre of the blade’s edge. The unetched sam- tin-bronze containing mean values of 13.5% Sn and 0.6% ple shows elongated CuFeS-inclusions, indicating a total S that were mainly present in CuFeS-inclusions. The sam- deformation of 30–40% at the very edge and about 10–20% ple was taken from the centre of the blade. The unetched towards the core in the sample. Etching the sample with sample shows elongated CuFeS-inclusions, which indicate a 1 3 125 Page 10 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Fig. 4 Microstructures. Knife inv.no. 72.484 from Pottschach: a Etched with ferric chloride. Note the elongated CuFeS- inclusions and the deformed grains of α-solid solution with deformed twins and strain lines. b Knife inv.no. 72.485 from Pottschach: b Unetched. Note the copper drops in the matrix, surrounded by corrosion. c Etched with ferric chloride. Knife inv.no. 10.964 from Prig- glitz: d Etched with ferric chlo- ride. Note the slightly deformed twins and strain lines of the polyhedric grains of α-solid solution. Also, the (α + δ) eutectoid is present. Knife inv. no. UF-22692.2188 (22.692) from Prigglitz: e Unetched. Slight coring is visible. f Etched with ferric chloride. Note the deformed polyhedric grains of α-solid solution with twins and strain lines total amount of deformation of 60–70% at the very edge and Prigglitz, inv. no. UF‑22692.2188 (22.692), knife about 10–20% towards the core. Etching the sample with fer- ric chloride revealed coring and very fine polyhedric grains X-ray fluorescence analyses of this sample should be consid- of α-solid solution with twins and strain lines (Fig. 4d). The ered qualitative, as some corrosion was present. The knife grains are severely deformed along the edge, and (α + δ) was formed from tin-bronze containing mean values of 10% eutectoid is present, indicating low temperature (< 520 °C) Sn with about 0.4% Sb, 0.2% Fe, and 0.1% Ni and As. The or shorter annealing at higher temperatures took place. The S and Fe are present in CuFeS-inclusions. The sample was applied deformation did not result in a broken eutectoid. The taken from the blade. The unetched sample shows slightly SEM images showed tiny, globular Pb-inclusions throughout elongated CuFeS-inclusions, which indicate a total amount the matrix. Corrosion in the sample follows intracrystalline of deformation of 30–40%. Etching the sample with ferric structures to a smaller degree, the dendritic features. Ele- chloride revealed coring and significantly deformed poly - ments such as Al, Si, and P were present and derived from hedric grains of α-solid solution with twins and strain lines the soil. Apart from the copper oxides and carbonates, tin (Fig. 4e–f). As the final working step, the edge of the knife oxides are also present. The hardness values of 245–254 HV was cold deformed. The corrosion follows both the previous on the very edge and 181–199 in the sample’s core confirm as-cast structure (dendrites) as well as the grain boundaries the microstructural observations. of the α-solid solution equiaxed grains. According to their colour under polarized light, copper carbonates (mainly azurite and malachite) are the main corrosion products. 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 11 of 19 125 The hardness values of 193–274 HV, with 274 HV on the grains of α-solid solution with twins and strain lines were very edge, make this the highest hardness value of the four visible (Fig. 5a). The presence of (α + δ) eutectoid indi- knives. cates short, low-temperature annealing, followed by cold deformation. As the final working step, the tip of the awl Awls was cold deformed. Corrosion in the sample follows the grain boundaries of the α-solid solution equiaxed grains, Prigglitz, inv. no. UF‑22692.1140A, awl and it expands intracrystallinearly. According to their col- our under polarized light and the EDXS analyses, copper The awl is made of tin-bronze containing mean values of carbonates (mainly azurite and malachite) are the main 9.5% Sn, 0.1% Sb, and 0.7% S, which is mainly present corrosion products on the awl’s surface, while copper in CuS-inclusions. The tip of the awl was sampled longi- (mainly cuprite) and tin oxides are visible in the inter- and tudinally and transversally (cross-section). The unetched intracrystallinearly. The hardness values of 193–228 HV longitudinal sample showed slightly elongated CuS-inclu- are relatively high for a 9.5% tin-bronze and correspond sions, indicating a total amount deformation of 20–30%, with the deformation applied in the final working step. while the cross-section only shows light deformation at a maximum of 15%. The (α + δ) eutectoid of the Cu-Sn system is visible in the unetched sample, and once etched with ferric chloride coring and fine, deformed equiaxed Fig. 5 Microstructures. Awl inv.no. UF-22692.1140A from Prigglitz: a Etched with Klemm II. Note coring and (α + δ) eutectoid. Awl inv.no. 1272 from Prigglitz: b Etched with ferric chloride. The CuS-inclu- sions are elongated. Awl inv.no. UF-22692.1672from Prigglitz: c Etched with ferric chloride. Note the elongated CuS- inclusions. Awl inv.no. UF-9958 from Prein: d Unetched. Note the corrosion, outlining the microstructural features. Cast- ing cake inv. no. UF-22692.675 from Prigglitz. e Unetched. Note the many CuS-inclusions and, in the centre, some CuSb- inclusions in the SEM image. White inclusions are rich in Sb (ca 35%) as well as Ag and As (below 1%). Belt clip inv.no. UF-22692.1673 from Prigglitz: f Etched with Klemm II. Heavy coring is visible 1 3 125 Page 12 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Prigglitz, inv. no. UF‑22692.1272, awl Prein, inv. no. UF‑9958, awl The awl was formed from tin-bronze containing mean values The awl is tin-bronze and contains mean values of 5% Sn and of 11% Sn and 0.3% S, which was mainly present in CuS- 0.7% Pb. Sulphur is mainly present in the CuFeS-inclusions, inclusions. The tip of the awl was sampled longitudinally, and Fe in trace amounts. The sample was cut transversally and unetched showed slightly elongated CuS-inclusions, from a fragment of the awl. Unetched, the sample shows indicating a total amount of deformation of 40–50%. After slightly elongated CuFeS-inclusions, indicating a total etching with Klemm II heavy coring was revealed, indicating amount of deformation of 0–20%, which is not surprising an inhomogeneous alloy (Fig. 5b). Both Klemm II and ferric for the cut. The total amount of longitudinal deformation chloride etched surfaces showed small, slightly deformed could not be measured. Etching the sample with ferric chlo- equiaxed grains of α-solid solution with twins as well as ride revealed coring and small, deformed equiaxed grains of strain lines. No (α + δ) eutectoid of the Cu-Sn system was α-solid solution with twins and strain lines. The corrosion visible, indicating that the awl underwent longer, or more follows the grain boundaries of the α-solid solution equi- frequent annealing followed by cold deformation. In the axed grains and also expands intracrystallinearly (Fig. 5d). final working step, the tip of the awl was cold worked. The According to the sample’s colour under polarized light, corrosion follows the dendritic structure. According to the copper carbonates (mainly azurite and malachite) are the corrosion colours under polarized light, copper carbonates main corrosion products on the awl’s surface, while cop- (mainly azurite and malachite) are the main products on the per (mainly cuprite) and tin oxides are visible inter- and awl’s surface. No inter- or intracrystalline corrosion was intracrystallinearly. The low hardness values of 160–181 HV noted. The hardness values of 187–206 HV are relatively correspond with the alloy composition. high for a 10% tin-bronze and correspond with the deforma- tion applied in the final working step. Other objects Prigglitz, inv. no. UF‑22692.1672, awl Prigglitz, inv. no. UF‑22692.675, casting cake The awl was formed from tin-bronze containing mean values The casting cake consists of rather pure copper with only of 14% Sn, 0.1% Sb, and 0.5% S, which was mainly present 1.7% S, 0.1% Fe, and small amounts of Sb (0.1%). Other in CuS-inclusions with low amounts of Ni. Nickel and Pb elements, such as Ni, Ag, As, and Pb, are present in trace are present in trace amounts. The tip of the awl was sam- amounts. The highly porous as-cast shows a homogenous pled longitudinally, and unetched showed severely elongated copper matrix without any coring or dendrites. No cuprite CuS-inclusions, indicating a total amount of deformation was noted under polarized light; however, CuO — mainly of 70–80% (Fig. 5c). After etching the sample with Klemm carbonates — is present in the corrosion and on the casting II and ferric chloride, light coring was revealed, indicat- cake’s surface. Globular, black CuS-inclusions — some of ing an almost homogenous alloy. Both Klemm II and fer- them containing up to 2% O and/or up to 1% Sb — are dis- ric chloride developed small, slightly deformed equiaxed tributed in various sizes all over the sample’s surface. There grains of α-solid solution with twins and strain lines. No are small, white inclusions that mainly contain Sb (35%) and (α + δ) eutectoid of the Cu-Sn system remained, indicating Ag and As below 1% (Fig. 5e). Hardness values are around more prolonged or more frequent annealing followed by cold 96–105 HV. deformation. In the final working step, the tip of the awl was cold worked. Half of the sample is massively corroded. The Prigglitz, inv. no. UF‑22692.1673, belt clip corrosion follows the grain boundaries and, intra-granularly, along the dislocations of single grains (both twins and strain The belt clip is made of tin-bronze with about 7.5% Sn, lines). According to the corrosion colours under polarized 0.7% Sb, and 0.2% S. The XRF sample contained corrosion, light, copper carbonates (mainly azurite and malachite) are so preference should be given to the SEM-EDXS chemi- the main corrosion products on the awl’s surface. Within the cal data; however, it is important to note that with XRF, corrosion, there was also SnO that was measured by EDXS. 0.3% Ni, As, Ag, and Pb were detected. One end of the belt Copper oxides (cuprite) can be found in the centre of the clip was pinched off, and the cross-section of the belt clip sample. The hardness values of 245–274 HV for the sample englobed in acrylic resin. The unetched sample revealed are the highest measured in this study. They are related to lightly deformed CuS-inclusions of about 20–30% of total both the high amount of Sn in the alloy and the intense cold deformation. Some of the inclusions also contain up to 2% deformation applied in the final step of production. of Sn. Etching the sample with Klemm II revealed heavy coring, indicating a non-homogenous alloy (Fig. 5f). The etchant developed undeformed, equiaxed grains of α-solid 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 13 of 19 125 solution with twins of about ca 30 × 40 μm in diameter. No the sample revealed elongated CuFeS-inclusions of about (α + δ) eutectoid of the Cu-Sn system remained, indicating 30–40% of total deformation. The inclusions also contain longer or more frequent annealing followed by cold defor- lesser amounts of Sb. Etching the sample with Klemm II mation. In the final working step, the belt clip was shortly revealed heavy coring, indicating an inhomogeneous alloy. annealed. In the corrosion, Ni and Sb were enriched. The The etchant developed small, ca 25 × 35 μm in diameter, corrosion follows both the dendritic structure and grain equiaxed grains of α-solid solution with twins (Fig. 6a). No boundaries and intracrystalline dislocations (annealing (α + δ) eutectoid of the Cu-Sn system remained, indicating twins and strain lines) of single grains. The hardness values longer or more frequent annealing followed by cold defor- of 92–128 HV correspond to annealing applied as a final mation. As the final working step, the belt clip was shortly working step. annealed. Under polarized light and supported by EDXS analyses, copper carbonates and oxides are present, as are Prigglitz, inv. no. UF‑22692.1652‑A, belt clip various tin oxides. Corrosion in the sample follows both the dendritic structure and grain boundaries and intracrystal- The belt clip is made of tin-bronze with about 8% Sn, 0.6% linearly between the dislocations (annealing twins) of single S (EDXS), 0.2% Fe, and 0.4% Sb. Nickel and As are also grains. The hardness values of 96–110 HV correspond to present in trace amounts, and Ag and Pb were not detected. annealing in the final working step. One end of the belt clip was pinched off, and the cross- section of the belt clip englobed in acrylic resin. Unetched, Fig. 6 Microstructures. Belt clip inv.no. UF-22692.1652 from Prigglitz: a Etched with Klemm II. Coring and fine equiaxed grains of α-solid solution with annealing twins. Rod inv.no. UF-22692.912 from Prigglitz: b Etched with Klemm II; much (α + δ) eutectoid and Cu-drops are visible. c SEM image. Note the Cu-drops and the massive (α + δ) eutectoid. Wire ID S013 from Kammerwandgrotte: d Etched with ferric chloride. Complete cross-section. Note the smaller grain size on the outside. Prigglitz, bracelet (inv.no. UF-22692.1780): e Unetched. Note the cop- per drop and the presence of (α + δ) eutectoid. The CuFeS- inclusions are not deformed. Pottschach, pin (inv.no. 72.488): f Etched with ferric chloride 1 3 125 Page 14 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Prigglitz, inv. no. UF‑22692.912, rod/wand eutectoid of the Cu-Sn system that contains up to 0.8% Sb. Etching the sample with ferric chloride and Klemm II The rod is made of tin-bronze with about 12% Sn, 0.5% S revealed coring and 25–40 μm equiaxed grains of α-solid (EDXS), and 0.6% Pb. Nickel and Sb are present in trace solution with twins. The presence of the (α + δ) eutectoid amounts, while Fe, As, and Ag were not detected. A cross- indicates a low temperature (< 520 °C) or shorter annealing section of one end of the rod was englobed in acrylic resin. time at higher temperatures. Of particular importance are The unetched sample shows a porous, as-cast, dendritic the drops of pure Cu in the sample surrounded by CuFeS microstructure with a few globular CuS-inclusions and inclusions (Fig. 6e). The drops indicate that not all of the Cu high amounts of (α + δ) eutectoid in the Sn-rich zones of was completely dissolved when the molten alloy was poured the alloy. The eutectoid may also contain some Fe. Of par- into the form. In the final working step, the bracelet was ticular importance are the drops of pure Cu surrounded by annealed. The corrosion follows both the dendritic struc- CuS-inclusions (Fig. 6b–c). These Cu-drops indicate that ture and grain boundaries and intracrystallinearly between not all of the Cu was dissolved entirely when the molten the dislocations (annealing twins) of single grains. As seen alloy was poured into the form. In the corrosion, copper and under polarized light, and according to the EDXS analyses, tin oxides were noted, while the CuS-inclusions were usu- both copper carbonates and oxides (shiny, dark-red cuprite ally not corroded. The hardness values of 176–245 HV are crystals) were present, as were various tin oxides. The hard- relatively high and relate both to the high amount of brittle ness values of 96–151 HV are in good agreement with an — but hard (α + δ) eutectoid (Mödlinger and Sabatini 2017) as-cast and annealed 14% tin-bronze. — and the high amount of Sn in the alloy. In comparison, hardness measurements in the centre of one of the Cu-drops Pottschach, inv. no. 72.488, pin showed 88 HV. It is also possible that a Sn-rich area beneath the Cu-drop was struck during measuring. The pin is made of tin-bronze with about 9.2% Sn, 0.4% S (EDXS), 0.1% Fe, and Sb. Nickel, As, Ag, and Pb are present in trace amounts. The sample was taken from the Kammerwandgrotte, ID S013, wire shaft of the pin, and the cross-section englobed in acrylic resin. The unetched sample revealed CuS-inclusions with The wire is made of a 12% tin-bronze with about 0.5% S a maximum total deformation of about 10%. Porosity in (EDXS), 0.1% Fe, and 0.2% Sb. Other elements, such as the sample significantly increased towards the centre, cor - Ni, As, and Pb, are present in trace amounts. Silver was not responding to the centre of the pin shaft. Etching the sam- detected, and S and Fe are mainly present in globular CuFeS- ple with ferric chloride and Klemm II revealed coring and inclusions. These inclusions also contain some Pb. Etching 25–40 μm equiaxed grains of α-solid solution with twins and the sample with ferric chloride revealed polyhedric grains strain lines (Fig. 6f). The absence of the (α + δ) eutectoid of different sizes with annealing twins and strain lines. The indicates high temperature or more prolonged annealing. latter are only present in the smaller grains (Fig. 6d). The As a final working step, the pin shaft was cold deformed. wire is porous and cracked in the sampled area, even though Corrosion in the sample does not follow the dendritic struc- it was subjected to light deformation. The slight deforma- ture or grain boundaries, or individual grain dislocations tion also resulted in smaller grains close to the surface and (annealing twins and strain lines). Instead, it follows a more bigger ones in the wire’s centre. Corrosion in the sample irregular pattern typically seen in microbial-induced corro- follows the inter- and intracrystalline structures, especially sion (Piccardo et al., 2013). As seen under polarized light, in the sample’s centre, consisting mainly of copper oxides and according to the EDXS analyses, both copper carbonates (cuprite) and carbonates (azurite, malachite). Hardness dif- and oxides (cuprite crystals) are present, as are various tin fers significantly from grain to grain. While the bigger grains oxides. Interestingly, the copper oxides form layers on the in the sample centre are rather soft (81–103 HV), the smaller pin’s shaft surface, while the carbonates are close to the core. ones on the edge are much harder (122–170 HV). The hardness values of 160–193 HV are in good agreement with a cold deformed, previously as-cast and annealed 11% tin-bronze. Prigglitz, inv. no. UF‑22692.1780, bracelet The bracelet is made of tin-bronze with about 12.8% Sn, Discussion 0.7% S (EDXS), and 0.1% Fe and Sb. Nickel is present in trace amounts. One end of the bracelet was pinched off, All of the axes and chisels in this study are made of tin- and the cross-section englobed in acrylic resin. Unetched, bronze with varying amounts of Sn ranging from 7.5 to 10%. the sample revealed globular CuFeS-inclusions and (α + δ) They all show coring, indicating that both the duration and 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 15 of 19 125 1 3 Table 3 Overview of selected metallographic features No Site Object ID CuS/Cu Fe S Def. incl.% Strain lines Twins Coring (α + δ) Max. HV 2-x 2 1 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1272 CuS 40–50 x x x - 205 2 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1140A CuS 20–30 x x x x 230 3 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1672 CuS 70–80 x x x - 275 4 Prigglitz-Gasteil, Axe (socketed) [S001] CuS 70–80 x x x x 300 Klausgraben 5 Prigglitz-Gasteil Belt clip UF-22692.1652 Cu Fe S 30–40 - x x - 110 2-x 2 6 Prigglitz-Gasteil Belt clip UF-22692.1673 CuS 20–30 - x x - 130 7 Prigglitz-Gasteil Bracelet UF-22692.1780 Cu Fe S 0 - x x x 150 2-x 2 8 Prigglitz-Gasteil Casting cake UF-22692.675 CuS - - - - - 105 9 Prigglitz-Gasteil Knife UF-10.964 Cu2-xFe2S globular; edge 60-70 ? x x x 255 10 Prigglitz-Gasteil Knife UF-22692.2188 Cu2-xFe2S 30–40 x x x - 275 11 Prigglitz-Gasteil Rod / wand UF-22692.912 CuS 0 - - as-cast x 245 12 Grünbach, Gelände Axe (end-winged) UF-19,452 CuS 30–40 x x x x 220 13 Reichenau, Kammer- Chisel [S041] CuS > 90 x x x x 240 wandgrotte 14 Reichenau, Kammer- Wire (bent) [S013] Cu2-xFe2S < 10 - x x - 170 wandgrotte 15 Pottschach Knife 72.485 Cu2-xFe2S - - x x - 145 16 Pottschach Knife 72.484 Cu2-xFe2S 10–20; 30–40 x x x - 230 17 Pottschach Pin 72.488 CuS 10 x x x - 195 18 Prein an der Rax Double-pointed ‘awl’ UF-9958 Cu2-xFe2S 0–20 x x x - 180 19 Sieding Axe (socketed) UF-5098 Cu2-xFe2S 10–20 x x x - 215 20 Ternitz, Gfieder Axe (socketed) [S042] Cu2-xFe2S 10–20 x x x - 240 125 Page 16 of 19 Archaeological and Anthropological Sciences (2021) 13:125 temperature of the annealing process were insufficient to no. UF-22692.2188) are not significantly deformed on the homogenize the alloy (Table 3). However, all of the axes edge, Prigglitz knife 10.964 shows 60–70% of total deforma- and chisels showed equiaxed grains of α-solid solution with tion but less final deformation than the other one from the twins and strain lines, indicating cold deformation in the same site. In combination with the high amounts of Sn and final working step due to annealing. CuS-inclusions were Fe, the result is a relatively high hardness of over 250 HV found in axes S001 (Prigglitz), S079 (Grünbach am Sch- on the edge. The Prigglitz knife inv. no. UF-22692.2188 neeberg), and the chisel from Kammerwandgrotte, and all shows the knives’ highest hardness value with up to 274 HV other axes contained CuFeS-inclusions. The total amount of (edge) and up to 193 HV (core; ca 2 mm from the edge). The deformation for the axes on their edges was astonishingly higher HV is due to the final deformation applied in the last low overall (usually < 10%), with only axe S001 showing working step. Hardness values are higher on the edges of 70–80% of total deformation in combination with (α + δ) three knives (UF-22692.2188, 10.964, 72.484), while one eutectoid. The axe also had the highest hardness values of knife shows a uniform distribution of similar values (knife all the objects (300 HV at the edge). Similarly, the chisel 72.485). Again, these measurements are in good agreement showed a significant total amount of deformation of the with the observed microstructures and annealing in the last edge (ca 90%), and in combination with the presence of assumed working step. (α + δ) eutectoid, it had high hardness values (240 HV). The Four tin-bronze double-pointed awls — three from Prig- hardness values are directly related to the alloy choice, the glitz and one from Prein — were studied. While two of the total amount of deformation, and especially the deforma- awls from Prigglitz are made of tin-bronze with about 10% tion applied in the final working step. The influence of the Sn, the third (inv. no. UF-22692.1672) contains more than final working step on the end product is demonstrated by the 14%. The awl from Prein contains far less at ca 5%. All socketed axe from Ternitz (10–20% total deformation) and four awls contain S, which is mainly present in the CuS- the chisel (90% total deformation and its eutectoid). Both inclusions, and Fe was only detected in trace amounts bronzes contain similar amounts of Sn and Fe, but the sock- in the awl from Prein. Interestingly, As and Ag were not eted axe underwent a higher degree of final deformation than detected in any of the awls, Ni at trace amounts in two the chisel, which resulted in far higher final hardness. (Prigglitz UF-22692.1672 and Prein) and Sb at about 0.1% Four tin-bronze knives — two from Pottschach and two in three (Prigglitz UF-22692.1672 and UF-22692.1140A, from Prigglitz — were studied. All four of them contain and Prein). The awl from Prein showed a relatively high relatively high amounts of Sn (9 to 15%). Moreover, one of amount of Pb at 0.7%, and of the other awls, only the Prig- the two Pottschach knives contains 1.2% Sb. All four knives glitz UF-22692.1672 showed traces of Pb. The four awls contain S and Fe, which are mainly present in the CuFeS- were studied metallographically and are characterized by inclusions. The four knives differ in their post-casting treat- very pure Cu in their production. The four awls, however, ment, however. While one knife from Prigglitz (inv. no. do not differ in their post-casting treatment but do in its 10.964) showed a high amount of total deformation and was intensity. All but one awl (inv. no. UF-22692.1672) showed cold worked after several annealing/cold deformation steps, heavy coring. While three awls show a total amount of defor- which is evident by higher hardness and finer grains, the mation of about 0–50% in the sampled area, only inv. no. other (inv. no. UF-22692.2188) showed less total deforma- UF-22692.1672 showed a much higher level of deforma- tion but a higher final cold deformation. The second knife’s tion at 70–80%. All four were cold deformed, and annealed, treatment resulted in higher hardness values on the edge, with cold deformation being the last step of production. even though its tin-amount is much lower (10 versus 15%). In one of the awls (inv. no. UF-22692.1140A), the (α + δ) Noteworthy, the blade of knife inv.no. 10.964 broke once, eutectoid is still present, indicating short, low-temperature was shortened, and attached to a new handle. annealing, followed by cold deformation. The Prigglitz awl The two Pottschach knives show less total deformation inv. no. UF-22692.1672 shows the highest hardness value than the ones from Prigglitz. Also, knife 72.484 shows slight of them all at 274 HV. This is due to the intensive total, deformation indications in the final working step and reaches and especially the final, deformation and the higher amount an edge hardness of 230 HV. Knife 72.485 does not show of Sn in the alloy. The other two awls from Prigglitz had a any indications of final deformation; here, annealing was maximum HV of 230 (inv. no. UF-22692.1140A) and 205 the last working step, resulting in low hardness values of (inv.no. UF-22692.1272). In agreement with the low amount 145 HV or less. The presence of undissolved copper grains of Sn in the alloy and the low total and final deformation, in the matrix of knife 72.485 indicates the use of ‘fresh’ the Prein awl showed the lowest hardness values between copper and tin to produce the alloy or the addition of ‘fresh’ 160–181 HV. copper to a recycled tin-bronze. All knives show a low The final annealing of both belt clips makes sense since a amount of total deformation in the core area (max. 20%). final cold deformation would have increased their brittleness. While the Pottschach knives and one from Prigglitz (inv. Belt clips need to be flexible. The clips’ production and their 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 17 of 19 125 hardness values are very similar, as is their chemical com- that objects were very much likely not made using recycled position with the exception of Ag in clip UF-22692.1673, tin-bronzes. which contains about 0.3% while none was detected in clip Regarding the objects’ function, all cutting edge objects UF-22692.1652. Concerning the rod/wand studied, a freshly were worked to improve their material properties, especially produced Cu-Sn alloy is presumed, or adding ‘fresh’ Cu to their edge hardness. Hardness values differed for the jew - an already existing and recycled tin-bronze, as the micro- ellery, except for the pin where the last working step was structure shows not-dissolved Cu-drops, often surrounded annealing, and hardness values are thus comparatively low at by CuS-inclusions. Neither Fe, As, or Ag were detected. The between 110 and 170 HV. These values suggest that elastic- tin-bronze wire was cast and, after some deformation and ity was more important than hardness. Only the as-cast rod/ following annealing, slightly deformed. The bracelet was wand from Prigglitz shows relatively higher hardness values, also cast and slightly deformed and then annealed. Drops of which are related to the presence of the eutectoid. pure Cu indicate that not all of the Cu was dissolved entirely Concerning cutting edge objects (axes, chisels, and pick- when the molten alloy was poured into the form. The brace- axe), hardness values range from 215 to 300 HV, highlight- let was annealed for a short time at lower temperatures in the ing that the material properties of the edges were intention- final working step, as (α + δ) eutectoid is still present. The ally improved for an ideal usability of the tools. The only pin was annealed and only slightly deformed after casting. exception is knife 72.485 from Pottschach with 145 HV. The absence of the (α + δ) eutectoid indicates high tempera- Hardness values depend on various factors such as alloy ture or more extended annealing. As a na fi l working step, the composition, thermal treatment, and deformation applied. pin shaft was cold deformed. For the objects studied, this is particularly the Sn and Fe Of particular interest are the undissolved drops of Cu in content. The presence of Fe, even at values as low as 0.15%, the CuSn-matrix, which were found in every fifth of the also reduces formability and causes cracks and surface objects (Ternitz, socketed axe (ID S042): twinned grain; defects (see Nerantzis 2015; Papadimitriou 2008). It also Pottschach, knife (72.485): grain; Prigglitz, rod/wand (UF- influences the eutectoid and, most importantly, the final 22692.912): drops with surrounding CuS; and Prigglitz, deformation treatment that was applied. As no direct cor- bracelet (UF-22692.1780): big drops). The drops range relation between Fe or Sn content, final deformation, and from 5 to 35 μm in diameter. Such unalloyed copper inclu- hardness values were detected (likely also related to the low sions (UCI) have been noted in other archaeological bronzes number of samples), we assume that Bronze Age smiths (Bosi et al. 2002). The UCI observed in the four objects simply stopped at a certain point during the final working discussed here do not relate to corrosion, which are usually step (cold deformation) once they reached a (for them) suf- irregularly shaped from pseudo-morphically replacing other ficiently good result. This does not necessarily need to be the phases and are instead due to the (s)melting process itself. highest possible hardness of the alloy, as was also observed For the objects in this study, not all of the Cu was completely often at Early Bronze Age axes from north Alpine regions dissolved when the molten alloy was poured into the casting (Kienlin 2008). mould. The CuS-layers around the copper drops of the rod/ wand (UF-22692.912) suggest the copper drops might have Conclusions already formed during the smelting process (Bosi et  al. 2002). Above 1105 °C, Cu and S (< 20%) are immiscible The Late Bronze Age site of Prigglitz-Gasteil is considered with a top layer of C u S and a bottom layer of Cu with about a regional centre of copper production and bronze working 2% S (copper-rich Cu–S solution). Upon cooling, the solid based on the evidence of an openwork copper ore mine and phase Cu S and the copper-rich Cu–S solution are present, a nearby bronze casting workshop. Metallographic analyses and slagging of solid Cu S takes place to obtain high-purity of different cutting tools and jewellery items from Prigglitz- copper. During cooling, spherical particles of Cu S contain- Gasteil, and six contemporaneous sites in the surrounding ing a copper-rich core might form, which are heavier than region, provide insights into the post-casting treatment of Cu S particles and therefore less likely to slag and remaining different kinds of bronze objects. This information helps us in the alloy to form UCI (Bosi et al. 2002). While singular understand the overall chaîne opératoire in metal produc- copper drops in crystallized form were noted for socketed tion, which is important in identifying local metalworking axe (ID S042) and the knife (72.485), many of them with traditions. up to 35 μm diameter, and most had already oxidized to As discussed in detail, objects with a cutting edge were CuO, were noted on bracelet (UF-22692.1780). For these worked according to their function. For instance, the sharp three objects, we can either assume that fresh copper was edges of axes and knives and the points of the awls had added to an already existing CuSn-alloy (recycling) or that undergone annealing and cold deformation cycles with the CuSn alloy was freshly produced. Hence, we can assume cold deformation as the final step in almost all cases. This 1 3 125 Page 18 of 19 Archaeological and Anthropological Sciences (2021) 13:125 were made. The images or other third party material in this article are sequence of treatments resulted in higher hardness. The included in the article’s Creative Commons licence, unless indicated total deformation on blade edges ranged from 10 to 20% otherwise in a credit line to the material. If material is not included in (one awl, two socketed axes), 30–50% (end-winged axe, two the article’s Creative Commons licence and your intended use is not awls, two knives), 60–70% (one knife, one awl, one sock- permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a eted axe), and beyond (chisel with over 90%). Interestingly, copy of this licence, visit http://cr eativ ecommons. or g/licen ses/ b y/4.0/ . these objects’ alloys do not seem to have been chosen inten- tionally to include higher Sn concentrations except for awl UF-22692.1672 and knife 10.964 from Prigglitz. Small jewellery objects, such as the belt clips, the brace- References let, and wire, which need to have a certain amount of flexi- bility to function, were worked far less with a total amount of Bosi C, Garagnani GL, Imbeni V, Martini C, Mazzeo R, Poli G (2002) Unalloyed copper inclusions in ancient bronze artefacts. 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Work on the cutting edge: metallographic investigation of Late Bronze Age tools in southeastern Lower Austria

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Abstract

This paper analyses 20 Late Bronze Age (ca 1080–800 BC) copper alloy objects to discern their manufacture and the skills of local craftsmen. Several tools and jewellery were studied that originated from a bronze workshop located immediately next to the Prigglitz-Gasteil copper ore mining site and several contemporaneous sites in the surrounding area. The samples were studied with optical microscopy (microstructurally), and SEM-EDXS and XRF (chemical analyses). Our analyses are part of a larger study and suggest that the Prigglitz region’s bronze production was not standardized. Particular alloys do not seem to have been chosen for object types or due to their intended use-function. Notably, approximately 20% of the objects contain unalloyed copper inclusions, which are most likely a result of the incomplete mixing of scrap metals and alloys during their production. Keywords Late Bronze Age · Eastern Alps · Austria · Mining site · Metallographic analysis · XRF analyses · Production of copper alloy objects · Chaîne opératoire Introduction Schneeberg (Mühlhofer, 1952; Trebsche et al., 2019, and Rauheneck near Baden (Calliano, 1894, 90). The raw metal Numerous bronze casting workshops have been found that that supplied these workshops is disputed; however recent belong to the Middle Danubian Urnfield Culture dating to archaeometallurgical investigations of copper alloys from the Late Bronze Age (ca 1300–800 BC) in eastern Austria, the region suggest that there were likely several ore min- southern Moravia, southwestern Slovakia, and western Hun- ing sites that supplied Late Bronze Age metalworkers in the gary (Lochner, 2013). Evidence of archaeological and metal- Middle Danube region (Czajlik, 2013; Zachar and Salaš, lurgical remains in these regions (e.g. casting moulds and 2018, 2019; Mödlinger and Trebsche, 2020). debris and semi-finished products) shows that metalworking During recent excavations at the Prigglitz-Gasteil site, in was concentrated in central hillforts at sites such as Szentvid the Neunkirchen district, an extraordinary Late Bronze Age near Velem (comitate of Vas), and Gór-Kápolnadomb (comi- casting workshop was discovered. The site is not located at a tate of Vas) and Várvölgy (comitate of Zala) in western Hun- hillfort but immediately next to a contemporaneously dated gary (Ilon, 1992, 1996, 2018; Müller, 2006; Czajlik, 2014). copper ore mine at the slopes of the Gahns mountain in In adjacent Lower Austria, metal workshops are assumed the Schneeberg-Rax region of southeastern Lower Austria. to have existed at the hillforts Schanzberg near Thunau am Excavations at the site from 2010 to 2014, and subsequent Kamp (Lochner, 2004, 2017), ‘Gelände’ near Grünbach am geophysical surveys and core drillings from 2017 to 2018 (Trebsche, 2013, 2015b, 2015a; Trebsche and Pucher, 2013; Haubner, et al., 2019), have shown that copper ore, mainly * Marianne Mödlinger chalcopyrite and pyrite mineralization, were extracted from marianne.moedlinger@gmail.com opencast mines at the site during the Late Urnfield Period Peter Trebsche (Ha B, ca 1080 to 800 BC). The dwellings and workshops peter.trebsche@uibk.ac.at of Late Bronze Age miners and craftsmen at the site were Dipartimento di Chimica e Chimica Industriale (DCCI), constructed on artificial terraces cut into the heaps of mining Università degli Studi di Genova, Genoa, Italy debris. During the excavations, two terrain terraces, T3 and Institut für Archäologien, Leopold-Franzens-Universität T4, were investigated in detail, yielding evidence for bronze Innsbruck, 6020 Innsbruck, Austria Vol.:(0123456789) 1 3 125 Page 2 of 19 Archaeological and Anthropological Sciences (2021) 13:125 casting activities. The evidence consists of numerous casting hilltop, and hoards, located within a radius of ca 15 km, drops and fine platy slags that predominantly belong to three were selected for metallographic investigation. The 20 met- occupation phases: T3-10, T3-08F, and T3-08A. allographic analyses presented in this paper are compared On the upper terrain terrace of T3, which according to to objects from the Mahrerdorf Late Bronze Age hoard a series of radiocarbon dates, was in use from the end of (Mödlinger and Trebsche 2020). the tenth century BC to the end of the ninth century BC (Trebsche, 2015b; Trebsche, in preparation), only casting waste and fragments of casting tools were found so that the Materials and methods spectrum of production is unknown. However, four finds from the  site are important as they indicate the produc- Selected objects and their site context tion of at least three categories of bronze objects: first, one fragment of a sandstone casting mould for a knife with a From the numerous copper alloy fragments found at, and in tang hilt (Griffdornmesser, probably type Baumgarten after one instance near, Prigglitz-Gasteil, almost all of the pre- Říhovský, 1972, 64–71; Trebsche, 2015b, 49, Fig.  2/7); served tools with cutting edges or points were selected for second, one sandstone casting cone for the production of metallographic analysis. These tools include a tanged Still- a socketed axe; third, a bronze casting cone that fits into fried-type knife (Fig. 2: 10; cf. Říhovský, 1972, 55–58; Jiráň the socket of small arrowheads, indicating on-site weapon 2002, 59–60; Veliačik 2012, 305–306), a tanged knife that production; fourth, a casting sprue that cannot be precisely had been reworked from a fragment (Fig. 2: 9; Říhovský, attributed to an artefact type but is the size appropriate for 1972, 76), and three double-pointed awls (Fig. 2: 1–3). One casting an object like a knife, razor, or sickle (Trebsche and socketed axe with curved decoration (Fig. 2: 4; cf. Mayer, Pucher, 2013, 127–128, Fig. 14/2). Hence, the workshop at 1977, 192–198) was found ca 500 m away at Klausgraben. Prigglitz-Gasteil seems to have produced a range of artefacts The jewellery selected for analysis included two belt clips that indisputably included arrowheads, knives (Griffdorn- (Fig. 2: 5–6), one fragment of a bracelet with a flat cross- messer), and socketed axes. section (Fig. 2: 7), and a rod or wand of unknown function No heavy tools, such as hammers, axes and pickaxes, (Fig. 2: 11). All the objects are copper-tin alloys except for a or weapons like swords, were found at the site; only small casting cake of unalloyed copper (Fig. 2: 8). Strictly speak- objects such as rings, belt clips, double-pointed tools, two ing, the local production of the bronze artefacts cannot be completely preserved knives, and two dress pins were dis- proven, as chemical and lead isotope analyses have shown covered during the excavations. Nevertheless, the number that mixing of different copper alloys and recycling played a of copper alloy artefacts found on terraces T3 and T4, in an significant role at the Prigglitz-Gasteil site (Mödlinger et al. area of ca 210 m , is high at about 250 weighing a total of ca 2021). 663 g. Most of the artefacts are remnants of the metalwork- For comparison to these alloys, objects from sev- ing processes with ca 200 casting drops and small bronze eral nearby sites were selected. The first is a gravesite fragments, and 23 other pieces from casting or recycling. In at Pottschach located 5 km away from Prigglitz-Gasteil a recent study of the chemistry and isotopic makeup of the (Kerchler, 1960). It was chosen because the same types Prigglitz-Gasteil metal finds and copper ores, we investi- and decoration of dress pins are found there (Trebsche and gated the chaîne opératoire of local copper production and Pucher, 2013, 122, Fig. 7/1–2). From the grave goods, two bronze working, as well as the regional distribution networks decorated tanged knives, a Velem-St. Vid type (Fig. 2: 15; of metal artefacts. In that study, we concluded that Prig- cf. Říhovský, 1972, 51–53) and a Baumgarten type (Fig. 2: glitz-Gasteil was an active copper mining, metal-making, 16; cf. Říhovský, 1972, 67–71), and one pin with a small and importation and recycling site, especially in the late vase head (Fig. 2: 17; cf. Říhovský, 1979, 198–207) were tenth/ninth centuries BC. Prigglitz-Gasteil sourced metal studied. The second site, the Kammerwandgrotte cave, or raw materials were exchanged at least in the Schwarza located 7 km from the Prigglitz mine at Reichenau an der Valley’s micro-region. However, additional investigations Rax where there is evidence for Early and LBA activities, of more distant LBA sites will be necessary to fully explore including metallurgy (Hottwagner and Lang, 1999), was the extent of exchange and the Prigglitz-Gasteil mining site’s selected. One chisel fragment (Fig.  2: 13) and one wire role (Mödlinger et al. 2021). fragment (Fig. 2: 14) from the cave were analysed due to The aim of this paper is to investigate the post-casting their compositional similarity to the copper produced at treatment of select bronze objects to gain insight into post- Prigglitz-Gasteil. These artefacts cannot be precisely dated casting manufacturing processes and the skills of regional by find contexts. In the third site, from the LBA mining craftsmen (Fig. 1). For this work, a series of 20 copper and region of Prein an der Rax, ca 13 km from Prigglitz, a bronze objects from the Prigglitz-Gasteil copper mining site, double-pointed bronze tool (Fig.  2: 18) was chosen for and the surrounding Late Bronze Age dated cemetery, cave, study. Smelting activities in this region have been dated by 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 3 of 19 125 Fig. 1 Location of Prigglitz-Gasteil and the surrounding find spots of the analysed finds in this paper (Cartography: © BEV (Bundesamt für Eich- und Vermessungswesen), 2021) radiocarbon to the Late Urnfield period (ninth century BC; In sum, the objects studied in this paper include four axes, Trebsche, 2015b, 43–47). Fourth, from the metalworking four knives, four awls, one casting cake, two belt clips, one centre likely located at the Gelände near Grünbach hillfort chisel,  two pieces of jewellery (bracelet, pin),  one wire in Schneeberg, one end-winged Haidach type axe (Mayer, fragment, and a bronze rod/wand (Table 1). X-ray fluores- 1977, 152–158; Fig. 2: 12) was selected. It belongs to a cence and Pb-isotope analyses of ca 125 finds from Prigglitz hoard dating to phase Ha A (ca 1200 to 1080 BC; Trebsche and the surrounding area, including the objects presented in et  al.,  2019). Fifth, almost all cutting tools (a pickaxe, this paper, are published elsewhere (Mödlinger et al. 2021). a chisel, an adze, two winged axes, and three socketed axes) from the Mahrersdorf hoard (Lauermann and Ram- Methodology mer, 2013, pl. 44–47) were sampled. Archaeometallurgi- cal analyses of this hoard have already been published in Microstructural characterization of the objects and chemi- a separate article (Mödlinger and Trebsche, 2020). And cal analyses using energy-dispersive X-ray spectroscopy finally, two LBA socketed axes found without context from (EDXS) were performed on freshly polished cross-sections Sieding (Fig. 2: 19) and at the mountain Gfieder in Ternitz taken at the edges of the blades for axes, chisels, and knives; (Fig. 2: 20), respectively, were chosen for comparison to tip for awls; centre of wires and bracelets; and end of belt the samples from Prigglitz. The specimen from Ternitz clips and pins (Fig. 2). Further, X-ray fluorescence (XRF) belongs to the type ‘mit bogenumrandetem Lappendekor chemical and high-resolution multi-collector inductively und abgesetzter Klinge’ (Mayer, 1977, 198–199), whereas coupled mass spectrometry (HR-MC-ICP-MS) Pb isotope the other has unique decoration and was classified as a analyses were later carried out on the same and on freshly special type (Mayer 1977, 204 no. 1175). polished samples (see Mödlinger et al. 2021). The EDXS 1 3 125 Page 4 of 19 Archaeological and Anthropological Sciences (2021) 13:125 1 3 Table 1 Metal objects sampled for metallographic analysis from Prigglitz and the surrounding area. Objects in ‘[]’ do not have inventory numbers and are instead labelled with the sampling number. ‘NHM’ corresponds to the Natural History Museum Vienna; ‘LNÖ’, State Collections of Lower Austria; and ‘SL’, Reinhard Lang’s private collection, Gloggnitz. The absolute chronol- ogy follows Sperber (2017) No Find spot Context Object Museum Inv. no Sampling Relative chronol- Absolute chronol- Type Reference ogy ogy 1 Prigglitz-Gasteil Mining site Double-pointed LNÖ UF-22692.1272 Tip Ha B2-3 960–800 BC - Unpublished ‘awl’ 2 Prigglitz-Gasteil Mining site Double-pointed LNÖ UF-22692.1140A Tip Ha B2-3 960–800 BC - Trebsche / Pucher, ‘awl’ 2013, Fig. 19/10 3 Prigglitz-Gasteil Mining site Double-pointed LNÖ UF-22692.1672 Tip Ha B2-3 960–800 BC - Unpublished ‘awl’ 4 Prigglitz-Gasteil, Isolated find near Axe (socketed) SL [S001] Edge Ha B 1080–800 BC With curved deco- Trebsche, 2015b, 47 Klausgraben mining site ration Fig. 2/3 5 Prigglitz-Gasteil Mining site Belt clip LNÖ UF-22692.1652 End Ha B2-3 960–800 BC - Unpublished 6 Prigglitz-Gasteil Mining site Belt clip LNÖ UF-22692.1673 End Ha B2-3 960–800 BC - Unpublished 7 Prigglitz-Gasteil Mining site Bracelet LNÖ UF-22692.1780 End Ha B2-3 960–800 BC - Unpublished 8 Prigglitz-Gasteil Mining site Casting cake LNÖ UF-22692.675 Border Ha B2-3 960–800 BC - Unpublished 9 Prigglitz-Gasteil Mining site Knife LNÖ UF-10,964 Edge Ha B2-3 960–800 BC (Reworked from a Říhovský, 1972, 76 fragment) no. 303 pl. 29/303 10 Prigglitz-Gasteil Mining site Knife LNÖ UF-22692.2188 Edge Ha B2-3 960–800 BC Type Stillfried Trebsche, 2015b, Fig. 2/6 11 Prigglitz-Gasteil Mining site Rod/wand LNÖ UF-22692.912 End Ha B2-3 960–800 BC - Trebsche / Pucher, 2013, Fig. 19/6 12 Grünbach, Hilltop settlement Axe (end-winged) LNÖ UF-19,452 Edge Ha A 1200–1080 BC Type Haidach Trebsche et al., Gelände 2019, 561 Fig. 5 13 Reichenau, Kam- Cave Chisel LNÖ [S041] Edge LBA? 1330–800 BC? - Hottwagner / Lang, merwandgrotte 1999, 779 Fig. 749 14 Reichenau, Kam- Cave Wire (bent) LNÖ [S013] End LBA? 1330–800 BC? - Hottwagner and merwandgrotte Lang, 1999, 779 Fig. 748 15 Pottschach Cemetery Knife NHM 72.485 Edge LBA 1330–800 BC ‘Griffdornmesser Říhovský, 1972, 52 vom Typ Velem no. 179 pl. 17/179 St. Vid’ 16 Pottschach Cemetery Knife NHM 72.484 Edge Ha B2-3 960–800 BC ‘Griffdornmesser Říhovský, 1972, 68 vom Typ Baum- no. 274 pl. 26/274 garten’ 17 Pottschach Cemetery Pin NHM 72.488 Shaft Ha B2-3 960–800 BC ‘Nadel mit kleinem Říhovský, 1979, Vasenkopf’ 203 no. 1706 pl. 62/1706 18 Prein an der Rax Smelting site Double-pointed LNÖ UF-9958 Tip Ha B2-3 960–800 BC - Hampl and May- ‘awl’ rhofer, 1963, 52 (Prein V) Archaeological and Anthropological Sciences (2021) 13:125 Page 5 of 19 125 analyses were performed using a JEOL JSM-6460LV SEM with an Oxford Instruments SDD XMax 20 under high vac- uum at IRAMAT-CRP2A, Bordeaux, France. The SEM was calibrated using the internally provided software database standards, as well as certified pure Si and Co standards for quantification. The results shown are the mathematical aver - age of 5–8 spectra of approximately 200 × 600 μm taken for 60 s each. The presence of minor and trace elements was supported by their detection in higher amount in the cor- rosion layers. The SEM-EDXS analyses were used to iden- tify different intermetallic compounds, inclusions, and the absence or presence (qualitative) of sulphur (S), which was not detected by XRF. The qualitative presence of each alloy- ing element was classified as major with wt.% > 1, minor between 1 and 0.3, and trace at < 0.3; their presence was normalized and is given in wt.% in Table 2. Chemical analysis was carried out on drilling samples using an ARL Quant’X (Thermo Fisher Scientific) XRF (bulk analyses) at 28 kV (with Pd filter) and 50 kV (with Cu filter), and on the surfaces of the samples polished for metallographic study using a Fischerscope X-ray XAN 150 (W-band) (point measurements) at 50 kV (Al-filter) using a 1 mm collimator SD-detector for 50 s. The measuring time/ spot of 1–2 measurements/sample depended on the sample size for both instruments. Each analysis was performed at the CEZA-laboratory in Mannheim, Germany, for the bulk and points, respectively. Quantification of the resultant analyses closely followed the procedure described in Lutz and Per- nicka (1996). Manganese, Co, Zn, Se, Cd, Te, and Bi were below the detection limit of the Fischerscope, and, since S was only measured with EDXS, the results shown in Table 2 should be considered qualitative. There are notable differ - ences between the ARL Quant’X and Fischerscope results (e.g. sample nos. 19a and b), which are due to all-inclusive bulk versus point measurements, the nature of the sample (drilling vs. metallographic cross-section), and the presence of inhomogeneities and corrosion. The error rate for both techniques is 5–10% for the major elements, and even lower for Cu, and 20–50% for minor and trace elements. Characterization of the sample’s microstructure was per- formed on prepared cross-sections. Each sample was mounted in cold acrylic resin and polished using 400–1200 SiC papers, followed by a diamond suspension paste of up to 0.25 μm granulometry. The samples were characterized using optical microscopy in both bright and dark fields, chemically analysed using EDXS, and then etched for metallographic examination using aqueous ferric chloride and Klemm II to show greater detail. While aqueous ferric chloride produces a grain contrast, Klemm II is a colour etchant, which colours grains depend- ing on their orientation; segregation also becomes visible and intermetallics are not etched. The total amount of deformation applied to each sample was calculated by measuring the shape factor (SF) of the CuS or CuFeS inclusions (see Mödlinger and 1 3 Table 1 (continued) No Find spot Context Object Museum Inv. no Sampling Relative chronol- Absolute chronol- Type Reference ogy ogy 19 Sieding Isolated find Axe (socketed) LNÖ UF-5098 Edge Ha B 1080–800 BC (Special type) Mayer, 1977, 204 no. 1175 pl. 84/1175 20 Ternitz, Gfieder Isolated find from Axe (socketed) SL [S042] Edge Ha B2-3 960–800 BC ‘mit bogenum- Lang, 2000, 599 hilltop settlement randetem Fig. 474 Lappendekor und abgesetzter Klinge’ 125 Page 6 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Fig. 2 Late Bronze Age objects from southeastern Lower Aus- tria. Numbers 1–3 and 5–11 are from Prigglitz-Gasteil; 4 from Prigglitz-Gasteil, Klausgraben; 12 Grünbach, Gelände; 13–14 Reichenau, Kammerwandgrotte; 15–17 Pottschach; 18 Prein an der Rax; 19 Sieding; and 20 Ternitz, Gfieder The drawings; nos. 1–3, 5–8, 10–12, 18 were done by Daniela Fehlmann and Ulrike Weinberger; 4, 13–14, 20 by Franz Drost; 9, 15–17, 19 are from unknown artist(s). The numbers correspond to those listed in Tables 1, 2, and 3 Piccardo 2013). Vickers hardness measurements were carried chemical compositions of the finds discussed in this paper out using a Leitz Durimet 72-1b instrument at 100 g load over are provided in Table 2. 10 s. An FT-9929195 test block from Future-Tech-Corporation was used as a standard. Axes and chisel Prigglitz‑Gasteil, ID S001, socketed axe Results A sample was taken on the edge of the axe’s blade. Analy- In the following, the results are focused on the metallo- sis of the sample showed 8.5 wt.% Sn and 0.6% S. Nickel graphic analyses. The chemical analyses are thoroughly was also present at about 0.1% with Fe, As, Sb, Ag, and discussed elsewhere (Mödlinger et al. 2021). However, the Pb in trace amounts. The unetched sample shows CuS- inclusions with about 60–70% deformation. Etching with 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 7 of 19 125 Table 2 The elemental percentages of each sample are given in isque (*) indicates drilling samples analysed by ARL Quant’X XRF. wt.%. Manganese, Co, Zn, Se, Cd, Te, and Bi were not detected in Noteworthy are the differing amounts of Sn in the socketed axe from the samples analysed with the Fischerscope (FS). All other sam- Sieding that appear with different analytical methods (see ‘Sieding, ples show ≤ 0.005 Mn, Se, and Te, 0.01 Co, < 0.1 Zn, < 0.01 Cd, inv. no. UF-5098, socketed axe’) and < 0.06 Bi. Use of the Fischerscope is indicated by FS. An aster- No Site Object Inv.no Cu Fe Ni As Ag Sn Sb Pb FS 1 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1272 89 n.d n.d n.d n.d 11.0 n.d n.d x 2 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1140A 90 n.d n.d n.d n.d 9.5 0.12 n.d x 3 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1672 86 n.d 0.07 n.d n.d 13.7 0.10 0.08 x 4 Prigglitz-Gasteil, Axe (socketed) [S001]* 91 < 0.05 0.12 0.021 0.008 8.5 0.092 0.011 Klausgraben 5 Prigglitz-Gasteil Belt clip UF-22692.1652 91 0.22 0.07 0.03 n.d 8.3 0.24 n.d x 6 Prigglitz-Gasteil Belt clip UF-22692.1673 88 0.06 0.28 0.32 0.28 10.3 0.37 0.34 x 7 Prigglitz-Gasteil Bracelet UF-22692.1780 87 0.13 0.04 n.d n.d 12.8 0.13 n.d x 8 Prigglitz-Gasteil Casting cake UF-22692.675* 100 0.11 0.06 0.012 0.010 0.017 0.095 0.012 9 Prigglitz-Gasteil Knife UF-10,964 84 0.73 0.05 n.d n.d 15.3 n.d 0.14 x 10 Prigglitz-Gasteil Knife UF-22692.2188 89 0.19 0.14 0.14 n.d 9.9 0.41 n.d x 11 Prigglitz-Gasteil Rod / wand UF-22692.912 87 n.d 0.03 n.d n.d 11.9 0.06 0.61 x 12 Grünbach, Gelände Axe (end-winged) UF-19,452 89 0.09 0.40 0.51 0.15 9.1 0.52 0.19 x 13 Reichenau, Kam- Chisel [S041] 91 n.d 0.15 0.19 0.08 7.5 0.25 0.39 x merwandgrotte 14 Reichenau, Kam- Wire (bent) [S013] 88 0.14 0.06 0.06 n.d 12.0 0.20 0.05 x merwandgrotte 15 Pottschach Knife 72,485* 89 0.36 0.06 0.132 0.087 9.2 1.24 0.019 16 Pottschach Knife 72,484* 89 0.05 0.07 0.021 0.016 10.6 0.214 0.020 17 Pottschach Pin 72,488* 90 0.10 0.07 0.015 0.020 9.2 0.130 0.007 18 Prein an der Rax Double-pointed ‘awl’ UF-9958 94 0.08 0.05 n.d n.d 5.2 0.10 0.69 x 19a Sieding Axe (socketed) UF-5089 [S022]* 92 0.11 0.13 0.051 0.011 7.7 0.095 0.102 19b Sieding Axe (socketed) UF-5089 [S039] 89 0.11 0.11 0.06 n.d 10.3 0.14 0.09 x 20 Ternitz, Gfieder Axe (socketed) [S003]* 91 0.16 0.06 0.01 0.005 8.7 0.02 0.005 ferric chloride reveals coring (zones with 9 to 15% Sn are Grünbach am Schneeberg, inv. no. UF‑19.452, clearly distinguishable) and small, equiaxed polyhedric median‑winged axe grains. The grains are deformed and show strain lines and annealing twins. In the matrix, (α + δ) eutectoid is present; The median-winged axe-type Freudenberg from Grün- due to its brittleness and the applied deformation, there are bach am Schneeberg was sampled on the edge and found many cracks (Fig. 3a). Their presence in the axe indicates to contain 9% Sn, 0.5% of As and Sb each, as well as 0.1% that annealing took place at relatively low temperatures Ag, 0.4% Ni, and 0.2% Pb. Iron is present in traces. The (i.e. < 520 °C), which counterintuitively still permitted the unetched sample shows ca 30–40% deformed, light grey formation of new grains. Corrosion in the sample mainly CuS-inclusions. Etching with ferric chloride reveals cor- consists of copper oxide inclusions (cuprite) and copper ing (indicating a non-complete homogenization) as well as carbonates. There are also corrosion layers of tin oxides on slightly deformed polyhedric grains with twins and strain the object’s surface, which are typical for bronze. Hardness lines. Some eutectoid is present. Corrosion can be found measurements give up to 297 HV values in tin-richer zones inter- and intracrystalline. On the edge of the sample, corro- and 245 HV in zones with less tin. In the more homogenous sion follows the dendritic structure. Also, bacterial-induced zone at the very edge, hardness reaches 254 HV, while the corrosion was noted (see Piccardo et al., 2013) (Fig. 3b). sample’s core is between 206 and 245 HV. Copper oxide (mainly cuprite) and copper carbonate layers cover the surface of the sample. Hardness measurements give about 151–221 HV values, with a harder edge than in the sample’s core. 1 3 125 Page 8 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Fig. 3 Microstructures. Axe ID S001 from Prigglitz-Gasteil: a SEM image showing coring, CuS-inclusions (dark grey), and broken (α + δ) eutectoid (light grey). Winged axe inv. no. UF-19.452 from Grünbach: b Unetched, in polarized light. Bacterial induced corrosion is visible. Chisel ID S041 from Kammerwandgrotte: c Unetched. Coring is visible as massively elongated CuS-inclu- sions. The corrosion follows the microstructural features inter- and intracrystallinearly. Socketed axe ID S042 from Ternitz: d Unetched. Coring is visible. At the centre, one can see (α + δ) eutectoid (light grey) with surrounding inter- and intracrystalline corrosion, under which are cuprite (dark grey, below the eutectoid) and a copper inclusion. The CuFeS- inclusions (dark grey) are not significantly deformed. e Etched with ferric chloride. Note the deformed grains of α-solid solu- tion with deformed twins and strain lines. Socketed axe inv.no. UF-5098 from Sieding: f Etched with ferric chloride. Note the deformed grains of α-solid solu- tion with deformed twins and strain lines Hardness measurements give about 202–237 HV values, Kammerwandgrotte, ID S041, chisel with a harder edge than in the core of the sample. The chisel was sampled on its edge and found to contain 7.1–8% Sn (depending on the analytical method used), 0.2% Ternitz (Gfieder), ID S042, socketed axe As, 0.1% Ni, 0.2% Sb, 0.4% Pb, and some S. The S was under the detection limit of the EDXS for bulk analyses but The socketed axe was sampled on its edge and found to contain 10.8% Sn using EDXS and 8.7% with XRF, and was detected in the CuS-inclusions. Iron and Ag are present in traces, and the unetched sample shows ca 90% deformed 0.7% S and about 0.16% Fe. Sulphur and Fe are mainly present in the CuFeS-inclusions. Nickel, As, Ag, Sb, and light grey CuS- and globular Pb-inclusions (Fig. 3c). Etch- ing with ferric chloride revealed slight coring, indicating Pb are present in trace amounts. The unetched sample shows slightly deformed CuFeS-inclusions, which indi- incomplete homogenization, and fine, slightly deformed, polyhedric grains with strain lines and twins. There is also cate a total deformation of about 10–20% in the sampled area (Fig.  3d). Etching the sample with ferric chloride (α + δ) eutectic, and corrosion is present both inter- and intracrystallinearly. Copper oxide crystals (cuprite; dark revealed an inhomogeneous microstructure — tin-rich areas contain up to 15% Sn, tin poor areas up to 6% — red in polarized light) and alternating copper oxides and carbonate layers cover the surface of the sample. Tin oxides and severely deformed equiaxed grains of α-solid solution (Fig. 3e). The grains show deformed annealing twins as are present, as are P, Si, and Ca, which derive from the soil. well as strain lines, and (α + δ) eutectoid is present. The 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 9 of 19 125 deformation and presence of eutectoid indicate annealing ferric chloride revealed equiaxed grains of α-solid solution at low temperature (< 520 °C) or short annealing at higher with twins (Fig. 4a). Only at the very edge, congruent with temperatures with a final heavy deformation. Some cop- the significantly more deformed CuFeS-inclusions in this per drops are also visible in the matrix, and the corrosion area did the grains show deformation and show strain lines follows both the original dendritic structure and, in small with slight coring. areas, the grain boundaries and the intracrystalline struc- As the final working step, the edge of the chisel was cold tures of the α-solid solution equiaxed grains. Both copper deformed. The corrosion follows both the deformed α-solid oxides (cuprite) and copper carbonates (mainly azurite and solution equiaxed grains’ grain boundaries and the intra- malachite) are visible in polarized light, as is cuprite as granular annealing twins. Under polarized light, the sample inclusions. The hardness values are 206–242 HV on the showed both copper oxides (cuprite) and carbonates (mainly very edge and slightly lower (193–221 HV) 3 mm inward, azurite and malachite). The hardness values of 206–228 HV corresponding to high final deformation. on the very edge correspond with microstructural observa- tions (higher levels of total deformation of CuFeS-inclusions Sieding, inv. no. UF‑5098, socketed axe and grain deformation and strain lines) and the relatively high amount of Sn. The core of the sample dissimilarly The socketed axe was sampled on its edge and contained showed 132–151 HV. 7.7–11.4% Sn, 0.5% S, and about 0.1% Fe, Ni, Sb, and Pb. Sulphur and Fe are mainly present in the CuFeS-inclusions, Pottschach, inv. no. 72.485, knife and As and Ag are in trace amounts. The Sn composition varied by sample type, with XRF of the drilling samples The knife was sampled on its edge and found to be a tin- showing 7.7% and surface analyses of the metallographic antimony bronze containing mean values of 9% Sn, 1.2% Sb, sample at about 10.3%, similar to the 11.4% result from 0.1% As, 0.7% S, and 0.4% Fe. Sulphur and Fe are mainly the EDXS. The unetched sample shows slightly deformed present in CuFeS-inclusions, and Ni, Ag, and Pb are present CuFeS-inclusions, which indicate a total deformation of in trace amounts. The sample was taken from the edge at about 10–20%. Lead is present in small inclusions. Etching the centre of the blade. The unetched sample shows slightly the sample with ferric chloride revealed coring and a very elongated CuFeS-inclusions, which indicate a total amount fine grain structure (grain sizes smaller than 10, according of deformation of 20–30% at the very edge in the sampled to ASTM) (Fig. 3f). The equiaxed grains of α-solid solu- area, and about 10–20% in the core. Etching the sample with tion showed twins and strain lines. While the grains show ferric chloride revealed heavy coring and large equiaxed slight deformation on the very edge, they are slightly more grains (ca 30–60 μm in diameter) of α-solid solution with deformed in the sample’s core. The corrosion follows the twins (Fig. 4c). As the final working step, the knife’s edge inter- and intracrystalline structures of the grains. Calcium, was annealed. Some copper drops are visible in the matrix Cl, Si, and tin oxides were present in the corrosion, with (Fig. 4b). The corrosion follows the grain boundaries of the the former three deriving from the surrounding burial soil. α-solid solution equiaxed grains. According to their colour The most significant part of the corrosion is copper oxides under polarized light, copper carbonates (mainly azurite and (cuprite) and carbonates of mainly azurite and malachite. malachite) are the main corrosion products. The hardness The hardness values of 213–216 HV in the sample’s core are values of 128–143 HV confirm the microstructural obser - higher than on the very edge (166–170 HV). These hardness vations; though the edge received a higher amount of total values also correspond with the more deformed grains in the deformation, the annealing following the cold deformation sample’s core. resulted in an equally low hardness throughout the sample. Knives Prigglitz, inv. no. 10.964, knife Pottschach, inv. no. 72.484, knife X-ray fluorescence analyses could not be carried out with accuracy due to the presence of corrosion; however, it is The knife was sampled on its edge and found to contain worth pointing out that traces of Ni and Pb were detected. 11% Sn, 0.2% Sb, and 0.4% S. Sulphur and small amounts The following compositional percentages derive from the of Fe are mainly present in CuFeS-inclusions. Iron, Ni, As, SEM-EDXS analyses carried out on the polished metal- Ag, and Pb are present in trace amounts. The sample was lographic sample’s surface. The knife was formed from a taken from the centre of the blade’s edge. The unetched sam- tin-bronze containing mean values of 13.5% Sn and 0.6% ple shows elongated CuFeS-inclusions, indicating a total S that were mainly present in CuFeS-inclusions. The sam- deformation of 30–40% at the very edge and about 10–20% ple was taken from the centre of the blade. The unetched towards the core in the sample. Etching the sample with sample shows elongated CuFeS-inclusions, which indicate a 1 3 125 Page 10 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Fig. 4 Microstructures. Knife inv.no. 72.484 from Pottschach: a Etched with ferric chloride. Note the elongated CuFeS- inclusions and the deformed grains of α-solid solution with deformed twins and strain lines. b Knife inv.no. 72.485 from Pottschach: b Unetched. Note the copper drops in the matrix, surrounded by corrosion. c Etched with ferric chloride. Knife inv.no. 10.964 from Prig- glitz: d Etched with ferric chlo- ride. Note the slightly deformed twins and strain lines of the polyhedric grains of α-solid solution. Also, the (α + δ) eutectoid is present. Knife inv. no. UF-22692.2188 (22.692) from Prigglitz: e Unetched. Slight coring is visible. f Etched with ferric chloride. Note the deformed polyhedric grains of α-solid solution with twins and strain lines total amount of deformation of 60–70% at the very edge and Prigglitz, inv. no. UF‑22692.2188 (22.692), knife about 10–20% towards the core. Etching the sample with fer- ric chloride revealed coring and very fine polyhedric grains X-ray fluorescence analyses of this sample should be consid- of α-solid solution with twins and strain lines (Fig. 4d). The ered qualitative, as some corrosion was present. The knife grains are severely deformed along the edge, and (α + δ) was formed from tin-bronze containing mean values of 10% eutectoid is present, indicating low temperature (< 520 °C) Sn with about 0.4% Sb, 0.2% Fe, and 0.1% Ni and As. The or shorter annealing at higher temperatures took place. The S and Fe are present in CuFeS-inclusions. The sample was applied deformation did not result in a broken eutectoid. The taken from the blade. The unetched sample shows slightly SEM images showed tiny, globular Pb-inclusions throughout elongated CuFeS-inclusions, which indicate a total amount the matrix. Corrosion in the sample follows intracrystalline of deformation of 30–40%. Etching the sample with ferric structures to a smaller degree, the dendritic features. Ele- chloride revealed coring and significantly deformed poly - ments such as Al, Si, and P were present and derived from hedric grains of α-solid solution with twins and strain lines the soil. Apart from the copper oxides and carbonates, tin (Fig. 4e–f). As the final working step, the edge of the knife oxides are also present. The hardness values of 245–254 HV was cold deformed. The corrosion follows both the previous on the very edge and 181–199 in the sample’s core confirm as-cast structure (dendrites) as well as the grain boundaries the microstructural observations. of the α-solid solution equiaxed grains. According to their colour under polarized light, copper carbonates (mainly azurite and malachite) are the main corrosion products. 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 11 of 19 125 The hardness values of 193–274 HV, with 274 HV on the grains of α-solid solution with twins and strain lines were very edge, make this the highest hardness value of the four visible (Fig. 5a). The presence of (α + δ) eutectoid indi- knives. cates short, low-temperature annealing, followed by cold deformation. As the final working step, the tip of the awl Awls was cold deformed. Corrosion in the sample follows the grain boundaries of the α-solid solution equiaxed grains, Prigglitz, inv. no. UF‑22692.1140A, awl and it expands intracrystallinearly. According to their col- our under polarized light and the EDXS analyses, copper The awl is made of tin-bronze containing mean values of carbonates (mainly azurite and malachite) are the main 9.5% Sn, 0.1% Sb, and 0.7% S, which is mainly present corrosion products on the awl’s surface, while copper in CuS-inclusions. The tip of the awl was sampled longi- (mainly cuprite) and tin oxides are visible in the inter- and tudinally and transversally (cross-section). The unetched intracrystallinearly. The hardness values of 193–228 HV longitudinal sample showed slightly elongated CuS-inclu- are relatively high for a 9.5% tin-bronze and correspond sions, indicating a total amount deformation of 20–30%, with the deformation applied in the final working step. while the cross-section only shows light deformation at a maximum of 15%. The (α + δ) eutectoid of the Cu-Sn system is visible in the unetched sample, and once etched with ferric chloride coring and fine, deformed equiaxed Fig. 5 Microstructures. Awl inv.no. UF-22692.1140A from Prigglitz: a Etched with Klemm II. Note coring and (α + δ) eutectoid. Awl inv.no. 1272 from Prigglitz: b Etched with ferric chloride. The CuS-inclu- sions are elongated. Awl inv.no. UF-22692.1672from Prigglitz: c Etched with ferric chloride. Note the elongated CuS- inclusions. Awl inv.no. UF-9958 from Prein: d Unetched. Note the corrosion, outlining the microstructural features. Cast- ing cake inv. no. UF-22692.675 from Prigglitz. e Unetched. Note the many CuS-inclusions and, in the centre, some CuSb- inclusions in the SEM image. White inclusions are rich in Sb (ca 35%) as well as Ag and As (below 1%). Belt clip inv.no. UF-22692.1673 from Prigglitz: f Etched with Klemm II. Heavy coring is visible 1 3 125 Page 12 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Prigglitz, inv. no. UF‑22692.1272, awl Prein, inv. no. UF‑9958, awl The awl was formed from tin-bronze containing mean values The awl is tin-bronze and contains mean values of 5% Sn and of 11% Sn and 0.3% S, which was mainly present in CuS- 0.7% Pb. Sulphur is mainly present in the CuFeS-inclusions, inclusions. The tip of the awl was sampled longitudinally, and Fe in trace amounts. The sample was cut transversally and unetched showed slightly elongated CuS-inclusions, from a fragment of the awl. Unetched, the sample shows indicating a total amount of deformation of 40–50%. After slightly elongated CuFeS-inclusions, indicating a total etching with Klemm II heavy coring was revealed, indicating amount of deformation of 0–20%, which is not surprising an inhomogeneous alloy (Fig. 5b). Both Klemm II and ferric for the cut. The total amount of longitudinal deformation chloride etched surfaces showed small, slightly deformed could not be measured. Etching the sample with ferric chlo- equiaxed grains of α-solid solution with twins as well as ride revealed coring and small, deformed equiaxed grains of strain lines. No (α + δ) eutectoid of the Cu-Sn system was α-solid solution with twins and strain lines. The corrosion visible, indicating that the awl underwent longer, or more follows the grain boundaries of the α-solid solution equi- frequent annealing followed by cold deformation. In the axed grains and also expands intracrystallinearly (Fig. 5d). final working step, the tip of the awl was cold worked. The According to the sample’s colour under polarized light, corrosion follows the dendritic structure. According to the copper carbonates (mainly azurite and malachite) are the corrosion colours under polarized light, copper carbonates main corrosion products on the awl’s surface, while cop- (mainly azurite and malachite) are the main products on the per (mainly cuprite) and tin oxides are visible inter- and awl’s surface. No inter- or intracrystalline corrosion was intracrystallinearly. The low hardness values of 160–181 HV noted. The hardness values of 187–206 HV are relatively correspond with the alloy composition. high for a 10% tin-bronze and correspond with the deforma- tion applied in the final working step. Other objects Prigglitz, inv. no. UF‑22692.1672, awl Prigglitz, inv. no. UF‑22692.675, casting cake The awl was formed from tin-bronze containing mean values The casting cake consists of rather pure copper with only of 14% Sn, 0.1% Sb, and 0.5% S, which was mainly present 1.7% S, 0.1% Fe, and small amounts of Sb (0.1%). Other in CuS-inclusions with low amounts of Ni. Nickel and Pb elements, such as Ni, Ag, As, and Pb, are present in trace are present in trace amounts. The tip of the awl was sam- amounts. The highly porous as-cast shows a homogenous pled longitudinally, and unetched showed severely elongated copper matrix without any coring or dendrites. No cuprite CuS-inclusions, indicating a total amount of deformation was noted under polarized light; however, CuO — mainly of 70–80% (Fig. 5c). After etching the sample with Klemm carbonates — is present in the corrosion and on the casting II and ferric chloride, light coring was revealed, indicat- cake’s surface. Globular, black CuS-inclusions — some of ing an almost homogenous alloy. Both Klemm II and fer- them containing up to 2% O and/or up to 1% Sb — are dis- ric chloride developed small, slightly deformed equiaxed tributed in various sizes all over the sample’s surface. There grains of α-solid solution with twins and strain lines. No are small, white inclusions that mainly contain Sb (35%) and (α + δ) eutectoid of the Cu-Sn system remained, indicating Ag and As below 1% (Fig. 5e). Hardness values are around more prolonged or more frequent annealing followed by cold 96–105 HV. deformation. In the final working step, the tip of the awl was cold worked. Half of the sample is massively corroded. The Prigglitz, inv. no. UF‑22692.1673, belt clip corrosion follows the grain boundaries and, intra-granularly, along the dislocations of single grains (both twins and strain The belt clip is made of tin-bronze with about 7.5% Sn, lines). According to the corrosion colours under polarized 0.7% Sb, and 0.2% S. The XRF sample contained corrosion, light, copper carbonates (mainly azurite and malachite) are so preference should be given to the SEM-EDXS chemi- the main corrosion products on the awl’s surface. Within the cal data; however, it is important to note that with XRF, corrosion, there was also SnO that was measured by EDXS. 0.3% Ni, As, Ag, and Pb were detected. One end of the belt Copper oxides (cuprite) can be found in the centre of the clip was pinched off, and the cross-section of the belt clip sample. The hardness values of 245–274 HV for the sample englobed in acrylic resin. The unetched sample revealed are the highest measured in this study. They are related to lightly deformed CuS-inclusions of about 20–30% of total both the high amount of Sn in the alloy and the intense cold deformation. Some of the inclusions also contain up to 2% deformation applied in the final step of production. of Sn. Etching the sample with Klemm II revealed heavy coring, indicating a non-homogenous alloy (Fig. 5f). The etchant developed undeformed, equiaxed grains of α-solid 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 13 of 19 125 solution with twins of about ca 30 × 40 μm in diameter. No the sample revealed elongated CuFeS-inclusions of about (α + δ) eutectoid of the Cu-Sn system remained, indicating 30–40% of total deformation. The inclusions also contain longer or more frequent annealing followed by cold defor- lesser amounts of Sb. Etching the sample with Klemm II mation. In the final working step, the belt clip was shortly revealed heavy coring, indicating an inhomogeneous alloy. annealed. In the corrosion, Ni and Sb were enriched. The The etchant developed small, ca 25 × 35 μm in diameter, corrosion follows both the dendritic structure and grain equiaxed grains of α-solid solution with twins (Fig. 6a). No boundaries and intracrystalline dislocations (annealing (α + δ) eutectoid of the Cu-Sn system remained, indicating twins and strain lines) of single grains. The hardness values longer or more frequent annealing followed by cold defor- of 92–128 HV correspond to annealing applied as a final mation. As the final working step, the belt clip was shortly working step. annealed. Under polarized light and supported by EDXS analyses, copper carbonates and oxides are present, as are Prigglitz, inv. no. UF‑22692.1652‑A, belt clip various tin oxides. Corrosion in the sample follows both the dendritic structure and grain boundaries and intracrystal- The belt clip is made of tin-bronze with about 8% Sn, 0.6% linearly between the dislocations (annealing twins) of single S (EDXS), 0.2% Fe, and 0.4% Sb. Nickel and As are also grains. The hardness values of 96–110 HV correspond to present in trace amounts, and Ag and Pb were not detected. annealing in the final working step. One end of the belt clip was pinched off, and the cross- section of the belt clip englobed in acrylic resin. Unetched, Fig. 6 Microstructures. Belt clip inv.no. UF-22692.1652 from Prigglitz: a Etched with Klemm II. Coring and fine equiaxed grains of α-solid solution with annealing twins. Rod inv.no. UF-22692.912 from Prigglitz: b Etched with Klemm II; much (α + δ) eutectoid and Cu-drops are visible. c SEM image. Note the Cu-drops and the massive (α + δ) eutectoid. Wire ID S013 from Kammerwandgrotte: d Etched with ferric chloride. Complete cross-section. Note the smaller grain size on the outside. Prigglitz, bracelet (inv.no. UF-22692.1780): e Unetched. Note the cop- per drop and the presence of (α + δ) eutectoid. The CuFeS- inclusions are not deformed. Pottschach, pin (inv.no. 72.488): f Etched with ferric chloride 1 3 125 Page 14 of 19 Archaeological and Anthropological Sciences (2021) 13:125 Prigglitz, inv. no. UF‑22692.912, rod/wand eutectoid of the Cu-Sn system that contains up to 0.8% Sb. Etching the sample with ferric chloride and Klemm II The rod is made of tin-bronze with about 12% Sn, 0.5% S revealed coring and 25–40 μm equiaxed grains of α-solid (EDXS), and 0.6% Pb. Nickel and Sb are present in trace solution with twins. The presence of the (α + δ) eutectoid amounts, while Fe, As, and Ag were not detected. A cross- indicates a low temperature (< 520 °C) or shorter annealing section of one end of the rod was englobed in acrylic resin. time at higher temperatures. Of particular importance are The unetched sample shows a porous, as-cast, dendritic the drops of pure Cu in the sample surrounded by CuFeS microstructure with a few globular CuS-inclusions and inclusions (Fig. 6e). The drops indicate that not all of the Cu high amounts of (α + δ) eutectoid in the Sn-rich zones of was completely dissolved when the molten alloy was poured the alloy. The eutectoid may also contain some Fe. Of par- into the form. In the final working step, the bracelet was ticular importance are the drops of pure Cu surrounded by annealed. The corrosion follows both the dendritic struc- CuS-inclusions (Fig. 6b–c). These Cu-drops indicate that ture and grain boundaries and intracrystallinearly between not all of the Cu was dissolved entirely when the molten the dislocations (annealing twins) of single grains. As seen alloy was poured into the form. In the corrosion, copper and under polarized light, and according to the EDXS analyses, tin oxides were noted, while the CuS-inclusions were usu- both copper carbonates and oxides (shiny, dark-red cuprite ally not corroded. The hardness values of 176–245 HV are crystals) were present, as were various tin oxides. The hard- relatively high and relate both to the high amount of brittle ness values of 96–151 HV are in good agreement with an — but hard (α + δ) eutectoid (Mödlinger and Sabatini 2017) as-cast and annealed 14% tin-bronze. — and the high amount of Sn in the alloy. In comparison, hardness measurements in the centre of one of the Cu-drops Pottschach, inv. no. 72.488, pin showed 88 HV. It is also possible that a Sn-rich area beneath the Cu-drop was struck during measuring. The pin is made of tin-bronze with about 9.2% Sn, 0.4% S (EDXS), 0.1% Fe, and Sb. Nickel, As, Ag, and Pb are present in trace amounts. The sample was taken from the Kammerwandgrotte, ID S013, wire shaft of the pin, and the cross-section englobed in acrylic resin. The unetched sample revealed CuS-inclusions with The wire is made of a 12% tin-bronze with about 0.5% S a maximum total deformation of about 10%. Porosity in (EDXS), 0.1% Fe, and 0.2% Sb. Other elements, such as the sample significantly increased towards the centre, cor - Ni, As, and Pb, are present in trace amounts. Silver was not responding to the centre of the pin shaft. Etching the sam- detected, and S and Fe are mainly present in globular CuFeS- ple with ferric chloride and Klemm II revealed coring and inclusions. These inclusions also contain some Pb. Etching 25–40 μm equiaxed grains of α-solid solution with twins and the sample with ferric chloride revealed polyhedric grains strain lines (Fig. 6f). The absence of the (α + δ) eutectoid of different sizes with annealing twins and strain lines. The indicates high temperature or more prolonged annealing. latter are only present in the smaller grains (Fig. 6d). The As a final working step, the pin shaft was cold deformed. wire is porous and cracked in the sampled area, even though Corrosion in the sample does not follow the dendritic struc- it was subjected to light deformation. The slight deforma- ture or grain boundaries, or individual grain dislocations tion also resulted in smaller grains close to the surface and (annealing twins and strain lines). Instead, it follows a more bigger ones in the wire’s centre. Corrosion in the sample irregular pattern typically seen in microbial-induced corro- follows the inter- and intracrystalline structures, especially sion (Piccardo et al., 2013). As seen under polarized light, in the sample’s centre, consisting mainly of copper oxides and according to the EDXS analyses, both copper carbonates (cuprite) and carbonates (azurite, malachite). Hardness dif- and oxides (cuprite crystals) are present, as are various tin fers significantly from grain to grain. While the bigger grains oxides. Interestingly, the copper oxides form layers on the in the sample centre are rather soft (81–103 HV), the smaller pin’s shaft surface, while the carbonates are close to the core. ones on the edge are much harder (122–170 HV). The hardness values of 160–193 HV are in good agreement with a cold deformed, previously as-cast and annealed 11% tin-bronze. Prigglitz, inv. no. UF‑22692.1780, bracelet The bracelet is made of tin-bronze with about 12.8% Sn, Discussion 0.7% S (EDXS), and 0.1% Fe and Sb. Nickel is present in trace amounts. One end of the bracelet was pinched off, All of the axes and chisels in this study are made of tin- and the cross-section englobed in acrylic resin. Unetched, bronze with varying amounts of Sn ranging from 7.5 to 10%. the sample revealed globular CuFeS-inclusions and (α + δ) They all show coring, indicating that both the duration and 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 15 of 19 125 1 3 Table 3 Overview of selected metallographic features No Site Object ID CuS/Cu Fe S Def. incl.% Strain lines Twins Coring (α + δ) Max. HV 2-x 2 1 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1272 CuS 40–50 x x x - 205 2 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1140A CuS 20–30 x x x x 230 3 Prigglitz-Gasteil Double-pointed ‘awl’ UF-22692.1672 CuS 70–80 x x x - 275 4 Prigglitz-Gasteil, Axe (socketed) [S001] CuS 70–80 x x x x 300 Klausgraben 5 Prigglitz-Gasteil Belt clip UF-22692.1652 Cu Fe S 30–40 - x x - 110 2-x 2 6 Prigglitz-Gasteil Belt clip UF-22692.1673 CuS 20–30 - x x - 130 7 Prigglitz-Gasteil Bracelet UF-22692.1780 Cu Fe S 0 - x x x 150 2-x 2 8 Prigglitz-Gasteil Casting cake UF-22692.675 CuS - - - - - 105 9 Prigglitz-Gasteil Knife UF-10.964 Cu2-xFe2S globular; edge 60-70 ? x x x 255 10 Prigglitz-Gasteil Knife UF-22692.2188 Cu2-xFe2S 30–40 x x x - 275 11 Prigglitz-Gasteil Rod / wand UF-22692.912 CuS 0 - - as-cast x 245 12 Grünbach, Gelände Axe (end-winged) UF-19,452 CuS 30–40 x x x x 220 13 Reichenau, Kammer- Chisel [S041] CuS > 90 x x x x 240 wandgrotte 14 Reichenau, Kammer- Wire (bent) [S013] Cu2-xFe2S < 10 - x x - 170 wandgrotte 15 Pottschach Knife 72.485 Cu2-xFe2S - - x x - 145 16 Pottschach Knife 72.484 Cu2-xFe2S 10–20; 30–40 x x x - 230 17 Pottschach Pin 72.488 CuS 10 x x x - 195 18 Prein an der Rax Double-pointed ‘awl’ UF-9958 Cu2-xFe2S 0–20 x x x - 180 19 Sieding Axe (socketed) UF-5098 Cu2-xFe2S 10–20 x x x - 215 20 Ternitz, Gfieder Axe (socketed) [S042] Cu2-xFe2S 10–20 x x x - 240 125 Page 16 of 19 Archaeological and Anthropological Sciences (2021) 13:125 temperature of the annealing process were insufficient to no. UF-22692.2188) are not significantly deformed on the homogenize the alloy (Table 3). However, all of the axes edge, Prigglitz knife 10.964 shows 60–70% of total deforma- and chisels showed equiaxed grains of α-solid solution with tion but less final deformation than the other one from the twins and strain lines, indicating cold deformation in the same site. In combination with the high amounts of Sn and final working step due to annealing. CuS-inclusions were Fe, the result is a relatively high hardness of over 250 HV found in axes S001 (Prigglitz), S079 (Grünbach am Sch- on the edge. The Prigglitz knife inv. no. UF-22692.2188 neeberg), and the chisel from Kammerwandgrotte, and all shows the knives’ highest hardness value with up to 274 HV other axes contained CuFeS-inclusions. The total amount of (edge) and up to 193 HV (core; ca 2 mm from the edge). The deformation for the axes on their edges was astonishingly higher HV is due to the final deformation applied in the last low overall (usually < 10%), with only axe S001 showing working step. Hardness values are higher on the edges of 70–80% of total deformation in combination with (α + δ) three knives (UF-22692.2188, 10.964, 72.484), while one eutectoid. The axe also had the highest hardness values of knife shows a uniform distribution of similar values (knife all the objects (300 HV at the edge). Similarly, the chisel 72.485). Again, these measurements are in good agreement showed a significant total amount of deformation of the with the observed microstructures and annealing in the last edge (ca 90%), and in combination with the presence of assumed working step. (α + δ) eutectoid, it had high hardness values (240 HV). The Four tin-bronze double-pointed awls — three from Prig- hardness values are directly related to the alloy choice, the glitz and one from Prein — were studied. While two of the total amount of deformation, and especially the deforma- awls from Prigglitz are made of tin-bronze with about 10% tion applied in the final working step. The influence of the Sn, the third (inv. no. UF-22692.1672) contains more than final working step on the end product is demonstrated by the 14%. The awl from Prein contains far less at ca 5%. All socketed axe from Ternitz (10–20% total deformation) and four awls contain S, which is mainly present in the CuS- the chisel (90% total deformation and its eutectoid). Both inclusions, and Fe was only detected in trace amounts bronzes contain similar amounts of Sn and Fe, but the sock- in the awl from Prein. Interestingly, As and Ag were not eted axe underwent a higher degree of final deformation than detected in any of the awls, Ni at trace amounts in two the chisel, which resulted in far higher final hardness. (Prigglitz UF-22692.1672 and Prein) and Sb at about 0.1% Four tin-bronze knives — two from Pottschach and two in three (Prigglitz UF-22692.1672 and UF-22692.1140A, from Prigglitz — were studied. All four of them contain and Prein). The awl from Prein showed a relatively high relatively high amounts of Sn (9 to 15%). Moreover, one of amount of Pb at 0.7%, and of the other awls, only the Prig- the two Pottschach knives contains 1.2% Sb. All four knives glitz UF-22692.1672 showed traces of Pb. The four awls contain S and Fe, which are mainly present in the CuFeS- were studied metallographically and are characterized by inclusions. The four knives differ in their post-casting treat- very pure Cu in their production. The four awls, however, ment, however. While one knife from Prigglitz (inv. no. do not differ in their post-casting treatment but do in its 10.964) showed a high amount of total deformation and was intensity. All but one awl (inv. no. UF-22692.1672) showed cold worked after several annealing/cold deformation steps, heavy coring. While three awls show a total amount of defor- which is evident by higher hardness and finer grains, the mation of about 0–50% in the sampled area, only inv. no. other (inv. no. UF-22692.2188) showed less total deforma- UF-22692.1672 showed a much higher level of deforma- tion but a higher final cold deformation. The second knife’s tion at 70–80%. All four were cold deformed, and annealed, treatment resulted in higher hardness values on the edge, with cold deformation being the last step of production. even though its tin-amount is much lower (10 versus 15%). In one of the awls (inv. no. UF-22692.1140A), the (α + δ) Noteworthy, the blade of knife inv.no. 10.964 broke once, eutectoid is still present, indicating short, low-temperature was shortened, and attached to a new handle. annealing, followed by cold deformation. The Prigglitz awl The two Pottschach knives show less total deformation inv. no. UF-22692.1672 shows the highest hardness value than the ones from Prigglitz. Also, knife 72.484 shows slight of them all at 274 HV. This is due to the intensive total, deformation indications in the final working step and reaches and especially the final, deformation and the higher amount an edge hardness of 230 HV. Knife 72.485 does not show of Sn in the alloy. The other two awls from Prigglitz had a any indications of final deformation; here, annealing was maximum HV of 230 (inv. no. UF-22692.1140A) and 205 the last working step, resulting in low hardness values of (inv.no. UF-22692.1272). In agreement with the low amount 145 HV or less. The presence of undissolved copper grains of Sn in the alloy and the low total and final deformation, in the matrix of knife 72.485 indicates the use of ‘fresh’ the Prein awl showed the lowest hardness values between copper and tin to produce the alloy or the addition of ‘fresh’ 160–181 HV. copper to a recycled tin-bronze. All knives show a low The final annealing of both belt clips makes sense since a amount of total deformation in the core area (max. 20%). final cold deformation would have increased their brittleness. While the Pottschach knives and one from Prigglitz (inv. Belt clips need to be flexible. The clips’ production and their 1 3 Archaeological and Anthropological Sciences (2021) 13:125 Page 17 of 19 125 hardness values are very similar, as is their chemical com- that objects were very much likely not made using recycled position with the exception of Ag in clip UF-22692.1673, tin-bronzes. which contains about 0.3% while none was detected in clip Regarding the objects’ function, all cutting edge objects UF-22692.1652. Concerning the rod/wand studied, a freshly were worked to improve their material properties, especially produced Cu-Sn alloy is presumed, or adding ‘fresh’ Cu to their edge hardness. Hardness values differed for the jew - an already existing and recycled tin-bronze, as the micro- ellery, except for the pin where the last working step was structure shows not-dissolved Cu-drops, often surrounded annealing, and hardness values are thus comparatively low at by CuS-inclusions. Neither Fe, As, or Ag were detected. The between 110 and 170 HV. These values suggest that elastic- tin-bronze wire was cast and, after some deformation and ity was more important than hardness. Only the as-cast rod/ following annealing, slightly deformed. The bracelet was wand from Prigglitz shows relatively higher hardness values, also cast and slightly deformed and then annealed. Drops of which are related to the presence of the eutectoid. pure Cu indicate that not all of the Cu was dissolved entirely Concerning cutting edge objects (axes, chisels, and pick- when the molten alloy was poured into the form. The brace- axe), hardness values range from 215 to 300 HV, highlight- let was annealed for a short time at lower temperatures in the ing that the material properties of the edges were intention- final working step, as (α + δ) eutectoid is still present. The ally improved for an ideal usability of the tools. The only pin was annealed and only slightly deformed after casting. exception is knife 72.485 from Pottschach with 145 HV. The absence of the (α + δ) eutectoid indicates high tempera- Hardness values depend on various factors such as alloy ture or more extended annealing. As a na fi l working step, the composition, thermal treatment, and deformation applied. pin shaft was cold deformed. For the objects studied, this is particularly the Sn and Fe Of particular interest are the undissolved drops of Cu in content. The presence of Fe, even at values as low as 0.15%, the CuSn-matrix, which were found in every fifth of the also reduces formability and causes cracks and surface objects (Ternitz, socketed axe (ID S042): twinned grain; defects (see Nerantzis 2015; Papadimitriou 2008). It also Pottschach, knife (72.485): grain; Prigglitz, rod/wand (UF- influences the eutectoid and, most importantly, the final 22692.912): drops with surrounding CuS; and Prigglitz, deformation treatment that was applied. As no direct cor- bracelet (UF-22692.1780): big drops). The drops range relation between Fe or Sn content, final deformation, and from 5 to 35 μm in diameter. Such unalloyed copper inclu- hardness values were detected (likely also related to the low sions (UCI) have been noted in other archaeological bronzes number of samples), we assume that Bronze Age smiths (Bosi et al. 2002). The UCI observed in the four objects simply stopped at a certain point during the final working discussed here do not relate to corrosion, which are usually step (cold deformation) once they reached a (for them) suf- irregularly shaped from pseudo-morphically replacing other ficiently good result. This does not necessarily need to be the phases and are instead due to the (s)melting process itself. highest possible hardness of the alloy, as was also observed For the objects in this study, not all of the Cu was completely often at Early Bronze Age axes from north Alpine regions dissolved when the molten alloy was poured into the casting (Kienlin 2008). mould. The CuS-layers around the copper drops of the rod/ wand (UF-22692.912) suggest the copper drops might have Conclusions already formed during the smelting process (Bosi et  al. 2002). Above 1105 °C, Cu and S (< 20%) are immiscible The Late Bronze Age site of Prigglitz-Gasteil is considered with a top layer of C u S and a bottom layer of Cu with about a regional centre of copper production and bronze working 2% S (copper-rich Cu–S solution). Upon cooling, the solid based on the evidence of an openwork copper ore mine and phase Cu S and the copper-rich Cu–S solution are present, a nearby bronze casting workshop. Metallographic analyses and slagging of solid Cu S takes place to obtain high-purity of different cutting tools and jewellery items from Prigglitz- copper. During cooling, spherical particles of Cu S contain- Gasteil, and six contemporaneous sites in the surrounding ing a copper-rich core might form, which are heavier than region, provide insights into the post-casting treatment of Cu S particles and therefore less likely to slag and remaining different kinds of bronze objects. This information helps us in the alloy to form UCI (Bosi et al. 2002). While singular understand the overall chaîne opératoire in metal produc- copper drops in crystallized form were noted for socketed tion, which is important in identifying local metalworking axe (ID S042) and the knife (72.485), many of them with traditions. up to 35 μm diameter, and most had already oxidized to As discussed in detail, objects with a cutting edge were CuO, were noted on bracelet (UF-22692.1780). For these worked according to their function. For instance, the sharp three objects, we can either assume that fresh copper was edges of axes and knives and the points of the awls had added to an already existing CuSn-alloy (recycling) or that undergone annealing and cold deformation cycles with the CuSn alloy was freshly produced. Hence, we can assume cold deformation as the final step in almost all cases. This 1 3 125 Page 18 of 19 Archaeological and Anthropological Sciences (2021) 13:125 were made. The images or other third party material in this article are sequence of treatments resulted in higher hardness. The included in the article’s Creative Commons licence, unless indicated total deformation on blade edges ranged from 10 to 20% otherwise in a credit line to the material. If material is not included in (one awl, two socketed axes), 30–50% (end-winged axe, two the article’s Creative Commons licence and your intended use is not awls, two knives), 60–70% (one knife, one awl, one sock- permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a eted axe), and beyond (chisel with over 90%). Interestingly, copy of this licence, visit http://cr eativ ecommons. or g/licen ses/ b y/4.0/ . these objects’ alloys do not seem to have been chosen inten- tionally to include higher Sn concentrations except for awl UF-22692.1672 and knife 10.964 from Prigglitz. Small jewellery objects, such as the belt clips, the brace- References let, and wire, which need to have a certain amount of flexi- bility to function, were worked far less with a total amount of Bosi C, Garagnani GL, Imbeni V, Martini C, Mazzeo R, Poli G (2002) Unalloyed copper inclusions in ancient bronze artefacts. 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Fundberichte aus Öster- metals and alloys during recycling. reich 38:779 Ilon G (1992) Keftiubarren ingot from an Urn-Grave Culture set- Acknowledgements This project was funded by the Austrian Science tlement at Gór-Kápolndadomb (C. Vas). Acta Archaeologica Fund (FWF), project no. P30289-G25 (‘Life and Work at the Bronze Academiae Scientiarum Hungaricae 44:239–259 Age Mine of Prigglitz’). We would like to thank Hofrat Dr. Anton Ilon G (1996) Beiträge zum Metallhandwerk der Urnenfelderkultur Kern, the head of the Prehistoric Department at the Museum of Natu- - Gór (Komitat Vas, Ungarn). Vorläufiger Bericht. In: Jerem E, ral History, Vienna, and Hofrat Dr. Ernst Lauermann, former head of Lippert A (eds) Die Osthallstattkultur. Akten des Internation- the Prehistoric Department at the State Collections of Lower Austria, alen Symposiums, Sopron, 10.-14. Mai 1994, Archaeolingua who both kindly permitted us to sample the objects. 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Archaeological and Anthropological SciencesSpringer Journals

Published: Jul 2, 2021

Keywords: Late Bronze Age; Eastern Alps; Austria; Mining site; Metallographic analysis; XRF analyses; Production of copper alloy objects; Chaîne opératoire

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