Materials Characterization 97 (2014) 74–82
Contents lists available at ScienceDirect
Materials Characterization
journal homepage: www.elsevier.com/locate/matchar
Metallography and microstructure interpretation of some archaeological
tin bronze vessels from Iran
Omid Oudbashi a,⁎, Parviz Davami b
a
Department of Conservation of Historic Properties, Faculty of Conservation, Art University of Isfahan, Hakim Nezami Street, Sangtarashha Alley, P.O. Box; 1744, Isfahan, Iran
Faculty of Material Science and Engineering, Sharif University of Technology/Razi Applied Science Foundation, No. 27, Fernan St., Shahid Ghasem Asghari Blvd., km 21 of Karadj Makhsous Road,
Tehran, Iran
b
a r t i c l e
i n f o
Article history:
Received 31 May 2014
Received in revised form 28 August 2014
Accepted 12 September 2014
Available online 16 September 2014
Keywords:
Sangtarashan
Tin bronze
SEM–EDS
Metallography
Alloying
Sulphidic inclusion
Thermo-mechanical operations
a b s t r a c t
Archaeological excavations in western Iran have recently revealed a significant Luristan Bronzes collection from
Sangtarashan archaeological site. The site and its bronze collection are dated to Iron Age II/III of western Iran
(10th–7th century BC) according to archaeological research. Alloy composition, microstructure and manufacturing technique of some sheet metal vessels are determined to reveal metallurgical processes in western Iran in the
first millennium BC. Experimental analyses were carried out using Scanning Electron Microscopy–Energy Dispersive X-ray Spectroscopy and Optical Microscopy/Metallography methods. The results allowed reconstructing the
manufacturing process of bronze vessels in Luristan. It proved that the samples have been manufactured with a
binary copper–tin alloy with a variable tin content that may relates to the application of an uncontrolled procedure to make bronze alloy (e.g. co-smelting or cementation). The presence of elongated copper sulphide inclusions showed probable use of copper sulphide ores for metal production and smelting. Based on
metallographic studies, a cycle of cold working and annealing was used to shape the bronze vessels.
© 2014 Elsevier Inc. All rights reserved.
1. Introduction
The investigation of microstructure and alloy composition of archaeological metal artefacts is an interesting and important subject to determine metalworking techniques in the ancient world. Tin bronze is the
first alloy used in most regions around the world, for example, the
first tin bronze artefacts appear in west of Iranian Plateau at the end of
Chalcolithic period (end of 4th millennium BC) [1–3].
The Luristan region is located in the west of Iran, which is one of the
important cradles of the Iranian Plateau. In archaeological context,
Luristan is the highland folded region in the Central Zagros mountain
chain, in western Iran. Thousands of ancient bronze artefacts with exquisite modelling, fine style, and outstanding manufacturing skill have
been unearthed in the Luristan area. The emergence of significant
bronze production is an important archaeological/technological phenomenon during the Iron Age in the Luristan region. The Luristan
Bronzes include a series of decorated bronze artefacts similar in specific
local style, dating to the Iron Age II/III (1000–650 BC) [4–10]. During the
past 10 years, some archaeological excavations were carried out in Iron
Age site of Sangtarashan in eastern Luristan (known as Pish-i Kuh).
Sangtarashan is situated about 35 km of southeast of Khorramabad
(capital of Lorestan province). The site has been excavated by Iranian
⁎ Corresponding author.
E-mail addresses: o.oudbashi@aui.ac.ir (O. Oudbashi), pdavami@razi-foundation.com
(P. Davami).
http://dx.doi.org/10.1016/j.matchar.2014.09.007
1044-5803/© 2014 Elsevier Inc. All rights reserved.
archaeologists, Ata Hassanpour and Mehrdad Malekzadeh. Archaeological evidence proves that the site contains the remains of an Iron Age II
sanctuary with stony architecture. Also about 2000 bronze artefacts
have been discovered together with some other objects such as iron,
bone, stone and pottery. In fact, the majority of objects recovered from
Sangtarashan are different kinds of bronzes in the Luristan Bronzes
style such as spouted and simple vessels, sculptural object such as finials, and weaponry artefacts. [11].
In this paper, some recent excavated bronze artefacts belonging to
the Sangtarashan archaeological site were examined to determine
alloying and manufacturing characteristics and processes during the
Iron Age period. The metallurgical research concerning bronze production in Sangtarashan has become a unique opportunity to understand
the Iron Age bronze production in this western region of the Iranian Plateau. The study also comprises a discussion concerning the elemental
and microstructural features of some bronze vessels.
2. Materials and methods
2.1. Archaeological samples
To study the microstructure and alloy composition of bronzes from
the Iron Age Luristan, a collection of twenty two bronze samples was selected from the Sangtarashan archaeological site. These include broken
metallic vessels that have been unearthed during archaeological excavations between 2009 and 2011 (Fig. 1). Some samples were analysed
O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
75
Fig. 1. Some broken vessels from all selected samples belonging to Sangtarashan archaeological site.
and previously published [3,11] but these were reconsidered in this
study next to other samples to compare and develop statistical interpretations. In total, twenty five pieces were chosen from 22 metallic vessels
including 22 pieces from the vessel bodies (Nos. ST.01-10 to ST.22-11), a
piece including the spout of a vessel (ST.02-10/2) and two small pins
(ST.09-10/2 and ST.10-10/2). This selection was based on the fact that
some bronze vessels from Sangtarashan are made with two separate
pieces such as the case with spouted vessels in which the spout is
manufactured by a bronze fragment that has been joined to the body
with large metal pins. Therefore, one spout and two pins from three
vessels are analysed.
2.2. Experimental
Small samples from the metal artefacts and fragments were prepared and mounted for metallographic preparation. For this purpose, a
cross section from each piece was prepared by embedding samples in
epoxy resin. Preparation for analysis was followed by grinding them
with silicon carbide papers (400–2000 grit size). Finally, the cross sections were polished with a diamond paste (1 μm).
Microstructural observations and chemical composition analysis
were carried out with optical microscopy and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM–EDS)
methods. Cross-sections were observed with a BK-POL/BK-POLR
manufactured by Alltion Company, China, under bright field (BF) illumination. Samples were observed before and after etching with alcoholic
ferric chloride (FeCl3) solution. Mounted cross-sections were observed
in a VEGA II, TESCAN scanning electron microscope equipped with a
secondary electron detector (SE) and a backscattered electron detector
(BSE) with elemental analysis system (EDS) model Rontec Quantax/
QX2, Germany, in SEM laboratory of Razi Metallurgical Research Center,
Tehran, Iran used for semi-quantitative elemental analyses.
The metallic remains in cross sections were analysed by Energy
Dispersive Spectrometry (EDS) on areas of about 10000 μm2 (about
100 × 100 μm) to detect the entire alloy composition and to avoid effects of phase concentrations in the final results.
3. Results and discussion
3.1. Alloy composition
SEM–EDS investigation was employed to determine alloy components in a semi-quantitative manner. Table 1 shows results of alloy composition in 25 samples from 22 vessels carried out by SEM–EDS method.
According to Table 1 it is obvious that all twenty two vessels are made of
bronze alloy. Also, it is clear that the main alloying elements of all samples are Cu and Sn whereas Pb, Zn and Ni are considered to be impurities
in the alloy composition. The percent of Cu content varies from 83.81 up
to 95.11 and the Sn 4.18 up to 13.36. Through these analyses one can
observe that the Sn contents show different values.
Lead is detected in minor concentrations in all samples. Only in two
samples, ST.13-10 and ST.15-10, it is observed in a considerable amount,
over 2%. Worth mentioning is that arsenic has been detected in low
amounts and as a minor component (less than 1%) in all samples,
while arsenic has been detected as a significant alloying element in
many Iranian prehistoric copper alloys [1].
Generally, it is evident that the samples were made of a binary
copper–tin alloy, and that other elements are impurities that entered
the alloy during ore smelting and were not added deliberately.
According to the results of semi-quantitative chemical analysis, it is
apparent that bronze vessels are produced by Cu–Sn or tin bronze
alloy with a variable tin content and some metallic impurities. The
variety of Sn content proves that the bronze alloy is not made by a controlled alloying process to reach a homogenous bronze composition by
adding a distinct amount of tin to copper and melting them [12,13].
76
O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
Table 1
Results of SEM–EDS analysis of alloy in 25 bronze samples from Sangtarashan (wt.%).
ST.01-10
ST.02-10
ST.02-10/2
ST.03-10
ST.04-10
ST.05-10
ST.06-10
ST.07-10
ST.08-10
ST.09-10
ST.09-10/2
ST.10-10
ST.10-10/2
ST.11-10
ST.12-10
ST.13-10
ST.14-10
ST.15-10
ST.16-10
ST.17-10
ST.18-10
ST.19-10
ST.20-10
ST.21-10
ST.22-11
Cu
Sn
Pb
As
Zn
Ag
P
Ni
Fe
Sb
Si
S
88.61
90.79
89.30
86.18
84.88
90.40
89.89
87.40
86.83
83.81
95.11
90.59
92.26
89.27
91.68
85.61
87.44
90.92
90.06
90.54
88.90
90.27
87.45
91.69
86.41
11.32
7.75
10.70
9.43
13.36
9.51
8.87
9.60
11.63
12.78
4.18
8.76
6.29
9.78
8.15
11.45
10.24
5.05
9.31
6.94
9.68
8.18
11.20
6.90
11.45
–
0.61
–
0.81
1.16
–
0.27
1.23
0.26
0.42
0.56
0.24
0.03
0.22
–
2.27
0.78
2.45
0.38
1.04
0.43
0.38
0.69
0.72
–
0.02
0.03
–
0.73
0.22
0.03
0.04
0.04
0.03
0.03
0.13
0.03
0.46
0.21
0.03
0.03
0.02
0.05
0.03
0.42
0.26
0.18
0.05
0.04
0.45
–
0.01
–
1.23
0.02
0.01
–
0.41
0.29
1.42
–
0.01
0.58
0.01
0.01
0.01
0.01
0.54
0.01
0.01
0.01
–
0.01
0.01
–
–
0.67
–
0.54
–
–
–
0.48
0.56
0.80
–
0.27
–
–
0.09
0.44
0.74
0.69
0.21
0.89
0.54
–
0.49
0.52
–
0.03
0.14
–
0.24
0.20
0.03
–
0.13
0.17
0.28
0.02
0.10
–
0.07
0.02
0.18
0.27
0.29
–
0.15
0.16
–
0.08
0.10
–
–
–
–
0.42
0.01
–
0.59
0.41
–
–
–
–
–
–
–
–
–
0.01
–
0.01
0.01
0.15
0.01
–
1.13
–
–
–
0.42
0.01
0.01
–
0.32
0.23
0.39
–
–
0.38
–
–
–
–
–
–
–
–
0.20
–
–
0.55
–
–
–
–
–
–
–
–
–
–
–
–
–
0.36
–
–
0.45
0.01
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
0.08
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
0.15
–
0.34
–
–
0.07
–
–
–
–
–
–
–
–
–
–
–
0.20
–
–
–
The varying bronze composition might have originated due to one of
following processes of bronze production:
1. Co-smelting copper and tin ores in crucible to produce a bronze alloy
[12,14],
2. Alloying by adding a variable amount of cassiterite (SnO2) to the metallic copper and melting in crucible (cementation of metallic copper
with cassiterite) [14–16].
3. Using a complex Sn-bearing copper ore [17].
In a co-smelting process, an admixture of sulphidic/oxidic copper
ores and tine ore (cassiterite) are smelted in crucible to produce metallic tin bronze. The product is tin bronze with impurities. Also, alloy composition will vary with each smelting procedure. Second method
implies adding the tin ore (SnO2) to the melted metallic copper in a crucible. The product may be similar to what is obtained in the first method.
Varying amount of cassiterite and the small size of bronze ingots produced in each smelting processes, results in bronze ingots with variable
tin content and consequently, in bronze artefacts with different levels of
tin [3,13,16,18–20]. Using a complex Cu–Sn ore may be another method
of bronze production in the ancient time. Results of geochemical and
metal analyses provide some evidences for smelting complex Cu–Sn
ores from Deh Hosein to produce tin bronzes in the Luristan region during the Bronze Age of Iran at the third millennium BC [17,21]. But there
is no evidence for the exploitation of the Deh Hosein ancient mine to extensive bronze metallurgy in the Luristan region during the first millennium BC. Nevertheless, each of the described processes may have been
used for bronze production in the Luristan Iron Age bronze artefacts.
In some cases, melting broken objects or imported bronze ingots is another method for bronze production but in view of the extensive bronze
production in Luristan Iron Age and considering the high amount of
bronze finds in this region, this is unlikely and it seems that bronze
production would have existed as a local industry in western Iran.
As noted above, other metallic elements are identified as minor and
trace elements. Only in some cases, the Pb amount is significant. Lead is
insoluble in copper and appears as fine globules spread in the copper
matrix. In the copper–lead system and during solidification of leadcontaining copper, all of the alpha copper phase will solidify before
the lead–copper eutectic is formed. Subsequently, it will cause the
formation of Pb globules in the grain boundaries or within the grains
of the copper solid solution [22–24]. Nevertheless, Pb may not be
considered as an alloying element as it has been detected as a minor
or trace element in many samples. Only in some cases it is present in
about 2 wt.%., and in some published literature, a lead amount of
more than 2% is considered as an intentional alloy component [25,26].
Lead may be considered as an intentional alloying addition even in
low amounts, if it would be absent in the original copper ore [27] but
usually, the prehistoric copper alloy artefacts in the Iranian Plateau
have minor/trace amounts of lead that shows that it might derive as impurity from copper or tin metallic ores [5,28–30]. On the other hand, it
may be due to the limitations of EDS as an analytical tool or concentration of lead globules in the analysed areas. In fact, the presence of lead
was observed in the alloy, but the amount was not high enough to
allow the total composition to change to a ternary Cu–Sn–Pb alloy,
which was commonly used in metallurgy of same or later periods in different regions of the ancient world [31,32]. Also as noted above, in many
ancient copper alloys from Iran, arsenic has been detected as an important alloying element, and indeed, many copper ores in Iran are Asbearing [1,3,12,33]. Nevertheless, arsenic is detected as a trace element
in many samples which shows that the ore deposit used for metal
smelting in this region has not been rich in arsenic. On the other hand,
analytical investigations on some other bronze collections from Luristan
Iron Age also shows the use of binary tin bronze alloy to produce metallic artefacts with low concentration of other elements such as Pb and As
[2,34]. Thus, the copper ore deposits extracted for copper and bronze
production in western Iran might not have contained considerable As
concentration or copper arsenide minerals [12].
Chemical composition of three separate metal pieces from three vessels (ST.02-10/2, ST.09-10/2 and ST.10-10/2) shows that the spout and
pins used for producing common spouted vessels in Luristan are also
manufactured with binary Cu–Sn alloys similar to the alloy that is
used for body production. The Sn amount is variable in these pieces
and other elements are detected as minor/trace contents.
3.2. Microstructure
Metallographic samples of all bronze vessels were taken and examined under the optical microscope and SEM. SEM-BSE and optical
microscopy (OM) micrographs of bronze samples before etching show
very thin metal sheets with numerous scattered dark inclusions in
metallic matrix that are elongated in latitude of cross section which
O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
Fig. 2. Microstructure of some vessels before etching, including elongated copper sulphide
inclusions and intergranular corrosion attacks distributed in bronze matrix.
appear as a grey-green colour in OM observations (Figs. 2, 3). The thickness of the metallic sheet in all samples is lower than 1 mm and in some
areas reaches to about 300 μm. Only in the edges of the vessels a thickness more than 1 mm is measured. Some inclusions have remained unchanged in internal corrosion/oxidation layers under original surface of
the metal objects. On the other hand, some very fine, globular bright inclusions are visible in the metallic matrix in high magnification BSE micrographs (Fig. 3). Also, corrosion layers have formed over the surface of
the bronze samples. In some cases, these have penetrated the metal/
corrosion interface as intergranular corrosion attacks along the grain
boundaries. This phenomenon sometimes has caused formation of
some pseudomorphic replacements of bronze microstructure with
corrosion/oxidation products. The pseudomorphic replacements also
partially reveal metallurgical and microstructural features of metallic
grains such as strain lines or slip bands without intentional etching
with chemical reagents (Fig. 3).
To reveal grains' microstructure and the manufacturing process,
samples were etched in alcoholic FeCl3 solution [22]. After etching, the
77
microstructure of the bronze samples shows a typical grain structure
consisting with worked and recrystallized grains of α solid solution of
copper–tin with twinned and strain lines within the grains (Fig. 3).
The twin lines usually are observed as straight. Strain lines are visible
in some grains especially near the surface of the metal sheets. This microstructure is common in copper alloys and other FCC metals [22,35].
Based on the OM micrographs, grain size is not similar in all samples;
also it is not homogeneous in all areas of each individual sample.
The metallographic studies on bronze samples state that all vessels
are shaped during a cycle of cold working and annealing. This is apparent from equi-axed and recrystallized α-solid solution grains. In some
cases, some slip lines are visible within the grains that may identify
the final operation as cold working. Shaping by hammering on cold
copper alloys may lead to a phenomenon named work-hardening. To
remove this problem, the ancient metalworkers applied heat treatment
(annealing) to return workability to the bronze piece. This heat treatment will improve the bronze mechanical properties because after
mechanical work, a subsequent heat treatment would help to recover
ductility, by promoting a recrystallization process [22,36,37]. In copper
and its alloys, the heating temperature for annealing is 500–800 °C
[22]. This operation causes the formation of a grain microstructure as
observed in these vessels. Also, the amount of mechanical/thermal operation on the metal piece influences the grain size in the final product,
meaning a smaller grain size may be due to more times of working and
heating cycles. For example, the grain sizes in samples ST.08-10, ST.1310 and ST.14-10 are apparently different (Fig. 4), and the grain sizes in
sample ST.08-10 is more than 100 μm while it is 50 μm or less in two
other samples. In fact, the samples with small grain sizes have been
subjected to more working to reach the final shape and thickness [22].
All microstructures reveal the presence of numerous inclusions different in number, shape and size. To identify the chemical composition,
some elongated and globular inclusions were analysed by SEM–EDS microanalysis. The results showed that the grey-green elongated inclusions are composed of copper and sulphur with a low content of iron
and tin. Copper is detected as the major element within about 70–85%
while sulphur is detected between 5 and 27% in different samples. Tin
and iron concentrations are detected less than 10% in weight. The
white inclusions in BSE micrographs are high lead metallic compounds
with, in some cases, more than 70% of Pb (Fig. 5). Based on the Cu–Pb
diagram [22], the chemical composition of Pb globules in Cu–Pb alloys
is nearly a 100% of Pb and the presence of some copper, tin and iron in
these inclusions might be due to influences from the surrounding
phase compositions in the EDS microanalysis such as alpha copper
solid solution matrix.
The presence of Cu–S inclusions in the bronze matrix may be due to
using sulphidic copper ores for smelting and producing copper.
Smelting copper sulphide ores has been common in ancient metallurgy
to extract metallic copper [18,38,39]. In fact, some copper sulphides
didn't transform to metallic copper during the smelting processes and
are currently visible as small dark inclusions in the bronze microstructure; these may belong to unchanged original copper sulphide ores or
these are by-product copper sulphide compounds that are formed during the smelting process but remained in the bronze microstructure,
similar to products of matte production in the process of copper
smelting [14,40]. These inclusions appear as segregated phases due to
their low miscibility in molten copper [41]. A low iron amount in inclusions composition may be due to the presence of iron in copper ores or
to use iron–copper sulphides such as chalcopyrite (CuFeS2) [39]. It must
be considered that, copper sulphide inclusions are more resistant than
bronze alloy against corrosion/alteration events and remain unchanged
in the internal corrosion layers (Fig. 3).
According to binary the Cu–Sn system equilibrium phase diagram,
the maximum dissolution limit of Sn in Cu solid solution is 15.8 wt.%
[22,35,36] and the α-copper phase would be the only phase in the microstructure of an alloy with up to 15% Sn when a homogenizing heat
treatment, as annealing, is performed [37]. However, the common
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O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
Fig. 3. SEM-BSE micrograph of bronze samples, copper sulphide inclusions, corrosion layers and pseudomorphic replacement are visible as well as fine lead globules.
dissolution limit of the tin amount noticed in literature for tin bronze
objects is 14 wt.% and it is rare to find a tin bronze with higher amount
of tin with a homogenous the α-solid solution phase [22,42]. Fig. 6 represents the specified area of Sn amount range determined in
Sangtarashan bronzes in weight percent on the metastable (casting
and annealing conditions) Cu–Sn diagram. According to the diagrams,
in casting conditions two phases may be formed during solidification
of bronzes with similar composition as the Sangtarashan bronzes:
alpha solid solution and alpha + delta eutectoid while after annealing,
only the α phase may be present in these bronzes and all eutectoid
phase will transform to Cu–Sn solid solution during heat treatment
[22,43]. The microstructure of samples shows a homogenous α solid solution without evidences of unchanged eutectoid phases besides the
alpha phase. Only some circular inclusions or phases are visible in the
sample ST.22-11 micrograph. EDS analysis showed that it has been composed with copper and tin, 62.34 and 33.90 wt.%, respectively, with a
low amount of nickel, 3.76 wt.% (Fig. 7). It is an intermetallic Cu–Sn
phase that may be formed due to some conditions during melt solidification and which is now visible as a segregated phase. Based on the Cu–
Sn diagram (Fig. 6) and composition and microstructure of the
intermetallic phases, it seems that it is composed by an alpha + delta
eutectoid phase which is a common intermetallic phase in archaeological bronzes.
This eutectoid phase starts to appear as a result of segregation in the
microstructure of low-tin bronzes (about 5% to 15% tin), depending on
the cooling conditions of the alloy within the alpha dendrites in twophased bronzes [22,36,42]. In the segregation of bronzes during
solidification, usually alpha + delta (α + δ) eutectoid is the common
intermetallic phase, but it has a permanent composition with 27% of
tin [22,44–47], while the tin amount in the intermetallic phase of sample ST.22-11 is about 34%. This may be due to limitations of spot analysis
by SEM–EDS. It could be interpreted by the metastable Cu–Sn diagram
(Fig. 6), in which it is apparent that α + δ eutectoid phase can be available beside alpha solid solution in the annealed condition in the Cu–Sn
system [22,36].
The sample has 11.45% of tin. In bronzes with this Sn amount it is
probable that intermetallic Cu–Sn compounds are formed due to casting
operation. But in many cases, these phases could be removed by heating
the bronze piece, e.g., during annealing [48]. In fact, in many cases
thermomechanical operations lead to the removal of probable
O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
79
Age) in Luristan [21,30] but there is no evidence for ore mining in the
Luristan region from the Iron Age. Other proposed processes are also
possible but no evidence is found by archaeological research in the
Luristan region on archaeometallurgical activities of bronze production.
Nevertheless, various amounts of tin in metal pieces may prove the application of an uncontrolled smelting system for tin bronze production
during that time. Archaeometallurgical studies on some bronze artefacts
in the Luristan style in some Iron Age sites in Western Luristan show a
variety of Sn content as well as a low amount of other alloying elements
in the composition. For example, Fleming et al. [34] analysed 22 bronze
vessels from War Kabud site in Luristan beside some other bronze artefacts. The tin amount in these bronze vessels is between 2.6% and 18.2%
and other elements are detected as minor/trace contents. Also, metallographic examination on a vessel from War Kabud presents a similar
microstructure to the Sangtarashan vessels with twinned grains and
some strain lines in the grains as well as elongated sulphidic inclusions
dispersed in the bronze matrix [2,34]. On the other hand, analytic
results of some Luristan bronzes in the Ashmolean Museum also
provide the characteristics that are found in the alloy composition in
the Sangtarashan bronze vessels [10]. Although, despite the large
amount of Luristan bronzes in several museums, a hiatus about
archaeometallurgical studies in this field is apparent in the literature.
The microstructure of bronzes showed that the metalworkers have
applied mechanical operations and subsequent heat treatment to transform bronze ingots to final thin sheet metallic vessels. This is proved by
the presence of worked and recrystallized grains, elongated inclusions
and strain lines in some grains especially near surface of metallic sheets.
Also, grain size is different in bronze samples and in several regions of
one sample that implies a variety in degree of deformation used to
shape the bronze vessels.
Thus, the microstructure and composition of the studied bronzes reveal that the following process can be suggested for these bronze
artefacts:
1. Bronze production with co-smelting or cementation processes, perhaps in crucible to produce bronze prills with some impurities, the
copper ores were sulphidic,
2. Melting bronze prills and producing bronze ingots,
3. Using ingots for casting sheets or pieces of bronze (optional),
4. Cold working on sheets or pieces to shape the vessels,
5. Annealing of work-hardened sheets to return workability,
6. A continuous thermo-mechanical process to reach the final shape of
the vessels.
Fig. 4. Microstructure of three bronze vessels after etching in alcoholic FeCl3, a) ST.08-10,
b) ST.13-10, and c) ST.14-10, the microstructures are consisting of worked and recrystallized bronze grains with twinning and strain lines, the elongated sulphidic inclusions are
visible unetched. The twin lines are usually straight; strain lines are visible more near
the surface of the metal sheets and the grain size is variable in the samples.
segregations that occur in the metal structure during casting and solidification [22,36].
3.3. Bronze metalworking
Based on these results, smelting and metalworking processes in
Sangtarashan Iron Age bronzes produce binary Cu–Sn alloys with
some impurities such as Pb and As, as well as dispersed copper sulphide
inclusions. In fact, the bronze alloy is obtained by smelting copper sulphides as copper ores. There are some possibilities for bronze production in this area and period but there is no absolute evidence for
metallurgical activities in the Luristan region. As noted above, the
bronze alloy may be produced by one of these processes: co-smelting,
cementation or using complex Cu–Sn ores. With regard to literature,
using complex Cu–Sn ores is attested in third millennium BC (Bronze
By this process, bronze vessels are manufactured with a microstructure and characteristics that have been explained above. Certainly, some
small differences such as strain lines and grain sizes are present, but this
manufacturing process can be suggested for all bronze vessels.
4. Conclusions
Microstructural study on some bronze vessels from the Sangtarashan
Iron Age site in western Iran was carried out by microscopy and microanalysis methods. Results of 25 individual pieces from 22 vessels showed
that all samples were manufactured with a variable composition of Cu–Sn
or tin bronze alloy with some impurities such as lead and arsenic. In fact,
chemical composition showed that the bronze production may have been
performed by an uncontrolled production method, such as co-smelting or
cementation, by using copper sulphide ores and tin oxide. Hereby bronze
alloys with different tin amounts have been produced in each smelting
process. Other elements such as Pb and As are considered as impurities
that may derive from the original metallic ores. Specifically, the low arsenic content in the Luristan bronzes may entail the application of some
specific copper ores apart from those used in the Chalcolithic/Bronze
age of the Iranian Plateau. Also, the microstructure of bronze vessels
shows the application of cold working (hammering) and subsequent
heat treatment (annealing) as a cyclic procedure to transform a bronze
80
O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
Fig. 5. SEM-BSE micrograph and SEM–EDS analysis of inclusions scattered in bronze matrix, elongated dark Cu–S inclusions (A) and, bright Pb globules (B) in sample ST.01-10.
Fig. 6. Metastable Cu–Sn diagram, left) normal casting conditions, right) annealing conditions (after [22,43]). Range of determined tin in all bronze samples has specified on two diagrams
and shows that two phases including alpha solid solution and alpha + delta eutectoid may form during solidification in casting condition, but in annealed condition, the eutectoid phase
may transform to alpha solid solution in the specified range of Sn.
O. Oudbashi, P. Davami / Materials Characterization 97 (2014) 74–82
81
Fig. 7. SEM-BSE micrograph and SEM–EDS analysis of circular intermetallic phases in sample ST.22-11.
ingot into thin sheet vessels. The Significant issue is the similarity in composition and microstructure between the Sangtarashan bronze vessels
and some other bronze artefacts (especially vessels) from other Iron
Age sites in Luristan such as War Kabud. Finally, based on the results
and their interpretations, the application of microscopic methods can
help to establish manufacturing techniques and characteristics of archaeological metal artefacts.
Acknowledgments
Authors are thankful from Ata Hassanpour and Dr. Mehrdad
Malekzadeh, Archaeological Campaign of Sangtarashan Site for their
help to allow access to the bronze samples, Natalie Cleeren, University
of Antwerp for reading and editing the original text, Prof. David A.
Scott, UCLA, Dr. Luc Robbiola, Université Toulouse 2 Le Mirail, Dr.
Emanoel Ribeiro de Almeida, Dental Morelli Ltda, Atefeh Shekofteh,
Dr. S. Mohammadamin Emami and Dr. Mohammad Mortazavi, Art University of Isfahan and Behnam Rahmani, RMRC for their valuable helps,
comments and opinions.
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