When decommissioning of nuclear facilities happens, large amounts of radioactive wastes are released. Because costs of nuclear decommissioning are enormous, effective and economical decontamination technologies are needed to remove radioactive wastes. During NPP operation, corrosion product called Chalk River Unidentified Deposits (CRUD) is generated. CRUD is an accumulation of substances and corrosion products consisting of dissolved ions or solid particles such as Ni, Fe, and Co on the surface of the NPP fuel rod coating. CRUD is slowly eroded by the circulation of hot pressurized water and later deposits on the fuel rod cladding or external housing, thereby reducing heat production by the nuclear fuel. Decontamination of radiologically contaminated metals must be performed before disposal, and several methods for decontaminating CRUD are being studied in many countries. Decontamination technology is an alternative to reducing human body covering and reducing radioactive waste disposal costs, and much research and development has been conducted to date. Currently, the importance of decontamination is emerging as the amount of waste stored in radioactive waste storage is close to saturation, and the amount of radioactive waste generated must be minimized through active decontamination. In this study, a preliminary study was conducted on the removal of CRUD by multiple membrane in an electro-kinetic process using an electrochemicalbased decontamination method. Preliminary research to develop a technology to electrochemically remove CRUD by using a self-produced electrochemical cell to check the pH change over time of the CRUD cell according to voltage, electrolyte, membrane and pH change.

During the operation of a nuclear power plant (NPP), corrosion products called CRUD (Chalk River unidentified deposit) accumulate on the surface of the primary system. The CRUD components of pressurized light water reactors or heavy water reactors, represented by (NixFe1-x)(FeyCr1-y)2O4, are composed of Fe3O4, NiFe2O4, FeCr2O4, NiCr2O4, etc. Radionuclide such as Co-60 are deposited within this CRUD, so the entire deposited material must be dissolved and removed for decontamination. Chemical decontamination has the advantage of being able to decontaminate a wide metal surface, but has the disadvantage of generating a large amount of secondary waste. Recently, chemical decontamination methods that add an electrodynamic process are being studied to overcome these shortcomings. This technology is a method of dissolving CRUD by applying an electric field in the anodic compartment of a cell separated by CEM. It is a method of accelerating CRUD dissolution by generating a large amount of hydrogen ions in the anodic compartment. Dissolved metal ions pass through the CEM (cation exchange membrane) and move to the cathodic compartment (pH > 12), where they are removed by adsorption or precipitation process. Therefore, the speciation characteristics between decontamination agent (oxalic acid) and metal ions are very important. In this study, we investigated the speciation characteristics of Fe(II), Ni(II), Co(II) - oxalate, which are important complex species in CRUD dissolution cells. The thermodynamic equilibrium constant for hydrolysis of each ion and of M(II)-oxalate were collected and speciation characteristics were analyzed using the MINEQL 5.0 program. From the speciation characteristics of M(II)-oxalate, effective radionuclide removal methods in an electrodynamic cell were considered.

It has been known that as oxide layer (ZrO2) forms on the nuclear fuel cladding during irradiation in nuclear power plants, the corrosion kinetics are influenced by various parameters such as chemical environments. One of those environments, crud deposition driven by coolant chemistry has an adverse effect on the formation of oxide (ZrO2) and leads to increase thickness of the layer. In this study, crud formation was performed through loop experiment equipment on the surface of intentionally-made oxide layer (ZrO2) on cladding tubes and then the composition and characteristics of cruds were examined for the investigation of nuclear power plant environment. As a result, various cruds in composition and microstructure were formed depending on the exquisite methods and conditions such as metal ion concentration.

Corrosion products generated from the oxidation of structure materials are deposited on the surface of coolant systems, forming CRUD (Corrosion Related Unidentified Deposits). The CRUD deposition on the fuel surface has influenced the heat transfer through the fuel rod. When CRUD was deposited on a fuel surface, heat resistance may increase, and this increase in heat resistance leads to the increase in temperature distribution from cladding to coolant. Also, the temperature distribution is related to the radiolytic and chemical reactions within the CRUD deposits. This influence may be enough to change the pH distribution within the CRUD deposits. To estimate the influence of thermal resistance, the composition, microstructure, and vapor fraction within the CRUD should be considered, by investigating the thermal conductivity model of CRUD deposits. Therefore, in this study, the CRUD thermal conductivity was studied through the literature study, by considering composition, capillary flow characteristics, and vapor fraction. For the uncertainty parameters, a sensitivity study was conducted to check the degree of influence on thermal conductivity. The effective thermal conductivity was applied to the radiochemistry model within the CRUD deposits and an analysis of the influence in radiolysis reaction within the CRUD deposits with a fixed thickness.

국내 원자력발전소의 가동년수 경과에 따른 방사능 오염증가로 제염공정에 대한 관심은 점차 점증되어 가고 있다. 화학제염은 방사성폐기물의 생성과 방사선량율을 낮추는데 매우 중요하다. 이에 앞서, 원전 주요계통 및 부품 등의 화학제염을 위해서는 대상 재질에 적합한 산화제 및 제염제를 우선 선정하여야 한다. 이를 위해서는 제염대상물 혹은 제염대상 계통에서 채취한 크러드에 대한 각종 분석을 실시하여 크러드의 화학조성 및 결정구조에 대한 정보를 확보해야 하나 실제적으로 방사능을 띤 계통으로부터 시료를 직접 채취할 수 있는 특별한 프로그램이 마련되어 있지 않는 한 극히 제한된 방사능을 띠고 있는 부식산화물의 자료만을 얻을 수 있다. 크러드의 조성은 모재의 성분과도 밀접한 관계가 있기 때문에 재장전 주기에 따라서도 차이가 많다. 따라서 가능한 한 제염대상을 선정한 다음 제염대상으로 채취한 크러드에 대한 각종 분석자료를 확보하거나 분석을 실시하여야 한다. 본 논문은 미확보 시료에 대한 대안으로 모의크러드를 다양한 방법으로 제조하는 기술에 대해 언급하였다. 금속 산화물과 금속 수화물이 12가지의 각기 다른 방법으로 실제 시료와 유사한 화학조성과 결정구조를 지닌 모의크러드의 합성에 사용되어졌다. CRUD#4(압력용기속의 금속산화물)와 CRUD#10(하이드라진 전 처리후 도가니속의 금속산화물)시료가 Type 1, 2에 대해 가장 양호하게 합성되어졌다. 이들 크러드 시료들은 특별한 장비를 사용하지 않고도 짧은 시간 내에 반응이 이루어지고 많은 량의 시료를 쉽게 합성할 수 있게 됨으로서 제염제와 제염공정을 개발하는데 매우 유용하게 활용될 수 있을 것으로 기대된다.

발전소 내 방사화 부식생성물의 대부분을 차지하고 있는 니켈 페라이트계 부식생성물을 모사 발생시키기 위한 고온 고압용 장치를 제작하여 연구를 수행하였다. 배관형 포집기를 이용한 부식생성물 발생장치로부터 방사화 부식생성물과 가장 유사한 부식생성물을 얻을 수 있었다. 발전소에서 입자성 부식생성물이 발생되는 원리인 온도에 따른 용해도 차이를 구현하기 위하여 270C에서 부식반응이 일어나 상대적으로 높은 온도를 가진 포집용 장치에 부식생성물이 포집되도록 장치를 제작하였으며 , 발생된 부식생성물은 주사전자현미경 관찰과 EDAX를 통한 조성분석으로 그 특성을 관찰하였다. 부식생성물은 포집 된 위치 에 따라서 침상 형태의 산화물과 결정 형태의 산화물로 나뉘었으며, 조성 분석 결과 결정 형태의 부식생성물이 니켈 페라이트로서 발전소에서 발생되는 입자성 부식생성물과 유사한 것을 알 수 있었다.