アルカリ性条件における炭素鋼の腐食に伴う硝酸イオンの化学的変遷挙動

Chemical transition of nitrate ions accompanied with corrosion of carbon steel under alkaline conditions

本田 明; 加藤 卓; 建石 剛*; 今北 毅*; 増田 薫*; 加藤 修*; 西村 務*

Honda, Akira; Kato, Takashi; Tateishi, Tsuyoshi*; Imakita, Tsuyoshi*; Masuda, Kaoru*; Kato, Osamu*; Nishimura, Tsutomu*

放射性廃棄物を地下に処分したときの放射性物質の移行現象は、環境の酸化還元状態や配位子濃度によって影響を受ける可能性があるため、セメント環境を想定したアルカリ性条件で硝酸イオンの金属による還元挙動を検討した。その結果、亜硝酸イオン濃度1.0mol/Lの場合及び硝酸イオン濃度1.0mol/Lの場合と硝酸イオンも亜硝酸イオンも含まない場合の同一電位での電流密度を比較すると、それぞれおよそ2桁から3桁程度及び1桁から2桁程度大きいにもかかわらず、炭素鋼の腐食速度は、硝酸塩の濃度の影響は受けないかむしろ低下し、腐食反応系がアノード支配型であることがわかった。また炭素鋼の腐食に伴う硝酸イオンの還元過程は、硝酸イオン亜硝酸イオンアンモニアなる逐次反応と考えられる。また、アノード支配型の腐食反応におけるカソード過程として、硝酸イオンの還元反応は、水の還元反応と競合すると考えられる。硝酸イオン濃度が高い場合(e.g. 1.0mol/L)には、硝酸イオンの共存しない場合と比較して、腐食に伴う水素発生速度が1/100から1/500と非常に小さくなった。アンモニアの生成速度は、硝酸イオン濃度が1.0E-3mol/Lから1.0mol/Lの範囲でほとんど影響はなかった。

Migration of radioactive material can be affected by the redox condition and the concentration of ligands in the repository of radioactive waste. It is possible that radioactive waste contains nitrate which can affect the migration behavior of radioactive nuclides by both changing the redox condition of the environment and acting as a ligand. On the other hand, several researchers observed the reduction of nitrate ions in ammonia due to the iron. Ammonia has a potential to ligand for radioactive nuclides. Nitrate can also affect the rate of hydrogen gas evolution accompanied by metal corrosion through changing the rest potential of metal by its oxidizing nature. Carbon steel was, therefore, immersed in an aqueous solution of sodium nitrate in a closed system for observing both the chemical interaction between metal and nitrate, and the effect of nitrate on the hydrogen gas evolution rate. The experimental pH range of the solution was 10.0-13.5 which corresponds to the pH range of pore fluid of cementitious material. The cathodic current density shows a Tafel equation type potential dependency in the aqueous solution containing nitrate or nitrite. In spite of the acceleration of cathodic reaction due to the existence of nitrate, the corrosion rates of carbon steel were not accelerated in the nitrate solutions. This fact suggests that the system is controlled by the anodic reaction. The nitrate reduction accompanied by the corrosion of carbon steel is considered to be a series reaction such as nitrate nitrite ammonia. The nitrate reduction reaction compete with the water reduction reaction within the anodic controlled condition, therefore nitrate strongly reduced the hydrogen evolution rate. The generation rates of ammonia were independent of the concentration of nitrate.