11

NEOLITHICNEOLITHICMETALLURGYMETALLURGY

ININANATOLIAANATOLIA

STAGES OF EARLY COPPERSTAGES OF EARLY COPPERMETALLURGY IN ANATOLAMETALLURGY IN ANATOLA

•• Non-metallic period (prior to 8200 BC)Non-metallic period (prior to 8200 BC)

•• Single metal period (after 8200 BC). Mainly nativeSingle metal period (after 8200 BC). Mainly nativecopper is shaped for simple tools and beads.copper is shaped for simple tools and beads.

•• Beginning of extractive metallurgy (after 5000 BC).Beginning of extractive metallurgy (after 5000 BC).Reduction of copper ores.Reduction of copper ores.

•• Advanced metallurgy (after 4000 BC). Reduction ofAdvanced metallurgy (after 4000 BC). Reduction ofpolymetallic ores, first alloys of copper.polymetallic ores, first alloys of copper.

•• Industrial Period (after 2800 BC). Production ofIndustrial Period (after 2800 BC). Production ofbronze followed by iron during the 1st millennium BC.bronze followed by iron during the 1st millennium BC.

MALACHITE BEADS FROMMALACHITE BEADS FROMAAŞŞAAĞĞI PINAR, KIRKLARELI PINAR, KIRKLARELİİ

EARLIEST NATIVE COPPEREARLIEST NATIVE COPPEROBJECTS IN ANATOLIAOBJECTS IN ANATOLIA

•• Çayönü: Over 100 simple native copperÇayönü: Over 100 simple native copperimplements, (8200-7500) BC.implements, (8200-7500) BC.

•• AAşışıklklıı Höyük: Many copper beads, (7800-Höyük: Many copper beads, (7800-7600) BC.7600) BC.

•• Nevali Nevali ÇoriÇori: Copper bead, (7500) BC.: Copper bead, (7500) BC.•• HacHacıılarlar: Copper bead, (~6000 BC): Copper bead, (~6000 BC)•• Mersin: 2 needles, (~6000 BC)Mersin: 2 needles, (~6000 BC)•• Can Hasan: Macehead, (~6000) BC.Can Hasan: Macehead, (~6000) BC.

22

SITES OF EARLY NATIVE METALSSITES OF EARLY NATIVE METALS

1:Can Hasan, 2: 1:Can Hasan, 2:AAşışıklklıı Höyük, 3: Çatal Höyük, 4. Höyük, 3: Çatal Höyük, 4. HacHacıılarlar,, 5: 5: Yümük TepeYümük Tepe, 6: Nevali , 6: Nevali ÇoriÇori, 7: Çayönü, 8: Ramad,, 7: Çayönü, 8: Ramad,

COPPER BELT OF NEAREASTCOPPER BELT OF NEAREAST

Native CopperNative CopperExamplesExamples

ÇAYÖNÜÇAYÖNÜ

33

ÇAYÖNÜ METAL OBJECTSÇAYÖNÜ METAL OBJECTSMICROSTRUCTURE OF ÇAYÖNÜMICROSTRUCTURE OF ÇAYÖNÜ

METAL OBJECTSMETAL OBJECTS

CHEMICAL ANALYSIS OFCHEMICAL ANALYSIS OFÇAYÖNÜ METALSÇAYÖNÜ METALS

AAŞŞIKLI HÖYÜKIKLI HÖYÜK

44

AAŞŞIKLI HÖYÜK METAL BEADSIKLI HÖYÜK METAL BEADS

CAN HASAN MACE HEADCAN HASAN MACE HEAD CHEMICAL ANALYSISCHEMICAL ANALYSIS

Silver crystals whichSilver crystals whichMeans copper is notMeans copper is notmeltedmelted

55

RECOGNIZING OBJECTS MADERECOGNIZING OBJECTS MADEFROM NATIVE COPPERFROM NATIVE COPPER

•• The grain size is generally very course (0.1 to 1 mmThe grain size is generally very course (0.1 to 1 mmand above)and above)

•• Grains have long irregular twins from geologicalGrains have long irregular twins from geologicalstrains causing partial crystallizationstrains causing partial crystallization

•• Metal is free of inclusions, especially copper oxides.Metal is free of inclusions, especially copper oxides.

•• Copper tends to be very pure although arsenic andCopper tends to be very pure although arsenic andsilver can occur.silver can occur.

OBTAINING COPPER FROMOBTAINING COPPER FROMITS ORESITS ORES

EXTRACTIVE METALLURGYEXTRACTIVE METALLURGY

COPPER SOURCES OF TURKEYCOPPER SOURCES OF TURKEYCOPPER ORESCOPPER ORES

NAMENAME FORMULAFORMULA %Cu%CuAntheriteAntherite CuCu33SOSO44(OH)(OH)44 53.853.8AzuriteAzurite 2CuCO2CuCO22CU(OH)CU(OH)22 55.155.1BorniteBornite CuCu55FeSFeS44 63.363.3ChalcositeChalcosite CuCu22SS 79.879.8ChalcopyriteChalcopyrite CuFeSCuFeS22 34.534.5CovelliteCovellite CuSCuS 66.566.5CupriteCuprite CuCu22OO 88.888.8EnargiteEnargite CuCu33AsAs55SS44 48.548.5MalachiteMalachite CuCOCuCO33Cu(OH)Cu(OH)22 57.357.3Native copperNative copper CuCu 100100

66

SOME COPPER ORESSOME COPPER ORES

AzuriteAzurite ChalcopyriteChalcositeChalcosite

MalachiteCupriteTenantite

SMELTING OF SMELTING OF ““OXIDE ORESOXIDE ORES””

•• Rich relatively pure oxidized secondary copper ores areRich relatively pure oxidized secondary copper ores areused during the earliest copper smelting in antiquity.used during the earliest copper smelting in antiquity.

•• Reduction can be achieved in a crucible or in a smallReduction can be achieved in a crucible or in a smallfurnace by heating the ore only with carbon.furnace by heating the ore only with carbon.

•• Also known as Also known as slagless slagless process since the ores do notprocess since the ores do notcontain impurities or gangue minerals.contain impurities or gangue minerals.

•• Copper produced was very pure with only trace of ironCopper produced was very pure with only trace of ironimpurity.impurity.

FORMATION OFFORMATION OFSECONDARY ORESSECONDARY ORES

GARSTANGEXCAVATION

1940’s

MERSMERSİİN YÜMÜKTEPEN YÜMÜKTEPE

77

Tools from Tools from Mersin Mersin made out ofmade out ofsmelted copper (5000-4900 BC)smelted copper (5000-4900 BC)

REDUCTION OF SULPHIDE ORESREDUCTION OF SULPHIDE ORES•• The earliest evidence is observed by the 4thThe earliest evidence is observed by the 4th

millennium BC.millennium BC.•• Since sulphur interfered with the reduction Since sulphur interfered with the reduction

process, complex technology was needed.process, complex technology was needed.•• The ores were partially roasted to remove someThe ores were partially roasted to remove some

or all of the sulphur as SOor all of the sulphur as SO22..•• Since ores were of lower grade, siliceousSince ores were of lower grade, siliceous

impurities were to be removed by using ironimpurities were to be removed by using ironfluxing agent.fluxing agent.

•• Copper produced contain higher levels of ironCopper produced contain higher levels of ironimpurity.impurity.

ROASTING OF SULPHIDICROASTING OF SULPHIDICCOPPER ORESCOPPER ORES

CuFeSCuFeS22 + 4O + 4O2 2 CuSOCuSO44 + FeSO + FeSO44

2CuS + 7/2O 2CuS + 7/2O22 CuO.CUSO CuO.CUSO44 + SO + SO22

2CuFeS2CuFeS22 + 13/2O + 13/2O22 2CuO + 4SO 2CuO + 4SO22

88

COMPOSITION OF MATTE AND BLISTER COPPERCOMPOSITION OF MATTE AND BLISTER COPPER

0.030.030.10.1SbSb

0-0.10-0.10-0.010-0.01AgAg

0-100x100-100x10-4-40-15x100-15x10-4-4AuAu

0.00050.00050.50.5ZnZn

0-0.10-0.10.50.5PbPb

0-0.30-0.30-0.50-0.5AsAs

0.5-0.80.5-0.82-32-3OO

0.02-010.02-0120-2520-25SS

0.10.110-4010-40FeFe

98.5-99.598.5-99.535-6535-65CuCu

BLISTER Cu (%)BLISTER Cu (%)MATTE (%)MATTE (%)TRACE ELEMENTS IN COPPERTRACE ELEMENTS IN COPPER

RESULTING FROM ORES AND SMELTINGRESULTING FROM ORES AND SMELTING

•• Iron is the major element. Since iron isIron is the major element. Since iron isadded as a fluxing agent, copper obtainedadded as a fluxing agent, copper obtainedfrom low grade ores may have 2-10 % Fe.from low grade ores may have 2-10 % Fe.

•• Most copper ores contain certain amount ofMost copper ores contain certain amount ofmetals such as As, Sb, Bi, Pb, Ag, Au, Ni,metals such as As, Sb, Bi, Pb, Ag, Au, Ni,Co and Zn. These elements will partitionCo and Zn. These elements will partitionbetween the metal and the slag dependingbetween the metal and the slag dependingon the smelting conditions.on the smelting conditions.

PARTITION OF TRACE ELEMENTS OFPARTITION OF TRACE ELEMENTS OFCOPPER ORES DURING SMELTINGCOPPER ORES DURING SMELTING

SLAG METAL BOTHSLAG METAL BOTH Fe Fe CoCo Zn Zn Mn Mn NiNi As* As*

PbPb Sb* Sb*AgAgAuAu

* Volatile elements. * Volatile elements.

Fe CONTENT OF BRONZES FROM VARIOUS CULTURESFe CONTENT OF BRONZES FROM VARIOUS CULTURES

55550.040.041616Cycladic (EBII)Cycladic (EBII)

14140.270.27104104Spain (Phoenician)Spain (Phoenician)

95950.040.044949Spain (LBA)Spain (LBA)

79790.050.05195195Spain (Chalcolithic)Spain (Chalcolithic)

440.270.27129129British (Roman)British (Roman)

29290.180.185656British (IA)British (IA)

79790.050.05773773British (BA)British (BA)

26260.230.2330623062Roman ( Etruscan)Roman ( Etruscan)

660.330.33250250Egypt (New Kingdom)Egypt (New Kingdom)

82820.030.031414Egypt (Predynastic)Egypt (Predynastic)

% of artifacts% of artifacts

Below 0.05% FeBelow 0.05% Fe

Average FeAverage Fe

Content (%)Content (%)Sample sizeSample sizeCultureCulture

99

CHALCOLITHIC CULTURESCHALCOLITHIC CULTURES

This is the period that yielded the earliest copperThis is the period that yielded the earliest coppersmelting evidence in Anatolia. The period is dividedsmelting evidence in Anatolia. The period is dividedinto three periods, roughly corresponding to culturalinto three periods, roughly corresponding to culturalinteractions with Mesopotamia:interactions with Mesopotamia:

•• Early Chalcolithic (6th millennium BC) is also knownEarly Chalcolithic (6th millennium BC) is also knownas the Halaf Period.as the Halaf Period.

•• Middle Chalcolithic (5th millennium BC) is alsoMiddle Chalcolithic (5th millennium BC) is alsoknown as the Obeid Period.known as the Obeid Period.

•• Late Chalcolithic (4th millennium BC) is also knownLate Chalcolithic (4th millennium BC) is also knownas the Uruk Period.as the Uruk Period.

METALLURGY DURINGMETALLURGY DURINGTHE LATE CHALCOLTHICTHE LATE CHALCOLTHIC

PERIODPERIOD(4th Millennium BC)(4th Millennium BC)

EARLY MESOPOTAMIAN SITESEARLY MESOPOTAMIAN SITESPOSSIBLE METAL RESOURCES FOR EARLYPOSSIBLE METAL RESOURCES FOR EARLY

MESOPOTAMIAN SITESMESOPOTAMIAN SITES

1) Southeastern Anatolian sources1) Southeastern Anatolian sourcesRReached via Euphrates andeached via Euphrates andTigris rivers.Tigris rivers.

2) Copper sources in the2) Copper sources in theZagros mountainsZagros mountains

3) Sources of Oman reached3) Sources of Oman reachedVVia the gulf by sea trade.ia the gulf by sea trade.

1010

URUK TRADE NETWORKURUK TRADE NETWORKEAST AND SOUTHEASTERNEAST AND SOUTHEASTERN

ANATOLIAN SITESANATOLIAN SITES

METALLURGICAL ACHIEVEMENTSMETALLURGICAL ACHIEVEMENTSDURING LATE CHALCOLITHICDURING LATE CHALCOLITHIC

•• Sulfide ores of copper were smelted at theSulfide ores of copper were smelted at theDegirmentepe.Degirmentepe.

•• Arslantepe metallurgists were utilizingArslantepe metallurgists were utilizingpolymetallic ores and were producing some of thepolymetallic ores and were producing some of theearliest examples of Cu-As alloys.earliest examples of Cu-As alloys.

•• Silver was produced by cupellation at Silver was produced by cupellation at FatmalFatmalııKalecikKalecik

•• Copper was produced in workshops of proto-Copper was produced in workshops of proto-urban sites such as Tulintepe, Norsuntepe,urban sites such as Tulintepe, Norsuntepe,Hacinebi, Degirmentepe, Arslantepe etc. byHacinebi, Degirmentepe, Arslantepe etc. byexploiting the rich local sources.exploiting the rich local sources.

URUK TRADE NETWORK URUK TRADE NETWORK

•• Uruk trade period took place between 3700-3100 BC.Uruk trade period took place between 3700-3100 BC.•• Trader from Uruk came to Anatolia along Tigris andTrader from Uruk came to Anatolia along Tigris and

Euphrates valleys.Euphrates valleys.•• They established small enclaves in local AnatolianThey established small enclaves in local Anatolian

settlements.settlements.•• There were also settlements that were completelyThere were also settlements that were completely

Mesopotamian in nature such as Hassek Höyük and HabubaMesopotamian in nature such as Hassek Höyük and HabubaKabire.Kabire.

•• Anatolian miners and smelters produced the copper desired byAnatolian miners and smelters produced the copper desired bythe urbanized Mesopotamian cultures.the urbanized Mesopotamian cultures.

•• The copper was via the rivers.The copper was via the rivers.•• By 3100 BC, the Uruk trade network collapsed suddenly.By 3100 BC, the Uruk trade network collapsed suddenly.

•• Metallurgy in the eastern and southeastern Metallurgy in the eastern and southeastern AnatoliaAnatolia declined declinedconsistently afterwards.consistently afterwards.

1111

HACINEBI TEPEHACINEBI TEPE

HACINEBI CHRONOLOGYHACINEBI CHRONOLOGY URUK EVIDENCE IN HACINEBIURUK EVIDENCE IN HACINEBI

An Uruk houseAn Uruk house Tokens in stamped containerTokens in stamped container

Beveled Rim Bowls (BRB)Beveled Rim Bowls (BRB) Wall cones (Uruk decoration)Wall cones (Uruk decoration)

1212

EXAMPLES OF URUK POTTERYEXAMPLES OF URUK POTTERYMETAL FINDS AT HACINEBIMETAL FINDS AT HACINEBI

METALLURGY AT HACINEBIMETALLURGY AT HACINEBI ChemicalChemicalanalysis ofanalysis ofHacinebiHacinebi

metallurgicalmetallurgicalfindsfinds

Mold for casting Mold for casting CCopper ingotsopper ingots

1313

SEM OF A CRUCIBLE FRAGMENTSEM OF A CRUCIBLE FRAGMENT