Technical Papers and Discussions -Miscellaneous Metals and Alloys - The Thermoelectric Properties and Electrical Conductivity of Bismuth-selenium Alloys (Metals Tech., Jan. 1948, TP 2313) With discussion

This investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy—the thermoelectric efficiency—has been discussed by Telkesl in a recent review of the subject. She gives the thermoelectric efficiency as: W o Efficiency = -Wo ______________i____________ TR-TC+ O2TR-Tc) where W, = power output in external load (watts) Wi = rate of heat input to hot junction (watts) TE,T, = temperature of hot and cold junctions (oA) K1,Kz = thermal conductivity of the two thermocouple materials (watts/cm°C) p,,pz = electrical resistivity of the two thermocouple materials (ohm cm) 9 = thermoelectric power (volts0/C) For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of pfoperties. Bismuth-selenium Alloys work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson who gives the diagram reproduced in There are two intermediate phases in this system, BiSe and Bi²Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedra1 crystal