Cu-Sn PHASE DIAGRAM COPPER-TIN ALLOYS EARLY BRONZE AGES OF ANATOLIA (3200 - 1000 BC) 14% Sn in COPPER Solid solution 20% Sn in COPPER 1 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: SnO2 + C Sn + CO2 MICROSTRUCTURE OF BRONZE EARLIEST BRONZES 2 ANATOLIAN COPPER MINES PERCENTAGE OF BRONZE OBJECTS BEFORE 2200 BC Bakı Bakır Bronz Where is the tin??? McKerrell, 1977 PERCENTAGE OF BRONZE OBJECTS AFTER 2200 BC BRONZES OF ANATOLIA Bakı Bakır Bronz • 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 2600-2400 BC McKerrell 1977 3 SITES THAT YIELDED BRONZE OBJECTS DURING 3rd. MILLENNIUM BC MAP OF SOUTH CENTRAL ANATOLIA AMUQ FIGURINES 4 ALACAHÖYÜK EBA TOMBS AMUQ AXE ALACAHÖYÜK EBA METALS Alacahöyük EBA Metals 14 14 Number of Samples ALACAHÖYÜK EBA OBJECTS 12 11 12 10 8 6 4 2 0 0 Cu As>1.0 Sn>2.0 As & Sn Esin 1967 5 As DISTRIBUTION IN EBA ALACAHÖYÜK METALS Sn DISTRIBUTION OF EBA ALACAHÖYÜK METALS As Content of EBA Alacahöyük Metals Sn Content of EBA Alacahöyük Metals 5 4 4 3 3 2 1 5 5 Number of Samples Number of Samples 5 0 1-2 2-3 3-4 % As 4-5 0 Esin 1967 3rd MILLENNIUM MESOPOTAMIAM SITES 4 3 2 1 >5 4 4 1 2-4 0 4-6 6-8 % Sn 8-10 >10 Esin 1967 TRESURES FROM UR 6 TROY TROIA HOARD CEREMONIAL AXES OF TROY Green Nephrite Jade Lapis Lazuli 7 TIN FROM AFGHANISTAN MAJOR COPPER DEPOSITS OF ANATOLIA Possible tin deposits Where is the tin??? MAP OF SOUTH CENTRAL ANATOLIA De Jesus 1985 ALADAĞ ALADAĞLAR FROM KESTEL 8 CELALLER VILLAGE ENTRANCE TO KESTEL UNDERGROUND WORKINGD KESTEL MINE ORE DRESSING INSTALLATION AT KESTEL MINE 9 ENTRANCE TO KESTEL MINE FIRE SETTING PACKETS AT KESTEL KESTEL TIN MINE (2800-2200 BC) KESTEL GALERIES 10 KESTEL MINE PLAN C-14 DATE FOR KESTEL CHARCOAL HEMATITE VEIN RICH IN CASSITERITE ÖRNEK SAYISI KESTEL HEMAT‹T CEVHER‹NDE KALAY 16 14 12 10 8 6 4 2 0 <0.01 0.01-0.05 0.05-1.0 >0.10 % KALAY The average tin content of Kestel cassiterite was 0.065 % The highest value observed was 0.79%. 11 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. SnF4 + 2H2O SnO2 + 4HF HF released attacks some of the existing rocks to form minerals such as topaz, tourmaline and fluorspar. SURFACE WORKINGS AT KESTEL CASSITERITE (SnO2) Underground workings 12 KESTEL KASSITERITE SEM OF KESTEL KASITERITE VIEEW OF GÖLTEPE FROM KESTEL Göltepe 13 GÖLTEPE WORKSHOP GÖLTEPE C-14 RESULTS MATERIALS RELATED TO METALURGY AT GÖLTEPE • Hematite ores • Powderd ore samples • Crushing and grinding tools • Crucibles • Metal objects ORE GRINDING TOOLS AT GÖLTEPE 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 14 ORE GRINDING ÖRNEK SAYISI GÖLTEPE HEMAT‹T CEVHERLER‹NDE KALAY GRINDING STONES GÖLTEPE STORAGE VESSELS 20 18 16 14 12 10 8 6 4 2 0 <0.01 0.01-0.05 0.05-0.10 >0.10 % KALAY The average tin concentration at Göltepe hemative was 0.072%. Higest tin content was 0.64 %. 15 • 60 Samples (between 0.05 kg -10 kg) • Average tin content 0.43 %(0.02 - 1.73) • 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. GROUND ORE SAMPLES FROM GÖLTEPE GÖLTEPE Ö⁄ÜTÜLMÜfi CEVHERLER‹N KALAY ‹ÇER‹⁄‹ 25 ÖRNEK SAYISI POWDERED MATERIALS 20 15 10 5 0 <0.10 0.10-0.30 0.30-0.70 0.70-1.00 >1.00 % KALAY Average tin content of powdered ore samples of Göltepe was 0.42%. Highest tin value was 1.73%. 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 GÖLTEPE CRUCIBLES TIN CONTENT OF POTTERY ACCRETIONS SEM PICTURE OF GÖLTEPE CRUCIBLE FRAGMENT Average tin content of 41 crucible fracments was O.39 % (Between 0.02-3.65%) MRN # 1329 320 4288 4604 3021 % Tin 1.05 1.09 2.05 2.21 3.65 17 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 Çubuk 4570 93.4 Bilezik 2412 89.3 Igne 1893 88.0 Spiral 4692 83.6 Tup 4672 80.0 Halka 4137 78.4 Igne 3110 71.3 Kolye 3993 2.18 Kulçe 2604 nd *ppm cinsinden %Sn 0.10 12.2 11.1 12.0 12.0 4.75 1.49 1.11 nd %Ag nd 0.02 0.06 0.02 0.01 0.03 0.12 91.2 0.11 %Pb 0.17 0.01 0.24 0.54 0.15 0.05 0.89 0.01 98.2 %As nd 0.03 0.06 0.06 0.03 0.02 1.21 nd 0.01 %Sb 0.01 0.06 0.15 0.39 0.02 nd 0.57 0.25 0.62 %Co nd nd 0.01 nd nd nd 0.01 nd 0.01 Au* 13.4 46.0 1.23 27.6 - %Fe 0.06 0.08 0.16 0.35 0.62 0.29 1.08 0.41 0.09 %Ni nd 0.05 nd 0.06 0.26 0.02 0.02 0.03 0.01 %Zn nd 0.04 0.07 0.03 nd 0.02 0.09 1.16 nd SILVER NECLACE %Bi nd 0.02 nd o.01 0.01 0.01 nd 0.18 nd Ag Cu Sn Zn Fe Sb Bi 91.2% 2.18% 1.11% 1.16% 0.41% 0.25% 0.18% MRN 3993 18 TIN METALLURGY AT GÖLTEPE VANING KESTEL CASSITERITE • Hematite ores that contain 600-700 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 NEED OF THE NEAR EAST DURING THE EARLY BRONZE AGE 3rd MILENNIUM SITES WITH BRONZE • 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 28002200 BC, the annual tin production at Goltepe is estimated to be about 1.2-1.4 tons/year. 20 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. TEAM • • • • • • • K. Aslı Aslıhan Yener Necip Pehlivan Ergün Kaptan Ahmet Çağ Çağatay Brian Earl Behin Aksoy Brenda Craddock • • • • • Hakan Çı Çıtakoğ takoğlu A. Mieke Adriaens Martha Goodway Pamela Vandiver Lynn Willies 21
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