Highly radioactive waste is solidified to restrict leaching, retain its shape, and maintain its structural stability to prevent it from affecting humans and the environment as much as possible. This operation should be performed consistently regardless of whether the waste is homogeneous or heterogeneous. However, currently, there are no specific performance requirements for heterogeneous waste in Korea. This study reviewed domestic research results and the status of overseas applications, and proposed immobilization requirements for heterogeneous waste to be applied in Korea. IAEA safety standards, domestic laws, and waste acceptance criteria were reviewed. The status of heterogeneous waste immobilization in countries such as the United States, France, and Spain was reviewed. Most countries treat heterogeneous waste by encasing it in concrete, and impose immobilization requirements on this concrete. Based on these data, safety standards for the thickness, compressive strength, and diffusion limit of this concrete material were proposed as immobilization requirements for heterogeneous waste disposal in Korea. Quantitative values for the above requirements need to be derived through quantitative assessments based on the characteristics of domestic heterogeneous waste and disposal facilities.

Various dry active wastes (DAWs) have been accumulated in nuclear power plants since the DAWs are mostly combustible. KAERI has developed a thermochemical treatment process for the used decontamination paper as an operational waste to substitute for incineration process and to decontaminate radionuclides from the DAWs. The thermochemical process is composed of thermal decomposition in a closed vessel, chlorination of carbonated DAWs, separation of soluble chlorides captured in water by hydroxide precipitation, and immobilization of the precipitate. This study examined the third and fourth steps in the process to immobilize Co-60 by fabricating a stable wasteform. Precipitation behaviors were investigated in the chloride solution by adding 10 M KOH. It was shown that the precipitates were composed of Mg(OH)2 and Al(OH)3. Then, the glass-ceramic wasteform for the precipitates were produced by adding additive mixtures in which silica and boron oxide were blended with various ratios. The wasteform was evaluated in terms of volume reduction ratio, bulk density, compressive strength, and leachability.

Radioactive cesium is a heat generated and semi-volitile nuclide in spent nuclear fuel (SNF). It is released gasous phase by head-end treatment which is a pretreatment of pyroprocessing. One of the capturing methods of gasous radioactive cesium is using zeolite. After ion-exchanged zeolite, it is transformed to ceramic waste form which is durable ceramic structure by heat treatment. Various ceramic wasteforms for Cs immobilization have been researched such as cesium aluminosilicate (CsAlSi2O6), cesium zirconium phosphate (CsZr2(PO4)3), cesium titanate (CsxAlxTi8-xO16, Cs2TiNb6O18) and CsZr0.5W1.5O6. The cesium pollucite is composed to aluminosilicate framework and cesium ion incorporated in matrix materials lattices. Many researchers are reported that the pollucite have high chemical durability. In this study, the Cesium pollucite was fabricated using mixtures of aluminosilicate denoted Absorbent product (AP) and Cs2CO3 by calcination and pelletized by cold pressing. The characterization of fabricated pollucite powder and pellets was analyzed by XRD, TGA, SEM, SEMEDS and XRF. The chemical durability of pollucite powder was evaulated by PCT-A and ICP-MS and OES. Thus, the optimal pressure condition without breaking the pellets which is low Cs2O/AP ratio and pelletizing pressure was selected. The long-term leaching test was performed using MCC-1 method for 28 days with the fabricated pollucite pellets. The leachate of leaching test was allard groundwaster and Deionized water and replaced 5 contact periods which is 3 hours, 3 days, 7 days, 14 days and 28 days and analyzed by ICPMS. The leaching rate was shown two stages. The first stage was rapid and relatively large amount of nuclides were leached. The leaching rate was decreased in the second stage. The fractional release rate of this study was shown same trend. These results were similar to previous studies.

Radioactive carbon, C-14, can be generated by the neutron capture reaction of O-17 during the nuclear power plant operation. Since C-14 is classified as an intermediate level waste radionuclide, it is required that an effective separation process for C-14. C-14 is mainly absorbed on activated carbon in the air cleanup system. Therefore, the main generation source of C-14 during the nuclear power plant decommissioning is spent activated carbon. KAERI has been developing the treatment of spent activated carbon. In this process, C-14 can be desorbed as a gaseous oxide form from the spent activated carbon at high-temperature vacuum conditions. This radioactive carbon dioxide can be captured into alkaline earth metal incorporated glass and can be transformed into carbonate form. However, the carbonate (e.g. CaCO3 and SrCO3) is dispersive. When the radioactive carbonates are disposed into a geological repository, they should be immobilized to remove future uncertainty. This study examined the stabilization/immobilization of the radioactive carbonates by the cement hydration process. Cement wasteform incorporated with calcium carbonate and strontium carbonate was produced under various waste loading (e.g. 20wt%, 40wt%, and 60wt% of CaCO3 and SrCO3, respectively). Then we evaluated mechanical and chemical durability by measuring compressive strength and leachability according to standard test methods specified in the waste acceptance criteria of the Gyeongju low and intermediate level waste repository (WAC-SIL-2022-1). Also, microstructure and thermal characteristics were investigated by SEM-EDS and TGA analysis.

Immobilization of radioactive borate waste containing a high boron concentration using cement waste form has been challenged because the soluble borate phase such as boric acid reacts with calcium compounds, hindering the hydration reaction in cement waste form. Metakaolin-based geopolymer waste form which has a pure aluminosilicate system without calcium can be a promising alternative for the cement; however, secondary B-O-Si networks are formed by a reaction between borate and silicate, resulting in poor mechanical characteristics such as low compressive strength and final setting retardation. Thus, it is important to optimize the Si/Al molar ratio and curing temperature which are critical parameters of geopolymer waste form to increase borate waste loading and enhance the durability of geopolymer. Here, metakaolin-based geopolymer waste form to immobilize simulant radioactive borate waste was fabricated by varying the Si/Al molar ratio and curing temperature. The 7 days-compressive strength results reveals that the Si/Al molar ratio of 1.4 and curing at 60°C is advantageous to achieving high waste loading (30wt%). In addition, geopolymer waste forms with the highest borate waste loading exceeded the 3.445 MPa after the waste form acceptance criteria such as thermal cycling, gamma irradiation, and water immersion tests. The leachability index of boron was 7.56 and the controlling leaching mechanism was diffusion. The thermal cycling and gamma irradiation did not significantly change the geopolymer structure. The physically incorporated borate waste was leached out from geopolymer waste form during leaching and water immersion tests. Considering these results, metakaolin-based geopolymer waste form with a low Si/Al ratio is a promising candidate for borate waste immobilization, which has been difficult using cement.