Wide-area surface decontamination is essential during the sudden release of radioisotopes to the public, such as nuclear accidents or terrorist attacks. A spray coating composed of a reversible complex between poly (vinyl alcohol) (PVA) and phenylboronic acid-grafted poly (methyl vinyl ether-alt-mono-sodium maleate) (PBA–g–PMVE–SM) was developed to remove radioactive cesium from surfaces. The simultaneous spay of PVA and PBA–g–PMVE–SM aqueous polymer solutions containing Cs adsorbent to contaminated surfaces resulted in the spontaneous formation of a PBA–diol ester bond-based gel-like coating. The Cs adsorbent suspended in the gel-like coating selectively removed Cs-137 from the Cs-contaminated surface. The used gel-like coating were removed from surfaces by simple water rinsing. This recovery way has advantages compared with costly incineration to remove the organic materials for final disposal/storage of the radioactive waste. Thus, our spray coating is suitable for practical wide-area surface decontamination. In radioactive tests, the hydrogel containing Cs-adsorbent showed substantial Cs-137 removal efficiencies of 96.996% for painted cement and 63.404% for cement, which are 2.33 times better than the values for the commercial surface decontamination coating agent DeconGel.
Copper hexacyanoferrate (Cu-HCF), which is a type of Prussian Blue analogue (PBA), possesses a specific lattice structure that allows it to selectively and effectively adsorb cesium with a high capacity. However, its powdery form presents difficulties in terms of recovery when introduced into aqueous environments, and its dispersion in water has the potential to impede sunlight penetration, possibly affecting aquatic ecosystems. To address this, sponge-type aluminum oxide, referred to as alumina foam (AF), was employed as a supporting material. The synthesis was achieved through a dip-coating method, involving the coating of aluminum oxide foam with copper oxide, followed by a reaction with potassium hexacyanoferrate (KHCF), resulting in the in-situ formation of Cu-HCF. Notably, Copper oxide remained chemically stable, which led to the application of 1, 3, 5-benzenetricarboxylic acid (H3BTC) to facilitate its conversion into Cu-HCF. This was necessary to ensure the proper transformation of copper oxide into Cu-HCF on the AF in the presence of KHCF. The synthesis of Cu-HCF from copper oxide using H3BTC was verified through X-ray diffraction (XRD) analysis. The manufactured adsorbent material, referred to as AF@CuHCF, was characterized using Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). These analyses revealed the presence of the characteristic C≡N bond at 2,100 cm-1, confirming the existence of Cu-HCF within the AF@CuHCF, accounting for approximately 3.24% of its composition. AF@CuHCF exhibited a maximum adsorption capacity of 34.74 mg/g and demonstrated selective cesium adsorption even in the presence of competing ions such as Na+, K+, Mg2+, and Ca2+. Consequently, AF@CuHCF effectively validated its capabilities to selectively and efficiently adsorb cesium from Cs-contaminating wastewater.
The magnetic Cs adsorbent functionalized with hierarchical titanium-ferrocyanide were fabricated for the highly efficient magnetic removal of radioactive cesium from water. The new magnetic Cs adsorbent has a core–shell structure that comprises a Fe3O4 core, an interlayer of SiO2, and a titanium-ferrocyanide-shell with hierarchical nanostructure. At first, the magnetic Fe3O4 nanoparticles synthesized via a hydrothermal reaction were coated with SiO2. Then, TiO2 were coated on the surface of SiO2 coated magnetic nanoparticles. Finally, the hierarchical titanium-ferrocyanide composed of 2-dimensional TiFC flakes was fabricated on the surface of core-shell MNP@SiO2@TiO2 microparticles using a TiO2 sacrificial template via a simple reaction with potassium ferrocyanide (FC) based on the Kirkendall-type diffusion. The resulting magnetic Cs adsorbent shows higher adsorption capacity of 416 mg/g than other magnetic Cs adsorbents (below 200 mg/g) because of the increased effective surface area of hierarchical titanium-ferrocyanide. Therefore, our Magnetic Cs adsorbent functionalized with hierarchical titanium-ferrocyanide has excellent potential for the treatment of various 137Cs-contaminated sources.
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 Cesium is fission products of spent nuclear fuelwith high heat generating nuclide, having a 30 years half-life. Particularly, it is important to make stable waste form because Cs-137 have high solubility and mobility at ground water. The ceramic waste form has higher thermal and structural stability and lower solubility than glass and cement waste form. Various ceramic waste forms for Cs immobilization have been researched such as aluminosilicate (CsAlSi2O6), phosphate (CsZr2(PO4)3), titanate (CsxAlxTi8-XO16) and CsZr0.4W1.5O6. Cs pollucite is incorporated radio-Cesium to aluminosilicate framework by inorganic ion-exchange with zeolite. Therefore, it is an extremely stable structure. In previous study, we are prepared Cs pollucite pellet with various ratio of Cs precursor/matrix materials, and attempted to evaluate applicability as ceramic waste form. Cs pollucite is produced by mixing Mullite and SiO2 obtained by heat treatment Kaolinite with Cs2CO3 in ratios of 0.5, 0.6, 0.7, 0.8. Optimized ratio was 0.5 revealed single pollucite phase and the others exhibited CsAlSiO4 phase with pollucite. Cs pollucite of ratio 0.5 was pelletized under various conditions and evaluated performance as waste form. herein, the pellets were cracked on surface and edges broken. Therefore, Cs pollucite having high ratio of matrix materials contained Si and Al was prepared and pelletized, and then waste form was evaluated. The Cs pollucite powder is ratio of Cs precursor/matrix materials were 0.1, 0.2, 0.3, 0.4. Pollucite powder was mixed with 1.5, 2.0wt% Polyvinyl alcohol as binder, and dried at 70°C for overnight. Afterward, these powders obtained were pressed using punch-die apparatus at 50, 100 bar for 1 hour and the pellets with about dia. 25 mm and height 10 mm was acquired. These pellets were sintered at 1,400°C for 5 hours. Subsequently, the waste forms were evaluated physicochemical test such as compression strength, thermal conductivity, thermal expansion and leaching properties analysis.
오염수로부터 자성분리가 가능하며, 방사성 세슘을 효율적으로 제거하기 위한 코발트 페로시아나이드(cobalt ferrocyanide, CoFC) 혹은 니켈 페로시아나이드(nickel ferrocyanide, NiFC)가 도입된 자성입자 흡착제를 제조하였다. Fe3O4 나노 입자는 공침법을 이용해 제조하였고, Co2+와 Ni2+ 이온을 입자 표면에 도입시키기 위해 금속이온과 금속 배위결합(metalcoordination) 을 하는 카르복실기를 포함한 숙신산(succinic acid, SA)을 자성나노입자(magnetic nanoparticles, MNPs) 표 면에 코팅하였다. CoFC와 NiFC는 자성나노입자 표면에 도입된 Co2+ 혹은 Ni2+ 이온이 hexacynoferrate와 결합하여 형성된 다. 제조된 CoFC-MNPs 그리고 NiFC-MNPs는 각각 43.2 emu·g-1, 47.7 emu·g-1의 우수한 포화자화 값을 보여주었다. X- 선 회절분석(XRD), 퓨리에 변환 적외선 분광분석(FT-IR), 나노입자 입도 분석기(DLS), 투과전자현미경(TEM) 등의 분석을 통해 흡착제의 물성을 파악하고, 세슘에 대한 흡착 성능을 알아보았다. 흡착실험을 평가하기 위해 Langmuir/Freundlich 등 온흡착식을 이용해 실험 결과 값을 곡선맞춤 하였고, CoFC-MNPs와 NiFC-MNPs의 최대흡착량(qm)은 각각 15.63 mg·g-1, 12.11 mg·g-1이다. CoFC-MNPs와 NiFC-MNPs는 방사성 세슘에 대해서도 최저 99.09%의 제거율을 가지며, 경쟁이온의 존재에도 방사성 세슘만을 선택적으로 흡착한다.
본 연구에서는 고염/고방사성 폐액 내 함유된 주요 고방사성핵종인 Cs 제거를 목적으로 고효율의 복합 흡착제(potassium cobalt ferrocyanide (PCFC)-loaded chabazite (CHA)) 합성 및 이의 적용성을 평가하였다. 복합 흡착제는 Cs을 비롯한 다 른 입자를 수용할 수 있는 CHA를 지지체로 선정하였으며, CoCl2 및 K4Fe(CN)6 용액의 단계적인 함침/침전을 통해 PCFC를 CHA 세공 내에 고정화함으로써 합성하였다. 복합 흡착제의 합성 시 평균 입자크기가 10 ㎛ 이상의 CHA를 지지체로 사용할 경우, PCFC 입자는 안정적인 형태로 고정화되었다. 또한, 합성 시 복합 흡착제의 정제를 증가시키는 세척 방법을 최적화함으로써, 복합 흡착제의 물리적 안정성이 향상되었다. 최적의 합성법을 통해 얻은 복합 흡착제에 의한 Cs 흡착 시, 담수(무염 조건) 및 해수(고염 조건)에서 모두 빠른 흡착 속도를 보였으며, 염 농도와 무관하게 비교적 높은 분배계수 값(104 mL·g-1 이상)을 나타내었다. 그러므로, 본 연구에서 합성한 복합 흡착제는 CHA 및 PCFC가 각각 가지고 있는 물리적 안정성과 Cs 에 높은 선택성 등을 고려하여 촤적화한 소재이며, 고염/고방사성폐액에 함유되어 있는 Cs을 고효율로 신속하게 제거할 수 있음을 알 수 있다.
원자력 발전소 중대사고에 의해 방사성 세슘(137Cs)이 지하수계로 유출될 경우를 가정하여, 연구 지역의 깊이에 따른 암석매질의 특성을 규명하고 세슘의 흡착계수를 정량적으로 평가하였다. 대상지역인 신고리 원전 3, 4호기의 지하 암석매질은 주로 석영 및 장석류로 이루어진 화강암 계열이며, 운모류를 10~20% 함유하고 있다. 비교적 얕은 심도(6.3~7.4 m)의 파쇄대에서 2차 광물인 녹니석이 일부 포함되어 있었지만, 기반암에서는 거의 발견되지 않았다. 137Cs의 흡착분배계수(Kd)는 파쇄대 지역에서 약 880~960 mL/g로 기반암 지역에서의 820~840 mL/g보다 비교적 높게 나타났으며, 이는 파쇄대에 포함되어 있는 풍화생성물인 2차 광물들에 의한 영향으로 판단된다. 따라서 137Cs이 지하 매질로 유출될 경우 대부분은 천부 지역에 흡착되어 세슘에 의한 오염 확산 속도가 지연될 것이라고 예상되며, 이러한 결과는 원자력 발전소 안정성 평가인자 자료로 활용될 것으로 기대된다.