Geopolymer, also known as alkali aluminum silicate, is used as a substitute for Portland cement, and it is also used as a binder because of its good adhesive properties and heat resistance. Since Davidovits developed Geopolymer matrix composites (GMCs) based on the binder properties of geopolymer, they have been utilized as flame exhaust ducts and aircraft fire protection materials. Geopolymer structures are formed through hydrolysis and dehydration reactions, and their physical properties can be influenced by reaction conditions such as concentration, reaction time, and temperature. The aim of this study is to examine the effects of silica size and aging time on the mechanical properties of composites. Commercial water glass and kaolin were used to synthesize geopolymers, and two types of silica powder were added to increase the silicon content. Using carbon fiber mats, a fiber-reinforced composite material was fabricated using the hand lay-up method. Spectroscopy was used to confirm polymerization, aging effects, and heat treatment, and composite materials were used to measure flexural strength. As a result, it was confirmed that the longer time aging and use of nano-sized silica particles were helpful in improving the mechanical properties of the geopolymer matrix composite.

The need for the development of sustainable, efficient, and green radioactive waste disposal methods is emerging with the saturation of spent nuclear waste storage facilities in the Republic of Korea. Conventional radioactive waste management methods like using cement or glass have drawbacks such as high porosity, less chemical stability, high energy consumption, carbon dioxide production, and the generation of secondary wastes, etc. To address this gigantic issue of the planet, we have designed a study to explore the potential of alternative materials having easy processability, low carbon emissions and more chemical stability such as ceramic (hydroxyapatite, HAP) and alkali-activated materials (geopolymers, GP) to capture the simulated radioactive cobalt ions from the contaminated water and directly solidify them at low temperatures. Physical and mechanical properties of HAP alone and 15wt% GP incorporated HAP (HAP-GP- 15) composite were studied and compared. The surface of both materials was fully sorbed with an excess amount of Co(II) ions in the aqueous system. Co(II) sorbed powders were separated from aqueous media using a centrifuge machine operating at 5,000 RPM for 10 minutes and dried at 100°C for 8 hours. The dried powders were then placed in stainless steel molds, and shaped into cylindrical pellets using a uniaxial press at a pressure of 1 metric ton for 1 minute. The pellets were sintered at 1,100°C for 2 hours at a heating rate of 10°C/min. Following this, the water absorption, density, porosity, and compressive strength of the polished pellets were measured using standard methods. Results showed that HAP has a greater potential for decontamination and solidification of Co(II) due to its higher density (2.65 g/cm3 > 1.90 g/cm3), less open porosity (16.2±2.9% < 42.4 ±0.9%) and high compressive strength (82.1±10.2 MPa > 6.9±0.8 MPa) values at 1,100°C compared to that of HAP-GP-15. Nevertheless, further study with different constituent ratio of HAP and GP at various temperatures is required to fully optimize the HAP-GP matrix for waste solidifications.

The immobilization of low- and intermediate-level radioactive waste (LILW) is crucial for its final disposal in repositories. While cementitious waste forms have conventionally been used for immobilizing various LILWs, they suffer from several issues, including poor durability, low resistance to leaching, and limited waste loading capacity. As an alternative, alkali or acid-activated geopolymer waste forms have garnered global attention. Unlike cementitious waste forms, geopolymer waste forms exhibit excellent physicochemical characteristics due to their three-dimensional amorphous structure and low calcium content. In this work, we provide an overview of geopolymer waste form research being conducted in countries such as Japan, the United Kingdom, the European Union, and South Korea. We specifically focus on the immobilization of soil waste, spent ion exchange resins, organic liquid waste, and evaporator concentrate (borate waste). We also identify the factors influencing the physicochemical characteristics of geopolymer waste forms and their immobilization performance. We propose a guide for optimizing the molar mixing formulations of geopolymer waste forms, including the selection of appropriate precursor materials. Additionally, we discuss the future prospects and significant challenges in the field of geopolymer waste forms that need to be addressed for their application in radioactive waste management.

The sustainability of the nuclear power industry hinges increasingly on the safe, long-term disposal of radioactive waste. Despite significant innovations and advancements in nuclear fuel and reactor design, the quest for a permanent solution to handle accumulating radioactive waste has received comparatively less attention. Conventionally, two widely recognized solidification methods, namely cementation for low and intermediate-level waste and vitrification for high-level waste, have been favored due to their simplicity, affordability, and availability. Recently, geopolymers have emerged as an appealing alternative, gaining attention for their minimal carbon footprint, robust chemical and mechanical properties, cost-effectiveness, and capacity to immobilize a broad spectrum of radionuclides, including radioactive organic compounds. This study delves into the synthesis of metakaolin-based geopolymers tailored for the immobilization of fission products like cesium (Cs) and molybdenum (Mo). The investigation unfolded in two key steps. In the initial step, we optimized the alkali content to prevent the occurrence of efflorescence, a potential issue. Remarkably, as the Na2O/Al2O3 ratio increased from 0.82 to 1.54, we observed significant enhancements in both compressive strength (11.45 to 27.07 MPa) and density (up to 2.23 g/cm3). This suggests the importance of careful adjustment in achieving the desired geopolymer characteristics. The second phase involved the incorporation of 2wt% of Cs and Mo, both individually and as a mixture, into the geopolymer matrix. We prepared the GP paste, which was poured into cylindrical molds and cured at 60°C for one week. To scrutinize the crystallinity, phase purity, and bonding type of the developed matrix, we employed XRD and FTIR techniques. Additionally, we conducted standard compressive strength tests (following ASTM C39/C39M-17b) to assess the stacking durability and robustness of the developed waste form, vital for storage, handling, transportation, and disposal in a deep geological repository. Furthermore, to evaluate the chemical durability, diffusivity and leaching of the GP waste matrix, we employed the ASTM standard Product Consistency Test (PCT: C 1285-02) and American nuclear society’s devised leaching test (ANS 16.1). It is noteworthy that the introduction of Cs and Cs/Mo in the GP matrix led to a reduction of more than 50% and 60% in compressive strength, respectively. This outcome may be attributed to the interference of Cs and Mo with the geopolymerization process, potentially causing the formation of new phases. However, it is crucial to emphasize that both developed matrices exhibited an acceptable normalized leaching rate of less than 10-5 g·m-2·d-1. This finding underscores the promising potential of the GP matrix for the immobilization of cationic and anionic radioactive species, paving the way for more sustainable nuclear waste management practices.

The homogeneity of radioactive spent ion exchange resins (IERs) distribution inside waste form is one of the important characteristics for acceptance of waste forms in long-term storage because heterogenous immobilization can lead to the poor structural stability of waste form. In this study, the homogeneity of metakaolin-based geopolymer waste form containing simulant IERs was evaluated using a laser-induced breakdown spectroscopy (LIBS) and statistical approach. The cation-anion mixed IERs (IRN150) were used to prepare the simulant spent IERs contaminated by non-radioactive Cs, Fe, Cr, Mn, Ni, Co, and Sr (0.44, 8.03, 6.22, 4.21, 4.66, 0.48, and 0.90 mg/g-dried IER, respectively). The K2SiO3 solution to metakaolin ratio was kept constant at 1.2 and spent IERs loading was 5wt%. For the synthesis of homogeneous geopolymer waste form, spent IERs were mixed with K2SiO3 solution and metakaolin first, and then the fresh mixture slurry was poured into plastic molds (diameter: 2.9 cm and height: 6.0 cm). The heterogeneous geopolymer waste form was also fabricated by stacking two kinds of mixtures (8wt% IERs loading in bottom and 2wt% in top) in one mold. Geopolymers were cured for 7d (1d at room temperature and 6d at 60°C). The hardened geopolymers were cut into top, middle, and bottom parts. The LIBS spectra and intensities for Cs were obtained from the top and bottom of each part. Cs was selected for target nuclide because of its good sensitivity for measurement. Shapiro-Wilk test was performed to determine the normality of LIBS data, and it revealed that data from the homogeneous sample is normal distribution (p-value = 0.9246, if p-value is higher than 0.05, it is considered as normal distribution). However, data from the heterogeneous sample showed abnormal distribution (p-value = 7.765×10-8). The coefficient of variation (CoV) was also calculated to examine the dispersion of data. It was 31.3% and 51.8% from homogeneous and heterogeneous samples, respectively. These results suggest that LIBS analysis and statistical approaches can be used to evaluate the homogeneity of waste forms for the acceptance criterion in repositories.

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.

본 논문에서는 지오폴리머의 상변화를 관찰하기 위하여 나노인덴테이션 데이터를 가우시안 믹스쳐 모델로 분석하는 방법을 제시 하였다. 지오폴리머는 일반 시멘트 대비 CO2 발생량을 줄일 수 있어 시멘트 대체 재료로써 많은 연구가 이루어지고 있다. 기존 연구들 로부터 최적의 실리콘/알루미늄 비율을 찾았으나 1.8 초과에서 압축강도 저하의 원인은 아직 불분명하다. 본 연구에서는 실리콘/알루 미늄 비율이 재료에 미치는 영향을 조사하고자 나노인덴테이션 실험을 수행하였다. 실험 결과를 가우시안 믹스쳐 모델로 상분석하였 고, 실리콘/알루미늄 비율이 증가할수록 재료가 균질거동을 하는 것을 관찰할 수 있었다. 본 연구결과는 강도저하를 규명하는데 직접 적인 근거로 활용될 수 있을 것으로 기대된다.

Two waste forms, namely cement and geopolymer, were investigated and tested in this study to solidify the corrosive sludge generated from the surface and precipitates of the tubes of steam generators in nuclear power plants. The compressive strength of the cement waste form cured for 28 days was inversely proportional to waste loading (24.4 MPa for 0wt% to 2.7 MPa for 60wt%). The corrosive sludge absorbed the free water in the hydration reaction to decrease the cementation reaction. When the corrosive sludge waste loading increased to 60wt%, the cement waste form showed decreased compressive strength (2.7 MPa), which did not satisfy the acceptance criteria of the repository (3.45 MPa). Meanwhile, the compressive strength of the geopolymer waste form cured for 7 days was proportional to waste loading (23.6 MPa for 0wt% to 31.9 MPa for 40wt%). The corrosive sludge absorbed the free water in the geopolymer when the water content decreased, such that a compact geopolymer structure could be obtained. Consequently, the geopolymer waste forms generally showed higher compressive strengths than cement waste forms.