• Title/Summary/Keyword: $UO_3$

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Characteristics of Powder Prepared from Unirradiated $UO_2$ Pellets by Oxidation and Reduction Method ($UO_2$ 소결체의 산화/환원에 의해 제조된 분말 특성)

  • 김봉구;송근우;이정원;배기광;양명승;박현수
    • Journal of the Korean Ceramic Society
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    • v.32 no.4
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    • pp.471-481
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    • 1995
  • Unirradiated UO2 pellets were pulverized by oxidation in air at 40$0^{\circ}C$, and the oxidized powders were reduced in H2 and CO atmospheres at $600^{\circ}C$. During the oxidation of UO2 at 40$0^{\circ}C$, intergranular cracks which caused the spallation were mainly developed by the volume contraction due to the formation of intermediate phase (U4O9 or U3O7). As oxidation proceeded, U3O8 finally formed. As the oxidation/reduction cycles were repeated, the powder surface became coarser, specific surface area was increased and average particle size was decreased. The sintered densities of the powder were increased by the oxidation/reduction cycle due to the characteristic changes of the powder.

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UO22+ Ion-Selective Membrane Electrode Based on a Naphthol-Derivative Schiff's Base 2,2'-[1,2-Ethandiyl bis(nitriloethylidene)]bis(1-naphthalene)

  • Shamsipur, Mojtaba;Saeidi, Mahboubeh;Yari, Abdullah;Yaganeh-Faal, Ali;Mashhadizadeh, Mohammad Hossein;Azimi, Gholamhasan;Naeimi, Hossein;Sharghi, Hashem
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.629-633
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    • 2004
  • A new PVC membrane electrode for $UO_2^{2+}$ ion based on 2,2'-[1,2-ethanediyl bis (nitriloethylidene)]bis(1-naphthalene) as a suitable ionophore was prepared. The electrode exhibites a Nernstian response for $UO_2^{2+}$ ion over a wide concentration range ($1.0{\times}10^{-1}-1.0{\times}10^{-7}$M) with a slope of 28.5 ${\pm}$ 0.8 mV/decade. The limit of detection is $7.0{\times}10^{-8}$M. The electrode has a response time of < 20 s and a useful working pH range of 3-4. The proposed membrane sensor shows good discriminating abilities towards $UO_2^{2+}$ ion with regard to several alkali, alkaline earth transition and heavy metal ions. It was successfully used to the recovery of uranyl ion from, tap water and, as an indicator electrode, in potentiometric titration of $UO_2^{2+}$ ion with Piroxycam.

Scaling Up Fabrication of UO2 Porous Pellet With a Simulated Spent Fuel Composition (모의 사용후핵연료 조성의 UO2 다공성펠렛 제조 스케일 업)

  • Jeon, Sang-Chae;Lee, Jae-Won;Yoon, Joo-Young;Cho, Yung-Zun
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.15 no.4
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    • pp.343-353
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    • 2017
  • Processing and equipment were tailored for engineering scale fabrication of $UO_2$ porous pellets, a feed material for the electrolytic reduction process in the PRIDE (PyRoprocessing Integrated DEmonstration) facility at KAERI (Korea Atomic Energy Research Institute). The starting materials, $UO_2$ powder and pre-milled surrogate oxide powders, were proportioned to simulate the chemical composition of spent fuel (so-called Simfuel). The Simfuel powders were homogenized by mixing, compacted into a pellet shape, and finally heat treated using a tumbling mixer, rotary press, and sintering furnace. After sintering at $1450^{\circ}C$ for 24 h in $4%\;H_2-Ar$, the average bulk density of the $UO_2$ Simfuel pellets was $6.89g{\cdot}cm^{-3}$, which meets the standard of the following electrolytic reduction process. In addition, the results of a microstructural analysis demonstrated that the sintered Simfuel $UO_2$ porous pellets accurately simulate the properties of spent fuel in terms of the formation of second phases. These results provide essential information for the massive fabrication of $UO_2$ porous pellets for engineering scale pyroprocessing research.

Crystal Structure Analysis of Uranium Oxides (산화우라늄의 결정구조 분석)

  • 김정석;최용남;이창희;김시향;이영우
    • Journal of the Korean Ceramic Society
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    • v.38 no.11
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    • pp.967-972
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    • 2001
  • The crystal and defect structures of U $O_{x}$(x=2.0, 2.03, 2.14, 2.19, 2.20 and 2.26) were analysed by rietveld refinement and the results were compared to the U-O phase diagram. Neutron diffraction data were collected in the temperature range of RT~100$0^{\circ}C$. The specimens of x=2.14, 2.19, and 2.20 consisted of two phase: $UO_{2+x}$(Fm3m, a≒5.4$\AA$) and $U_4$$O_{9}$(I43d, a≒21.8$\AA$). The proportion of the $UO_{2+x}$(Fm3m) phase increased with increasing the temperature. The variation of the proportion of the two phases with temperature in the U $O_{2.2}$ and U $O_{2.18}$ samples showed some deviation from the expected values from the phase diagram especially at the high temperature range. The phase transitions ${\gamma}$longrightarrow$\beta$longrightarrow$\alpha$ of $U_4$$O_{9}$ were discussed in relation with the phase separation.eparation.ion.

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Sintering Behavior of $Cr_2 O_3$-doped $UO_2$ Pellets

  • Kim, Keon-Sik;Song, Kun-Woo;Yang, Jae-Ho;Kang, Ki-Won;Jung, Youn -Ho;Kim, Gil-Moo
    • Nuclear Engineering and Technology
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    • v.35 no.1
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    • pp.14-24
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    • 2003
  • This work investigates the effects of Cr$_2$O$_3$ and oxygen potential on grain growth and densification of UO$_2$ pellets. Powder mixtures of UO$_2$ and 0.03-0.4wt% Cr$_2$O$_3$ were pressed and sintered in 3 different gas atmospheres: the $H_2O$-to-H$_2$ ratios were 5$\times$10$^{-4}$ , 1$\times$10$^{-2}$ and 3$\times$10$^{-2}$ In the first gas atmosphere the Cr$_2$O$_3$ contents below 0.2 wt% have an insignificant effect on grain size, but the Cr$_2$O$_3$ contents more than 0.3 wt% promote grain growth in the inner zone of a pellet but not in the outer zone. In both the second and third atmospheres, the grain size increases with the Cr$_2$O$_3$ content. With the same level of Cr$_2$O$_3$ content the grain size is larger in the second atmosphere than in the third. Sintering behavior and developed microstructure are discussed in terms of the reduction of C$r^2$O$^3$ to Cr, the dissolution of C$r^2$O$^3$ in UO$_2$, and liquid phase sintering.

Spectroscopic Studies on U(VI) Complex with 2,6-Dihydroxybenzoic acid as a Model Ligand of Humic Acid (분광학을 이용한 흄산의 모델 리간드인 2,6-Dihydroxybenzoic acid와 우라늄(VI)의 착물형성 반응에 관한 연구)

  • Cha, Wan-Sik;Cho, Hye-Ryun;Jung, Euo-Chang
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.9 no.4
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    • pp.207-217
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    • 2011
  • In this study the complex formation reactions between uranium(VI) and 2,6-dihydroxybenzoate (DHB) as a model ligand of humic acid were investigated by using UV-Vis spectrophotometry and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The analysis of the spectrophotometric data, i.e., absorbance changes at the characteristic charge-transfer bands of the U(VI)-DHB complex, indicates that both 1:1 and 1:2 (U(VI):DHB) complexes occur as a result of dual equilibria and their distribution varies in a pH-dependent manner. The stepwise stability constants determined (log $K_1$ and log $K_2$) are $12.4{\pm}0.1$ and $11.4{\pm}0.1$. Further, the TRLFS study shows that DHB plays a role as a fluorescence quencher of U(VI) species. The presence of both a dynamic and static quenching process was identified for all U(VI) species examined, i.e., ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$. The fluorescence intensity and lifetimes of each species were measured from the time-resolved spectra at various ligand concentrations, and then analyzed based on Stern-Volmer equations. The static quenching constants (log $K_s$) obtained are $4.2{\pm}0.1$, $4.3{\pm}0.1$, and $4.34{\pm}0.08$ for ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$, respectively. The results of Stern-Volmer analysis suggest that both mono- and bi-dentate U(VI)-DHB complexes serve as groundstate complexes inducing static quenching.

Study on the Elution Behaviors of Uranium and Vanadium in the Various Acids by Anion Exchange Chromatography (음이온 교환크로마토그래피법에 의한 여러가지 산에서 우라늄과 바나듐의 용리현상에 관한연구)

  • Ki-Won Cha;Jong-Hun Kim
    • Journal of the Korean Chemical Society
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    • v.28 no.5
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    • pp.309-314
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    • 1984
  • The species and equilibria of uranium and vanadium have been investigated in the various concentration of perchloric, hydrochloric and sulfuric acid by anion exchange chromatography. In the concentration range of $0.01\;{\sim}\;0.5M$ hydrochloric and $0.01\;{\sim}\;0.5M$ perchloric acid, uranium seems to be $UO_2^{2+}$species and in higher concentration than 0.5M hydrochloric acid $UO_2^{2+}$seems to form the chloride complex ion as $UO_2Cl^+$, $UO_2Cl_2$, $UO_2Cl_3^-$ and $UO_2Cl_4^{2-}$ according to the increase of the hydrochloric acid concentration. In the dilute(0.01N) sulfuric acid the adsorbability of uranium on anion exchange resin is strong and then decreases with increasing the sulfuric acid concentration. From this result we conclude that $UO_26{2+}$ formed the complex ion as $UO_2(SO_4)_2^{2-}$. In the perchloric acid of $0.01\;{\sim}\;0.5N$ concentration the existing equilibrium of vanadium and its constant calculated at $20^{\circ}C$ is $1.9{\times}108$ for $H_2V_{10}O_{28}^{4-}$ + $14H^+$ = $10VO_2^+ + 8H_2O$. The elution behaviors of vanadium in the hydrochloric and sulfuric acid are smiliar to those in perchloric acid.

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New Cryptand Complexes of Lanthanides(Ⅲ) and Dioxouranium(Ⅵ) Nitrates

  • Oh-Jin Jung;Chil-Nam Choi;Hak-Jin Jung
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.130-137
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    • 1991
  • The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.