PART VI - Communications - The Reactions of Liquid Titanium and Hafnium with Carbon

The layer growth method has been used to investigate the reaction kinetics of liquid titanium and hafnium with carbon and the [liq] - [liq + TiC] and [liq] - [liq + HfC] phase boundaries at temperatures above 1800°C. The equipment and experimental procedures used in this investigation are basically identical to those described in an earlier paper' on the Zr-C reaction. Temperature control, however, was improved significantly by connecting a Latronics Colo-Ratio automatic pyrometer and a controller to the power source. The subsequent temperature variations were ±10°C; previously ±20°C was obtained using manual controls. The absolute accuracy of the pyrometer, however, must be considered to be only ±40°C.* The spectrographic analyses of the materials used in this study are listed in Table I. The isothermal reactions of titanium (1800° to 2700°C) and hafnium (2300" to 3000°C) with carbon (graphite crucibles) resulted in the formation of carbon-saturated liquid metal and layers of Tic and HfC, respectively. The thicknesses of the carbide layers, determined from metallographic measurements at 100 times, as a function of carburization time and temperature are given in Figs. 1 and 2. At each temperature, parabolic growth behavior for these reactions was observed and could be expressed as x2 =Kpt, where X is scale thickness (corrected for heating and coolingL), Kp the parabolic growth constant, and t the isothermal carburization time. Values of Kp as a function of temperature for the carbides are shown in Fig. 3 and listed in Table 11. The growth constants are expressible as: kpTiC = 0.2 exp(-61,800/RT) sq cm per sec for Tic and Kp HfC = 2.62 exp(-95,300/RT) sq cm per sec for HfC. The liquidus phase boundaries were determined from metal samples treated in graphite crucibles for different times ranging from 4 to 100 min at each of the temperatures indicated in Table 11. Metallographic examination revealed that the carbide precipitates were distributed uniformly throughout the frozen metal matrices. This is attributed to the rapid cooling rates (800°C per min) and the small difference in density between the precipitated carbide and the liquid metal.