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Stibnite mineral (mainly Sb 2 S 3 ) has been employed for the synthesis of tetrahedrite Cu 12 Sb 4 S 13  bulk material by spark plasma sintering. High purity Cu 12 Sb 4 S 13  can be quickly obtained by two sintering procedures at temperatures from the range of 420 °C to 440 °C for 1 h. Appropriate reduction of Cu content (Cu 12+x Sb 4 S 13 , x ⩽ –0.05) or CuS content (Cu 12−y Sb 4 S 13−y , y = 0.1 or 0.3) was beneficial to fabricate Cu 12 Sb 4 S 13 . The secondary resintering improved the purity of Cu 12 Sb 4 S 13  material. The first-order magnetic phase transformation with magnetic hysteresis effect was confirmed by the behavior of susceptibility, heat capacity and resistivity. The magnetization showed a linear increase with increasing field (up to 7 T) and non-saturation behavior was observed. The impurities in stibnite mineral Sb 2 S 3  had a weak influence on the transformation temperature but affected the low-temperature magnetization value (~0.15, close to natural tetrahedrite). Similar transformation was observed by the analysis of heat capacity. The properties such as electrical resistivity, Seebeck coefficient and thermal conductivity were also measured for Cu 11:9 Sb 4 S 13  and Cu 11:9 Sb 4 S 12:9 . The maximum figure of merit ZT of Cu 11:9 Sb 4 S 12:9  was 0.22 at 367 K.

materials science poland

The influence of self-doping of stibnite ore with impurities on the preparation, heat capacity, magnetic and transport properties of tetrahedrite Cu12Sb4S13