• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.4
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• pp.207-212
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• 2009

In this study, a thermal behavior of $PrCl_3$ as one of the lanthanide chlorides in LiCl-KCl molten salts was investigated in an oxidizing condition. First, a thermo-gravimetric analysis (TGA) of $PrCl_3$ was carried out by an injection of $O_2$ gas. Based on the results, an oxidation of $PrCl_3$ in the molten salts was performed by sparging $O_2$ gas with changing temperatures. According to the TGA data of $PrCl_3$, a dissociation of $PrCl_3$ occurred rapidly by about $380^{\circ}C$ and a conversion of $PrCl_3$ to $PrCl_3$ was completed at about $600^{\circ}C$. The thermal behavior of $PrCl_3$ in LiCl-KCl molten salts by sparging $O_2$ gas was similar to that of $PrCl_3$ in the TGA test, and PrOCl as a insoluble compound in the molten salts was precipitated into the bottom of the molten salts. A conversion of $PrCl_3$ to PrOCl in the molten salts occurred actively at a higher temperature than $650^{\circ}C$. And it would be possible to estimate a conversion status of $PrCl_3$ to PrOCl by measuring a $Cl_2$ concentration in a flue gas generated from an oxidation test of $PrCl_3$ in LiCl-KCl molten salts.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.4
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• pp.261-267
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• 2010

The pyrometallurgical nuclear fuel recycle process, called pyroprocessing, has been known as a promising nuclear fuel recycling technology. Pyroprocessing technology is crucial to advanced nuclear systems due to increased nuclear proliferation resistance and economic efficiency. The basic concept of pyroprocessing is group actinide recovery, which enhances the nuclear proliferation resistance significantly. One of the key steps in pyroprocessing is "electrowinning" which recovers group actinides with lanthanide from the spent nuclear fuels. In this study, a vertical cadmium distiller was manufactured. The evaporation rate of pure cadmium in vertical cadmium distiller varied from 12.3 to $40.8g/cm^2/h$ within a temperature range of 773 923 K and pressure below 0.01 torr. Uranium - cadmium alloy was fabricated by electrolysis using liquid cadmium cathode in a high purity argon atmosphere glove box. The distillation behavior of pure cadmium and cadmium in uranium - cadmium alloy was investigated. The distillation behavior of cadmium from this study could be used to develop an actinide recovery process from a liquid cadmium cathode in a cadmium distiller.

• Journal of the Korean Chemical Society
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• v.43 no.6
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• pp.628-635
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• 1999

Direct preparative method of 2,6-diformyl-p-cresol and 2-hydroxy-3-hydroxy-5-methylbenzaldehyde from 2,6-bis(hydroxymethyl)-4-methylphenol using activated $Mn(IV)O_2$ was described. Hexadentate compartmental Iigands, $H_4L[A]\;and\; H_4L[B]$ were prepared by condensation reactions of 2-hydroxy-3-hydroxy methyl-5-methylbenzaldehyde with ethylenediamine and 1,3-diaminopropane respectively. By the reaction of macrocycle($H_4[20]DOTA$) with Ln(III) nitrate {Ln(III)=Pr, Sm, Cd, Dy }, discrete mononuclear Ln(III) complexes of the type $[Ln(H_2[20]DOTA)(ClO_4)(H_2O)]\;{\cdot}\;3H_2O$ were synthesized in the solid state. $[Ln([20]DOTA)(NO_3)(H_2O)](NO_3)_2\;{\cdot}\;xH_2O$ was placed in methanol for 2 days, and $[Ln([20]DOTA)(NO_3)(CH_3OH)]^{2+}$ was formed. The equilibrium constants(K) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various auxiliary ligand, $L_a$(=salicylic acid, p-chlorobenzoic acid, benzoic acid, acetic acid, 4-bromophenol) were determined spectroscopically at 25$^{\circ}C$ and 0.1M $NaClO_4$. The K values calculated were in the order of salicylic acid > p-chlorobenzoic acid > benzoic acid > acetic acid > 4-bromophenol, while pKa of auxiliary ligands was in the opposite trend.

• Journal of the Korean Institute of Telematics and Electronics D
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• v.35D no.10
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• pp.51-59
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• 1998

($Na_{1/2}Ln_{1/2}$)$TiO_3$ceramics have a high relative dielectric constant and a positive temperature coefficient of resonant frequency ($\tau_f$)(where Ln represents a lanthanide: $La^{+3}$, $Pr^{+3}$, $Nd^{+3}$ and $Sm^{+3}$). On the other hand, $MgTiO_3$ ceramic has a high Qf value and a negative temperature coefficient. So We have investigated the microwave dielectric properties of $xMgTiO_3$-(1-x) ($Na_{1/2}Ln_{1/2}$)$TiO_3$. In these systems, there are no clues on solid-solution and secondary phase. There are mixed phases with $MgTiO_3$and ($Na_{1/2}Ln_{1/2}$)$TiO_3$ phases. Its dielectric characteristics (Qf, temperature coefficient and dielectric constant) are intermediate between ($Na_{1/2}Ln_{1/2}$)$TiO_3$ and $MgTiO_3$ and are predictable by the logarithmic mixing rule. The dielectric ceramic compositions temperature coefficient each approximates to zero at Ln=La, x=0.9, Ln=Pr, x=0.87, and Ln=Nd, x=0.84. At this time, there are Qf values in the range of 55,000 to 28,00GHz and relative dielectric constants in the range of 22 to 25.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.588-595
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• 1989

Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.19-32
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• 2010

Electrolytic reduction technology is essential for the purpose of adopting pyroprocessing into spent oxide fuel as an alternative option in a back-end fuel cycle. Spent fuel consists of various metal oxides, and each metal oxide releases an oxygen element depending on its chemical characteristic during the electrolytic reduction process. In the present work, an electrolytic reduction behavior was estimated for voloxidized spent fuel based on the assumption that each metal-oxygen system is independent and behaves as an ideal solid solution. The electrolytic reduction was considered as a combination of a Li recovery and chemical reactions between the metal oxides such as uranium oxide and the produced Li metal. The calculated result revealed that most of the metal oxides were reduced by the process. It was evaluated that a reduced fraction of lanthanide oxides increased with a decreasing $Li_2O$ concentration. However, most of the lanthanides were expected to be stable in their oxide forms. In addition, a semi-empirical model for describing $U_3O_8$ electrolytic reduction behavior was proposed by considering Li diffusion and a chemical reaction between $U_3O_8$ and Li. Experimental data was used to determine model parameters and, then, the model was applied to calculate the reduction yield with time and to estimate the required time for a 99.9% reduction.

• Journal of the Korean Chemical Society
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• v.48 no.6
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• pp.577-582
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• 2004

The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.16 no.1
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• pp.32-37
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• 2006

Rare-earth niobates, ag (Ln = Y, La, Gd) are well-known self-activated phosphors due to charge transfer in $NbO^{3-}_4$ showing a broad and strong emission band in the spectral region around 410 nm. In order to find new blue and red phosphors for FED, $LaNbO_4$ : X (X = Bi, Eu) phosphors are prepared through solid-state reactions at high temperature. The optimum reaction condition for these phosphors to give maximum emission intensity is obtained when it is first fired at $1250^{\circ}C$ for 2 h followed by second firing at $1400^{\circ}C$ for 1 h. Under irradiation at 254 nm, $1mol\%\;Bi^{3+}$ doped $LaNbO_4$ phosphor shows strong blue emission band with a range of $420\~450nm$. Also $10mol\%\;Eu^{3+}$ doped $LaNbO_4$ phosphor shows the maximum emission intensity at about 610 nm. Emission peaks at $415\~460nm$, $530\~560nm$and $570\~620nm$are observed in phosphors below $10mol\%\;Eu^{3+}$ doped $LaNbO_4$. Similar results are obtained in cathodoluminescent property of these phosphors.

• Korean Journal of Materials Research
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• v.32 no.1
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• pp.9-13
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• 2022

Bullets flying with a light from the back are called "tracers". Tracers are ignited by the combustion gas of the propellant and emit bright light that allows the shooter to visually trace the flight path. Therefore, tracers mark the firing point for allies to assist shooters to hit target quickly and accurately. Conventional tracers are constructed with a mixture of an oxidizing agent, raw metal, and organic fuel. Upon ignition, the inside of the gun can be easily contaminated by the by-products, which can lead to firearm failure during long-term shooting. Moreover, there is a fire risk such as forest fires due to residual flames at impact site. Therefore, it is necessary to develop non-combustion type luminous material; however, this material must still use the heat generated from the propellant, so-called "thermoluminescence (TL)". This study aims to compare the TL emission of Dy³⁺, La³⁺ and Ho³⁺ doped MgB₄O₇ phosphors prepared by solid state reaction. The crystal structures of samples were determined by X-ray diffraction and matched with the standard pattern of MgB₄O₇. Luminescence of various doses (200 ~ 15,000 Gy) of gamma irradiated Dy³⁺, La³⁺ and Ho³⁺ (at different concentrations of 5, 10, 15 and 20 %) doped MgB₄O₇ were recorded using a luminance/color meter. The intensity of TL yellowish (CIE x = 0.401 ~ 0.486, y = 0.410 ~ 0.488) emission became stronger as the temperature increased and the total gamma-ray dose increased.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.143-158
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• 1990

Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.