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SUPERIOR COPPER METALLURGY OF EASTERN INDIA AND BANGLADESH IN MEDIEVAL PERIOD: FROM PURE COPPER TO HIGHTIN BRONZES

Prasanta K. Datta* Pranab K. Chattopadhyay*

Introduction The history of East India and Bangladesh has been pushed back to Paleolithic, Chalcolithic and subsequent early historic times by the findings of archaeological excavations at Paharpur[1], Bangarh[2], Pandu Rajar Dhibi[3], Mangalkot[4], Mahasthan[5], Wari-Bateswar[6] and elsewhere around Singhbhum copper belt. Other than the mass of copper-bearing materials collected from the explored sites, very often a large number of copper tools, in caches, so called copper hoards have been obtained at places nearby. Whatever be the source, fortunately metals preserve their history of processing, of their chemical extraction and physical transformation, in their microstructures. Therefore, a study of their microstructures can predict their production processes, if assisted with suitable archaeological evidences of mines, slag, crucibles or molds. Characterisation of four copper samples taken from different sites in chronological order starting with in and around Christian era from 1st millennium B.C. to 1st millennium A.D. to reconstruct the remarkable development of copper metallurgy, in Eastern India and Bangladesh. 2.0 Description of samples 2.1 Fragment of a bar-celt, Khuntitoli, (Ranchi), Manbhum Copper hoard The fragment (Fig.1) is the cutting end of the bar-celt[7] used in scooping the earth of agricultural field, locally known as khurpi. This is a pure copper casting (99%) but full of gas holes and seems to be made in open molds with poor gating. The purity (over 99%) is an excellent example of pure copper, though melting and casting techniques deserve more improvement for good casting production. 2.2 A double-ended axe, Khuntitoli, (Ranchi), Manbhum Copper hoard The axe (Fig.2) has in plan, convex lead edge; slightly concave side edges which converge towards the rounded butt[8],[9]. It weighs around 600 gms and has length around 160 mm and thickness 5 mm at the midriff. Made of pure copper (over 99%) the metal was probably deoxidized with arsenic before pouring in a closed mold. The beautifully cast piece was then probably hot-forged in super plastic temperature to develop sharp edges, while residual cast structure were allowed to remain in central section. 2.3 A broken disc of a copper lump, Aguibani, Medinipur A part of the copper disc (Fig.3) solidified at the bottom of a crucible in form of a half-round is the end product of an extraction heat. Though shrinkage is not missing and weighs only around 200 gms. it exhibits the size (diameter) of the crucible in use. The purity (over 99.5% Cu) and the softness achieved in annealed condition suggest a deep knowledge of metallurgy. 2.4 A broken part of a bronze bowl, Gazole, (Rangmahal), Malda The broken fragment of a high-tin bronze bowl (Fig. 4) is an example of copper alloying and copper alloy forging. The half-mm thick section of the bowl demonstrates a high degree of metallurgical skill in complex shaping of a

difficult hard phase alloy by open-die forging. The corrosion resistance and superior hardness of tin bronze might be a common knowledge that enhanced its wide use in historical period. 3.0 Microstructure of samples 3.1 Optical Microscopy The results are shown in Fig.5 to Fig.8. In the sample of the bar-celt (Fig. 5), the remnants of dendrites are visible, with wide distribution of micro-voids and inclusions as well as diffusive layers of dendrite arms revealing unsound knowledge either in foundry or in heat treatment. The sample (Fig. 6), of axe shows the break down of coarse dendritic structure in form of equi-axed grains, free from gas holes with segregation of inclusions and second phase particles mostly in grain boundaries. This indicates not only superior techniques of foundry like degassing, closed molds, gating etc. but also the development of good working and heat treatment practice using recrystallization-recovery-grain growth mechanism for producing sound metals. The sound material has become softer (HK 60-61) than that of the bar-celt, as indicated by the microhardness (HK 70-71) readings. The copper lump (Fig. 7), which is an ingot, contains mostly equiaxed grains with globular Cu-Cu2O eutectics or deoxidation products and low-melting constituents of insoluble lead widely distributed. The shrinkage void indicates sound metal revealing deoxidation techniques (here by arsenic) and good annealing treatment of hard arsenical copper (HK 183 - 185). The bronze sample (Fig. 8), reveals the preferred orientation of hard second phase alphadelta in the forging direction in the matrix of -phase (HK 276 - 283). It also vindicates the capability of those people to hot forge a high tin (over 20%) bronze in a narrow forging temperature range a remarkable feat indeed in those poor conditions in medieval period. Considering Europeans were not conversant in hot forging of high tin bronzes even as late as sixteenth century as recorded by Vannoccio Bringucchio in Pirotechnica (1540) of Papal Foundry in Rome.[10] This was a great achievement by East Indian metal workers. Good strength of the material proves the soundness as well as excellent manual forging practice . 3.2 Scanning Electron Microscopy Under scanning electron microscope, the bar-celt confirms the wide presence of inclusions of oxides (Fig. 9) and sulphides and micro-shrinkages. Most of the trace elements are Ni, Co, Sn and Bi, which are present in Singhbhum chalcopyrites,[11]thereby confirming the natural sources of copper ore and its extraction. The structure of the axe is the proof of sound metal, which contains arsenides (Fig.10) along with usual oxides and sulphides, as residual deoxidation products. The central portion, after etching, reveals cast structures (Fig 10, RHS), which still retains the dendrites of pure copper undisturbed. The unetched copper lump shows (Fig 11, RHS) the irregular shrinkage cavities. The wide presence of white arsenides (Fig. 11) confirms the intentional addition of arsenic to refine and deoxidise the metal at the ingot stage. EDAX result (Fig. 11, centre) also proves the presence of lead arsenides and copper sulphides, generally present in Singhbhum ores The etched structure also indicates ingot pattern due to slow cooling (~1 K/Sec) obtained from the dendritic arm spacing, calculated of ~100 m, as is expected in a shut-down crucible. In case of the bronze sample the interconnected - phase (Fig. 12) look more roundish in nature, indicating very close under annealing below transformation temperature like process annealing in carbon steel. The SEM study establishes the argument that the production process of pure copper from nearby chalcopyrites was continuously refined over hundreds of years to a useful technology unmatched in the ancient world. The eastern

people could also develop the technology of copper alloying and forming of high tin bronze, not easily available else where in India or abroad. 4.0 X Ray Diffraction (XRD), Differential Thermal Analysis (DTA) and Thermo gravimetric Analysis (TGA) Results.

Table I and II provide X ray diffraction patterns produced by samples. Bar celt, Axe and Lump show basically - Cu phase as predominate phase with minor phases, almost non-existent. Bronze sample indicate the / presence of or metastable - phase, along with - Cu phase. Some peaks remain to be identified. For Axe, a prominent endo peak at (812oC) and a small endow peak (482oC) were observed in DTA. Similarly for copper lump small endo peaks around (351oC) and (682oC) were observed. All these DTA & TGA results of copper samples suggest the presence of some amount of low melting constituents, probably of tin, zinc, lead, arsenic and others in these systems. 5.0 Reconstruction of copper technology Logistics of Production

Copper mines (Hazaribagh, Baragunda, Mosabani and Rakha of Jharkhand)[12],[13], quality wood charcoal (Sal = shorea robusta wood), fired crucibles, slag heaps, tuyers, alloying metals like Tin, (Ranchi, Hazaribagh, Bastar)[14], [15] or imports from Thailand or Malay, copper products copper hoards, copper plaques[16], Pala- Kurkihar- Jhewari Bronzes[17] and lastly copper related names Tamajuri (Heaps of copper), Tamralipta (Pasted with copper), Kansabati (Carrier of Bronze), Shilabati (Carrier of Stone-Copper Ore), Aguibani (Forest of Fire agun), Mosabani (Forest of crucibles musa), provide ample evidences for the development of copper metallurgy over two millennia in East India. 5.2 Extraction Process Dry balls (large pellets) of powdered copper (sulphide) ores and wood charcoal, bonded with cow-dung and clay as flux, were stacked in a cylindrical crucible, fitted with a slag notch (in form of a terracotta pipe) at the bottom and a blast pipe at the top to blow air. The charged crucible was placed in a underground hole and the mass was ignited at the top with occasional air blast. The ignition temperature of chalcopyrite is only 3000 C[18]. Iron suphide (FeS) got roasted to iron oxide (FeO) and fluxed with silica were melted out as viscous (viscosity 500 1000 cP) liquid fayalite (sp. gr. 3 3.7) while remaining FeS Cu2S mixture forming fluid (viscosity 10 cP), heavy matte (sp. gr. 4.4) at the high temperature percolated to the bottom (Fig. 12). During trickling, on further air blowing FeS again got smelted to FeO and produced fayalite separating it from Cu-phase, due to the excess silica present in the system. The collected white metal rich in copper ( 80%) (sp. gr. 5.2), afterward, due to air blowing converted itself to blister copper. The process resembles the copper extraction process of present Nepal [19], (Gajurel and Baidya,1984), and also the Continuous Process Technology of advanced countries like Noranda, Mitsubishi, or Ausmelt process.[20] In Figure 13 reconstructed furnace is shown and Figure 14 includes Thermodynamic reactors as practiced in most modern continuous melt process, which closely resembles, the ancient crucible copper extraction of East Indian metal workers. The sample of bar-celt is a forged form of blister copper a copper with enough dissolved, residual oxygen which expose itself in from of blisters over the copper surface. Later on this type of copper was deoxidized with arsenicbearing ore, llingite/ orpiment, so that the material of axe is less gassy. Afterwards the intentional degassing was made by small amount of arsenic which volatilizes after deoxidizing but some of it remains as residual arsenides that are found in the structure of the copper lump, from Aguibani. 5.3 Basic chemistry of the Process

Copper pyrometallurgical extraction process is a stepwise selective oxidation (while iron extraction is a reduction process) of copper iron sulphide ores (chalcopyrite) by i) roasting ii) smelting iii) converting operations. During these reactions (SO2) sulphur di-oxide, (FeO) iron oxide (removed as a slag after fluxing) and finally metallic (Cu) copper are produced with some heat generated. Modern processes combine the three steps together sequentially in a single continuous process[21], which is, autogeneous in character and made the extraction convenient and energy economic. Surprisingly, East Indian copper workers attempted the same and successfully extracted pure copper very cheap probably first time in the world, without any help of modern chemistry (thermodynamics). (i) Roasting:
2 FeS + 3O2 = 2 FeO (from air) + 2 SO2 + Heat (Gangue, iron sulphide) (Iron oxide) (Sulphur dioxide)

Roasting conducted with air at temperatures between 5000 and 7000C, mostly removes Fe & S, increasing concentration of Cu in the product with generation of some heat to facilitate the next reaction. (ii) Smelting: The process combines simultaneous generation of liquid metal phase (in form of metallic sulphide mixtures) known as matte and liquid slag phase (in form of fayalite) for the removal of the gangue, iron. The product rich in copper is matte (35~50% Cu and balance iron sulphide). Therefore, two separate identities develop - one of which is the product matte and the other is the discard fayalite slag. 5.4 Thermodynamics of the process: From thermodynamic point of view, the process hinges on three basic points: (i) During initial roasting, just sufficient oxygen should be supplied to the reactor (here in crucible) so as to oxidize iron sulphide to iron oxide for removal of the gangue (here FeS) at moderate temperature and to oxidize carbon and hydrocarbons to carbon mono-oxide or di-oxide for generation of heat, but inadequate for magnetite (Heavy, sp. gr. 5.0-5.5) formation or sulphate production. Burning of hydro-carbons (cow-dung) raises the localized temperature (~12500C) quickly, but also arrest magnetite (Fe3O4) generation due to the less oxidizing atmosphere with overall low temperature (500-5000C), as otherwise there is a chance of moving down of heavy gangue component as magnetite (sp. gr 5.0-5.5), ahead of (sulphide) matte (sp. gr. 4.4) which can settle below to contaminate final blister copper (sp. gr. 7.8). In comparison, in Near East, Mesopotamian metal workers of Sinai region might have used high temperature by generating huge heat [the presence of superb quality charcoal from wild pistachio, haloxylon amodendron had been reported by Agarwal,[22] to accelerate the process, which favoured magnetite formation[23]. (ii) Excess supply of silica separates gangue component (iron) in form of immiscible light liquid slag phase from fluid heavy metal phase of copper at the smelting temperature (1200 0C). The application of alumina (in clay) and lime, this further stabilise the isolation of slag from metal phase in two separate zones (like oil-water separation). [24] The (~50% Cu, sp. gr. 4.6) matte is heavier with very low viscosity, ~10 cP, so is naturally fluid, while the smelting slag (sp. gr. 3-3.7) is lighter but viscous (500-2000 cP), (so is rather slow to move) having complete separate identity, floats over liquid metal phase. The presence of silica causes then to separate into two immiscible liquid phases an invention of eastern copper workers without the knowledge of modern chemistry. The amount of silica (SiO2) as a flux is also significant. According to FeO Fe2O3 SiO2 phase diagram (1200o C), the amount should be at least 40-42% - which may be higher due to the presence of lime CaO [25]. A slag analysis from Parihati[26] copper producing center confirms this: 65.1% SiO2, 10.3% Al2O3, 9.2% Fe2O3, 0.4% TiO2, 2.5% MgO, 9.5% CaO, 0.07% MnO. This is unique as in Near East (Mesopotamia or Sumer), men used iron ore[27] as flux,

thereby forming magnetite, which ultimately produced iron contaminated hard copper, difficult to forge or work and the slag analyses show silica around 40% and not in excess. Comparatively, men in Bengal could completely isolate iron from copper due to the presence of excess silica, and produced soft, almost pure, malleable copper (HV 60 or less) - easy to forge, and so having high demand in the world market. (iii) On progress of smelting, after deslagging through the slag notch the Cu-rich matte (~80% Cu) known as the white metal is collected below, and is converted to blister copper by oxidation avoiding contamination. The presence of blow holes (Fig.1) is the probable proof of this premise as blow holes are caused by the entrapped gases during casting. This is also unique, as in Near East, no slag notch was used in the crucible and deslagging was absent; the total slag and metal prills was allowed to solidify in the hole[28] and the metal was separated from the brittle slag by stone hammering. Differences between Near East and East India copper technologies are given Table III. 5.5 Copper Forming Technology Floor molding[29] using existing stone pattern of bar celt might had been used in East India to cast the bar-celt by direct pouring in an open mold. It gave a fast cooling rate of ~ 70 K/Sec as calculated from DAS, ~ 17 m from micro structure. A better foundry practice was adopted for the casting of the axe, where top mold box could have covered the flat floor mold with horizontal gating and vertical sprue as is the case commonly practiced by Andhra tribal casters even to day[30]. The given cooling rate ~ 15 K/Sec, was corresponding to DAS of 30-40 m, justify the probability. Sandy clay was the probable molding system. Forging was done to give proper shape to the axe after casting. But it could not develop the desired hardness, (Fig.6) commonly needed for cutting tools. Yet the important thing is that people knew the hot forging characteristics of copper - as copper is super plastic only above 500550 0C.[31] Cold forging could have made the axe harder but brittle, unsuitable for normal use. The copper lump was the bun-shaped ingot obtained by allowing the pure liquid copper to cool at the bottom of the crucible. The ingot was probably around 120 mm in diameter with maximum thickness in the central region as 12mm. slow cooling within the crucible is vindicated by the large secondary dendritic arm spacing of 100 m. From the shape of the ingot it seems the crucible had a half-round inside cavity at the bottom and the internal configuration tapered to 150 mm in diameter towards the bottom. The open-die forging of high tin bronze presumably was done on a concave grooved stone anvil[32] (Mukherjee, 1978), using heavy stone hammers in the super plastic temperature zone [33] (Rollason, 1975) around 600 - 7000C within a uniform solid solution region. Starting with a flat ingot and finishing with a good forging texture after deep sinking is a remarkable achievement in ancient time. This is particularly important as only with more than 22% SnCu alloy has good forging properties above 5000C due to an unique single phase region over eutectoid reaction[34] which was not thermodynamically known from the phase diagram (Fig. 15) at that ancient time. 6.0 Conclusions Optical microscopy and SEM observations confirm the development of chemical metallurgy for the extraction of pure copper from chalcopyrites. Also the gradual progress of physical metallurgy from unsound blister copper stage or ingot structure to the fine texture of wrought bronzes continued by the people of East India in medieval period. The application of crucible shaped furnace with slag notch at the bottom while air-blast at the top, fluxing with silica, deoxidation with first arsenic or tin and later on zinc in historical period are quite unique and characteristically different from medieval copper technologies available in other parts of the world. Each of these establishes the notion about the indigenous origin of copper technology in East India although some assimilation of outside knowledge cannot be discounted.

Acknowledgements The authors express their sincere thanks for Ms. Mira Roy, Man in India, Ranchi and Dr. Gautam Sengupta, Member Secretary, CASTEI, Kolkata for the provision of samples for testing. Shanaj Husne Jahan has helped a lot for publishing this esteemed Journal.

Abbreviations Sp.Gr. Specific gravity. cP m HV HK Centi Poise, unit of viscosity. Micro-meter (10-6 m). ( in m.) (Hwang, et. al, 1998)[35] Micro hardness in Vickers Diamond scale. Micro hardness in Knoop Diamond scale. DAS Secondary Dendritic Arm Spacing, = 101.R 0.42(R Cooling Rate, K/Sec)

Table I XRD Results Sample: Bar-Celt- Axe, Cu lump Radiation: Cu / Fe 35 kV / 30 mA Wavelength, K = 1.791
N0. 1 2 3 Angle(2 ) 50.8o 59.2o 88.6o d, 2.088 1.813 1.282 I / Io 100 41 30 (Ref:

The result show predominant - Cu phase on the basic of main peaks, with some minor Cu phases JCPDS, 1978).[36]

Table II XRD Results Sample: Gazole Bronze (23.62% Sn- Cu) Radiation: CU / NI 35 kV / 30 mA Wavelength, K = 1.540598
N0. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Angle(2 ) 22.895 30.050 32.606 39.219 41.726 42.337 44.459 49.117 52.750 58.353 71.066 78.132 85.863 87.325 109.850 d, 3.8813 2.9714 2.7441 2.2952 2.1629 2.1332 2.0344 1.8534 1.7340 1.5801 1.3254 1.2223 1.1309 1.1157 0.9412 I / Io 84.2 70.8 70.4 82.2 71.4 69.3 100.0 32.1 30.6 31.8 28.0 23.0 29.0 24.7 17.8

XRD result indicate the presence of " (peak no. 4,5,7,8,11,12,13), - metastable (1,3,4,6) and - Cu phase (7,9,12) of Copper Tin system. (compared with JCPDS, 1978, 06 0621, 17 0865).[37]

Table III Tabulation of Differences


Near East Process East Indian Process Rich Chalcopyrite ores probablyLean ore Fine powders of were used in small granules: Chalcopyrite were used: (a) Less Silica in ore. (a) More silica - making it almost self (b) Less surface area was exposed in fluxing. chemical reaction. (b) More specific surface area giving option of quick liberation of sulphide ores for chemical reaction. More heat is required for oreLess heat is required for chemical liberation energy requirement wasreaction. Therefore, it was energy high. efficient. Iron ore was used as flux, therebySilica was used as flux in form of contaminating sulphide ore with theclay/cow dung mixture making production of miscible slag andimmiscible fayalite slag which metal phase. separates it self from metal phase. Removal of gangue, was notGangue, in form of light liquid slag possible, for non availability ofwas removed from metal phase notches so the product was ironthrough bottom notch, making metal contaminated copper. more cleaner.

Ores

Energy

Flux

Slag notch

Iron contaminated copper cannot be Deoxidation by arsenic ore or later Deoxidation easily deoxidized. Tin or Zinc was possible. Tin Bronze (10 - 22% tin) is not Bronze malleable for hot forging. Casting Preparation was done only. High tin bronze (over 22% tin) has a single phase region, which has good forging properties.

Figure 1. BarCelt.

Figure 2. Double-ended Axe

Figure 3. Disc of a Copper Lump

Figure 4. Part of a Bronze Bowl

BAR CELT Figure 5. (LHS) Partially annealed dendritic pattern resembling cast structure (125 X). Microhardness markings are on the right hand structure (Load 10 gm) which indicate higher hardness than the hardness of the blister copper.

AXE Figure 6. (LHS) Preferential segregation of the second phase particles at the grain boundaries can be seen with usual microhardness readings on the right hand side structure (Load 10 gm) which are similar to copper.

COPPER LUMP Figure 7. (LHS) Equiaxed grain structure with random distribution of second phase is observed. (Inset) Some lead (Pb) particles. Microhardness readings show harder material (Load 50 gm), confirming the presence of arsenic bearing second phase

BRONZE BOWL Figure 8. (LHS) Banding of second phase - , in Bronze indicates hot forged structure, matrix is phase.Microhardness readings indicate the presence of , - phase (HK 323, Load 10 gm).

Co 0.33 Ni 0.36 Cu 48.12

Cu 69.89 S 30.11

Cu 100.00

O 46.18 S 24.38 All in Atomic S 10.71 Cu 62.18 Percentage Co 0.42 Se 8.73

Base Metal

O 50.40

Sn 0.79 Sulphide inclusion (Irregular, black) Cu 24.30

Ni .58 (Irregular, gray)

Pb 4.71

Oxide inclusion (Round, gray) Bi 15.02

As 1.78

Selenium Copper Sulphide

(White)

Complex sulphide, oxide, arsenide

Figure 9

Figure 10

Figure 11

Figure 9. Unetched microstructure is full of different inclusions as indicated above. Bulk phase is copper, along with different metals in trace amounts even Pb, Bi, Co, Se and Arsenides are rare. Figure 10. Microstructure of axe is the proof of sound metal, with arsenides along with usual oxides and sulphides. Figure 11. Microstructure showing cast structures pure undisturbed copper showing the irregular shrinkage cavity.

- matrix

Figure 12: Discontinuous phases in the matrix indicate interrupted manual forging operation (500X); second phase also indicates fibrous texture. SEM confirms the observation of wrought structure (50X). phase is the matrix while is the second phase rounded due to slow cooling. Small amount of phase can be seen in the central region as well as at the grain boundary.

Figure 13: Reconstructed furnace as practiced by Nepalese copper worker, reported by Gajurel and Baidya, and found in archaeological excavations at Nalanda or elsewhere in India, reported by Prof. A.K. Biswas et al. Dr. H.C. Bharadwaj etc. where silica (SiO2) was used as a flux to drive out iron oxide in form of immiscible liquid slag through the bottom slag notch and produced pure copper free from iron. (LHS). Figure 14: (RHS) Thermodynamic reactors as practiced in most modern continuous melt process, which closely resembles, the ancient crucible copper extraction of East Indian metal workers.

Figure 15
Figure 15: A part of Cu-Sn phase diagram. The part shows the relevant bronze compositions as used in bronze forging. The singlephase region, below the peritectic temperature of 7980 C, extends from 22% to 25.5% tin.

* Professor, Department of Metallurgy and Material Science, Jadavpur University, Kolkata, India. * Senior Fellow, Centre for Archaeological Studies and Training, Eastern India, Kolkata, India. [1] K.N. Diksit, Excavations at Paharpur Bengal, Memoirs of Archaeological Survey of India, No. 55, 1938, Delhi. [2] K.G. Goswami, Excavations at Bangarh (1938-41), Asutosh Museum Memoir, No. 1, 1948, Calcutta: University of Calcutta, India [3] P.C. Dasgupta, P. (1964). The Excavations at Pandu Rajar Dhibi Bull. Directorate of Archaeology, West Bengal, No.2, 1964, Calcutta [4] A. Ray and S.K. Mukherjee, Excavation at Mangalkot, Pratnasamiksha, Vol. 1, 1992, pp. 107-125 [5] M.S. Alam and J.F. Salles (2001) First Interim Report (1993-1999) France- Bangladesh joint venture excavations at Mahasthangarh, Dhaka: Department of Archaeology, 2001. [6] K.K. Basa and S.S.M. Rahaman Bronze knobbed bowls from Wari, Bangladesh: Implications for trade, Journal of Bengal Art, Vol. 3, 1998, pp. 291-98. [7] J.C. Brown Copper Hoards from Ranchi, Journal of Bihar and Orissa Research Society, Vol. 1, 1915, pp.125-26. [8] S.C. Roy, A find of ancient bronze artifacts in Ranchi district, Journal of Bihar and Orissa Research Society, Vol. 2: 1916, pp. 482-83. [9] P. Yule and M. Thiel-Horstmann, The prehistoric metal objects in the S.C. Roy collection, Ranchi, Man in India, Vol. 65,. No. 2: 1985, pp. 121-138. [10] E.G. West, Copper and its alloys Ellis Horwood Series- 1982, p 107. [11] D.K. Mitra, Seminar on Copper Metallurgy in India, Met. Engg., Jadavpur University, Calcutta, 1984, pp. 18-19. [12] A.K. Biswas, Minerals and Metals in Ancient India, New Delhi: D.K. Printworld, 1996, pp. 187-88. [13] H.C. Bhardwaj, List of Ancient Mines, Aspects of Ancient Indian Technology, Delhi: Motilal Banarsidas, 1979, pp. 191-193. [14] M. Mukherjee, Metal Development in India, Met. Engg., Jadavpur University, 1978, pp. 3-6. [15] B.B. Lal, Further copper hoards from the Gangetic basin and a review of the problem, Ancient India, No.7, 1951 pp. 20-39 [16] D.C. Sircar, Aspects of Early Indian Economic Life, Sec.-III, Bulletin Indian Museum V-XIV, No.1 & 2,1979, pp. 26-29. [17] R. Chatterjee, Important Hoards and Finds in East Indian Bronzes, Ed. S.K. Mitra, Calcutta University, 1979, pp. 125-32. A.K. Bhattacharya, Jhewari Bronze Buddhas, Calcutta: Indian Museum, 1989. [18] W.G. Davenport and A.K. Biswas, Extractive Metallurgy of Copper, 1978, p. 69. [19] C.L. Gajurel, K.K. Baidya, Copper Extraction Process Traditional Arts and Crafts of Nepal, Delhi: S. Chand), 1984, p. 12. [20] R. Matusewicz and J. Sofra, Non-ferrous Metals in the New Millennium, Ed. R. Bhima Rao, K. Sarveswara Rao, V.N. Misra (Allied Pub.), 2001, pp. 71-94.
[21] W.G. Davenport and A.K. Biswas, op. cit. p.86 (iii) Converting: (a) Complete FeS - elimination or slag forming stage from matte 2FeS + 3O2 + SiO2 2FeO .SiO2 + 2SO2 (Iron sulphide) (From air) (Silica, flux) (Fayalite slag) The liquid Copper Sulphide (Cu ~80%) remains in the reactor known as white metal. (b) Blister (Pure) Copper Forming Stage: Cu2S + O2 2Cu + SO2 + Heat (White metal) (from air) (Blister Copper)

It is to be noted that copper forming (2nd stage) does not occur until the matte contains less than 1% Fe (iron).

[22] D.P. Agarwal, The Copper Bronze Age in India, Munsiram Manoharlal, New Delhi. 1971, p. 110. [23] W.G. Davenport and A.K. Biswas, op. cit. p. 14 [24] W.G. Davenport and A.K. Biswas, op. cit. pp. 91, 96. [25] W.G. Davenport and A.K. Biswas, op. cit. p. 88. [26] M. L. Datta, Spectrographic Determination of Minor Constituents in Ancient Copper Slag Trans. Indian Institute of Metals, V-85, No.5, 1982, pp. 487-88. [27] B. Rothenberg, Excavations at Timna Site 39 a Chalcolithic Copper smelting site and Furnace and its Metallurgy Report on Timna Site 39A IAMS Monograph, No.1, Archaeo-Metallurgy, 1978, pp. 21 [28] B. Rothenberg, (1978) op. cit. p. 21 [29] M. Mukherjee, Metal craftsmen of India, Calcutta: Anthropological Survey of India, 1978, pp. 204-210. [30] M. Mukherjee, op. cit., 1978, pp. 210-230. [31] C.J. Smithells (1978). Metal Reference Book, London: Butterworthh Heinmen. [32] Mukherjee, op. cit. 1978, pp. 210-213. [33] E.C. Rollason, Metallurgy for Engineers (ELBS), 1975, pp. 300-318. [34] E.G. West (1982), op. cit. p 185. [35] P.D. Hwang, et.al. Journal Material Engineering and Performance, Vol. 7(4), 1998, pp. 495 503. [36] JCPDS, Selected Powdered Diffraction Data for Metals and Alloys, 1978, Ed. [37] JCPDS, Selected Powdered Diffraction Data for Metals and Alloys, 1978, Ed.

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