COPPER-TIN ALLOYS EARLY BRONZE AGES OF ANATOLIA ( BC)

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1 Cu-Sn PHASE DIAGRAM COPPER-TIN ALLOYS EARLY BRONZE AGES OF ANATOLIA ( BC) Solid solution 14% Sn in COPPER 20% Sn in COPPER 1

Copper and tin ore cassiterite may be smelted together. 3.

2 HARDNESS OF BRONZE PREPARATION OF Cu-Sn ALLOYS 1. Metallic copper and tin can be melted together at desired proportions. 2. Copper and tin ore cassiterite may be smelted together. 3. Cementation method can be used in which cassiterite is added to the surface of molten copper under charcoal in a furnace where the tin is reduced directly into the melt: SnO 2 + C Sn + CO 2 MICROSTRUCTURE OF BRONZE EARLIEST BRONZES 2

3 ANATOLIAN COPPER MINES PERCENTAGE OF BRONZE OBJECTS BEFORE 2200 BC Bakır Bronz Where is the tin??? McKerrell, 1977 PERCENTAGE OF BRONZE OBJECTS AFTER 2200 BC Bakır Bronz BRONZES OF ANATOLIA Figurines of Tell Atchana in the Amuq plain dated to around 3000 BC Bronzes of Troy II, dated to 2800 BC Bronzes of Alacahoyuk and Horoztepe dated to the 2nd half of 3rd millennium BC Bronze objects from the royal tombs at Ur Mesopotamia BC McKerrell

4 SITES THAT YIELDED BRONZE OBJECTS DURING 3rd. MILLENNIUM BC MAP OF SOUTH CENTRAL ANATOLIA AMUQ FIGURINES 4

5 ALACAHÖYÜK EBA TOMBS AMUQ AXE ALACAHÖYÜK EBA OBJECTS ALACAHÖYÜK EBA METALS Number of Samples Alacahöyük EBA Metals Cu As>1.0 Sn>2.0 As & Sn Esin

As DISTRIBUTION IN EBA ALACAHÖYÜK METALS As Content of EBA

Sn Content of EBA Alacahöyük Metals 5 5 5 5 Number of

Number of Samples 4 3 2 1 4 4 1 0 2-4 4-6 6-8 8-10 >10 %

6 As DISTRIBUTION IN EBA ALACAHÖYÜK METALS As Content of EBA Alacahöyük Metals Sn DISTRIBUTION OF EBA ALACAHÖYÜK METALS Sn Content of EBA Alacahöyük Metals Number of Samples >5 % As Esin 1967 Number of Samples >10 % Sn Esin rd MILLENNIUM MESOPOTAMIAM SITES TRESURES FROM UR 6

7 TROY TROIA HOARD CEREMONIAL AXES OF TROY Green Nephrite Jade Lapis Lazuli 7

8 TIN FROM AFGHANISTAN Possible tin deposits MAJOR COPPER DEPOSITS OF ANATOLIA Where is the tin??? De Jesus 1985 MAP OF SOUTH CENTRAL ANATOLIA ALADAĞLAR LAR FROM KESTEL 8

9 CELALLER VILLAGE KESTEL MINE ENTRANCE TO KESTEL UNDERGROUND WORKINGD ORE DRESSING INSTALLATION AT KESTEL MINE 9

10 ENTRANCE TO KESTEL MINE KESTEL TIN MINE ( BC) FIRE SETTING PACKETS AT KESTEL KESTEL GALERIES 10

11 C-14 DATE FOR KESTEL CHARCOAL KESTEL MINE PLAN KESTEL HEMAT T CEVHER NDE KALAY HEMATITE VEIN RICH IN CASSITERITE ÖRNEK SAYISI < >0.10 % KALAY The average tin content of Kestel cassiterite was % The highest value observed was 0.79%. 11

UNUTULIZED HEMATITE ORE AT KESTEL WITHOUT

some of the existing rocks to form minerals such

12 UNUTULIZED HEMATITE ORE AT KESTEL WITHOUT CASSITERITE FORMATION OF CASSITERITE Tin is related to granite family rocks. In acidic Igneous magma tin is mainly found as compounds Of fluorine and boron. SnF 4 + 2H 2 O SnO 2 + 4HF HF released attacks some of the existing rocks to form minerals such as topaz, tourmaline and fluorspar. SURFACE WORKINGS AT KESTEL CASSITERITE (SnO 2 ) Underground workings 12

13 KESTEL KASSITERITE SEM OF KESTEL KASITERITE VIEEW OF GÖLTEPE FROM KESTEL Göltepe 13

GÖLTEPE WORKSHOP MATERIALS RELATED TO METALURGY AT

and grinding tools Crucibles Metal objects GÖLTEPE

15 date to 3rd millennium BC 1 date to 4th century

14 GÖLTEPE WORKSHOP MATERIALS RELATED TO METALURGY AT GÖLTEPE Hematite ores Powderd ore samples Crushing and grinding tools Crucibles Metal objects GÖLTEPE C-14 RESULTS Total of 18 C-14 samples analyzed. 15 date to 3rd millennium BC 1 date to 4th century BC 2 date to 8th century AD ORE GRINDING TOOLS AT GÖLTEPE 14

ORE GRINDING GRINDING STONES GÖLTEPE HEMAT T

ÖRNEK SAYISI 20 18 16 14 12 10 8 6 4 2 0 <0.

10 % KALAY The average tin concentration at

15 ORE GRINDING GRINDING STONES GÖLTEPE HEMAT T CEVHERLER NDE KALAY GÖLTEPE STORAGE VESSELS ÖRNEK SAYISI < >0.10 % KALAY The average tin concentration at Göltepe hemative was 0.072%. Higest tin content was 0.64 %. 15

POWDERED MATERIALS 60 Samples (between 0.05 kg -10 kg) Average tin content 0.43 %(0.02-1.

16 POWDERED MATERIALS 60 Samples (between 0.05 kg -10 kg) Average tin content 0.43 %( ) In the 10 samples studied, 51 % has particle size under 74 micron (Average size of Kestel cassiterite is 75µ). About half of the powdered material was attracted by a magnet. When hematite is heated to high temperature, it turns into magnetite. E-ray photoelectron spectroscopy analysis showed the existance of metalic tin. GÖLTEPE Ö ÜTÜLMÜfi CEVHERLER N KALAY ÇER ÖRNEK SAYISI < >1.00 % KALAY Average tin content of powdered ore samples of Göltepe was 0.42%. Highest tin value was 1.73%. GROUND ORE SAMPLES FROM GÖLTEPE NATURE OF POWDERED MATERIAL FROM GÖLTEPE Unenriched original hematite ore. Enriched ore before smelting. Discarted material left from enrichment process, Powdered slag from which metalic prills are collected 16

$fracments was O.$ 39 % (Between 0.

17 GÖLTEPE CRUCIBLES TIN CONTENT OF POTTERY ACCRETIONS Average tin content of 41 crucible fracments was O.39 % (Between %) SEM PICTURE OF GÖLTEPE CRUCIBLE FRAGMENT MRN # % Tin

DISTRIBUTION OF TIN IN THE SAME FRAGMENT METAL SAMPLES FROM GÖLTEPE MRN 4672 MRN 4653 MRN 4137 MRN 4692 MRN 2900 ELEMETAL ANALYSIS RESULTS OF GÖLTEPE

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 nd Spiral 4692 83.6 12.0 0.02 0.54 0.06 0.39 nd 46.

02 0.01 Igne 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.

18 DISTRIBUTION OF TIN IN THE SAME FRAGMENT METAL SAMPLES FROM GÖLTEPE MRN 4672 MRN 4653 MRN 4137 MRN 4692 MRN 2900 ELEMETAL ANALYSIS RESULTS OF GÖLTEPE METALS Ornek NRN# %Cu %Sn %Ag %Pb %As %Sb %Co Au* %Fe %Ni %Zn %Bi Çubuk nd 0.17 nd 0.01 nd nd nd nd Bilezik nd Igne nd 0.07 nd Spiral nd o.01 Tup nd nd 0.01 Halka nd nd Igne nd Kolye nd 0.25 nd Kulçe 2604 nd nd nd nd *ppm cinsinden MRN 3993 SILVER NECLACE Ag 91.2% Cu 2.18% Sn 1.11% Zn 1.16% Fe 0.41% Sb 0.25% Bi 0.18% 18

600-700 ppm cassiterite were not utilized.

Powdered hematite ores contained 13 times

developed to recognize the tin content in

19 TIN METALLURGY AT GÖLTEPE VANING KESTEL CASSITERITE Hematite ores that contain ppm cassiterite were not utilized. The hematite ores found at Göltepe contained 5 times more cassiterite than Kestel ores. Powdered hematite ores contained 13 times more cassiterite A method must have been developed to recognize the tin content in hematite ores. VANNED (CONCENTRATED) KESTEL CASSITERITE ASSAYING CASSITERITE 19

TIN PRILL FROM SEMLTING EXPERIMENT GÖLTEPE SMELTING EXPERIMENT TIN

tin used within the entire Near East around 2000 BC amounts to no more

between 70 and 400 tons/year It has been estimated that 100,000 tons

If an average of 1% cassiterite was present in the ore, this would

This will correspond to 800 tons of tin metal.

20 TIN PRILL FROM SEMLTING EXPERIMENT GÖLTEPE SMELTING EXPERIMENT TIN NEED OF THE NEAR EAST DURING THE EARLY BRONZE AGE It is estimated that tin used within the entire Near East around 2000 BC amounts to no more than 5 tons/year (British output of tin within 12th century AD was between 70 and 400 tons/year It has been estimated that 100,000 tons of ore have been removed from Kestel. If an average of 1% cassiterite was present in the ore, this would correspond to 1,000 tons of cassiterite. This will correspond to 800 tons of tin metal. Since Kestel has been operated between BC, the annual tin production at Goltepe is estimated to be about tons/year. 3rd MILENNIUM SITES WITH BRONZE 20

21 ALTERNATIVES SUGGESTED FOR THE KESEL/GÖLTEPE WORKINGS It could not be a tin mine since tin remains is very low It mush have been a gold mine Hematite is mined here to be used as oigment Hematite is mined here to be used as a fluxing agent for the smelting of galena from Bereketli maden. Where are thte slags? Sinced tin metal contains high a mounts of iron. İt cannott be used in bronze production. There is no tin mineralization in Turkey. K. Aslıhan Yener Necip Pehlivan Ergün Kaptan Ahmet Çağatay atay Brian Earl Behin Aksoy Brenda Craddock TEAM Hakan ÇıtakoÇ takoğlu A. Mieke Adriaens Martha Goodway Pamela Vandiver Lynn Willies 21

INTORDUCTION TO ANCIENT METALLURGY

1 INTORDUCTION TO ANCIENT METALLURGY ANCIENT METALS METAL SYMBOL MP O C BP O C DENSITY GOLD Au 1060 2970 19.3 SILVER Ag 961 2210 10.5 COPPER Cu 1083 2695 8.92 LEAD Pb 327 1725 11.3 ZINC Zn 420 906 7.14