Activation energy of phase transformations at high-temperature synthesis of tungsten carbide by electrothermal explosion under pressure

Abstract

The effect of activation energy on phase transformations (transitions) in the W–C system during the synthesis induced by an external heat source was investigated by electrothermal explosion (ETE) under pressure. The ETE technology combines self-propagating high-temperature synthesis (SHS) with additional sample heating by Joule heat – electric current passing through the synthesized mixture, and it makes it possible to determine the chemical reaction rate that is highly susceptible to external impacts such as pressure, concentration, sample shape, any film present on combustion products, etc. The chemical reaction rate, i.e. external source current, may be controlled by changing the activation energy. The study was conducted in the following conditions: temperature Т = 293÷3700 K; carbon concentration of 49.8–50.2 at.%; quasi-static compression at P = 96 MPa; external source voltage and current density V = 10 V, I = 20 МА/m2, respectively; samples 8 mm in diameter weighing 6 g. The Т–τ thermogram of the W–C system was used to determine the following parameters: four stages of the synthesis process, temperatures of special points of phase transformations, temperature boundaries of phases and process activation energy. Thermograms of intermediate states are presented as isothermal plateaus of phase transformations. The analysis of experimental results and the physical representation of the process make it possible to assert that temperature plateau parameters are the effective value of activation energy for synthesis mode maintenance. Each of the 4 W–C mixture synthesis stages is described. Pre-explosion stage I – sample heating in the temperature range of Т = 293÷563К, endothermic reaction, effective activation energy for synthesis mode maintenance Q = 2.96 kJ, and taking into account 1-mole mass Еа = 111.6 kJ/mol. Low-temperature (563–1190 К) stage II – ignition, Q = 5.46 kJ, Еа = 109.2 kJ/mol. High-temperature stage (III) in the range of Т = 1190÷2695К, order–disorder transformation, Q = 14.25 kJ, Еа = 424 kJ/mol. Finally, Stage IV occurs in the range of Т = 2695÷3695К, Q = 14.31 kJ, Еа = 143.2 kJ/mol. It was shown that the limiting stage with the highest activation energy is the melting process.