Modeling the radiolysis of supercritical water by fast neutrons: density dependence of the yields of primary species at 400°c.

A reliable understanding of radiolysis processes in supercritical water (SCW)-cooled reactors is crucial to developing chemistry control strategies that minimize the corrosion and degradation of materials. However, directly measuring the chemistry in reactor cores is difficult due to the extreme conditions of high temperature and pressure and mixed neutron and gamma-radiation fields, which are incompatible with normal chemical instrumentation. Thus, chemical models and computer simulations are an important route of investigation for predicting the detailed radiation chemistry of the coolant in a SCW reactor and the consequences for materials. Surprisingly, information on the fast neutron radiolysis of water at high temperatures is limited, and even more so for fast neutron irradiation of SCW. In this work, Monte Carlo simulations were used to predict the G values for the primary species e(-)aq, H(•), H2, (•)OH and H2O2 formed from the radiolysis of pure, deaerated SCW (H2O) by 2 MeV monoenergetic neutrons at 400°C as a function of water density in the range of ∼0.15-0.6 g/cm(3). The 2 MeV neutron was taken as representative of a fast neutron flux in a reactor. For light water, the moderation of these neutrons after knock-on collisions with water molecules generated mostly recoil protons of 1.264, 0.465, 0.171 and 0.063 MeV. Neglecting oxygen ion recoils and assuming that the most significant contribution to the radiolysis came from these first four recoil protons, the fast neutron yields were estimated as the sum of the G values for these protons after appropriate weightings were applied according to their energy. Calculated yields were compared with available experimental data and with data obtained for low-LET radiation. Most interestingly, the reaction of H(•) atoms with water was found to play a critical role in the formation yields of H2 and (•)OH at 400°C. Recent work has underscored the potential importance of this reaction above 200°C, but its rate constant is still controversial.

Calculation of the yields for the primary species formed from the radiolysis of liquid water by fast neutrons at temperatures between 25-350°C.

Monte Carlo simulations were used to calculate the yields for the primary species (e(-)aq, H(•), H2, (•)OH and H2O2) formed from the radiolysis of neutral liquid water by mono-energetic 2 MeV neutrons at temperatures between 25-350°C. The 2 MeV neutron was taken as representative of a fast neutron flux in a reactor. For light water, the moderation of these neutrons generated elastically scattered recoil protons of ∼1.264, 0.465, 0.171 and 0.063 MeV, which at 25°C, had linear energy transfers (LETs) of ∼22, 43, 69 and 76 keV/µm, respectively. Neglecting the radiation effects due to oxygen ion recoils and assuming that the most significant contribution to the radiolysis came from these first four recoil protons, the fast neutron yields could be estimated as the sum of the yields for these protons after allowance was made for the appropriate weightings according to their energy. Yields were calculated at 10(-7), 10(-6) and 10(-5) s after the ionization event at all temperatures, in accordance with the time range associated with the scavenging capacities generally used for fast neutron radiolysis experiments. The results of the simulations agreed reasonably well with the experimental data, taking into account the relatively large uncertainties in the experimental measurements, the relatively small number of reported radiolysis yields, and the simplifications included in the model. Compared with data obtained for low-LET radiation ((60)Co γ rays or fast electrons), our computed yields for fast neutron radiation showed essentially similar temperature dependences over the range of temperatures studied, but with lower values for yields of free radicals and higher values for molecular yields. This general trend is a reflection of the high-LET character of fast neutrons. Although the results of the simulations were consistent with the experiment, more experimental data are required to better describe the dependence of radiolytic yields on temperature and to test more thoroughly our modeling calculations.