On formation of electrically conductive phases under electrothermal activation of ferruginous carbonates

Abstract

Purpose. Study of the formation of an electrically conductive phase in carbonates using siderite as an example and determination of the temperature dependence of its formation and silicon content during simultaneous heating and the action of a weak electric field. Methodology. Analysis and generalization of the results of experimental studies. Physicochemical analytical studies have been performed using electron and optical microscopy, petrographic and X-ray phase analysis, thermogravimetric analysis and differential scanning calorimetry, and gas chromatography. Phase equilibria in the “iron oxides – carbon – carbon oxides” system have been evaluated using data on the standard change in the Gibbs energy Evaluation. Findings. Formation of electrically conductive phases in siderite has been studied. The dependence of new phase formation on heating and the magnitude of the electric field strength have been determined. The regularities of the change in threshold temperatures of phase transitions in samples of siderite and calcite containing silicon impurities have been established. Originality. Due to the thermally stimulated increase in the concentration of mobile charge carriers in intergranular space, the electric field of point charges takes the prominent part in the formation of the end product of chemical reactions. The additional effect of electric current on the increasing destabilization of chemical bonds between surface atoms leads to the formation and transport of ions, to a decrease in the energy barrier of nuclei formation of the electrically conductive phase near the active centres. The abrupt increase in electrical conductivity is due to the spontaneous formation of the nuclei of a new phase and the transition of ionic conductivity to a mixed one or an electronic one primarily. A composite semiconductor is formed as a result of electrothermal activation of siderite. This semiconductor consists of a matrix-semiconductor representing the initial mineral and is penetrated by parallel-oriented highconductivity threads. Practical value. Experimental results show that such processes occurring in rock are quite real under the conditions of the earth’s crust, and the physical values of thermodynamic quantities (factors of metamorphism) are sometimes overestimated significantly in the interpretation of various geological events.