• Journal of Nuclear Fuel Cycle and Waste Technology
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• 제1권1호
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• pp.65-73
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• 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.

• 대한화학회지
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• 제29권6호
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• pp.615-622
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• 1985

옥살산과 아세트산 용액의 농도변화에 따른 우라늄과 바나듐의 음이온교환수지로부터의 용리거동 및, UV및 스펙트럼 변화로부터 이들 이온의 화학종과 평형관계를 연구하였다. 0.005~0.5M 옥산살산 용액속에서 우라늄과 바나듐은 각각 $UO_2(C_2O_4)_2^{2-}$, $UO_2(C_2O-4)_3^{4-}$ 및 $VO_2(C_2O_4)_2^{3-}$의 화학종으로 존재하고, 0.01~0.1M의 아세트산 용액에서 우라늄은 $VO_2(Ac)_2^0$, $UO_2(Ac)_3^{1-}$의 화학종으로 존재하며, 바나듐은 $VO_2^++2Ac^-=VO_2(Ac)_2^-$의 평형이 이루어짐을 확인하였다.

• 한국세라믹학회지
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• 제30권4호
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• pp.279-288
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• 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.

• 한국세라믹학회지
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• 제47권6호
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• pp.590-597
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• 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
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• 제20권3호
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• pp.155-164
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• 1988

$UO_2$ Pellet의 침출도식을 유도하고 실험 자료와 비교검토 하였다. 침출속도 모델은 산소의 Pellet 내부고의 침투로 인한 $UO_2$의 산화과정과 침투 깊이에 따른 산화 $UO_2$의 용해 및 이동과정을 고려하여 얻어 졌다. 이 모델에 의하면 침출속도는 전이상태와 정상상태의 두 영역으로 나뉘어질 수 있으며 변화하는 양상은 초기의 산화상태에 따라 달라진다. 또한 이 모델식은 $UO_2$의 산화반응을 유사한 다른 침출구조에 적용할 수 있어서 일반적 인 침출현상의 해석에 사용될 수 있다.

• 한국세라믹학회지
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• 제35권6호
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• pp.559-568
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• 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
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• 제32권6호
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• pp.559-565
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• 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.

• 방사성폐기물학회지
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• 제7권3호
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• pp.133-141
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• 2009

시간분해 레이저 유도 형광 분광학을 이용하여 ${UO_2}^{2+}$, $UO_2(OH)^+$, ${(UO_2)}_2{(OH)_2}^{2+}$, ${(UO_2)}_3{(OH)_5}^+$와 같은 우라늄(VI) 화학종 규명 연구를 수행하였다. 들뜸 파장의 변화에 따른 화학종 규명 감도를 조사하였다. 266nm의 들뜸 파장을 이용할 경우, 나노 몰 농도의 U(VI) 화합물을 구분할 수 있는 화학종 규명 감도를 얻었다. 이온 세기가 0.1 M, pH가 1인 조건에서 ${UO_2}^{2+}$ 이온의 형광 스펙트럼과 형광 수명을 측정하였다. 488, 509, 533, 559nm파장의 특징적인 형광 봉우리를 관측하였고, 측정한 형광 수명은 $1.92{\pm}0.17{\mu}s$ 이었다. U(VI) 가수분해 화합물의 형광 스펙트럼과 형광 수명의 변화를 이 값을 기준으로 비교하였다. 장파장 방향으로 이동한 형광 봉우리와 길어진 형광 수명을 가진 가수분해 화합물의 특징적인 양상을 보고한다.

• Nuclear Engineering and Technology
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• 제31권2호
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• pp.182-191
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• 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.

• 한국세라믹학회지
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• 제42권11호
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• pp.729-736
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• 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 $600^{\circ}C$.