The feeder pipes of the primary cooling system in a pressurized heavy water reactor (PHWR) are composed of carbon steel SA 106 GR.B. On the surface of this structural material, corrosion oxide layers including radionuclides are formed due to the presence of active species from water decomposition products caused by radiation, as well as the high temperature and high-pressure environment. These oxide layers decrease the heat transfer efficiency of the primary cooling system and pose a risk of radiation exposure to workers and the environment during maintenance and decommissioning, making effective decontamination essential. In this study, we simulated the formation of the corrosion oxide layer on the surface of carbon steel SA 106 GR.B, characterized the formed corrosion oxide layer, and investigated the dissolution characteristics of the corrosion oxide layer using oxalic acid (OA), a commercial chemical decontamination agent. The corrosion oxide layer formed has a thickness of approximately 4 μm and consists of hematite ( Fe2O3) and magnetite ( Fe3O4). The carbon steel coupons with formed oxide layers were dissolved in 10 mM and 20 mM OA solutions, resulting in iron ion concentrations of 220 ppm and 276 ppm in the OA respectively. In 10 mM and 20 mM OA, the corrosion depths of the coupons were 8.93 μm and 10.22 μm, with corrosion rates of 0.39 mg/cm2·h and 0.45 mg/cm2·h, respectively. Thus, this demonstrates that higher OA concentrations lead to increased dissolution and corrosion of steel.

The radiation field generated in the primary cooling system of a nuclear power plant tends to increase in intensity as radionuclides bind to the oxide film on the internal surface of the primary system, which is operated at high temperature and pressure, and as the number of years of operation increases. Therefore, decontamination of the primary cooling system to reduce worker exposure and prevent the spread of contamination during maintenance and decommissioning of nuclear power plants uses the principle of simultaneous elution of radionuclides when the corrosion oxide film dissolves. In general, a multi-stage chemical decontamination process is applied, taking into account the spinel structure of the corrosion oxide film formed on the surface of the primary cooling system, i.e. an oxidative decontamination step is applied first, followed by a reductive decontamination step, which is repeated several times to reach the desired decontamination goal. Currently, permanganic acid is commonly used in oxidative decontamination processes to remove Cr from corrosion oxide films. In the reductive decontamination step to remove iron and nickel, organic acids such as oxalic acid are commonly used. However, organic acids are not suitable for the final radioactive waste form. A number of multi-stage chemical decontamination technologies for primary cooling systems have been developed and commercialized, including NP-CITROX, AP/NP-CANDECON, CANDERM, AP/NP-LOMI and HP/CORD-UV. Among these, HP/CORDUV is currently the most actively applied primary cooling system chemical desalination process in the world. In this study, KAERI has developed a new chemical decontamination technology that does not contain organic chemical decontamination agents, with a focus on securing an original technology for reducing the amount of decontamination waste while having equivalent or better decontamination performance than overseas commercial technologies, and compared it with the inorganic chemical agent-based HyBRID (Hydrazine Based Reductive Metal Ion Decontamination) chemical decontamination technology.