Synthesis of Transiton Metal Mixed Sulfides MTS3 (M=Ba, Pb, T=Ti, Zr) Using Sulfur Melt

"Ternary mixed sulfides of some transition metals MTS3 (M=Ba, ·Pb, T=Ti, Zr) were synthesized by a relatively low temperature process using sulfur melt. The mixture of starting materials, such as, metals and/or binary sulfides and a large excess of sulfur was reacted in a vacuum-sealed Pyrex or quartz ampoule at 350- 600 °C for one to three weeks. After the reaction, the remaining sulfur was completely removed by a process composed of filtration of sulfur melt and followed dissolution in CS2• The binary sulfides impurities coexisted in the products were removed by rinsing the products in water and acetone. By using the above method, BaTiS3, PbTiS3 and BaZrS3 'Were obtained in pure form. The effect of addition of halides on the yields of these ternary sulfides were also discussed.IntroductionThere have been a vast number of studies on the preparation and physical and /or chemical properties of mixed metal oxides. As is well known, some of such compounds exhibit excellent materials properties, causing them for use in mechanical, electronic, magnetic and chemical devices. Not a few mixed metal sulfides show similar physico-chemical properties to those of the corresponding mixed metal oxides. However, the study of the mixed sulfide crystals is rather sparse mainly due to difficulties in preparing these compounds. In various methods which have been adopted for preparing mixed sulfides, the simplest method would be the solid-solid reaction of the component binary sulfides or elements. However, there are always diffusional constraints with regard to the reactions in solid phases causing it necessary to heat the reactants at sufficiently high temperatures, viz. 800-1200°C. On the other hand, some mixed sulfides are unstable at high temperatures or to change their materials properties due to sulfur nonstoichiometry and structural modification depending on temperature, i.e., synthesis of such compounds needs to be made at lower temperatures. Processing in alkali halide melts is hopeful to overcome the above problems but to obtain the halide melts the temperatures above ~ 600 °C is needed. Low temperature reaction has been carried out for the preparation of Hg1.24TiS4, which was formed by the ·combination of TiS2 and molten Hg metal at 320°C[l]. Reaction of WS2 with LiBH4 melt at 350°C yielded LixWS2[2]. These sophisticated methods, however, can be applied only to the vary special cases."