처분장에서 지하수로 쉽게 유출될 수 있는 방사성 핵종들의 양을 예측하기 위하여 국내 PWR 사용후핵연료 팰렛들의 갭(gap) 및 입계에 있는 용해성 원소들의 재고량을 측정하였다. 연소도가 GWD/MTU를 갖는 연료봉에서 얻은 펠렛들에서 세슘의 갭 재고량이 로 나타났으며, 이는 핵분열 생성기체 유출률의 에 해당하였다. 그러나 핵분열 생성기체 유출 률이 1%이하인 연료봉에서 취한 40 GWD/MTU이하의 연소도를 갖는 펠렛들의 경우, 세슘의 갭 재고량들을 핵분열 생성기체 유출률과 연관시키기는 곤란하였다. 갭 및 입계내 스트론튬의 재고량은 동일 연료봉내 펠렛에서는 크게 다르지 않았으며, 요오드의 갭 재고량은 핵분열 생성기체 유출률보다 작거나 유사한 값을 갖는 것으로 평가되었다.

Isotopes of alkali and alkaline earth metals (AM and AEM) are the main contributors to the heat load and the radiotoxicity of spent fuel (SF) . These components are separated from the SF and dissolved in a molten LiCl in an electrolytic reduction process. A mass transfer model is developed to describe the diffusion behavior of Cs, Sr, and Ba in the SF into the molten salt. The model is an analytical solution of Fick's second law of diffusion for a cylinder which is the shape of a cathode in the electrolytic reduction process. And the model is also applied to depict the concentration profile of the oxygen ion which is produced by the electrolysis of LiO. The regressed diffusion coefficients of the model correlating the experimentally measured data are evaluated to be greater in the order of Ba, Cs, and Sr for the metal ions and the diffusion of the oxygen ion is slower than the metal ions which implies that different mechanisms govern the diffusion of the metal ions and the oxygen ions in a molten LiCl.

국내 포항 소재 R사의 구룡포산 천연 제올라이트의 물리·화학적 특성을 규명하기 위해 X-선 회절 분석, X-선 형광 분석, 열 시차·열 중량 분석, 양이온 교환능 분석 및 세슘(Cs), 스트론튬(Sr) 흡착 실험을 수행하였다. X- 선 회절 분석 결과 모데나이트, 휼란다이트, 클라이놉티로라이트 및 일라이트와 같은 광물이 함유되어 있으며, X- 선 형광 분석 결과 SiO2, Al2O3, CaO, K2O, MgO, Fe2O3 및 Na2O 원소가 함유되어 있었다. 양이온 교환능은 148.6 meq/100 g이었으며 열시차 및 열중량 분석 결과 600℃까지 열적으로 안정성이 우수한 것을 확인하였다. 시 간에 따른 흡착 평형 실험 결과 세슘(Cs)의 경우 30분이내 스트론튬(Sr)의 경우 8시간이내에 평형에 도달하였으며 세슘(Cs) 및 스트론튬(Sr)의 흡착률은 각각 80% 및 18%를 보이고 있었다. 단일 성분 등온 흡착 실험 결과 Langmuir model에 부합하였으며 세슘(Cs) 최대 흡착량은 131.5 mg/g으로 높게 나타났으며 반면 스트론튬(Sr) 최 대 흡착량은 29.5 mg/g로 낮은 흡착량을 나타내었다. 본 연구에 사용된 천연 제올라이트의 경우 클라이놉티로라 이트, 휼란다이트 및 모데나이트와 같은 8-ring을 포함하는 광물의 함량이 높아 세슘(Cs)에 대한 높은 선택성을 보 여주고 있다.

본 연구는 합성 모데나이트(Na6.6Al6.6Si41.4O96·20.4H2O, Na-MOR)를 이용한 다양한 중금속의 포획 연 구를 하기 위한 기초 단계로, 고분해능 X-선 분말 회절을 이용하여 치환체의 격자상수 및 부피 변화를 이해 하기 위한 목적으로 실험을 진행하였다. 열중량 분석법(Thermogravimetric analysis, TGA)으로 측정한 결과, 1가 양이온 치환체(Cs-MOR, Na-MOR)는 단위포 당 19.4, 20.4개의 물분자가 존재하였으며, 2가 양이온 치환 체(Pb-MOR, Sr-MOR, Cd-MOR)는 단위포 당 21, 23.1, 23.2개가 존재하는 것을 확인하였다. 측정한 모든 물 질은 사방정계에 속하는 Cmcm의 공간군을 가지는 것으로 확인할 수 있었다. 치환 전 물질인 Na-MOR과 비 교했을 때, 치환체의 (110)면과 (200)면의 회절강도가 명확하게 변화하였으나, 전체적인 피크의 위치는 거의 유사하게 나타나는 것을 확인할 수 있었다. 또한 Na-MOR에서는 확인이 되지 않았던 (220)면의 피크가 Pb-, Cd-, Sr-MOR에서 뚜렷하게 관찰되었다. 이를 통해서 양이온 치환에 따른 원자들의 분포 변화가 주로 ab-평 면상에서 나타나지만, 격자상수의 변화는 미세할 것으로 짐작할 수 있었다. Whole profile fitting 방법을 사용 하여 치환된 모데나이트의 미세한 격자상수의 변화를 관찰하였다. 치환체의 격자상수 및 격자부피의 변화는 치환된 양이온의 반경 및 전하수에 따라 서로 다른 경향성을 보였다. 1가 양이온의 경우, 이온반경이 증가할 수록 a-축의 길이는 증가하지만, 반면에 b- 및 c-축의 길이는 감소하였다. 2가 양이온의 경우, 이온반경이 증 가할수록 대체적으로 a-축의 길이가 감소하고, b- 및 c-축의 길이는 증가하였다. 격자부피는 1가 또는 2가 양 이온 치환체들이 각각 독립된 경향성을 가지며, 이온반경에 따라 증가하는 것을 확인할 수 있었다.

Zeolitic material, Z-Y3, was synthesized from coal fly ash (CFA) under low-alkaline conditions (NaOH/CFA ratio = 0.3 and NaOH solution concentrations of 0.0, 0.5, and 1.0 M) using a fusion/hydrothermal method. The adsorption capacities of the fabricated Z-Y3 samples for Cs and Sr ions and the desorption capacity of Na ions were evaluated. The XRD patterns of the Z-Y3 sample fabricated using a 1.0 M NaOH solution (Z-Y3 (1.0 M)) indicated the successful synthesis of a zeolitic material, because the diffraction peaks of Z-Y3 coincided with those of the Na-A zeolite in the 2θ range of 7.18-34.18. Moreover, the SEM images revealed that morphology of the Z-Y3 (1.0 M) sample, which presented zeolitic materials characteristics, consisted of sharp-edged cubes. The adsorption isotherms of Cs and Sr ions on all the fabricated Z-Y3 samples were described using the Langmuir model, and the maximum adsorption capacities of Cs and Sr were calculated to be 0.14-0.94 mmol/g and 0.19-0.78 mmol/g, respectively. The desorption of Na ions from the Cs and Sr ions adsorbed Z-Y3 samples followed the Langmuir desorption model. The maximum desorption capacities of Na ions from the Cs and Sr ions adsorbed Z-Y3 (1.0 M) samples were 1.28 and 1.49 mmol/g, respectively.

A zeolitic material (Z-Y2) was synthesized from Coal Fly Ash (CFA) using a fusion/hydrothermal method under low-alkali condition (NaOH/CFA = 0.6). The adsorption performance of the prepared zeolite was evaluated by monitoring its removal efficiencies for Sr and Cs ions, which are well-known as significant radionuclides in liquid radioactive waste. The XRD (X-ray diffraction) patterns of the synthesized Z-Y2 indicated that a Na-A type zeolite was formed from raw coal fly ash. The SEM (scanning electron microscope) images also showed that a cubic crystal structure of size 1~3㎼ was formed on its surface. In the adsorption kinetic analysis, the adsorption of Sr and Cs ions on Z-Y2 fitted the pseudo-second-order kinetic model well, instead of the pseudo-first-order kinetic model. The second-order kinetic rate constant (k2) was determined to be 0.0614 g/mmol·min for Sr and 1.8172 g/mmol·min for Cs. The adsorption equilibria of Sr and Cs ions on Z-Y2 were fitted successfully by Langmuir model. The maximum adsorption capacity (qm) of Sr and Cs was calculated as 1.6846 mmol/g and 1.2055 mmol/g, respectively. The maximum desorption capacity (qdm) of the Na ions estimated via the Langmuir desorption model was 2.4196 mmol/g for Sr and 2.1870 mmol/g for Cs. The molar ratio of the desorption/adsorption capacity (qdm/qm) was determined to be 1.44 for Na/Sr and 1.81 for Na/Cs, indicating that the amounts of desorbed Na ions and adsorbed Sr and Cs ions did not yield an equimolar ratio when using Z-Y2.

The removal of Sr ion and Cs ion was investigated to evaluate adsorption properties by using SAN-Zeolite beads immobilized with styrene acrylonitrile (SAN). The adsorption capacities increased with the decrease of SAN/zeolite ratio (SAR) from 2.5 to 0.83. The relationship of adsorption capacity (qe) and SAR was described by experimental equation such as qe=20.88＋137.81e-1.96SAR (r2=0.9980). The adsorption kinetics of Sr ion and Cs ion with SAN-Zeolite beads were fitted well by the pseudo-second-order model. The maximum adsorption capacities of Sr ion and Cs ion calculated from Langmuir isotherm model were 66.97 mg/g and 81.97 mg/g, respectively.

PVC-Zeolite composite was prepared by immobilizing zeolite with polyvinyl chloride (PVC). The prepared PVC-Zeolite beads were characterized by using X-ray diffractometer (XRD), fourier transform infrared spectrometer (FTIR), thermo gravimetric analyzer (TGA), and scanning electron microscopy (SEM). The removal properties of Sr and Cs ions from aqueous solution were investigated in batch experiment. The removal efficiencies of Sr and Cs ions by the PVC-Zeolite beads were dependent on the initial pH of solution. The removal efficiencies sharply increased at below pH 4 and was kept constant at pH 4 or more. The adsorption kinetics of Sr and Cs ions by the PVC-Zeolite beads were fitted well by the pseudosecond- order model (r2>0.99) more than pseudo-first-order model. The maximum adsorption capacities of Sr and Cs ions calculated from Langmuir isotherm model were 39.37 mg/g and 55.87 mg/g, respectively.

The adsorption characteristics of Sr and Cs ions were investigated by using PS-zeolite beads prepared by immobilizing zeolite with polysulfone (PS). The adsorption kinetics of Sr and Cs ions by PS-zeolite beads was described well by the pseudo-second-order model. The maximum adsorption capacities of Sr and Cs ions calculated from Langmuir isotherm model were 65.0 mg/g and 76.4 mg/g, respectively. In the binary system of Sr ion and Cs ion, the adsorption capacities of each ion decreased with increasing mole ratio of mixed counterpart ion, and Cs ion showed the higher hinderance than Sr ion. We found that thermodynamic properties of Sr and Cs ions on absorption reaction were spontaneous and endothermic at 293 to 323 K.

The adsorption characteristics of Sr ions and Cs ions in single and binary solution by zeolite A were investigated in batch experiment. The adsorption rate of Sr ions and Cs ions by zeolite A obeyed pseudo-second-order kinetic model in single and binary solution. The initial adsorption rates (h) and adsorption capacities of both ions obtained from pseudo-second-order kinetic model, and the values were decreased with increasing concentration of the competitive ions (0~1.5 mM). Also, adsorption isotherm data in binary solution were well fitted to the extended Langmuir model, the maximum adsorption capacities of Sr and Cs calculated from the model were 1.78 mmol/g and 1.64 mmol/g, respectively. The adsorption of Sr and Cs ions by zeolite A was carried out in the presence of other cations such as Na+, K+, Mg2+, and Ca2+. The results showed that the zeolite A can maintain a relatively high adsorption capacity for Sr and Cs ions and exhibits a high selectivity in the presence of competitive cations. The effect of competition had an order of Ca2+>K+>Mg2+>Na+ for Sr ions and K+>Ca2+>Na+>Mg2+ for Cs ions at the same cation concentration.

Zeolite was synthesized from power station waste, coal fly ash, as an alternative low-cost adsorbent and investigated for the removal of Sr(II) and Cs(I) ions from single- and binary metal aqueous solutions. In order to investigate the adsorption characteristics, the effects of various operating parameters such as initial concentration of metal ions, contact time, and pH of the solutions were studied in a batch adsorption technique. The Langmuir model better fitted the adsorption isotherm data than the Freundlich model. The pseudo second-order model was found more applicable to describe the kinetics of system. The adsorption capacities of Sr(II) and Cs(I) ions obtained from the Langmuir model were 1.7848 mmol/g and 0.7640 mmol/g, respectively. Although the adsorption capacities of individual Sr(II) and Cs(I) ions was less in the binary-system, the sum of the total adsorption capacity (2.3572 mmol/g) of both ions in the binary-system was higher than the adsorption capacity of individual ion in the single-system. Comparing the homogeneous film diffusion model with the homogeneous particle diffusion model, the adsorption was mainly controlled by the particle diffusion process.

The adsorption behaviors of strontium and cesium ions on fly ash, natural zeolites, and zeolites synthesized from fly ash were investigated. The zeolites synthesized from fly ash had greater adsorption capabilities for strontium and cesium ions than the original fly ash and natural zeolites. The maximum adsorption capacity of synthetic zeolite for strontium and cesium ions was 100 and 154 mg/g, respectively. It was found that the Freundlich isotherm model could fit the adsorption isotherm. The distribution coefficients (Kd) for strontium and cesium ions were also calculated from the adsorption isotherm data. The distribution coefficients decreased with increasing equilibrium concentration of strontium and cesium ions in solution. By studying the removal of cesium and strontium ions in the presence of calcium, magnesium, sodium, potassium, sulfate, nitrate, nitrite, and EDTA (in the range of 0.01 - 5 mM) it was found that these coexistence ions competed for the same adsorption sites with strontium and cesium ions.

The adsorption of Cs-137 and Sr-90 onto kaolinite in prescence of major groundwater cations (Ca2+, K+, Na+) with different concentrations was simulated by using triple-layer surface complexation model (TL-SCM). The site density (8.73 sites/nm2) of kaolinite used for TL-SCM was calculated from it's CEC and specific surface area. TL-SCM modeling results indicate that concentrations dependence on 137Cs and 90Sr adsorption onto kaolinite as a function of pH is best modeled as an outer-sphere surface reaction. This suggests that Cs+ and Sr2+ are adsorbed at the β-layer in kaolinite-water interface where the electrolytes, Nacl, KCl and CaCl2, bind. However, TL-SCM results on Sr adsorption show a discrepancy between batch data and fitting data in alkaline condition. This may be due to precipitation of SrCO3 and complexation such as SrOH+. Intrinsic reaction constants of ions obtained from model fit are as follows: Kintcs=10-2.10, KintSr=10-2.30, KintK=10-2.80, KintCa=10-3.10 and KintNa=10-3.32. The results are in the agreement with competition order among groundwater ions (K+〉Ca2+〉Na+) and sorption reference of nuclides (Cs-137〉Sr-90) at kaolinite-water interface showed in batch test.