Materials Characterization 97 (2014) 74-82

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Metallographyandmicrostructureinterpretationofsomearchaeological CrossMark 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
b
Faculty of Material Science and Engineering, Sharif University of Technology/Razi Applied Science Foundation, No. 27, Fernan St., Shahid Ghasem Asghari Blvd., km21 of
Karadj Makhsous Road, Tehran, Iran

ARTICLE INFO ABSTRACT

Article history: Archaeological excavations in western Iran have recently revealed a significant Luristan Bronzes collection from
Received 31 May 2014 Sangtarashan archaeological site. The site and its bronze collection are dated to Iron Age II/III of western Iran
Received in revised form 28 August 2014 (10th-7th century BC) according to archaeological research. Alloy composition, microstructure and manufacturing
Accepted 12 September 2014
Available online 16 September 2014
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
Keywords:
Sangtarashan process of bronze vessels in Luristan. It proved that the samples have been manufactured with a binary copper-tin alloy
Tin bronze with a variable tin content that may relates to the application of an uncontrolled procedure to make bronze alloy (e.g. co-
SEM-EDS smelting or cementation). The presence of elongated copper sulphide inclusions showed probable use of copper sulphide
Metallography ores for metal production and smelting. Based on metallographic studies, a cycle of cold working and annealing was used
Alloying
Sulphidic inclusion to shape the bronze vessels.
Thermo-mechanical operations © 2014 Elsevier Inc. All rights reserved.

1. Introduction in the Luristan Bronzes style such as spouted and simple vessels, sculptural
object such as finials, and weaponry artefacts. [11].
The investigation of microstructure and alloy composition of archae- In this paper, some recent excavated bronze artefacts belonging to the
ological metal artefacts is an interesting and important subject to determine Sangtarashan archaeological site were examined to determine alloying and
metalworking techniques in the ancient world. Tin bronze is the first alloy used manufacturing characteristics and processes during the Iron Age period. The
in most regions around the world, for example, the first tin bronze artefacts metallurgical research concerning bronze production in Sangtarashan has
appear in west of Iranian Plateau at the end of Chalcolithic period (end of 4th become a unique opportunity to understand the Iron Age bronze production in
millennium BC) [1-3]. this western region of the Iranian Plateau. The study also comprises a
The Luristan region is located in the west of Iran, which is one of the discussion concerning the elemental and microstructural features of some
important cradles of the Iranian Plateau. In archaeological context, Luristan is bronze vessels.
the highland folded region in the Central Zagros mountain chain, in western
Iran. Thousands of ancient bronze artefacts with exquisite modelling, fine 2. Materials and methods
style, and outstanding manufacturing skill have been unearthed in the Luristan
area. The emergence of significant bronze production is an important 2.1. Archaeological samples
archaeological/technological phenomenon during the Iron Age in the Luristan
To study the microstructure and alloy composition of bronzes from the
region. The Luristan Bronzes include a series of decorated bronze artefacts
Iron Age Luristan, a collection of twenty two bronze samples was selected
similar in specific local style, dating to the Iron Age II/III (1000-650 BC) [4-
from the Sangtarashan archaeological site. These include broken metallic
10]. During the past 10 years, some archaeological excavations were carried
vessels that have been unearthed during archaeological excavations between
out in Iron Age site of Sangtarashan in eastern Luristan (known as Pish-i Kuh).
2009 and 2011 (Fig. 1). Some samples were analysed
Sangtarashan is situated about 35 km of southeast of Khorramabad (capital of
Lorestan province). The site has been excavated by Iranian 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

http://dx.doi.org/10.1016/j.matchar.2014.09.007
1044-5803/© 2014 Elsevier Inc. All rights reserved.

* Corresponding author.
E-mail addresses: [email protected] (O. Oudbashi), [email protected] (P. Davami).
 75 0,。uàbashi, р. Da١ ?Qn١٦ 1 Mate^às Character^ahon 97 (2014)74-82

٠
‫ااأ‬
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 Dispersive Spectrometry (EDS) on areas of about 10000 pm (about 100 X 100
2

to other samples to compare and develop statistical interpretations. In total, pm) to detect the entire alloy composition and to avoid effects of phase
twenty five pieces were chosen from 22 metallic vessels including 22 pieces concentrations in the final results.
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 3. Results and discussion
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 3.1. Alloy composition
joined to the body with large metal pins. Therefore, one spout and two pins
from three vessels are analysed. SEM-EDS investigation was employed to determine alloy components in a
semi-quantitative manner. Table 1 shows results of alloy composition in 25
22. Е^ебтеп® 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
Small samples from the metal artefacts and fragments were prepared and clear that the main alloying elements of all samples are Cu and Sn whereas Pb,
mounted for metallographic preparation. For this purpose, a cross section from Zn and Ni are considered to be impurities in the alloy composition. The
each piece was prepared by embedding samples in epoxy resin. Preparation for percent of Cu content varies from 83.81 up to 95.11 and the Sn 4.18 up to
analysis was followed by grinding them with silicon carbide papers (400-2000 13.36. Through these analyses one can observe that the Sn contents show
grit size). Finally, the cross sections were polished with a diamond paste (1 different values.
pm). Lead is detected in minor concentrations in all samples. Only in two
Microstructural observations and chemical composition analysis were samples, ST.13-10 and ST.15-10, itis observed in a considerable amount, over
carried out with optical microscopy and scanning electron microscopy 2%. Worth mentioning is that arsenic has been detected in low amounts and as
equipped with energy dispersive X-ray spectroscopy (SEM-EDS) methods. a minor component (less than 1%) in all samples, while arsenic has been
Cross-sections were observed with a BK-POL/BK-POLR manufactured by detected as a significant alloying element in many Iranian prehistoric copper
Alltion Company, China, under bright field (BF) illumination. Samples were alloys [1].
observed before and after etching with alcoholic ferric chloride (FeCl 3) Generally, it is evident that the samples were made of a binary copper-tin
solution. Mounted cross-sections were observed in a VEGA II, TESCAN alloy, and that other elements are impurities that entered the alloy during ore
scanning electron microscope equipped with a secondary electron detector smelting and were not added deliberately.
(SE) and a backscattered electron detector (BSE) with elemental analysis According to the results of semi-quantitative chemical analysis, it is
system (EDS) model Rontec Quantax/ QX2, Germany, in SEM laboratory of apparent that bronze vessels are produced by Cu-Sn or tin bronze alloy with a
Razi Metallurgical Research Center, Tehran, Iran used for semi-quantitative variable tin content and some metallic impurities. The variety of Sn content
elemental analyses. The metallic remains in cross sections were analysed by proves that the bronze alloy is not made by a controlled alloying process to
Energy reach a homogenous bronze composition by adding a distinct amount of tin to
copper and melting them [12,13].
 。。.
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Table 1
Results of SEM-EDS analysis of alloy in 25 bronze samples from Sangtarashan (wt.%).

Cu Sn Pb As Zn Ag P Ni Fe Sb Si S

ST.01-10 88.61 11.32 - 0.02 - - 0.03 - - - -

ST.02-10 90.79 7.75 0.61 0.03 0.01 0.67 0.14 - - - -
ST.02-10/2 89.30 10.70 - - - - - - - -
ST.03-10 86.18 9.43 0.81 0.73 1.23 0.54 0.24 0.42 0.42 - - -
ST.04-10 84.88 13.36 1.16 0.22 0.02 - 0.20 0.01 0.01 - - 0.1
ST.05-10 90.40 9.51 - 0.03 0.01 - 0.03 - 0.01 - - 5 -
ST.06-10 89.89 8.87 0.27 0.04 - - - 0.59 - - - 0.3
ST.07-10 87.40 9.60 1.23 0.04 0.41 0.48 0.13 0.41 0.32 - - 4 -
ST.08-10 86.83 11.63 0.26 0.03 0.29 0.56 0.17 - 0.23 - - -
ST.09-10 83.81 12.78 0.42 0.03 1.42 0.80 0.28 - 0.39 - - 0.0
ST.09-10/2 95.11 4.18 0.56 0.13 - - 0.02 - - - 7 -
ST.10-10 90.59 8.76 0.24 0.03 0.01 0.27 0.10 - - - -
ST.10-10/2 92.26 6.29 0.03 0.46 0.58 - - - 0.38 - - -
ST.11-10 89.27 9.78 0.22 0.21 0.01 - 0.07 - - 0.36 0.08 -
ST.12-10 91.68 8.15 - 0.03 0.01 0.09 0.02 - - - -
ST.13-10 85.61 11.45 2.27 0.03 0.01 0.44 0.18 - - - -
ST.14-10 87.44 10.24 0.78 0.02 0.01 0.74 0.27 - - 0.45 - -
ST.15-10 90.92 5.05 2.45 0.05 0.54 0.69 0.29 0.01 - 0.01 - -
ST.16-10 90.06 9.31 0.38 0.03 0.01 0.21 - - - - -
ST.17-10 90.54 6.94 1.04 0.42 0.01 0.89 0.15 0.01 - - - -
ST.18-10 88.90 9.68 0.43 0.26 0.01 0.54 0.16 0.01 - - - -
ST.19-10 90.27 8.18 0.38 0.18 - - - 0.15 0.20 - - 0.2
ST.20-10 87.45 11.20 0.69 0.05 0.01 0.49 0.08 0.01 - - - 0 -
ST.21-10 91.69 6.90 0.72 0.04 0.01 0.52 0.10 - - - -
ST.22-11 86.41 11.45 - 0.45 - - - 1.13 0.55 - - -

The varying bronze composition might have originated due to one of following more than 2% is considered as an intentional alloy component [25,26]. Lead
processes of bronze production: 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
1. Co-smelting copper and tin ores in crucible to produce a bronze alloy
[12,14], copper alloy artefacts in the Iranian Plateau have minor/trace amounts of lead
2. Alloying by adding a variable amount of cassiterite (SnO 2) to the metallic that shows that it might derive as impurity from copper or tin metallic ores
copper and melting in crucible (cementation of metallic copper with [5,28-30]. On the other hand, it may be due to the limitations of EDS as an
cassiterite) [14-16]. analytical tool or concentration of lead globules in the analysed areas. In fact,
3. Using a complex Sn-bearing copper ore [17]. 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,
In a co-smelting process, an admixture of sulphidic/oxidic copper ores and which was commonly used in metallurgy of same or later periods in different
tine ore (cassiterite) are smelted in crucible to produce metallic tin bronze. The regions of the ancient world [31,32]. Also as noted above, in many ancient
product is tin bronze with impurities. Also, alloy composition will vary with copper alloys from Iran, arsenic has been detected as an important alloying
each smelting procedure. Second method implies adding the tin ore (SnO ) to 2
element, and indeed, many copper ores in Iran are As- bearing [1,3,12,33].
the melted metallic copper in a crucible. The product may be similar to what is Nevertheless, arsenic is detected as a trace element in many samples which
obtained in the first method. Varying amount of cassiterite and the small size shows that the ore deposit used for metal smelting in this region has not been
of bronze ingots produced in each smelting processes, results in bronze ingots rich in arsenic. On the other hand, analytical investigations on some other
with variable tin content and consequently, in bronze artefacts with different bronze collections from Luristan Iron Age also shows the use of binary tin
levels of tin [3,13,16,18-20]. Using a complex Cu-Sn ore may be another bronze alloy to produce metallic artefacts with low concentration of other
method of bronze production in the ancient time. Results of geochemical and elements such as Pb and As [2,34]. Thus, the copper ore deposits extracted for
metal analyses provide some evidences for smelting complex Cu-Sn ores from copper and bronze production in western Iran might not have contained
Deh Hosein to produce tin bronzes in the Luristan region during the Bronze considerable As concentration or copper arsenide minerals [12].
Age of Iran at the third millennium BC [17,21]. But there is no evidence for Chemical composition of three separate metal pieces from three vessels
the exploitation of the Deh Hosein ancient mine to extensive bronze metallurgy (ST.02-10/2, ST.09-10/2 and ST.10-10/2) shows that the spout and pins used
in the Luristan region during the first millennium BC. Nevertheless, each of for producing common spouted vessels in Luristan are also manufactured with
the described processes may have been used for bronze production in the binary Cu-Sn alloys similar to the alloy that is used for body production. The
Luristan Iron Age bronze artefacts. In some cases, melting broken objects or Sn amount is variable in these pieces and other elements are detected as
imported bronze ingots is another method for bronze production but in view of minor/trace contents.
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 3.2. Microstructure
production would have existed as a local industry in western Iran.
As noted above, other metallic elements are identified as minor and trace Metallographic samples of all bronze vessels were taken and examined
elements. Only in some cases, the Pb amount is significant. Lead is insoluble under the optical microscope and SEM. SEM-BSE and optical microscopy
in copper and appears as fine globules spread in the copper matrix. In the (OM) micrographs of bronze samples before etching show very thin metal
copper-lead system and during solidification of lead- containing copper, all of sheets with numerous scattered dark inclusions in metallic matrix that are
the alpha copper phase will solidify before the lead-copper eutectic is formed. elongated in latitude of cross section which
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
 77 0,。uàbashi, р. Da١ ?Qn١٦ 1 Mate^às Character^ahon 97 (2014)74-82

and recrystallized grains of a 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 a-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.13- 10 and ST.14-10 are
apparently different (Fig. 4), and the grain sizes in sample ST.08-10 is more
than 100 pm while it is 50 pm 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% ofPb (Fig. 5). Based on the
Cu-Pb diagram [22], the chemical composition ofPb globules in Cu-Pb alloys
is nearly a 100% ofPb 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
Fig. 2. Microstructure of some vessels before etching, including elongated copper sulphide copper during the smelting processes and are currently visible as small dark
inclusions and intergranular corrosion attacks distributed in bronze matrix. 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
appear as a grey-green colour in OM observations (Figs. 2, 3). The thickness of
bronze microstructure, similar to products of matte production in the process of
the metallic sheet in all samples is lower than 1 mm and in some areas reaches
copper smelting [14,40]. These inclusions appear as segregated phases due to
to about 300 pm. Only in the edges of the vessels a thickness more than 1 mm
their low miscibility in molten copper [41]. A low iron amount in inclusions
is measured. Some inclusions have remained unchanged in internal
composition may be due to the presence of iron in copper ores or to use iron -
corrosion/oxidation layers under original surface of the metal objects. On the
copper sulphides such as chalcopyrite (CuFeS2) [39]. It must be considered
other hand, some very fine, globular bright inclusions are visible in the
that, copper sulphide inclusions are more resistant than bronze alloy against
metallic matrix in high magnification BSE micrographs (Fig. 3). Also,
corrosion/alteration events and remain unchanged in the internal corrosion
corrosion layers have formed over the surface of the bronze samples. In some
layers (Fig. 3).
cases, these have penetrated the metal/ corrosion interface as intergranular
According to binary the Cu-Sn system equilibrium phase diagram, the
corrosion attacks along the grain boundaries. This phenomenon sometimes has
maximum dissolution limit of Sn in Cu solid solution is 15.8 wt.% [22,35,36]
caused formation of some pseudomorphic replacements of bronze
and the a-copper phase would be the only phase in the microstructure ofan
microstructure with corrosion/oxidation products. The pseudomorphic
alloy with up to 15% Sn when a homogenizing heat treatment, as annealing, is
replacements also partially reveal metallurgical and microstructural features of
performed [37]. However, the common
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 FeCl 3 solution [22]. After etching, the microstructure
of the bronze samples shows a typical grain structure consisting with worked
 。。.
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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 bronzes.
14 wt.% and it is rare to find a tin bronze with higher amount of tin with a This eutectoid phase starts to appear as a result of segregation in the
homogenous the а-solid solution phase [22,42]. Fig. 6 represents the specified microstructure of low-tin bronzes (about 5% to 15% tin), depending on the
area of Sn amount range determined in Sangtarashan bronzes in weight percent cooling conditions of the alloy within the alpha dendrites in two- phased
on the metastable (casting and annealing conditions) Cu-Sn diagram. bronzes [22,36,42]. In the segregation of bronzes during solidification, usually
According to the diagrams, in casting conditions two phases may be formed alpha + delta (a + ‫ )ة‬eutectoid is the common intermetallic phase, but it has a
during solidification of bronzes with similar composition as the Sangtarashan permanent composition with 27% of tin [22,44-47], while the tin amount in the
bronzes: alpha solid solution and alpha + delta eutectoid while after annealing, intermetallic phase of sample ST.22-11 is about 34%. This may be due to
only the а phase may be present in these bronzes and all eutectoid phase will limitations of spot analysis by SEM-EDS. It could be interpreted by the
transform to Cu-Sn solid solution during heat treatment [22,43]. The
metastable Cu-Sn diagram (Fig. 6), in which it is apparent that а + ‫ ة‬eutectoid
microstructure of samples shows a homogenous а solid solution without
evidences of unchanged eutectoid phases besides the alpha phase. Only some phase can be available beside alpha solid solution in the annealed condition in
circular inclusions or phases are visible in the sample ST.22-11 micrograph. the Cu-Sn system [22,36].
EDS analysis showed that it has been composed with copper and tin, 62.34 and The sample has 11.45% of tin. In bronzes with this Sn amount it is
33.90 wt.%, respectively, with a low amount of nickel, 3.76 wt.% (Fig. 7). It is probable that intermetallic Cu-Sn compounds are formed due to casting
an intermetallic Cu-Sn phase that may be formed due to some conditions operation. But in many cases, these phases could be removed by heating the
during melt solidification and which is now visible as a segregated phase. bronze piece, e.g., during annealing [48]. In fact, in many cases
Based on the Cu- Sn diagram (Fig. 6) and composition and microstructure of thermomechanical operations lead to the removal of probable
the intermetallic phases, it seems that it is composed by an alpha + delta
eutectoid phase which is a common intermetallic phase in archaeological
79 0,。uàbcshi, р. Da١ ?Qn١٦ 1 Matehals Characterizahon 97 (2014)74-82

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.
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.
Fig. 4. Microstructure of three bronze vessels after etching in alcoholic FeCl 3, a) ST.08-10,
b) ST.13-10, and c) ST.14-10, the microstructures are consisting of worked and recrystal-
lized bronze grains with twinning and strain lines, the elongated sulphidic inclusions are 4. Conclusions
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. 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
segregations that occur in the metal structure during casting and solidification
samples were manufactured with a variable composition of Cu-Sn or tin bronze
[22,36].
alloy with some impurities such as lead and arsenic. In fact, chemical
composition showed that the bronze production may have been performed by
‫ا‬١ ；^‫عا‬
an uncontrolled production method, such as co-smelting or cementation, by
33. BYDnze ‫ألل)خاحعاآآ‬/01＜
using copper sulphide ores and tin oxide. Hereby bronze alloys with different
tin amounts have been produced in each smelting process. Other elements such
Based on these results, smelting and metalworking processes in as Pb and As are considered as impurities that may derive from the original
Sangtarashan Iron Age bronzes produce binary Cu-Sn alloys with some metallic ores. Specifically, the low arsenic content in the Luristan bronzes may
impurities such as Pb and As, as well as dispersed copper sulphide inclusions. entail the application of some specific copper ores apart from those used in the
In fact, the bronze alloy is obtained by smelting copper sulphides as copper Chalcolithic/Bronze age of the Iranian Plateau. Also, the microstructure of
ores. There are some possibilities for bronze production in this area and period bronze vessels shows the application of cold working (hammering) and
but there is no absolute evidence for metallurgical activities in the Luristan subsequent heat treatment (annealing) as a cyclic procedure to transform a
region. As noted above, the bronze alloy may be produced by one of these bronze
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
 。。.
74-82 ٢ ‫اجذ‬٢ ‫ا‬٦٠٢ ‫ث؛أاحا‬٦٠ ‫ئآلا‬٢ ‫ا‬١ ‫اخ‬0 ‫ل؟ اآ‬7 ‫عآللم‬01 ‫لمصأ‬١ uàbcsMEDaYamM Matehak 80

SEMMAG： 2.50 kx WD： 23.85 mm ‫لسدلسدا‬ VEGAUTESCAN 1 I I

SEM HV: 15.00 k٧ Det: BSE Detector 10 um .I 0٦ ‫غ‬111‫ حمإ‬X, 1.1111,1...‫شءإغ‬,‫ت‬, I ' ' -
Date(m٠):11H9/11 Vac: HiVac RAZIM ٥ è KeV

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.

Usual Casting Conditions

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 speci fied on two diagrams and
shows that two phases including alpha solid solution and alpha + delta eutectoid may form during solidi fication in casting condition, but in annealed condition, the eutectoid phase may
transform to alpha solid solution in the specified range of Sn.
81 0,。uàbcshi, р. Da١ ?Qn١٦ 1 Matehals Characterizahon 97 (2014)74-82

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 com- Iran, Iran. Antiq. XLVIII (2013) 147-174.
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