• Journal of Nuclear Fuel Cycle and Waste Technology
• /
• v.1 no.1
• /
• pp.65-73
• /
• 2013

Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.

• Journal of the Korean Chemical Society
• /
• v.29 no.6
• /
• pp.615-622
• /
• 1985

The chemical species formed by uranium and vanadium and their equilibria have been investigated in the various concentrations of oxalic and acetic acids by the ion exchange chromatography and UV-Vis spectrophotometry. Uranyl and vanadyl ions seem to be form the complex as $UO_2(C_2O_4)_2=$, $UO_2(C_2O_4)_3^{4-}$ and $VO_2(C_2O_4)-2^{3-}$ respectively in the concentration range of 0.005∼0.05M oxalic acid concentration. In the case of acetic acid the equilibria of $UO_2^{2+}+3Ac^-=UO_2(Ac)_3^-$ and $VO_2^++2Ac^-=VO_2(Ac)_2^-$ were existed individually according to the increase of acetic acid concentration.

• Journal of the Korean Ceramic Society
• /
• v.30 no.4
• /
• pp.279-288
• /
• 1993

A study on calcination and reduction of AUC(ammonium uranyl carbonate, (NH4)4UO2(CO3)3) has been carried out by using TG-DTA in N2, air and H2 atmospheres, respectively. Phases of various intermediate obtained during thermal analysis of AUC in different atmospheres were confirmed by XRD. Powder characteristics of each intermediate were investigated by measuring particle size and specific surface area, and also observed by SEM. As a results, regardless of applied atmosphere AUC was calcined into amorphous UO3, which was converted to $\alpha$-U3O8 Via $\alpha$-UO3 in both H2 and N2 atmosphere, but directly into $\alpha$-UO3 in air atmosphere. Further reduction of U3O8 was only detectable in hydrogen atmosphere. During calcination and reduction, average particle size was reduced to less than 30% of original value without morphology change. Specific surface area was dramatically increased with release of NH3, CO2 and H2O from AUC powder and reached maximum value around 25$0^{\circ}C$, and then gradually decreased with the increase of temperature due to sintering effect of uranium oxides such as UO3 and U3O8. It was also found that the change of average crystallite size and pore size were closely related to the changes of specific surface area of uranium oxides.

• Journal of the Korean Ceramic Society
• /
• v.47 no.6
• /
• pp.590-597
• /
• 2010

HTGR using a TRISO coated particles as nuclear raw fuel material can be used to produce clean hydrogen gas and process heat for a next-generation energy source. For these purposes, a TRISO coated particle was prepared with 3 pyro-carbon (buffer, IPyC, and OPyC) layers and 1 silicone carbide (SiC) layer using a CVD technique on a spherical $UO_2$ kernel surface as a fissile material. In this study, a spherical $UO_2$ particle was prepared using a modified sol-gel method with a vibrating nozzle system, and TRISO coating fabrication was carried out using a fluidized bed reactor with coating gases, such as acetylene, propylene, and methyltrichlorosilane (MTS). As the results of this study, a spherical $UO_2$ kernel with a sphericity of 1+0.06 was obtained, and the main process parameters in the $UO_2$ kernel preparation were the well-formed nature of the spherical ADU liquid droplets and the suitable temperature control in the thermal treatment of intermediate compounds in the ADU, $UO_3$, and $UO_2$ conversions. Also, the important parameters for the TRISO coating procedure were the coating temperature and feed rate of the feeding gas in the PyC layer coating, the coating temperature, and the volume fraction of the reactant and inert gases in the SiC deposition.

• Nuclear Engineering and Technology
• /
• v.20 no.3
• /
• pp.155-164
• /
• 1988

A rate equation for UO$_2$ pellet leaching has been derived and compared with some experimental results. The leach rate model comprises the processes of oxygen penetration into UO$_2$ pellets and the dissolution and transport of oxidized UO$_2$ depending on the penetration depth of oxygen. The model may be analyzed with two regions of transient and steady state behaviors, which should depend on the initial oxidation state of pellets. Also this model can be utilized in the analyses of general leach processes if the oxidation reaction of UO$_2$ is replaced with similar mechanism of those processes.

• Journal of the Korean Ceramic Society
• /
• v.35 no.6
• /
• pp.559-568
• /
• 1998

Studies of preparation condition and characteristics of AUC(ammonium uranyl carbonate) were carried out to optimize AUC process with different reactor sizes and precipitation methos. As results four types of precipitates with different chemical compositions and morphologies were obtained from the reaction of {{{{ {(NH }_{4 }) { }_{2 } {CO }_{3 } }} with {{{{ {UO }_{2 }( {NO }_{3 }) { }_{2 } }} solution. A phase diagram has been made and crystal structure and chemical composition of each phase have been characterized by using SEM X-ray IR and thermal analysis. It was found that ammonium uranyl carbonate {{{{ {(NH }_{4 }) { }_{4 } {UO }_{2 } {(CO }_{3 }) { }_{3 } }} with monoclinic crystal morphology could be syn-thesized when the mole ratio of in {{{{ {(NH }_{4 }) { }_{2 } {CO }_{3 }/ {UO }_{2 } {(NO }_{3 }) { }_{2 } }} in the solution was higher than 5 Also a mechanism and a precipitating condition on rounding of the AUC particle were examined in the course of the AUC pre-cipitation. The rounding of the AUC particle was possible only by external circulation using pump not by internal circulation using agitator.

• Nuclear Engineering and Technology
• /
• v.32 no.6
• /
• pp.559-565
• /
• 2000

The sintering behavior of UO$_2$-Gd$_2$O$_3$fuel pellets under H$_2$gas has been investigated using dilatometry and XRD methods. The addition of TiO$_2$or Al(OH)$_3$increased the density and grain size. A density of 95% TD and a grain size larger than 6 ${\mu}{\textrm}{m}$ are achieved by the addition of 0.1 wt% TiO$_2$or Al(OH)$_3$. It was found that the densification of UO$_2$-Gd$_2$O$_3$pellets was suppressed in the temperature range of 1300 to 150$0^{\circ}C$, compared to UO$_2$pellets. The formation of a (U,Gd)O$_2$solid solution is the main reason for the suppression of densification. The role of TiO$_2$in densification and grain growth is discussed on the basis of the densification cuwe and ceramography.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.7 no.3
• /
• pp.133-141
• /
• 2009

Study on the chemical speciation of uranium(VI) species, ${UO_2}^{2+}$, $UO_2(OH)^+$, ${(UO_2)}_2{(OH)_2}^{2+}$, ${(UO_2)}_3{(OH)_5}^+$, has been peformed by using time-resolved laser-induced fluorescence spectroscopy. Speciation sensitivity which depends on the excitation wavelength was investigated. We obtained the speciation sensitivity in the order of $10^{-9}$ M concentration of U(VI) compounds at the excitation wavelength of 266 nm. The fluorescence spectrum and lifetime of ${UO_2}^{2+}$ were carefully measured at pH 1 and ion strength of 0.1 M. The spectrum showed the four characteristic peaks located around 488, 509, 533, 559nm and the fluorescence lifetime of $1.92{\pm}0.17{\mu}s$. The wavelength shifts of fluorescence peaks and the change of lifetimes for uranium hydrolysis compounds were compared with those of ${UO_2}^{2+}$. We report on the characteristic features, the shifts of peaks to the longer wavelength direction and the prolonged lifetimes, in the fluorescence of the U(VI) hydrolysis compounds.

• Nuclear Engineering and Technology
• /
• v.31 no.2
• /
• pp.182-191
• /
• 1999

The sorption of UO$_{2}$$^{2+}$ onto goethite and kaolinite under various experimental conditions was successfully interpreted using surface complexation modeling (SCM). The SCM approach used in this work is the triple-layer model (TLM) in which weakly bonded ions are modeled as outer-sphere (ion-pair) complexes and strongly bonded ions as inner-sphere (surface coordination) complexes. The change of ionic strength did not affect the U(VI) sorption onto goethite, thus the formation of inner-sphere surface complexes, (FeO)$_2$UO$_2$ and (FeO)$_2$(UO$_2$)$_3$OH$_{5}$ was assumed to simulate the effects of ionic strength and goethite concentration. On the other hand, the U(VI) sorption onto kaolinite showed ionic strength dependence, thus the formation of AlO-UO$_{2}$$^{2+}$(outer-sphere complex) and SiO(UO$_2$)$_3$OH$_{5}$ (inner-sphere complex) was assumed to simulate the experimental data. In the presence of carbonates, the sorption of U(VI) onto kaolinite decreased in the weakly alkaline pH range. This was well simulated assuming the formation of a outer-sphere surface complex, A1OH$^{2+}$- (UO$_2$)$_2$CO$_3$OH$_3$. Since SCM approach uses thermodynamic data such as surface complexation constants, it is more predictive than empirical modeling approach in which conditional values such as partition coefficient are used. used.

• Journal of the Korean Ceramic Society
• /
• v.42 no.11 s.282
• /
• pp.729-736
• /
• 2005

HTGR (High Temperature Gas-cooled Reactor) is spotlighted to next generation nuclear power plant for producing the clean hydrogen gas and the electricity. In this study, the spherical $UO_3$ gel particles were prepared by the external gelation process, and the characteristics of these particles were analyzed the particle shape, composition of precipitate, and thermal decomposition characteristics with the Streoscope, FT-IR, and X-ray diffractometer. Raw material of the ADUN (Acid Deficient Uranyl Nitrate) solution, which has [$NO_3$]/[U] mole ratio = 1.75, was obtained from dissolution of the $U_{3}O_{8}$ powder with concentrated $HNO_3$, and its concentration is 3.5 M-U/l. The broth solution is prepared with the ADUN, urea, PVA, and THFA solution. The droplets of the broth solution was made through a nozzle system. From this study, we obtained the following results; 1) an externel chemical gelation process is a suitable method in the spherical $UO_3$ particle production, 2) the particle shape are changed by an urea mixing time, THFA volume, and the viscosity of the broth solution, 3) the amorphous $UO_3$ particles obtained from these experiments was converted to $U_{3}O_{8}$ and then $UO_2$ by heat treatment in hydrogen atmosphere at $600^{\circ}C$.