The smelting of copper in the third millennium cal BC Trentino, north-eastern Italy

This paper presents observations and analyses on seven slag pieces from two third-millennium cal BC (Late Copper Age/Early Bronze Age) rock shelters in the Trentino, north-eastern Italy: La Vela di Valbusa and the Riparo di Monte Terlago. We review previous work on contemporary slags from the region and show that the smelting did not follow the well-known ‘Timna’, ‘Eibner’ or so-called ‘Chalcolithic’ copper smelting processes. We show that ethnographic accounts of copper smelting in the Himalayas (Sikkim and Nepal) illuminate the smelting process, in particular the lack of preliminary roasting or ore beneficiation by washing, the use of slags as fluxes for the first smelt (matte smelting) and the use of wooden (?) implements to lift the hot slags from the furnace during the smelt. The rock inclusions in the slag are consistent with an ore origin from mines at Calceranica or Vetriolo, as previously reported in the literature.

Molecular Dynamics Simulation on Microstructure and Physicochemical Properties of FexO-SiO2-CaO-MgO-“NiO” Slag in Nickel Matte Smelting under Modulating CaO Content

To improve the conditions of extracting iron from nickel smelting residues, the composition modulating from FexO-SiO2-CaO-MgO-“NiO” slag source for matte smelting using high MgO nickel sulfide concentrate was carried out. Based on the molecular dynamics simulation and experimental characterization, the effect of CaO content in nickel slags on the physicochemical properties, the microstructure evolution, and the feasibility of subsequent iron extraction were analyzed. The results showed that, for nickel smelting slag with 9 wt.% MgO, 13–15 wt.% CaO and Fe/SiO2 ratio of 1.2, the melting temperature of nickel slag was lower than 1200 °C, and the viscosity was lower than 0.22 Pa·s at 1350 °C. The electric conductivity was similar to that of the industrial slag, and the interfacial tension between slag and matte was relatively large, which ensured a good separating characteristic. It not only met the requirements for the slag performances in the existing flash smelting process but also improved conditions for the subsequent iron extraction. Additionally, it could be adapted to the current situation where an increasing MgO content exists in the nickel sulfide concentrate.

Impact of MgO and K2O on Slag-Nickel Matte Equilibria

Slag chemistry of the direct nickel matte smelting was studied in typical industrial high-grade nickel matte smelting conditions at 1400 °C and 0.1 atm pSO2. The experimental technique used involved equilibration, quenching and direct elemental phase composition analysis by Electron Probe X-ray Microanalysis. Magnesia and potassia, a typical gangue constituent of sulfidic nickel concentrates and a common impurity of industrial grade silica flux (sand), respectively, were adopted as slag modifiers in concentrations typical to industrial operations. Their effects on oxidation degree of the nickel-copper-iron matte and equilibrium concentrations of Ni and Cu in the slag were studied as a function of oxygen partial pressure. Solubility of silica in the slag increased significantly with additions of MgO and K2O in the constrained case studied, at silica saturation. Equilibrium concentrations of Ni and Cu in the slag containing MgO and K2O were about a quarter lower compared to the pure iron silicate slag, in the entire oxygen partial pressure range studied.

Behavior of Ga, In, Sn, and Te in Copper Matte Smelting

The distributions of Ga, In, Sn, and Te between copper-iron mattes and silica-saturated iron silicate slags over a wide range of matte grades 55 to 75 pct Cu were determined at 1300 °C using a gas-phase equilibration-quenching technique and direct phase composition analysis by Electron Probe X-ray Microanalysis and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry. Alumina from aluminum, a typical minor element of electric and electronic copper scrap, and lime were adopted as slag modifiers for increasing the trace element recoveries. Gallium and tin were distributed predominantly in the slag, indium preferred sulfide matte at low matte grades and slag at high, whereas tellurium strongly favored the sulfide matte in particular in high matte grades. The slag modifiers alumina and lime had a minor impact on the distribution coefficients of gallium and tin, but for indium and tellurium the distribution coefficients were more strongly affected by the basic oxides. The strong tendencies of tin and tellurium to vaporize at the experimental temperature were confirmed.