1

COPPER-TIN ALLOYSEARLY BRONZE AGES

OF ANATOLIA(3200 - 1000 BC)

Cu-Sn PHASE DIAGRAM

Solidsolution

14% Sn in COPPER 20% Sn in COPPER

2

HARDNESS OF BRONZEHARDNESS OF BRONZE PREPARATION OF Cu-Sn ALLOYSPREPARATION OF Cu-Sn ALLOYS

1.1. Metallic copper and tin can be meltedMetallic copper and tin can be meltedtogether at desired proportions.together at desired proportions.

2.2. Copper and tin ore cassiterite may beCopper and tin ore cassiterite may besmelted together.smelted together.

3.3. Cementation method can be used in whichCementation method can be used in whichcassiterite is added to the surface ofcassiterite is added to the surface ofmolten copper under charcoal in a furnacemolten copper under charcoal in a furnacewhere the tin is reduced directly into thewhere the tin is reduced directly into themelt:melt:SnOSnO2 2 + C Sn + CO+ C Sn + CO22

MICROSTRUCTURE OF BRONZEMICROSTRUCTURE OF BRONZE EARLIEST BRONZESEARLIEST BRONZES

3

ANATOLIAN COPPER MINESANATOLIAN COPPER MINES

Where is the tin???Where is the tin???

PERCENTAGE OF BRONZEPERCENTAGE OF BRONZEOBJECTS BEFORE 2200 BCOBJECTS BEFORE 2200 BC

BakBakıırr

BronzBronz

McKerrell, 1977

PERCENTAGE OF BRONZEPERCENTAGE OF BRONZEOBJECTS AFTER 2200 BCOBJECTS AFTER 2200 BC

BakBakıırr

BronzBronz

McKerrell 1977

BRONZES OF ANATOLIABRONZES OF ANATOLIA

•• Figurines of Tell Atchana in the Amuq plainFigurines of Tell Atchana in the Amuq plaindated to around 3000 BCdated to around 3000 BC

•• Bronzes of Troy II, dated to 2800 BCBronzes of Troy II, dated to 2800 BC

•• Bronzes of Alacahoyuk and Horoztepe datedBronzes of Alacahoyuk and Horoztepe datedto the 2nd half of 3rd millennium BCto the 2nd half of 3rd millennium BC

•• Bronze objects from the royal tombs at UrBronze objects from the royal tombs at Ur

Mesopotamia 2600-2400 BCMesopotamia 2600-2400 BC

4

SITES THAT YIELDED BRONZE OBJECTSSITES THAT YIELDED BRONZE OBJECTSDURING 3rd. MILLENNIUM BCDURING 3rd. MILLENNIUM BC

MAP OF SOUTH CENTRALMAP OF SOUTH CENTRALANATOLIAANATOLIA

AMUQ FIGURINES

5

AMUQ AXEAMUQ AXE

ALACAHÖYÜK EBA TOMBS

ALACAHÖYÜK EBA OBJECTSALACAHÖYÜK EBA OBJECTS ALACAHÖYÜK EBA METALSALACAHÖYÜK EBA METALS

11

12

14

0

0

2

4

6

8

10

12

14

Nu

mb

er

of

Sam

ple

s

Cu As>1.0 Sn>2.0 As & Sn

Alacahöyük EBA Metals

Esin 1967

6

As DISTRIBUTION IN EBAAs DISTRIBUTION IN EBAALACAHÖYÜK METALSALACAHÖYÜK METALS

5

3

4

0 01

2

3

4

5

Nu

mb

er

of

Sa

mp

les

1-2 2-3 3-4 4-5 >5

% As

As Content of EBA Alacahöyük Metals

Esin 1967

Sn DISTRIBUTION OF EBASn DISTRIBUTION OF EBAALACAHÖYÜK METALSALACAHÖYÜK METALS

1 0

4 4

5

1

2

3

4

5

Nu

mb

er o

f S

amp

les

2-4 4-6 6-8 8-10 >10

% Sn

Sn Content of EBA Alacahöyük Metals

Esin 1967

3rd MILLENNIUM3rd MILLENNIUMMESOPOTAMIAM SITESMESOPOTAMIAM SITES TRESURES FROM URTRESURES FROM UR

7

TROYTROYTROIATROIA

HOARDHOARD

CEREMONIAL AXES OF TROYCEREMONIAL AXES OF TROY

Green Nephrite

Jade

Lapis Lazuli

8

TIN FROM AFGHANISTANTIN FROM AFGHANISTAN

Possible tindeposits

MAJOR COPPER DEPOSITSMAJOR COPPER DEPOSITSOF ANATOLIAOF ANATOLIA

Where is the tin???Where is the tin??? De Jesus 1985

MAP OF SOUTH CENTRALMAP OF SOUTH CENTRALANATOLIAANATOLIA ALADAALADAĞĞLAR FROM KESTELLAR FROM KESTEL

9

CELALLER VILLAGECELALLER VILLAGE KESTEL MINEKESTEL MINE

ENTRANCE TO KESTELENTRANCE TO KESTELUNDERGROUND WORKINGDUNDERGROUND WORKINGD ORE DRESSINGORE DRESSING

INSTALLATION ATINSTALLATION ATKESTEL MINEKESTEL MINE

10

ENTRANCE TO KESTEL MINEENTRANCE TO KESTEL MINE KESTEL TIN MINE (2800-2200 BC)KESTEL TIN MINE (2800-2200 BC)

FIRE SETTING PACKETS AT KESTELFIRE SETTING PACKETS AT KESTELKESTEL GALERIESKESTEL GALERIES

11

C-14 DATE FOR KESTEL CHARCOAL KESTEL MINE PLANKESTEL MINE PLAN

HEMATITEHEMATITEVEIN RICHVEIN RICH

ININCASSITERITECASSITERITE

The average tin content of Kestel cassiterite was 0.065 %The highest value observed was 0.79%.

02468

10121416

ÖR

NE

K S

AY

ISI

<0.01 0.01-0.05 0.05-1.0 >0.10

% KALAY

KESTEL HEMAT‹T CEVHER‹NDE KALAY

12

UNUTULIZED HEMATITE OREUNUTULIZED HEMATITE OREAT KESTEL WITHOUT CASSITERITEAT KESTEL WITHOUT CASSITERITE FORMATION OF CASSITERITEFORMATION OF CASSITERITE

Tin is related to granite family rocks. In acidic Tin is related to granite family rocks. In acidic Igneous magma tin is mainly found as compoundsIgneous magma tin is mainly found as compoundsOf fluorine and boron.Of fluorine and boron.

SnFSnF44 + 2H + 2H22O SnOO SnO2 2 + 4HF+ 4HF

HF released attacks some of the existing rocks HF released attacks some of the existing rocks to form minerals such as topaz, tourmaline andto form minerals such as topaz, tourmaline andfluorspar. fluorspar.

SURFACESURFACEWORKINGSWORKINGS

ATATKESTELKESTEL

UndergroundUndergroundworkingsworkings

CASSITERITE (SnOCASSITERITE (SnO22))

13

KESTEL KASSITERITEKESTEL KASSITERITE

SEM OF KESTEL KASITERITESEM OF KESTEL KASITERITE VIEEW OF GÖLTEPE FROMVIEEW OF GÖLTEPE FROMKESTELKESTEL

GöltepeGöltepe

14

GÖLTEPE WORKSHOPGÖLTEPE WORKSHOP MATERIALS RELATED TOMATERIALS RELATED TOMETALURGY AT GÖLTEPEMETALURGY AT GÖLTEPE

•• Hematite oresHematite ores

•• Powderd ore samplesPowderd ore samples

•• Crushing and grinding toolsCrushing and grinding tools

•• CruciblesCrucibles

•• Metal objectsMetal objects

GÖLTEPE C-14 RESULTSGÖLTEPE C-14 RESULTS

Total of 18 C-14 samples analyzed.Total of 18 C-14 samples analyzed.

15 date to 3rd millennium BC15 date to 3rd millennium BC

11 date to 4th century BCdate to 4th century BC

22 date to 8th century ADdate to 8th century AD

ORE GRINDING TOOLSORE GRINDING TOOLSAT GÖLTEPEAT GÖLTEPE

15

ORE GRINDING GRINDING STONES

02468

101214161820

ÖR

NE

K S

AY

ISI

<0.01 0.01-0.05 0.05-0.10 >0.10

% KALAY

GÖLTEPE HEMAT‹T CEVHERLER‹NDE KALAY

The average tin concentration at Göltepe hemative was 0.072%.Higest tin content was 0.64 %.

GÖLTEPE STORAGE VESSELSGÖLTEPE STORAGE VESSELS

16

POWDERED MATERIALSPOWDERED MATERIALS

•• 60 Samples (between 0.05 kg -10 kg)60 Samples (between 0.05 kg -10 kg)•• Average tin content 0.43 %(0.02 - 1.73)Average tin content 0.43 %(0.02 - 1.73)•• In the 10 samples studied, 51 % has particle sizeIn the 10 samples studied, 51 % has particle size

under 74 micron (Average size of Kestelunder 74 micron (Average size of Kestelcassiterite is 75µ).cassiterite is 75µ).

•• About half of the powdered material wasAbout half of the powdered material wasattracted by a magnet. When hematite is heatedattracted by a magnet. When hematite is heatedto high temperature, it turns into magnetite.to high temperature, it turns into magnetite.

•• E-ray photoelectron spectroscopy analysisE-ray photoelectron spectroscopy analysisshowed the existance of metalic tin.showed the existance of metalic tin.

0

5

10

15

20

25

ÖR

NE

K S

AY

ISI

<0.10 0.10-0.30 0.30-0.70 0.70-1.00 >1.00

% KALAY

GÖLTEPE Ö⁄ÜTÜLMÜfi CEVHERLER‹N KALAY ‹ÇER‹⁄‹

Average tin content of powdered ore samples of Göltepe was 0.42%.Highest tin value was 1.73%.

GROUND ORE SAMPLESGROUND ORE SAMPLESFROM GÖLTEPEFROM GÖLTEPE

NATURE OF POWDEREDMATERIAL FROM GÖLTEPE

•• Unenriched original hematite ore.Unenriched original hematite ore.

•• Enriched ore before smelting.Enriched ore before smelting.

•• Discarted material left fromDiscarted material left from

enrichment process,enrichment process,

•• Powdered slag from which metalicPowdered slag from which metalic

prills are collectedprills are collected

17

GÖLTEPEGÖLTEPECRUCIBLESCRUCIBLES

TIN CONTENT OFTIN CONTENT OFPOTTERY ACCRETIONSPOTTERY ACCRETIONS

Average tin content of 41 crucible fracmentsAverage tin content of 41 crucible fracmentswas O.39 % (Between 0.02-3.65%)was O.39 % (Between 0.02-3.65%)

3.653.6530213021

2.212.2146044604

2.052.0542884288

1.091.09320320

1.051.0513291329

% Tin% TinMRN #MRN #

SEM PICTURE OF GÖLTEPESEM PICTURE OF GÖLTEPECRUCIBLE FRAGMENTCRUCIBLE FRAGMENT

18

DISTRIBUTION OF TIN INDISTRIBUTION OF TIN INTHE SAME FRAGMENTTHE SAME FRAGMENT

METAL SAMPLES FROMMETAL SAMPLES FROMGÖLTEPEGÖLTEPEMRN 4672

MRN 4137

MRN 4692MRN 2900

MRN 4653

Ornek NRN# %Cu %Sn %Ag %Pb %As %Sb %Co Au* %Fe %Ni %Zn %BiÇubuk 4570 93.4 0.10 nd 0.17 nd 0.01 nd 13.4 0.06 nd nd ndBilezik 2412 89.3 12.2 0.02 0.01 0.03 0.06 nd - 0.08 0.05 0.04 0.02

Igne 1893 88.0 11.1 0.06 0.24 0.06 0.15 0.01 - 0.16 nd 0.07 ndSpiral 4692 83.6 12.0 0.02 0.54 0.06 0.39 nd 46.0 0.35 0.06 0.03 o.01Tup 4672 80.0 12.0 0.01 0.15 0.03 0.02 nd 1.23 0.62 0.26 nd 0.01

Halka 4137 78.4 4.75 0.03 0.05 0.02 nd nd 27.6 0.29 0.02 0.02 0.01Igne 3110 71.3 1.49 0.12 0.89 1.21 0.57 0.01 - 1.08 0.02 0.09 nd

Kolye 3993 2.18 1.11 91.2 0.01 nd 0.25 nd - 0.41 0.03 1.16 0.18Kulçe 2604 nd nd 0.11 98.2 0.01 0.62 0.01 - 0.09 0.01 nd nd

ELEMETAL ANALYSIS RESULTSELEMETAL ANALYSIS RESULTSOF GÖLTEPE METALSOF GÖLTEPE METALS

*ppm cinsinden

SILVERSILVERNECLACENECLACE

AgAg 91.2%91.2%CuCu 2.18%2.18%SnSn 1.11%1.11%ZnZn 1.16%1.16%FeFe 0.41%0.41%SbSb 0.25%0.25%BiBi 0.18%0.18%

MRN 3993

19

TIN METALLURGY AT GÖLTEPETIN METALLURGY AT GÖLTEPE

•• Hematite ores that contain 600-700 ppm cassiteriteHematite ores that contain 600-700 ppm cassiteritewere not utilized.were not utilized.

•• The hematite ores found at The hematite ores found at Göltepe Göltepe contained 5contained 5times more cassiterite than Kestel ores.times more cassiterite than Kestel ores.

•• Powdered hematite ores contained 13 times morePowdered hematite ores contained 13 times morecassiteritecassiterite

•• A method must have been developed to recognizeA method must have been developed to recognizethe tin content in hematite ores.the tin content in hematite ores.

VANING KESTEL CASSITERITEVANING KESTEL CASSITERITE

VANNED (CONCENTRATED)VANNED (CONCENTRATED)KESTEL CASSITERITEKESTEL CASSITERITE

ASSAYING CASSITERITEASSAYING CASSITERITE

20

GÖLTEPEGÖLTEPESMELTINGSMELTINGEXPERIMENTEXPERIMENT

TIN PRILL FROM SEMLTINGTIN PRILL FROM SEMLTINGEXPERIMENTEXPERIMENT

TIN NEED OF THE NEAR EASTTIN NEED OF THE NEAR EASTDURING THE EARLY BRONZE AGEDURING THE EARLY BRONZE AGE

•• It is estimated that tin used within the entire Near EastIt is estimated that tin used within the entire Near Eastaround 2000 BC amounts to no more than 5 tons/yeararound 2000 BC amounts to no more than 5 tons/year

•• (British output of tin within 12th century AD was(British output of tin within 12th century AD wasbetween 70 and 400 tons/yearbetween 70 and 400 tons/year

•• It has been estimated that 100,000 tons of ore have beenIt has been estimated that 100,000 tons of ore have beenremoved from Kestel. If an average of 1% cassiteriteremoved from Kestel. If an average of 1% cassiteritewas present in the ore, this would correspond to 1,000was present in the ore, this would correspond to 1,000tons of cassiterite. This will correspond to 800 tons oftons of cassiterite. This will correspond to 800 tons oftin metal. Since Kestel has been operated between 2800-tin metal. Since Kestel has been operated between 2800-2200 BC, the annual tin production at Goltepe is2200 BC, the annual tin production at Goltepe isestimated to be about 1.2-1.4 tons/year.estimated to be about 1.2-1.4 tons/year.

3rd MILENNIUM SITES WITH BRONZE

21

ALTERNATIVES SUGGESTED FORALTERNATIVES SUGGESTED FORTHE KESEL/GÖLTEPE WORKINGSTHE KESEL/GÖLTEPE WORKINGS

•• It could not be a tin mine since tin remains is very lowIt could not be a tin mine since tin remains is very low•• It mush have been a gold mineIt mush have been a gold mine•• Hematite is mined here to be used as oigmentHematite is mined here to be used as oigment•• Hematite is mined here to be used as a fluxing agentHematite is mined here to be used as a fluxing agent

for the smelting of galena from Bereketli maden.for the smelting of galena from Bereketli maden.•• Where are thte slags?Where are thte slags?•• Sinced tin metal contains high a mounts of iron. Sinced tin metal contains high a mounts of iron. İİtt

cannott be used in bronze production.cannott be used in bronze production.•• There is no tin mineralization in Turkey.There is no tin mineralization in Turkey.

TEAMTEAM

•• K. AslK. Aslııhan Yenerhan Yener•• Necip PehlivanNecip Pehlivan•• Ergün KaptanErgün Kaptan•• Ahmet ÇaAhmet Çağğatayatay•• Brian EarlBrian Earl•• Behin AksoyBehin Aksoy•• Brenda CraddockBrenda Craddock

•• Hakan ÇHakan Çııtakotakoğğlulu

•• A. Mieke AdriaensA. Mieke Adriaens

•• Martha GoodwayMartha Goodway

•• Pamela VandiverPamela Vandiver

•• Lynn WilliesLynn Willies