2015 年 79 巻 7 号 p. 362-371
The oxidation behavior of Zircaloy-4 at high temperatures in a flowing Ar-H2O (saturated at 323 K) mixed gas was investigated using hydrogen and oxygen sensors installed at a gas outlet, and the utility of the gas sensing methods by using both sensors was examined. The generated amount of hydrogen was determined from the hydrogen partial pressure continuously measured by the hydrogen sensor, and the resultant calculated oxygen amount that reacted with the specimen was in close agreement with the mass gain gravimetrically measured after the experiment. This result demonstrated that the hydrogen partial pressure measurement using a hydrogen sensor is an effective method for examining the steam oxidation of this metal as well as monitoring the hydrogen evolution. The advantage of this method is that the oxidation rate of the metal at any time as a differential quantity is able to be obtained, compared to the oxygen amount gravimetrically measured as an integral quantity. When the temperature was periodically changed in the range of 1173 K to 1523 K, highly accurate measurements could be carried out using this gas monitoring method, although reasonable measurements were not gravimetrically performed due to the fluctuating thermo-buoyancy during the experiment. A change of the oxidation rate was clearly detected at a monoclinic tetragonal transition temperature of ZrO2. From the calculation of the water vapor partial pressure during the thermal equilibrium condition using the hydrogen and oxygen partial pressures, it became clear that a thermal equilibrium state is maintained when the isothermal condition is maintained, but is not when the temperature increases or decreases with time.
Based on these results, it was demonstrated that the gas monitoring system using hydrogen and oxygen sensors is very useful for investigating the oxidation process of the Zircaloy in steam.
