• Nuclear Engineering and Technology
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• v.38 no.6
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• pp.459-482
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• 2006

A geochemical approach to the long-term safety of waste disposal is discussed in connection with the significance of actinides, which shall deliver the major radioactivity inventory subsequent to the relatively short-term decay of fission products. Every power reactor generates transuranic (TRU) elements: plutonium and minor actinides (Np, Am, Cm), which consist chiefly of long-lived nuclides emitting alpha radiation. The amount of TRU actinides generated in a fuel life period is found to be relatively small (about 1 wt% or less in spent fuel) but their radioactivity persists many hundred thousands years. Geological confinement of waste containing TRU actinides demands, as a result, fundamental knowledge on the geochemical behavior of actinides in the repository environment for a long period of time. Appraisal of the scientific progress in this subject area is the main objective of the present paper. Following the introductory discussion on natural radioactivities, the nuclear fuel cycle is briefly brought up with reference to actinide generation and waste disposal. As the long-term disposal safety concerns inevitably with actinides, the significance of the aquatic actinide chemistry is summarized in two parts: the fundamental properties relevant to their aquatic behavior and the geochemical reactions in nanoscopic scale. The constrained space of writing allows discussion on some examples only, for which topics of the primary concern are selected, e.g. apparent solubility and colloid generation, colloid-facilitated migration, notable speciation of such processes, etc. Discussion is summed up to end with how to make a geochemical approach available for the long-term disposal safety of nuclear waste or for the performance assessment (PA) as known generally.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.996-1002
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• 1999

The oxalate precipitation of lanthanide and actinide by oxalic acid was investigated in the simulated radioactive liquid waste, which was composed of 17 elements of alkali, alkaline earth(Cs, Rb, Ba, Sr), transition metal(Zr, Fe, Mo, Ni, Pd, Rh), lanthanide(La, Y, Nd, Ce, Eu) and actinide(Np, Am) in nitric acid solution. The effect of concentrations of nitric acid and ascorbic acid on the precipitation yield of each element in the simulated solution was examined at 0.5 M oxalic acid concentration. The precipitation yields of the elements were usually decreased with nitric acid concentration, nevertheless, the precipitation yields of lanthanide and actinide were more than 99%. Palladium was precipitated due to the reduction of Pd(II) into Pd metal by the addition of ascorbic acid in the oxalate precipitation and then, the precipitation yields of Mo, Fe, Ni, Ba decreased by 10~20% with concentration of ascorbic acid. The reductive precipitation of Pd(II) into Pd metal by the addition of ascorbic acid into the simulated radwaste occurred at below 1 M nitric acid concentration and its yield showed maximum at the ascorbic acid concentration of 0.01~0.02 M. The hydrazine suppressed the reductive precipitation of Pd by the ascorbic acid.

• Journal of the Mineralogical Society of Korea
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• v.15 no.1
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• pp.78-84
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• 2002

New pyrochlore-type phases($A_2$$B_2$$O_{7}$) were synthesized in the systems: CaO-C$eO_2$-T$iO_2$, CaO-$UO_2$(T$hO_2$)-Z$rO_2$, CaO-$UO_2$(T$hO_2$)-$Gd_2$$O_3$-T$iO_2$-Z$rO_2$, 및 CaO-T$hO_2$-S$nO_2$. The starting materials were pressed with the pressure of 200~400 MPa and sintered at 1500~ 155$0^{\circ}C$ for 4~8 hours in air and at 1300~ 135$0^{\circ}C$ for 5 ~50 hours under oxygen atmosphere. The products were characterized using XRD, SEM/EDS and TEM. In the bulk compositions of CaCe$Ti_2$$O_{7}$, CaTh$Zr_2$$O_{7}$,($Ca_{0.5}$ Gd$Th_{0.5}$)(ZrTi)$O_{7}$) ($Ca_{0.5}$Gd$Th_{0.5}$)(ZrTi)$O_{7}$, ($Ca_{0.5}$G$dU_{0.5}$)(ZrTi)$O_{7}$ and CaTh$Sn_2$$O_{7}$ , pyrochlore was the major phase, together with other oxide phase $of_2$$O_{7}$ fluorite structure. In the samples with target compositions CaU$Zr_2$$O_2$및 $Ca_{0.5}$ G$dU_{0.5}$)$Zr_2$T$iO_{7}$ pyrochlore was not identified, but a fluorite-structured phase was detected. The formation factor as the stable phase depended on crystal chemical characteristics of the actinide and lanthanide elements of the system concerned.

• Nuclear Engineering and Technology
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• v.43 no.4
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• pp.329-334
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• 2011

Two conceptual flowsheets were developed for recycling used nuclear fuel. One flowsheet was developed for recycling used oxide nuclear fuel from light water reactors while the other was developed for recycling used metal fuel from fast spectrum reactors. Both flowsheets were developed from a set of design principles including efficient actinide recovery, nonproliferation, waste minimization and commercial viability. Process chemistry is discussed for each unit operation in the flowsheet.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.3
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• pp.369-376
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• 2018

The ability to recover the nearly limitless supply of uranium contained within the world's oceans would provide supply security to uranium based fuel cycles. Therefore, in addition to U.S. national laboratories conducting R&D on a system capable of harvesting seawater uranium, a number of collaborative university partners have developed alternative technologies to complement the national laboratory scheme. This works summarizes the systems analysis of such novel uranium recovery technologies along with their potential impacts on seawater uranium recovery. While implementation of some recent developments can reduce the cost of seawater uranium by up to 30%, other researchers have sought to address a weakness while maintaining cost competitiveness.

• Nuclear Engineering and Technology
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• v.53 no.2
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• pp.603-610
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• 2021

The major drawback of zirconia-based materials, in view of their applications as targets for minor actinide transmutation, is their poor thermal conductivity. The addition of MgO, which has high thermal conductivity, to zirconia-based materials is expected to improve their thermal conductivity. On these grounds, the present study aims at phase characterization and thermophysical property evaluation of neodymium-substituted zirconia (Zr_0.8Nd_0.2O_1.9; using Nd₂O₃ as a surrogate for Am₂O₃) and its composites with MgO. The composite was prepared by a solid-state reaction of Zr_0.8Nd_0.2O_1.9 (synthesized by gel combustion) and commercial MgO powders at 1773 K. Phase characterization was carried out by X-ray diffraction and the microstructural investigation was performed using a scanning electron microscope equipped with energy dispersive spectroscopy. The linear thermal expansion coefficient of Zr_0.8Nd_0.2O_1.9 increases upon composite formation with MgO, which is attributed to a higher thermal expansivity of MgO. Similarly, specific heat also increases with the addition of MgO to Zr_0.8Nd_0.2O_1.9. Thermal conductivity was calculated from measured thermal diffusivity, temperature-dependent density and specific heat values. Thermal conductivity of Zr_0.8Nd_0.2O_1.9-MgO (50 wt%) composite is more than that of typical UO₂ fuel, supporting the potential of Zr_0.8Nd_0.2O_1.9-MgO composites as target materials for minor actinides transmutation.

• Nuclear Engineering and Technology
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• v.52 no.5
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• pp.1013-1021
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• 2020

A combination of simultaneous thermal analysis, evolved gas analysis and non-ambient XRD techniques was used to characterise and investigate the conversion reactions of ammonium uranates into uranium oxides. Two solid phases of the ternary system NH₃ - UO₃ - H₂O were synthesised under specified conditions. Microspheres prepared by the sol-gel method via internal gelation were identified as 3UO₃·2NH₃·4H₂O, whereas the product of a typical ammonium diuranate precipitation reaction was associated to the composition 3UO₃·NH₃·5H₂O. The thermal decomposition profile of both compounds in air feature distinct reaction steps towards the conversion to U₃O₈, owing to the successive release of water and ammonia molecules. Both compounds are converted into α-U₃O₈ above 550 ℃, but the crystallographic transition occurs differently. In compound 3UO₃·NH₃·5H₂O (ADU) the transformation occurs via the crystalline β-UO₃ phase, whereas in compound 3UO₃·2NH₃·4H₂O (microspheres) an amorphous UO₃ intermediate was observed. The new insights obtained on these uranate systems improve the information base for designing and synthesising minor actinide-containing target materials in future applications.

• Applied Chemistry for Engineering
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• v.8 no.6
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• pp.1006-1013
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• 1997

This study was carried out to elucidate the chemical characteristics of mutual separation for Am and Eu, which were selected as a stand-in from minor actinide and rare earth elements, by solvent extraction with di-(2-ethylhexyl)phosphoric acid containing zirconium at batch system. As results, 92.3% of Am and 99.1% of Eu were coextracted with 1M DEHPA/n-dodecane containing zirconium (Zr $concentration=8.7g/{\ell}$) at 0.5M $HNO_3$ in the extraction step. The extraction yields of Am and Eu were proportionally increased with the concentration of Zr in Zr salt of 1M DEHPA/n-dodecane having the synergistic effect. In the lst stripping step for the selective separation of Am, 38.1% of Am and 3% of Eu were stripped with the mixed solution of 0.05M DTPA and 1M lactic acid adjusted pH of 3.0. At that time, the separation factor calculated from the distribution coefficients of Am and Eu was 14.2. In the 2nd Stipping step to remove the Eu remained the organic phase after the lst stripping step, 94.4% 0f Eu was stripped into aqueous phase with 6M $HNO_3$.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.4
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• pp.397-410
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• 2018

When considering the long-term safety assessment of spent-nuclear fuel management, americium is one of the most radio-toxic actinides. Although spectroscopic methods are widely used for the study of actinide chemistry, application of those methods to americium chemistry has been limited. Herein, we purified $^{241}Am$ to obtain a highly pure stock solution required for spectroscopic studies. Quantitative and qualitative analyses of purified $^{241}Am$ were carried out using liquid scintillation counting, and gamma and alpha radiation spectrometry. Highly sensitive absorption spectrometry coupled with a liquid waveguide capillary cell and time-resolved laser fluorescence spectroscopy were employed for the study of Am(III) hydrolysis and oxalate (Ox) complexation. $Am^{3+}$ ions under acidic conditions exhibit maximum absorbance at 503 nm, with a molar absorption coefficient of $424{\pm}8cm^{-1}{\cdot}M^{-1}$. $Am(OH)_3(s)$ colloidal particles formed under near neutral pH conditions were identified by monitoring the absorbance at around 506-507 nm. The formation of ${Am(Ox)_3}^{3-}$ was detected by red-shifts of the absorption and luminescence spectra of 4 and 5 nm, respectively. In addition, considerable enhancements of the luminescence intensities were observed. The luminescence lifetime of ${Am(Ox)_3}^{3-}$ increased from 23 to 56 ns, which indicates that approximately six water molecules are replaced by carboxylate ligands in the inner-sphere of the Am(III). These results suggest that ${Am(Ox)_3}^{3-}$ is formed through the bidentate coordination of the oxalate ligands.