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12. Cu-Sn Alloys. copy 2

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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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