Cultivation of aerobic granules in a novel configuration of sequencing batch airlift reactor.

PubMed

Rezaei, Laya Siroos; Ayati, Bita; Ganjidoust, Hossein

2012-01-01

Aerobic granules can be formed in sequencing batch airlift reactors (SBAR) and sequencing batch reactors (SBR). Comparing these two systems, the SBAR has excellent mixing condition, but due to a high height-to-diameter ratio (H/D), there is no performance capability at full scale at the present time. This research examined a novel configuration of SBAR at laboratory scale (with a box structure) for industrial wastewater treatment. To evaluate chemical oxygen demand (COD) removal efficiency and granule formation of the novel reactor (R1), in comparison a conventional SBAR (R2) was operated under similar conditions during the experimental period. R1 and R2 with working volumes of 3.6 L and 4.5 L, respectively, were used to cultivate aerobic granules. Both reactors were operated for 4 h per cycle. Experiments were done at different organic loading rates (OLRs) ranging from 0.6-4.5 kg COD/m3.d for R1 and from 0.72-5.4 kg COD/m3.d for R2. After 150 days of operation, large-sized black filamentous granules with diameters of 0.5-2 mm and 2-11 mm were formed in R1 and R2, respectively. In the second part of the experiment, the efficiency of removal of a toxic substance by aerobic granules was investigated using aniline as a carbon source with a concentration in the range 1.2-6.6 kg COD/m3.d and 1.44-7.92 kg COD/m3.d in R1 and R2, respectively. It was found that COD removal efficiency of the novel airlift reactor was over 97% and 94.5% using glucose and aniline as carbon sources, respectively. Sludge volume index (SVI) was also decreased to 30 mL/g by granulation in the novel airlift reactor.

Milestone report: The simulation of radiation driven gas diffusion in UO 2 at low temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, Michael William; Kuganathan, Navaratnarajah; Burr, Patrick A

2016-10-24

Below 1000 K it is thought that fission gas diffusion in nuclear fuel during irradiation occurs through atomic mixing due to radiation damage. This is an important process for nuclear reactor performance as it affects fission gas release, particularly from the periphery of the pellet where such temperatures are normal. Here we present a molecular dynamics study of Xe and Kr diffusion due to irradiation. Thermal spikes and cascades have been used to study the electronic stopping and ballistic phases of damage, respectively. Our results predict that O and Kr exhibit the greatest diffusivity and U the least, while Xemore » lies in between. It is concluded that the ballistic phase does not sufficiently account for the experimentally observed diffusion. Preliminary thermal spike calculations indicate that the electronic stopping phase generates greater fission gas displacement than the ballistic phase, although further calculation must be carried out to confirm this. A good description of the system by the empirical potentials is important over the very wide temperatures induced during thermal spike and damage cascade simulations. This has motivated the development of a parameter set for gas-actinide and gas-oxygen interactions that is complementary for use with a recent many-body potential set. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO 2, ThO 2, UO 2 and PuO 2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials

Development of Innovative Accident Tolerant High Thermal Conductivity UO 2-Diamond Composite Fuel Pellets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tulenko, James; Subhash, Ghatu

2016-01-01

The University of Florida (UF) evaluated a composite fuel consisting of UO 2 powder mixed with diamond micro particles as a candidate as an accident-tolerant fuel (ATF). The research group had previous extensive experience researching with diamond micro particles as an addition to reactor coolant for improved plant thermal performance. The purpose of this research work was to utilize diamond micro particles to develop UO 2-Diamond composite fuel pellets with significantly enhanced thermal properties, beyond that already being measured in the previous UF research projects of UO 2 – SiC and UO 2 – Carbon Nanotube fuel pins. UF ismore » proving with the current research results that the addition of diamond micro particles to UO 2 may greatly enhanced the thermal conductivity of the UO 2 pellets producing an accident-tolerant fuel. The Beginning of life benefits have been proven and fuel samples are being irradiated in the ATR reactor to confirm that the thermal conductivity improvements are still present under irradiation.« less

High resolution photoelectron imaging of UO{sup −} and UO{sub 2}{sup −} and the low-lying electronic states and vibrational frequencies of UO and UO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Czekner, Joseph; Lopez, Gary V.; Wang, Lai-Sheng

2014-12-28

We report a study of the electronic and vibrational structures of the gaseous uranium monoxide and dioxide molecules using high-resolution photoelectron imaging. Vibrationally resolved photoelectron spectra are obtained for both UO{sup −} and UO{sub 2}{sup −}. The spectra for UO{sub 2}{sup −} are consistent with, but much better resolved than a recent study using a magnetic-bottle photoelectron analyzer [W. L. Li et al., J. Chem. Phys. 140, 094306 (2014)]. The electron affinity (EA) of UO is reported for the first time as 1.1407(7) eV, whereas a much more accurate EA is obtained for UO{sub 2} as 1.1688(6) eV. The symmetricmore » stretching modes for the neutral and anionic ground states, and two neutral excited states for UO{sub 2} are observed, as well as the bending mode for the neutral ground state. These vibrational frequencies are consistent with previous experimental and theoretical results. The stretching vibrational modes for the ground state and one excited state are observed for UO. The current results for UO and UO{sub 2} are compared with previous theoretical calculations including relativistic effects and spin-orbit coupling. The accurate experimental data reported here provide more stringent tests for future theoretical methods for actinide-containing species.« less

Unusual ion UO(4)(-) formed upon collision induced dissociation of [UO(2)(NO(3))(3)](-), [UO(2)(ClO(4))(3)](-), [UO(2)(CH(3)COO)(3)](-) ions.

PubMed

Sokalska, Marzena; Prussakowska, Małgorzata; Hoffmann, Marcin; Gierczyk, Błazej; Frański, Rafał

2010-10-01

The following ions [UO(2)(NO(3))(3)](-), [UO(2)(ClO(4))(3)](-), [UO(2)(CH(3)COO)(3)](-) were generated from respective salts (UO(2)(NO(3))(2), UO(2)(ClO(4))(3), UO(2)(CH(3)COO)(2)) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO(4)(-) ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U(VI) compound, in which oxygen atoms bear unpaired electron and negative charge. Copyright © 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Simple (17) O NMR method for studying electron self-exchange reaction between UO2 (2+) and U(4+) aqua ions in acidic solution.

PubMed

Bányai, István; Farkas, Ildikó; Tóth, Imre

2016-06-01

(17) O NMR spectroscopy is proven to be suitable and convenient method for studying the electron exchange by following the decrease of (17) O-enrichment in U(17) OO(2+) ion in the presence of U(4+) ion in aqueous solution. The reactions have been performed at room temperature using I = 5 M ClO4 (-) ionic medium in acidic solutions in order to determine the kinetics of electron exchange between the U(4+) and UO2 (2+) aqua ions. The rate equation is given as R = a[H(+) ](-2)  + R', where R' is an acid independent parallel path. R' depends on the concentration of the uranium species according to the following empirical rate equation: R' = k1 [UO(2 +) ](1/2) [U(4 +) ](1/2)  + k2 [UO(2 +) ](3/2) [U(4 +) ](1/2) . The mechanism of the inverse H(+) concentration-dependent path is interpreted as equilibrium formation of reactive UO2 (+) species from UO2 (2+) and U(4+) aqua ions and its electron exchange with UO2 (2+) . The determined rate constant of this reaction path is in agreement with the rate constant of UO2 (2+) -UO2 (+) , one electron exchange step calculated by Marcus theory, match the range given experimentally of it in an early study. Our value lies in the same order of magnitude as the recently calculated ones by quantum chemical methods. The acid independent part is attributed to the formation of less hydrolyzed U(V) species, i.e. UO(3+) , which loses enrichment mainly by electron exchange with UO2 (2+) ions. One can also conclude that (17) O NMR spectroscopy, or in general NMR spectroscopy with careful kinetic analysis, is a powerful tool for studying isotope exchange reactions without the use of sophisticated separation processes. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE PAGES

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley; ...

2016-01-06

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

Hypoeutectic melting in the UO2-x-Gd2O3 system

NASA Astrophysics Data System (ADS)

Journeau, Christophe; Fouquart, Pascal; Domenger, Renaud; Allegri, Patrick

2017-05-01

Gadolinium is one of the best neutron absorber materials and its use can be considered as a sacrificial material in a Sodium Fast Reactor core catcher in view of preventing recriticallity. A series of experiments have been conducted in the VITI induction-heated facility to study the melting in the UO2-x-Gd2O3 system with 60-87 mol% gadolinia. These experiments have indicated that the eutectic composition is around 92 mol% Gd2O3 - 8 mol% UO2-x and that the liquidus line is close to that of Popov et al. [Atom. Energ. 110 (2011) pp. 221-229] phase diagram.

Hydrothermal syntheses, structures, and properties of the new uranyl selenites Ag(2)(UO(2))(SeO(3))(2), M[(UO(2))(HSeO(3))(SeO(3))] (M = K, Rb, Cs, Tl), and Pb(UO(2))(SeO(3))(2).

PubMed

Almond, Philip M; Albrecht-Schmitt, Thomas E

2002-03-11

The transition metal, alkali metal, and main group uranyl selenites, Ag(2)(UO(2))(SeO(3))(2) (1), K[(UO(2))(HSeO(3))(SeO(3))] (2), Rb[(UO(2))(HSeO(3))(SeO(3))] (3), Cs[(UO(2))(HSeO(3))(SeO(3))] (4), Tl[(UO(2))(HSeO(3))(SeO(3))] (5), and Pb(UO(2))(SeO(3))(2) (6), have been prepared from the hydrothermal reactions of AgNO(3), KCl, RbCl, CsCl, TlCl, or Pb(NO(3))(2) with UO(3) and SeO(2) at 180 degrees C for 3 d. The structures of 1-5 contain similar [(UO(2))(SeO(3))(2)](2-) sheets constructed from pentagonal bipyramidal UO(7) units that are joined by bridging SeO(3)(2-) anions. In 1, the selenite oxo ligands that are not utilized within the layers coordinate the Ag(+) cations to create a three-dimensional network structure. In 2-5, half of the selenite ligands are monoprotonated to yield a layer composition of [(UO(2))(HSeO(3))(SeO(3))](1-), and coordination of the K(+), Rb(+), Cs(+), and Tl(+) cations occurs through long ionic contacts. The structure of 6 contains a uranyl selenite layered substructure that differs substantially from those in 1-5 because the selenite anions adopt both bridging and chelating binding modes to the uranyl centers. Furthermore, the Pb(2+) cations form strong covalent bonds with these anions creating a three-dimensional framework. These cations occur as distorted square pyramidal PbO(5) units with stereochemically active lone pairs of electrons. These polyhedra align along the c-axis to create a polar structure. Second-harmonic generation (SHG) measurements revealed a response of 5x alpha-quartz for 6. The diffuse reflectance spectrum of 6 shows optical transitions at 330 and 440 nm. The trailing off of the 440 nm transition to longer wavelengths is responsible for the orange coloration of 6.

Experimental studies of Micro- and Nano-grained UO 2: Grain Growth Behavior, Sufrace Morphology, and Fracture Toughness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miao, Yinbin; Mo, Kun; Jamison, Laura M.

This activity is supported by the US Nuclear Energy Advanced Modeling and Simulation (NEAMS) Fuels Product Line (FPL) and aims at providing experimental data for the validation of the mesoscale simulation code MARMOT. MARMOT is a mesoscale multiphysics code that predicts the coevolution of microstructure and properties within reactor fuel during its lifetime in the reactor. It is an important component of the Moose-Bison-Marmot (MBM) code suite that has been developed by Idaho National Laboratory (INL) to enable next generation fuel performance modeling capability as part of the NEAMS Program FPL. In order to ensure the accuracy of the microstructure-basedmore » materials models being developed within the MARMOT code, extensive validation efforts must be carried out. In this report, we summarize the experimental efforts in FY16 including the following important experiments: (1) in-situ grain growth measurement of nano-grained UO 2; (2) investigation of surface morphology in micrograined UO 2; (3) Nano-indentation experiments on nano- and micro-grained UO 2. The highlight of this year is: we have successfully demonstrated our capability to in-situ measure grain size development while maintaining the stoichiometry of nano-grained UO 2 materials; the experiment is, for the first time, using synchrotron X-ray diffraction to in-situ measure grain growth behavior of UO 2.« less

Excision of uranium oxide chains and ribbons in the novel one-dimensional uranyl iodates K(2)[(UO(2))3(IO(3))(4)O(2)] and Ba[(UO(2)2(IO(3))(2)O(2)](H(2)O).

PubMed

Bean, A C; Ruf, M; Albrecht-Schmitt, T E

2001-07-30

The alkali metal and alkaline-earth metal uranyl iodates K(2)[(UO(2))(3)(IO(3))(4)O(2)] and Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) have been prepared from the hydrothermal reactions of KCl or BaCl(2) with UO(3) and I(2)O(5) at 425 and 180 degrees C, respectively. While K(2)[(UO(2))(3)(IO(3))(4)O(2)] can be synthesized under both mild and supercritical conditions, the yield increases from <5% to 73% as the temperature is raised from 180 to 425 degrees C. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), however, has only been isolated from reactions performed in the mild temperature regime. Thermal measurements (DSC) indicate that K(2)[(UO(2))(3)(IO(3))(4)O(2)] is more stable than Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) and that both compounds decompose through thermal disproportionation at 579 and 575 degrees C, respectively. The difference in the thermal behavior of these compounds provides a basis for the divergence of their preparation temperatures. The structure of K(2)[(UO(2))(3)(IO(3))(4)O(2)] is composed of [(UO(2))(3)(IO(3))(4)O(2)](2)(-) chains built from the edge-sharing UO(7) pentagonal bipyramids and UO(6) octahedra. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) consists of one-dimensional [(UO(2))(2)(IO(3))(2)O(2)](2)(-) ribbons formed from the edge sharing of distorted UO(7) pentagonal bipyramids. In both compounds the iodate groups occur in both bridging and monodentate binding modes and further serve to terminate the edges of the uranium oxide chains. The K(+) or Ba(2+) cations separate the chains or ribbons in these compounds forming bonds with terminal oxygen atoms from the iodate ligands. Crystallographic data: K(2)[(UO(2))(3)(IO(3))(4)O(2)], triclinic, space group P_1, a = 7.0372(5) A, b = 7.7727(5) A, c = 8.9851(6) A, alpha = 93.386(1) degrees, beta = 105.668(1) degrees, gamma = 91.339(1) degrees, Z = 1; Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), monoclinic, space group P2(1)/c, a = 8.062(4) A, b = 6.940(3) A, c = 21.67(1), beta= 98.05(1) degrees, Z = 4.

Synthesis and crystal structure of two new uranyl oxychloro-vanadate layered compounds: M7(UO 2) 8(VO 4) 2O 8Cl with M=Rb, Cs

NASA Astrophysics Data System (ADS)

Duribreux, I.; Saadi, M.; Obbade, S.; Dion, C.; Abraham, F.

2003-05-01

Two new alkali uranyl oxychloro vanadates M7(UO 2) 8(VO 4) 2O 8Cl with M=Rb, Cs, have been synthesized by solid-state reactions and their structures determined from single-crystal X-ray diffraction data. They crystallize in the orthorhombic system with space groups Pmcn and Pmmn, respectively. The a and b unit cell parameters are almost identical in both compounds while the c parameter in the Rb compound is doubled: Rb— a=21.427(5) Å, b=11.814(3) Å, c=14.203(3) Å, V=3595.1(1) Å 3, Z=4, ρmes=5.93(2) g/cm 3, ρcal=5.82(1) g/cm 3; Cs— a=21.458(3) Å, b=11.773(2) Å, c=7.495(1) Å, V=1893.6(5) Å 3, Z=2, ρmes=6.09(2) g/cm 3, ρcal=6.11(1) g/cm 3. A full-matrix least-squares refinement yielded R1=0.0221, w R2=0.0562 for 2675 independent reflections and R1=0.0386, w R2=0.1042 for 2446 independent reflections, for the Rb and Cs compounds, respectively. Data were collected with Mo( Kα) radiation and a charge coupled device (CCD) detector of a Bruker diffractometer. Both structures are characterized by [(UO 2) 8(VO 4) 2O 8Cl] n7 n- layers parallel to the (001) plane. The layers are built up from VO 4 tetrahedra, UO 7 and UO 6Cl pentagonal bipyramids, and UO 6 distorded octahedra. The UO 7 and UO 6Cl pentagonal bipyramids are associated by sharing opposite equatorial edges to form infinite chains (UO 5-UO 4Cl-UO 5) n parallel to the a axis. These chains are linked together by VO 4 tetrahedra, UO 6 octahedra, UO 7 corner sharing and UO 6Cl, Cl sharing. Both structures differ simply by the symmetry of the layers. The unit cell contains one centrosymmetric layer in the Cs compound, whereas in the two-layer unit cell of the Rb compound, two non-centrosymmetric consecutive layers are related by an inversion center. The layers appear to be held together by the alkali ions. The mobility of the M+ ions within the interlayer space in M7(UO 2) 8(VO 4) 2O 8Cl and carnotite analog compounds is compared.

Thermal-stress fracture and fractography in UO/sub 2/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, C.R.; Bandyopadhyay, G.

1976-01-01

Pressed and sintered UO/sub 2/ pellets were thermally shocked by quenching into a water bath at room temperature. The cracking behavior and strength degradation, as measured by the diametral compression technique, in these quench tests are discussed. Fractography of the thermally shocked specimens by scanning-electron microscopy indicated predominantly intergranular fracture in UO/sub 2/ in severe thermal-shock tests. The implication of this observation is that intergranular cracking may occur during the initial heat up in a reactor. Because fission gas bubbles tend to migrate toward the grain boundary, preferential microcracking along the boundary may strongly affect subsequent fission gas release behavior.

First identification and thermodynamic characterization of the ternary U(VI) species, UO2(O2)(CO3)2(4-), in UO2-H2O2-K2CO3 solutions.

PubMed

Goff, George S; Brodnax, Lia F; Cisneros, Michael R; Peper, Shane M; Field, Stephanie E; Scott, Brian L; Runde, Wolfgang H

2008-03-17

In alkaline carbonate solutions, hydrogen peroxide can selectively replace one of the carbonate ligands in UO2(CO3)3(4-) to form the ternary mixed U(VI) peroxo-carbonato species UO2(O2)(CO3)2(4-). Orange rectangular plates of K4[UO2(CO3)2(O2)].H2O were isolated and characterized by single crystal X-ray diffraction studies. Crystallographic data: monoclinic, space group P2(1)/ n, a = 6.9670(14) A, b = 9.2158(10) A, c = 18.052(4) A, Z = 4. Spectrophotometric titrations with H 2O 2 were performed in 0.5 M K 2CO 3, with UO2(O2)(CO3)2(4-) concentrations ranging from 0.1 to 0.55 mM. The molar absorptivities (M(-1) cm(-1)) for UO2(CO3)3(4-) and UO2(O2)(CO3)2(4-) were determined to be 23.3 +/- 0.3 at 448.5 nm and 1022.7 +/- 19.0 at 347.5 nm, respectively. Stoichiometric analyses coupled with spectroscopic comparisons between solution and solid state indicate that the stable solution species is UO2(O2)(CO3)2(4-), which has an apparent formation constant of log K' = 4.70 +/- 0.02 relative to the tris-carbonato complex.

FABRICATION DEVELOPMENT OF UO$sub 2$-STAINLESS STEEL COMPOSITE FUEL PLATES FOR CORE B OF THE ENRICO FERMI FAST BREEDER REACTOR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherubini, J.H.; Beaver, R.J.; Leitten, C.F. Jr.

1961-04-18

The development of an inexpensive composite fuel plate with a high burnup potential for application in a 500 deg C sodium environment as Core B of the Enrico Fermi Fast Breeder Reactor is described. The dispersion fuel product consists of 35 wt.% spheroidal UO/sub 2/ dispersed in type 347B stainless steel powder and clad with wrought type 347 stainless steel. Nominal over-all dimensions of Type II design fuel plates are 18.97 in. long x 2.406 in. wide x 0.112 in. thick with 0.005-in. cladding. Reliable processing methods for achieving a uniform distribution of spheroidal UO/sub 2/ in the matrix powdermore » and cladding the sintered powder compact by roll bonding are described. Examination of experimental plates reveals that the degree of UO/sub 2/ fragmentation and stringering encountered during processing is primarily a function of the degree of cold work employed in the finishing operation snd the starting quality of the UO/sub 2/ powder. Cladding studies indicate that a sound metallurgical bond can be achieved with an 87.5% reduction in thickness at 1200 deg C and that close processing control is required to meet the stringent tolerances specified. The developed process meets all criteria except possibly the surface finish requirement; occasionally, pitting occurs due to scale embedded during hot working. Detailed procedures covering composite plate manufacture are presented. (auth)« less

The UO2 ex-ADU powder preparation and pellet sintering for optimum efficiency: experimental and modeling studies

NASA Astrophysics Data System (ADS)

Hung, Nguyen Trong; Thuan, Le Ba; Van Tung, Nguyen; Thuy, Nguyen Thanh; Lee, Jin-Young; Jyothi, Rajesh Kumar

2017-12-01

The UO2 nuclear fuel pellet process for light water reactors (LWR) includes the conversion of uranium hexafluoride (UF6) into UO2 powder and the fabrication of UO2 pellets from such UO2 powder. In the paper, studies on UO2 pellet process from ammonium diuranate-derived uranium dioxide powder (UO2 ex-ADU powder) were reported. The UO2 ex-ADU powders were converted from ADU at various temperatures of 973 K, 1023 K and 1073 K and then UO2 pellets prepared from the powders were sintered at temperatures of 1923 K, 1973 K and 2023 K for times of 4 h, 6 h and 8 h. Response surface methodology (RSM) based on quadratic central composite design (CCD) type of face centered (CCF) improved by Box and Hunter was used to model the UO2 pellet process, using MODDE 5.0 software as an assessing tool. On the base of the proposed model, the relationship between the technological parameters and density of the UO2 pellet product was suggested to control the UO2 ex-ADU pellet process as desired levels.

Mixed-metal uranium(VI) iodates: hydrothermal syntheses, structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K, Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)].

PubMed

Sykora, Richard E; McDaniel, Steven M; Wells, Daniel M; Albrecht-Schmitt, Thomas E

2002-10-07

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.

Scale-4 Analysis of Pressurized Water Reactor Critical Configurations: Volume 2-Sequoyah Unit 2 Cycle 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman, S.M.

1995-01-01

The requirements of ANSI/ANS 8.1 specify that calculational methods for away-from-reactor criticality safety analyses be validated against experimental measurements. If credit for the negative reactivity of the depleted (or spent) fuel isotopics is desired, it is necessary to benchmark computational methods against spent fuel critical configurations. This report summarizes a portion of the ongoing effort to benchmark away-from-reactor criticality analysis methods using critical configurations from commercial pressurized-water reactors. The analysis methodology selected for all the calculations reported herein is based on the codes and data provided in the SCALE-4 code system. The isotopic densities for the spent fuel assemblies inmore » the critical configurations were calculated using the SAS2H analytical sequence of the SCALE-4 system. The sources of data and the procedures for deriving SAS2H input parameters are described in detail. The SNIKR code module was used to extract the necessary isotopic densities from the SAS2H results and provide the data in the format required by the SCALE criticality analysis modules. The CSASN analytical sequence in SCALE-4 was used to perform resonance processing of the cross sections. The KENO V.a module of SCALE-4 was used to calculate the effective multiplication factor (k{sub eff}) of each case. The SCALE-4 27-group burnup library containing ENDF/B-IV (actinides) and ENDF/B-V (fission products) data was used for all the calculations. This volume of the report documents the SCALE system analysis of three reactor critical configurations for the Sequoyah Unit 2 Cycle 3. This unit and cycle were chosen because of the relevance in spent fuel benchmark applications: (1) the unit had a significantly long downtime of 2.7 years during the middle of cycle (MOC) 3, and (2) the core consisted entirely of burned fuel at the MOC restart. The first benchmark critical calculation was the MOC restart at hot, full-power (HFP) critical

[La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] the first lanthanum uranyl-vanadate with structure built from two types of sheets based upon the uranophane anion-topology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mer, A.; Obbade, S.; Rivenet, M.

2012-01-15

The new lanthanum uranyl vanadate divanadate, [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] was obtained by reaction at 800 Degree-Sign C between lanthanum chloride, uranium oxide (U{sub 3}O{sub 8}) and vanadium oxide (V{sub 2}O{sub 5}) and the structure was determined from single-crystal X-ray diffraction data. This compound crystallizes in the orthorhombic system with space group P2{sub 1}2{sub 1}2{sub 1} and unit-cell parameters a=6.9470(2) A, b=7.0934(2) A, c=25.7464(6) A, V=1268.73(5) A{sup 3}, Z=4. A full matrix least-squares refinement yielded R{sub 1}=0.0219 for 5493 independent reflections. The crystal structure is characterized by the stacking of uranophane-type sheets {sup 2}{sub {infinity}}[(UO{sub 2})(VO{sub 4})]{sup -}more » and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +} connected through La-O bonds involving the uranyl oxygen of the uranyl-vanadate sheets. The double layers result from the connection of two {sup 2}{sub {infinity}}[La(UO{sub 2})(VO{sub 4}){sub 2}]{sup -} sheets derived from the uranophane anion-topology by replacing half of the uranyl ions by lanthanum atoms and connected through the formation of divanadate entities. - Graphical abstract: A view of the three-dimensional structure of [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})]. Highlights: Black-Right-Pointing-Pointer New lanthanum uranyl vanadate divanadate has been synthesized. Black-Right-Pointing-Pointer Structure was determined from single-crystal X-ray diffraction data. Black-Right-Pointing-Pointer Structure is characterized by uranophane-type sheets and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +}.« less

Hydrogen suppresses UO 2 corrosion

NASA Astrophysics Data System (ADS)

Carbol, Paul; Fors, Patrik; Gouder, Thomas; Spahiu, Kastriot

2009-08-01

Release of long-lived radionuclides such as plutonium and caesium from spent nuclear fuel in deep geological repositories will depend mainly on the dissolution rate of the UO 2 fuel matrix. This dissolution rate will, in turn, depend on the redox conditions at the fuel surface. Under oxidative conditions UO 2 will be oxidised to the 1000 times more soluble UO 2.67. This may occur in a repository as the reducing deep groundwater becomes locally oxidative at the fuel surface under the effect of α-radiolysis, the process by which α-particles emitted from the fuel split water molecules. On the other hand, the groundwater corrodes canister iron generating large amounts of hydrogen. The role of molecular hydrogen as reductant in a deep bedrock repository is questioned. Here we show evidence of a surface-catalysed reaction, taking place in the H 2-UO 2-H 2O system where molecular hydrogen is able to reduce oxidants originating from α-radiolysis. In our experiment the UO 2 surface remained stoichiometric proving that the expected oxidation of UO 2.00 to UO 2.67 due to radiolytic oxidants was absent. As a consequence, the dissolution of UO 2 stopped when equilibrium was reached between the solid phase and U 4+ species in the aqueous phase. The steady-state concentration of uranium in solution was determined to be 9 × 10 -12 M, about 30 times lower than previously reported for reducing conditions. Our findings show that fuel dissolution is suppressed by H 2. Consequently, radiotoxic nuclides in spent nuclear fuel will remain immobilised in the UO 2 matrix. A mechanism for the surface-catalysed reaction between molecular hydrogen and radiolytic oxidants is proposed.

Spectroscopy of the UO+2 cation and the delayed ionization of UO2.

PubMed

Merritt, Jeremy M; Han, Jiande; Heaven, Michael C

2008-02-28

Vibronically resolved spectra for the UO+2 cation have been recorded using the pulsed field ionization zero electron kinetic energy (PFI-ZEKE) technique. For the ground state, long progressions in both the bending and symmetric stretch vibrations were observed. Bend and stretch progressions of the first electronically excited state were also observed, and the origin was found at an energy of 2678 cm(-1) above the ground state zero-point level. This observation is consistent with a recent theoretical prediction [Infante et al., J. Chem. Phys. 127, 124308 (2007)]. The ionization energy for UO2, derived from the PFI-ZEKE spectrum, namely, 6.127(1) eV, is in excellent agreement with the value obtained from an earlier photoionization efficiency measurement. Delayed ionization of UO2 in the gas phase has been reported previously [Han et al., J. Chem. Phys. 120, 5155 (2004)]. Here, we extend the characterization of the delayed ionization process by performing a quantitative study of the ionization rate as a function of the energy above the ionization threshold. The ionization rate was found to be 5 x 10(6) s(-1) at threshold, and increased linearly with increasing energy in the range investigated (0-1200 cm(-1)).

Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O

NASA Astrophysics Data System (ADS)

Mereiter, Kurt

2013-04-01

Albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O, triclinic, space group Pī, a = 13.569(2), b = 13.419(2), c = 11.622(2) Å, α = 115.82(1), β = 107.61(1), γ = 92.84(1)° (structural unit cell, not reduced), V = 1774.6(5) Å3, Z = 2, D c = 2.69 g/cm3 (for 17.5 H2O), is a mineral that was found in small amounts with schröckingerite, NaCa3F[UO2(CO3)3](SO4)ṡ10H2O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca2[UO2(CO3)3]ṡ ~ 11H2O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX = 1.511(2), nY = 1.550(2), nZ = 1.566(2), 2 V = 65(1)° ( λ = 589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO2 and H2O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1 = 0.0206 and wR2 = 0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO2(CO3)3]4- anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF2(Ocarbonate)3(H2O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO6, CaF2O2(H2O)4, CaFO3(H2O)4 and CaO2(H2O)6 coordination polyhedra. The crystal structure is built up from MgCa3F2[UO2(CO3)3]ṡ8H2O layers parallel to (001) which are linked by Ca[UO2(CO3)3]ṡ5H2O moieties into a framework of the composition MgCa4F2[UO2(CO3)3]ṡ13H2O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a

The crystal structures of α- and β-CdUO 4

NASA Astrophysics Data System (ADS)

Yamashita, Toshiyuki; Fujino, Takeo; Masaki, Norio; Tagawa, Hiroaki

1981-04-01

The structural parameters of α- and β-CdUO 4 crystals are determined by X-ray powder diffraction technique. α-CdUO 4 is rhombohedral and cell parameters are a = 6.233(3) Å and α = 36.12(5)°. β-CdUO 4 crystallizes in a C-centered orthorhombic cell with a = 7.023(4), b = 6.849(3), c = 3.514 (2) Å. The space groups are R overline3m for α-CdUO 4 and Cmmm for β-CdUO 4. α-CdUO 4: 1U in (000), 1Cd in ( {1}/{2}{1}/{2}{1}/{2}), 2O(1) in ±( uuu), 2O(2) in ±( vvv); u = 0.113, v = 0.350, Z = 1. β-CdUO 4: 2U in ( 000; {1}/{2}{1}/{2} 0 ), 2Cd in ( {1}/{2} 0 {1}/{2}; 0 {1}/{2}, {1}/{2}), 4O(1) in ( 0, ±y, 0; {1}/{2}, {1}/{2} ±y, 0 ), 4O(2) in ( ±x, 0, {1}/{2}; {1}/{2} ±x, {1}/{2}, {1}/{2}); x = 0.159, y = 0.278, Z = 2. β-CdUO 4 contains collinear uranyl UO 2+2 groups with a UO(1) distance of 1.91 Å, located either along or parallel to the c axis whereas the UO(1) bond length in α-CdUO 4 is 1.98 Å which is longer than the usual uranyl bond length.

Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

PubMed

Almond, Philip M; Albrecht-Schmitt, Thomas E

2002-10-21

The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta

The synthesis and crystal structure of α-Ca 3UO 6

NASA Astrophysics Data System (ADS)

Holc, J.; Golic̆, L.

1983-07-01

Single crystals of α-Ca 3UO 6 were grown from a UO 3CaCl 2CaO melt by the slow cooling method from 950°C. The crystal structure was determined by means of X-ray diffraction with R = 0.032 and Rw = 0.019. The structure of α-Ca 3UO 6 is of Mg 3TeO 6 type. α-Ca 3UO 6 is rhombohedral with a = 6.729 (1)Å, α = 90.30 (1)°, Z = 2, Dc = 4.955 g/cm 3, Dm = 4.79 g/cm 3, space group R overline3. Uranium and calcium atoms are six-coordinated. At 1200°C rhombohedral α-Ca 3UO 6 irreversibly transforms to monoclinic β-Ca 3UO 6.

High Pressure Low Temperature X-Ray Diffraction Studies of UO2 and UN single crystals.

NASA Astrophysics Data System (ADS)

Antonio, Daniel; Mast, Daniel; Lavina, Barbara; Gofryk, Krzysztof

Uranium dioxide is the most commonly used nuclear fuel material in commercial reactors, while uranium nitride also has many thermal and physical properties that make it attractive for potential use in reactors. Both have a cubic fcc lattice structure at ambient conditions and transition to antiferromagnetic order at low temperature. UO2 is a Mott insulator that orders in a complex non-collinear 3k magnetic structure at about 30 K, while UN has appreciable conductivity and orders in a simpler 1k magnetic structure below 52 K. Both compounds are characterized by strong magneto-structural interactions, understanding of which is vital for modeling their thermo-physical properties. While UO2 and UN have been extensively studied at and above room temperature, little work has been done to directly study the structure of these materials at low temperatures where magnetic interactions are dominant. In the course of our systematic studies on magneto vibrational behavior of UO2 and UN, here we present our recent results of high pressure X-Ray Diffraction (up to 35 GPa) measured below the Neel temperature using synchrotron radiation. Work supported by the Department of Energy, Office of Basic Energy Sciences, Materials Sciences, and Engineering Division.

Synchrotron characterization of nanograined UO 2 grain growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Kun; Miao, Yinbin; Yun, Di

2015-09-30

This activity is supported by the US Nuclear Energy Advanced Modeling and Simulation (NEAMS) Fuels Product Line (FPL) and aims at providing experimental data for the validation of the mesoscale simulation code MARMOT. MARMOT is a mesoscale multiphysics code that predicts the coevolution of microstructure and properties within reactor fuel during its lifetime in the reactor. It is an important component of the Moose-Bison-Marmot (MBM) code suite that has been developed by Idaho National Laboratory (INL) to enable next generation fuel performance modeling capability as part of the NEAMS Program FPL. In order to ensure the accuracy of the microstructuremore » based materials models being developed within the MARMOT code, extensive validation efforts must be carried out. In this report, we summarize our preliminary synchrotron radiation experiments at APS to determine the grain size of nanograin UO 2. The methodology and experimental setup developed in this experiment can directly apply to the proposed in-situ grain growth measurements. The investigation of the grain growth kinetics was conducted based on isothermal annealing and grain growth characterization as functions of duration and temperature. The kinetic parameters such as activation energy for grain growth for UO 2 with different stoichiometry are obtained and compared with molecular dynamics (MD) simulations.« less

The structure of liquid UO2-x in reducing gas atmospheres

NASA Astrophysics Data System (ADS)

Alderman, O. L. G.; Benmore, C. J.; Weber, J. K. R.; Skinner, L. B.; Tamalonis, A. J.; Sendelbach, S.; Hebden, A.; Williamson, M. A.

2017-02-01

High energy X-ray diffraction experiments performed on hypostoichiometric UO2-x liquids in reducing gas mixtures of 95%Ar:5%CO and 95%Ar:5%H2 are compared to that conducted in a pure Ar atmosphere [Skinner et al., Science 346, 984 (2014)]. The measurements are pertinent to severe accident scenarios at nuclear reactors, where core melts can encounter reducing conditions and further shed light on the oxide chemistry of the low valence states of uranium, particularly U(III), which become stable only at very high temperatures and low oxygen potentials. The radioactive samples were melted by floating small spheres of material using an aerodynamic levitator and heating with a laser beam. In the more reducing environments, a 1.7% shift to lower Q-values is observed in the position of the principal peak of the measured X-ray structure factors, compared to the more oxidizing Ar environment. This corresponds to an equivalent elongation in the U-U nearest neighbor distances and the U-U periodicity. The U-O peak (modal) bond-length, as measured from the real-space total correlation functions, is also observed to expand by 0.9-1.6% under reducing conditions, consistent with the presence of 15-27% U3+ cations, assuming constant U-O coordination number. The slightly larger U-U elongation, as compared to the U-O elongation, is interpreted as a slight increase in U-O-U bond angles. Difficulties concerning the determination of the hypostoichiometry, x, are discussed, along with the future directions for related research.

The structure of liquid UO 2-x in reducing gas atmospheres

DOE PAGES

Alderman, O. L. G.; Benmore, C. J.; Weber, J. K. R.; ...

2017-02-22

High energy X-ray diffraction experiments performed on hypostoichiometric UO 2-x liquids in reducing gas mixtures of 95%Ar:5%CO and 95%Ar:5%H 2 are compared to that conducted in a pure Ar atmosphere [Skinner et al., Science 346, 984 (2014)]. The measurements are pertinent to severe accident scenarios at nuclear reactors, where core melts can encounter reducing conditions and further shed light on the oxide chemistry of the low valence states of uranium, particularly U(III), which become stable only at very high temperatures and low oxygen potentials. The radioactive samples were melted by floating small spheres of material using an aerodynamic levitator andmore » heating with a laser beam. In the more reducing environments, a 1.7% shift to lower Q-values is observed in the position of the principal peak of the measured X-ray structure factors, compared to the more oxidizing Ar environment. This corresponds to an equivalent elongation in the U-U nearest neighbor distances and the U-U periodicity. The U-O peak (modal) bond-length, as measured from the real-space total correlation functions, is also observed to expand by 0.9–1.6% under reducing conditions, consistent with the presence of 15–27% U 3+ cations, assuming constant U-O coordination number. The slightly larger U-U elongation, as compared to the U-O elongation, is interpreted as a slight increase in U-O-U bond angles. Difficulties concerning the determination of the hypostoichiometry, x, are discussed, along with the future directions for related research.« less

Development of Macroscale Models of UO 2 Fuel Sintering and Densification using Multiscale Modeling and Simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenquist, Ian; Tonks, Michael

2016-10-01

Light water reactor fuel pellets are fabricated using sintering to final densities of 95% or greater. During reactor operation, the porosity remaining in the fuel after fabrication decreases further due to irradiation-assisted densification. While empirical models have been developed to describe this densification process, a mechanistic model is needed as part of the ongoing work by the NEAMS program to develop a more predictive fuel performance code. In this work we will develop a phase field model of sintering of UO 2 in the MARMOT code, and validate it by comparing to published sintering data. We will then add themore » capability to capture irradiation effects into the model, and use it to develop a mechanistic model of densification that will go into the BISON code and add another essential piece to the microstructure-based materials models. The final step will be to add the effects of applied fields, to model field-assisted sintering of UO 2. The results of the phase field model will be validated by comparing to data from field-assisted sintering. Tasks over three years: 1. Develop a sintering model for UO 2 in MARMOT 2. Expand model to account for irradiation effects 3. Develop a mechanistic macroscale model of densification for BISON« less

Surface reactions of ethanol over UO 2(100) thin film

DOE Office of Scientific and Technical Information (OSTI.GOV)

S. D. Senanayake; Mudiyanselage, K.; Burrell, A. K.

2015-10-08

The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure, and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO 3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH 3CH 2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C 1s, O 1s, and U 4f to investigate the bondingmore » mode, surface composition, electronic structure, and probable chemical changes to the stoichiometric-UO 2(100) [smooth-UO 2(100)] and Ar +-sputtered UO 2(100) [rough-UO 2(100)] surfaces. Unlike UO 2(111) single crystal and UO 2 thin film, Ar-ion-sputtering of this UO 2(100) did not result in noticeable reduction of U cations. Upon ethanol adsorption (saturation occurred at 0.5 ML), only the ethoxy (CH 3CH 2O –) species is formed on smooth-UO 2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO–) on the Ar +-sputtered UO 2(100) surface. Furthermore, all ethoxy and acetate species are removed from the surface between 600 and 700 K.« less

Microbes make average 2 nanometer diameter crystalline UO2 particles.

NASA Astrophysics Data System (ADS)

Suzuki, Y.; Kelly, S. D.; Kemner, K. M.; Banfield, J. F.

2001-12-01

It is well known that phylogenetically diverse groups of microorganisms are capable of catalyzing the reduction of highly soluble U(VI) to highly insoluble U(IV), which rapidly precipitates as uraninite (UO2). Because biological uraninite is highly insoluble, microbial uranyl reduction is being intensively studied as the basis for a cost-effective in-situ bioremediation strategy. Previous studies have described UO2 biomineralization products as amorphous or poorly crystalline. The objective of this study is to characterize the nanocrystalline uraninite in detail in order to determine the particle size, crystallinity, and size-related structural characteristics, and to examine the implications of these for reoxidation and transport. In this study, we obtained U-contaminated sediment and water from an inactive U mine and incubated them anaerobically with nutrients to stimulate reductive precipitation of UO2 by indigenous anaerobic bacteria, mainly Gram-positive spore-forming Desulfosporosinus and Clostridium spp. as revealed by RNA-based phylogenetic analysis. Desulfosporosinus sp. was isolated from the sediment and UO2 was precipitated by this isolate from a simple solution that contains only U and electron donors. We characterized UO2 formed in both of the experiments by high resolution-TEM (HRTEM) and X-ray absorption fine structure analysis (XAFS). The results from HRTEM showed that both the pure and the mixed cultures of microorganisms precipitated around 1.5 - 3 nm crystalline UO2 particles. Some particles as small as around 1 nm could be imaged. Rare particles around 10 nm in diameter were also present. Particles adhere to cells and form colloidal aggregates with low fractal dimension. In some cases, coarsening by oriented attachment on \\{111\\} is evident. Our preliminary results from XAFS for the incubated U-contaminated sample also indicated an average diameter of UO2 of 2 nm. In nanoparticles, the U-U distance obtained by XAFS was 0.373 nm, 0.012 nm

Formation of ternary CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) complexes under neutral to weakly alkaline conditions.

PubMed

Lee, Jun-Yeop; Yun, Jong-Il

2013-07-21

The chemical behavior of ternary Ca-UO2-CO3 complexes was investigated by using time-resolved laser fluorescence spectroscopy (TRLFS) in combination with EDTA complexation at pH 7-9. A novel TRLFS revealed two distinct fluorescence lifetimes of 12.7 ± 0.2 ns and 29.2 ± 0.4 ns for uranyl complexes which were formed increasingly dependent upon the calcium ion concentration, even though nearly indistinguishable fluorescence peak shapes and positions were measured for both Ca-UO2-CO3 complexes. For identifying the stoichiometric number of complexed calcium ions, slope analysis in terms of relative fluorescence intensity versus calcium concentration was employed in a combination with the complexation reaction of CaEDTA(2-) by adding EDTA. The formation of CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) was identified under given conditions and their formation constants were determined at I = 0.1 M Na/HClO4 medium, and extrapolated to infinitely dilute solution using specific ion interaction theory (SIT). As a result, the formation constants for CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) were found to be log β113(0) = 27.27 ± 0.14 and log β213(0) = 29.81 ± 0.19, respectively, providing that the ternary Ca-UO2-CO3 complexes were predominant uranium(vi) species at neutral to weakly alkaline pH in the presence of Ca(2+) and CO3(2-) ions.

Antiferromagnetic-ferromagnetic crossover in UO 2-TiO x multi-phase systems

NASA Astrophysics Data System (ADS)

Nakamura, Akio; Tsutsui, Satoshi; Yoshii, Kenji

2001-05-01

An antiferromagnetic (AF)-weakly ferromagnetic (WF) crossover has been found for UO 2-TiO x multi-phase systems, (1- y)UO 2+ yTiO x ( y=0.05-0.72, x=0, 1.0, 1.5 and 2.0), when these mixtures are heat treated at high temperature in vacuum. From the powder X-ray diffraction and electron-microprobe analyses, their phase assemblies were as follows: for x=0, 1.0 and 1.5, a heterogeneous two-phase mixture of UO 2+TiO x; for x=2.0, that of UO 2+UTi 2O 6 for y<0.67, showing characteristic microstructures, and for y>0.67 that of UTi 2O 6+TiO 2 (plus residual minor UO 2). Magnetic susceptibility ( χ) of the present UO 2 powder was confirmed to exhibit an antiferromagnetic sharp drop at TN (=30.5 K). In contrast, χ of these multi-phase systems was found to exhibit a sharp upturn at the respective TN, while their TN values remained almost constant with varying y. This χ upturn at TN is most pronounced for UO 2+Ti-oxide (titania) systems ( x=1.0, 1.5 and 2.0) over the wide mixture ratio above y˜0.10. These observations indicate that an AF-WF crossover is induced for these multi-phase systems, plausibly due to the interfacial magnetic modification of UO 2 in contact with the oxide partners.

Synthesis and an X-ray diffraction study of Rb{sub 2}[(UO{sub 2}){sub 2}(C{sub 2}O{sub 4}){sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serezhkina, L. B., E-mail: Lserezh@ssu.samara.ru; Peresypkina, E. V.; Neklyudova, N. A.

2010-09-15

The synthesis and X-ray diffraction study of compound Rb{sub 2}[(UO{sub 2}){sub 2}(C{sub 2}O{sub 4}){sub 3}], which crystallizes in the monoclinic crystal system, are performed. The unit cell parameters are as follows: a = 7.9996(6) A, b = 8.8259(8) A, c = 11.3220(7) A, {beta} = 105.394(2){sup o}, and V = 770.7(1) A{sup 3}; space group P2{sub 1}/n, Z = 2, and R{sub 1} = 0.0271. [(UO{sub 2}){sub 2}(C{sub 2}O{sub 4}){sub 3}]{sup 2-} layers belonging to the AK{sub 0.5}{sup 02}T{sup 11} crystal chemical group of uranyl complexes (A = UO{sub 2}{sup 2+}, K{sup 02} = C{sub 2}O{sub 4}{sup 2-}, and T{supmore » 11} = C{sub 2}O{sub 4}{sup 2-}) are uranium-containing structural units of the crystals. The layers are connected with outer-sphere rubidium cations by electrostatic interactions.« less

From {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} to {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite chains in A{sub 6}U{sub 2}Mo{sub 4}O{sub 21} (A=Na, K, Rb, Cs) compounds: Synthesis and crystal structure of Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagoubi, S.; Groupe de Radiochimie, Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud XI, 91406 Orsay Cedex; Obbade, S., E-mail: said.obbade@phelma.grenoble-inp.f

2011-05-15

A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610

Microstructure and mechanical properties of eutectic B2O3-UO2 ceramic composites solidified at different cooling rates

NASA Astrophysics Data System (ADS)

Yusufu, Aikebaier; Uno, Masayoshi

2018-02-01

The removal of nuclear debris from damaged reactors by drilling or cutting requires an understanding of various properties of the solidified debris, such as mechanical properties (hardness, fractural features, strength, etc.) and microstructural properties like porosity, which have a significant impact on the mechanical properties. In this study, B2O3-UO2 composites were prepared by the eutectic reaction as solidified samples of mock fuel debris with a wide variety of porosities, and the porosity dependence of the mechanical properties under compression were characterized to obtain fundamental data on the complicated fuel debris. The porous eutectic B2O3-UO2 (B2O3/UO2 atomic ratio = 0.225:0.775) samples were successfully prepared by solidification of the molten phase below 2073 K, and the porosity increased as the pore network developed as the cooling rate was decreased. The nano- and microhardness as well as Young's moduli of the eutectic B2O3-UO2 samples were higher than those of UO2. However, the compressive strengths of the eutectic B2O3-UO2 samples were lower than that of UO2, and they decreased as the porosity increased. All samples showed typical brittle fracturing behavior. The low-porosity samples showed a linear elastic step up to a sudden rupture, whereas the high-porosity samples exhibited two main regimes: a linear elastic region that can be attributed to pore-edge bending or face stretching; a zigzag step that is related to the progression of pore collapse.

METHOD FOR PREPARATION OF UO$sub 2$ PARTICLES

DOEpatents

Johnson, J.R.; Taylor, A.J.

1959-09-22

A method is described for the preparation of highdensity UO/sub 2/ particles within the size range of 40 to 100 microns. In accordance with the invention UO/sub 2/ particles are autoclaved with an aqueous solution of uranyl ions. The resulting crystals are reduced to UO/sub 2/ and the UO/sub 2/ is heated to at least 1000 deg C to effect densification. The resulting UO/sub 2/ particles are screened, and oversize particles are crushed and screened to recover the particles within the desired size range.

Polymorphism in Alkali Metal Uranyl Nitrates: Synthesis and Crystal Structure of γ-K(UO2)(NO3)3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Krivovichev, Sergey V.; Burns, Peter C.

2011-07-20

Single crystals of γ-K(UO2)(NO3)3 were prepared from aqueous solutions by evaporation. The crystal structure [orthorhombic, Pbca (61), a = 9.2559(3) Å, b = 12.1753(3) Å, c = 15.8076(5) Å, V = 1781.41(9) Å3, Z = 8] was determined by direct methods and refined to R1 = 0.0267 on the basis of 3657 unique observed reflections. The structure is composed of isolated anionic uranyl trinitrate units, [(UO2)(NO3)3]–, that are linked through eleven-coordinated K+ cations. Both known polymorphs of K(UO2)(NO3)3 (α- and γ-phases) can be considered as based upon sheets of isolated complex [(UO2)(NO3)3]– ions separated by K+ cations. The existence ofmore » polymorphism in the two K[UO2(NO3)3] polymorphs is due to the different packing modes of uranyl trinitrate clusters that adopt the same two-dimensional but different three-dimensional arrangements.« less

Peierls-Nabarro modeling of dislocations in UO2

NASA Astrophysics Data System (ADS)

Skelton, Richard; Walker, Andrew M.

2017-11-01

Under conditions of high stress or low temperature, glide of dislocations plays an important role in the deformation of UO2. In this paper, the Peierls-Nabarro model is used to calculate the core widths and Peierls stresses of ½<110> edge and screw dislocations gliding on {100}, {110}, and {111}. The energy of the inelastic displacement field in the dislocation core is parameterized using generalized stacking fault energies, which are calculated atomistically using interatomic potentials. We use seven different interatomic potential models, representing the variety of different models available for UO2. The different models broadly agree on the relative order of the strengths of the different slip systems, with the 1/2<110>{100} edge dislocation predicted to be the weakest slip system and 1/2<110>{110} the strongest. However, the calculated Peierls stresses depend strongly on the interatomic potential used, with values ranging between 2.7 and 12.9 GPa for glide of 1/2<110>{100} edge dislocations, 16.4-32.3 GPa for 1/2<110>{110} edge dislocations, and 6.8-13.6 GPa for 1/2<110>{111} edge dislocations. The glide of 1/2<110> screw dislocations in UO2 is also found to depend on the interatomic potential used, with some models predicting similar Peierls stresses for glide on {100} and {111}, while others predict a unique easy glide direction. Comparison with previous fully atomistic calculations show that the Peierls-Nabarro model can accurately predict dislocation properties in UO2.

High temperature investigation of the solid/liquid transition in the PuO2-UO2-ZrO2 system

NASA Astrophysics Data System (ADS)

Quaini, A.; Guéneau, C.; Gossé, S.; Sundman, B.; Manara, D.; Smith, A. L.; Bottomley, D.; Lajarge, P.; Ernstberger, M.; Hodaj, F.

2015-12-01

The solid/liquid transitions in the quaternary U-Pu-Zr-O system are of great interest for the analysis of core meltdown accidents in Pressurised Water Reactors (PWR) fuelled with uranium-dioxide and MOX. During a severe accident the Zr-based cladding can become completely oxidised due to the interaction with the oxide fuel and the water coolant. In this framework, the present analysis is focused on the pseudo-ternary system UO2-PuO2-ZrO2. The melting/solidification behaviour of five pseudo-ternary and one pseudo-binary ((PuO2)0.50(ZrO2)0.50) compositions have been investigated experimentally by a laser heating method under pre-set atmospheres. The effects of an oxidising or reducing atmosphere on the observed melting/freezing temperatures, as well as the amount of UO2 in the sample, have been clearly identified for the different compositions. The oxygen-to-metal ratio is a key parameter affecting the melting/freezing temperature because of incongruent vaporisation effects. In parallel, a detailed thermodynamic model for the UO2-PuO2-ZrO2 system has been developed using the CALPHAD method, and thermodynamic calculations have been performed to interpret the present laser heating results, as well as the high temperature behaviour of the cubic (Pu,U,Zr)O2±x-c mixed oxide phase. A good agreement was obtained between the calculated and experimental data points. This work enables an improved understanding of the major factors relevant to severe accident in nuclear reactors.

A novel open-framework with non-crossing channels in the uranyl vanadates A(UO 2) 4(VO 4) 3 ( A=Li, Na)

NASA Astrophysics Data System (ADS)

Obbade, S.; Dion, C.; Rivenet, M.; Saadi, M.; Abraham, F.

2004-06-01

A new sodium uranyl vanadate Na(UO 2) 4(VO 4) 3 has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. It crystallizes in the tetragonal symmetry with space group I4 1/ amd and following cell parameters: a=7.2267(4) Å and c=34.079(4) Å, V=1779.8(2) Å 3, Z=4 with ρmes=5.36(3) g/cm 3 and ρcal=5.40(2) g/cm 3. A full-matrix least-squares refinement on the basis of F2 yielded R1=0.028 and w R2=0.056 for 52 parameters with 474 independent reflections with I⩾2 σ( I) collected on a BRUKER AXS diffractometer with Mo Kα radiation and a CCD detector. The crystal structure is characterized by ∞2[(UO 2) 2(VO 4)] sheets parallel to (001) formed by corner-shared UO 6 distorted octahedra and V(2)O 4 tetrahedra, connected by V(1)O 4 tetrahedra to ∞1[UO 5] 4- chains of edge-shared UO 7 pentagonal bipyramids alternately parallel to the a- and b-axis. The resulting three-dimensional framework creates mono-dimensional channels running down the a- and b-axis formed by face-shared oxygen octahedra half occupied by Na. The powder of Li analog compound Li(UO 2) 4(VO 4) 3 has been synthesized by solid-state reaction. The two compounds exhibit high mobility of the alkaline ions within the two-dimensional network of non-intersecting channels.

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy.

PubMed

Goncharov, Vasiliy; Kaledin, Leonid A; Heaven, Michael C

2006-10-07

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.

Molybdenum-UO2 cerment irradiation at 1145 K

NASA Technical Reports Server (NTRS)

Mcdonald, G.

1971-01-01

Two molybdenum-UO2 cermet fuel pins were fission heated in a helium-cooled loop at a temperature of 1145 K and to a total burnup of 5.3 % of the U-235. After irradiation the fuel pins were measured to check dimensional stability, punctured at the plenums to determine fission gas release, and examined metallographically to determine the effect of irradiation. Burnup was determined in several sections of the fuel pin. The results of the postirradiation examination indicated: (1) There was no visible change in the fuel pins on irradiation under the above conditions. (2) The maximum swelling of the fuel pins was less than 1%. (3) There was no migration of UO2 and no visible interaction between the molybdenum and the UO2. (4) Approximately 12% of the fission gas formed was released from the cermet cone into the gas plenum.

Grain growth and pore coarsening in dense nano-crystalline UO 2+x fuel pellets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Tiankai; Mo, Kun; Yun, Di

Dense nano-sized UO 2+x pellets are synthesized by spark plasma sintering with controlled stoichiometries (UO 2.03 and UO 2.11) and grain sizes (~100 nm), and subsequently isothermally annealed to study their effects on grain growth kinetics and microstructure stability. The grain growth kinetics is determined and analyzed focusing on the interaction between grain boundary migration, pore growth and coalescence. Grains grow much bigger in nano-sized UO 2.11 than UO 2.03 upon thermal annealing, consistent with the fact that hyper-stoichiometric UO 2+x is beneficial for sintering due to enhanced U ion diffusion from excessive O ion interstitials. The activation energies ofmore » the grain growth for UO 2.03 and UO 2.11 are determined as ~1.0 and 1.3~2.0 eV, respectively. As compared with the micron-sized UO 2 in which volumetric diffusion dominates the grain coarsening with an activation energy of ~3.0 eV, the enhanced grain growth kinetics in nano-sized UO 2+x suggests that grain boundary diffusion controls grain growth. Lastly, the higher activation energy of more hyper-stoichiometric nano-sized UO 2.11 may be attributed to the excessive O interstitials pinning grain boundary migration.« less

Grain growth and pore coarsening in dense nano-crystalline UO 2+x fuel pellets

DOE PAGES

Yao, Tiankai; Mo, Kun; Yun, Di; ...

2017-03-25

Dense nano-sized UO 2+x pellets are synthesized by spark plasma sintering with controlled stoichiometries (UO 2.03 and UO 2.11) and grain sizes (~100 nm), and subsequently isothermally annealed to study their effects on grain growth kinetics and microstructure stability. The grain growth kinetics is determined and analyzed focusing on the interaction between grain boundary migration, pore growth and coalescence. Grains grow much bigger in nano-sized UO 2.11 than UO 2.03 upon thermal annealing, consistent with the fact that hyper-stoichiometric UO 2+x is beneficial for sintering due to enhanced U ion diffusion from excessive O ion interstitials. The activation energies ofmore » the grain growth for UO 2.03 and UO 2.11 are determined as ~1.0 and 1.3~2.0 eV, respectively. As compared with the micron-sized UO 2 in which volumetric diffusion dominates the grain coarsening with an activation energy of ~3.0 eV, the enhanced grain growth kinetics in nano-sized UO 2+x suggests that grain boundary diffusion controls grain growth. Lastly, the higher activation energy of more hyper-stoichiometric nano-sized UO 2.11 may be attributed to the excessive O interstitials pinning grain boundary migration.« less

Synthesis and characterization of UO(2)(2+)-ion imprinted polymer for selective extraction of UO(2)(2+).

PubMed

Singh, Dhruv K; Mishra, Shraddha

2009-06-30

Ion-imprinted polymers (IIPs) were prepared for uranyl ion (imprint ion) by formation of binary (salicylaldoxime (SALO) or 4-vinylpyridine (VP)) or ternary (salicylaldoxime and 4-vinylpyridine) complex in 2-methoxy ethanol (porogen) following copolymerization with methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking monomer using 2,2'-azobisisobutyronitrile as initiator. Control polymers (CPs) were also prepared under identical experimental conditions without using imprint ion. The above synthesized polymers were characterized by surface area measurement, microanalysis and FT-IR analysis techniques. The imprinted polymer formed with ternary complex of UO(2)(2+)-SALO-VP (1:2:2, IIP3) showed quantitative enrichment of uranyl ion from dilute aqueous solution and hence was chosen for detailed studies. The optimal pH for quantitative enrichment is 3.5-6.5. The adsorbed UO(2)(2+) was completely eluted with 10 mL of 1.0 M HCl. The retention capacity of IIP3 was found to be 0.559 mmol g(-1). Further, the distribution ratio and selectivity coefficients of uranium and other selected inorganic ions were also evaluated. Five replicate determinations of 25 microg L(-1) of uranium(VI) gave a mean absorbance of 0.032 with a relative standard deviation of 2.20%. The detection limit corresponding to three times the standard deviation of the blank was found to be 5 microg L(-1). IIP3 was tested for preconcentration of uranium(VI) from ground, river and sea water samples.

Comparative Studies on UO2 Fueled HTTR Several Nuclear Data Libraries

NASA Astrophysics Data System (ADS)

Hidayati, Anni N.; Prastyo, Puguh A.; Waris, Abdul; Irwanto, Dwi

2017-07-01

HTTR (High Temperature Engineering Test Reactor) is one of Generation IV nuclear reactors that has been developed by JAERI (former name of JAEA, JAPAN). HTTR uses graphite moderator, helium gas coolant with UO2 fuel and outlet coolant temperature of 900°C or higher than that. Several studies regarding HTTR have been performed by employing JENDL 3.2 nuclear data libraries. In this paper, comparative evaluation of HTTR with several nuclear data libraries (JENDL 3.3, JENDL 4.0, and JEF 3.1) have been conducted.. The 3-D calculation was performed by using CITATION module of SRAC 2006 code. The result shows some differences between those nuclear data libraries result. K-eff or core effective multiplication factor results are about 1.17, 1,18 and 1,19 (JENDL 3.3, JENDL 4.0, and JEF 3.1) at Begin of Life, also at the End of Life (after two years operation) are 1.16, 1.17 and 1.17 for each nuclear data libraries. There are some different result of K-eff but for neutron spectra results, those nuclear data libraries show the same result.

Selection of Nuclear Fuel for TREAT: UO 2 vs U 3O 8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glazoff, Michael Vasily; Van Rooyen, Isabella Johanna; Coryell, Benjamin David

The Transient Reactor Test (TREAT) that resides at the Materials and Fuels Complex (MFC) at Idaho National Laboratory (INL), first achieved criticality in 1959, and successfully performed many transient tests on nuclear fuel until 1994 when its operations were suspended. Resumption of operations at TREAT was approved in February 2014 to meet the U.S. Department of Energy (DOE) Office of Nuclear Energy’s objectives in transient testing of nuclear fuels. The National Nuclear Security Administration’s is converting TREAT from its existing highly enriched uranium (HEU) core to a new core containing low enriched uranium (LEU) (i.e., U-235< 20% by weight). Themore » TREAT Conversion project is currently progressing with conceptual design phase activities. Dimensional stability of the fuel element assemblies, predictable fuel can oxidation and sufficient heat conductivity by the fuel blocks are some of the critical performance requirements of the new LEU fuel. Furthermore, to enable the design team to design fuel block and can specifications, it is amongst the objectives to evaluate TREAT LEU fuel and cladding material’s chemical interaction. This information is important to understand the viability of Zr-based alloys and fuel characteristics for the fabrication of the TREAT LEU fuel and cladding. Also, it is very important to make the right decision on what type of nuclear fuel will be used at TREAT. In particular, one has to consider different oxides of uranium, and most importantly, UO 2 vs U 3O 8. In this report, the results are documented pertaining to the choice mentioned above (UO 2 vs U 3O 8). The conclusion in favor of using UO 2 was made based on the analysis of historical data, up-to-date literature, and self-consistent calculations of phase equilibria and thermodynamic properties in the U-O and U-O-C systems. The report is organized as follows. First, the criteria that were used to make the choice are analyzed. Secondly, existing historical data and

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

PubMed

Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

2001-12-05

The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO

In situ ligand synthesis with the UO{sub 2}{sup 2+} cation under hydrothermal conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frisch, Mark; Cahill, Christopher L.; Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC

A novel uranium (VI) coordination polymer, (UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(C{sub 5}H{sub 6}NO{sub 3}){sub 2} (1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/c, a=22.541(6) A, b=5.7428(15) A, c=15.815(4) A, {beta}=119.112(4){sup o}, Z=4, R{sub 1}=0.0237, wR{sub 2}=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO{sub 2} to form the oxalatemore » linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C{sub 2}O{sub 4}).nH{sub 2}O; 0{<=}n{<=}1) and a known uranyl oxalate [(UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(OH){sub 2}(H{sub 2}O){sub 2}.H{sub 2}O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state. - Graphical abstract: A novel homometallic coordination polymer (UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(C{sub 5}H{sub 6}NO{sub 3}){sub 2}, in the uranium-L-pyroglutamic acid system has been synthesized under hydrothermal conditions. The title compound consists of uranium pentagonal bipyramids bridged through both L-pyroglutamate and oxalate linkages to produce a 3D crystal structure. The oxalate anions are theorized to result from decarboxylation of L-pyroglutamic acid followed by subsequent coupling of CO{sub 2}.« less

Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO 3, U 2O 7, and UO 4

DOE PAGES

Guo, Xiaofeng; Wu, Di; Xu, Hongwu; ...

2016-09-01

The thermal decomposition of studtite (UO 2)O 2(H 2O) 2·2H 2O results in a series of intermediate X-ray amorphous materials with general composition UO 3+x (x = 0, 0.5, 1). As an extension of a structural study on U 2O 7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solutionmore » calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO 3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO 3+x materials that pose the risk of significant O 2 gas. Quantitative knowledge of the energy landscape of amorphous UO 3+x was provided for stability analysis and assessment of conditions for decomposition.« less

PREPARATION OF HIGH DENSITY UO$sub 2$

DOEpatents

Googin, J.M.

1959-09-29

A method is presented for the preparation of highdensity UO/sub 2/ from UF/sub 6/. In accordance with the invention, UF/sub 6/ is reacted with water and concentrated ammonium hydroxide is added to the resulting aqueous solution of UO/ sub 2/F/sub 2/. The resulting precipitate is calcined to U/sub 3/O/sub 8/ an d the U/sub 3/O/sub 8/ is reduced to UO/sub 2/ with a gaseous mixture comprised of carbon monoxide and carbon dioxide at a temperature of from 1600 to 1900 deg C.

Status Report on Irradiation Capsules Designed to Evaluate FeCrAl-UO 2 Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Field, Kevin G.; Howard, Richard H.

This status report provides the background and current status of a series of irradiation capsules that were designed and are being built to test the interactions between candidate FeCrAl cladding for enhanced accident tolerant applications and prototypical enriched commercial UO 2 fuel in a neutron radiation environment. These capsules will test the degree, if any, of fuel cladding chemical interactions (FCCI) between FeCrAl and UO 2. The capsules are to be irradiated in the Advanced Test Reactor (ATR) at Idaho National Laboratory to burn-ups of 10, 30, and 50 GWd/MT with a nominal target temperature at the interfaces between themore » pellets and clad of 350°C.« less

Simulation of xenon, uranium vacancy and interstitial diffusion and grain boundary segregation in UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders D.; Tonks, Michael R.; Casillas, Luis

2014-10-31

In light water reactor fuel, gaseous fission products segregate to grain boundaries, resulting in the nucleation and growth of large intergranular fission gas bubbles. Based on the mechanisms established from density functional theory (DFT) and empirical potential calculations 1, continuum models for diffusion of xenon (Xe), uranium (U) vacancies and U interstitials in UO 2 have been derived for both intrinsic conditions and under irradiation. Segregation of Xe to grain boundaries is described by combining the bulk diffusion model with a model for the interaction between Xe atoms and three different grain boundaries in UO 2 ( Σ5 tilt, Σ5more » twist and a high angle random boundary),as derived from atomistic calculations. All models are implemented in the MARMOT phase field code, which is used to calculate effective Xe and U diffusivities as well as redistribution for a few simple microstructures.« less

AGR-2 Irradiation Test Final As-Run Report, Rev 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collin, Blaise P.

2014-08-01

This document presents the as-run analysis of the AGR-2 irradiation experiment. AGR-2 is the second of the planned irradiations for the Advanced Gas Reactor (AGR) Fuel Development and Qualification Program. Funding for this program is provided by the U.S. Department of Energy as part of the Very High Temperature Reactor (VHTR) Technical Development Office (TDO) program. The objectives of the AGR-2 experiment are to: (a) Irradiate UCO (uranium oxycarbide) and UO 2 (uranium dioxide) fuel produced in a large coater. Fuel attributes are based on results obtained from the AGR-1 test and other project activities. (b) Provide irradiated fuel samplesmore » for post-irradiation experiment (PIE) and safety testing. (c) Support the development of an understanding of the relationship between fuel fabrication processes, fuel product properties, and irradiation performance. The primary objective of the test was to irradiate both UCO and UO 2 TRISO (tri-structural isotropic) fuel produced from prototypic scale equipment to obtain normal operation and accident condition fuel performance data. The UCO compacts were subjected to a range of burnups and temperatures typical of anticipated prismatic reactor service conditions in three capsules. The test train also includes compacts containing UO 2 particles produced independently by the United States, South Africa, and France in three separate capsules. The range of burnups and temperatures in these capsules were typical of anticipated pebble bed reactor service conditions. The results discussed in this report pertain only to U.S. produced fuel. In order to achieve the test objectives, the AGR-2 experiment was irradiated in the B-12 position of the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL) for a total irradiation duration of 559.2 effective full power days (EFPD). Irradiation began on June 22, 2010, and ended on October 16, 2013, spanning 12 ATR power cycles and approximately three and a half calendar years. The

Rates and mechanism of fluoride and water exchange in UO(2)F(5)(3-) and [UO(2)F(4)(H(2)O)](2-) studied by NMR spectroscopy and wave function based methods.

PubMed

Vallet, Valérie; Wahlgren, Ulf; Szabó, Zoltán; Grenthe, Ingmar

2002-10-21

The reaction mechanism for the exchange of fluoride in UO(2)F(5)(3-) and UO(2)F(4)(H(2)O)(2-) has been investigated experimentally using (19)F NMR spectroscopy at -5 degrees C, by studying the line broadening of the free fluoride, UO(2)F(4)(2-)(aq) and UO(2)F(5)(3-), and theoretically using quantum chemical methods to calculate the activation energy for different pathways. The new experimental data allowed us to make a more detailed study of chemical equilibria and exchange mechanisms than in previous studies. From the integrals of the different individual peaks in the new NMR spectra, we obtained the stepwise stability constant K(5) = 0.60 +/- 0.05 M(-1) for UO(2)F(5)(3-). The theoretical results indicate that the fluoride exchange pathway of lowest activation energy, 71 kJ/mol, in UO(2)F(5)(3-) is water assisted. The pure dissociative pathway has an activation energy of 75 kJ/mol, while the associative mechanism can be excluded as there is no stable UO(2)F(6)(4-) intermediate. The quantum chemical calculations have been made at the SCF/MP2 levels, using a conductor-like polarizable continuum model (CPCM) to describe the solvent. The effects of different model assumptions on the activation energy have been studied. The activation energy is not strongly dependent on the cavity size or on interactions between the complex and Na(+) counterions. However, the solvation of the complex and the leaving fluoride results in substantial changes in the activation energy. The mechanism for water exchange in UO(2)F(4)(H(2)O)(2-) has also been studied. We could eliminate the associative mechanism, the dissociative mechanism had the lowest activation energy, 39 kJ/mol, while the interchange mechanism has an activation energy that is approximately 50 kJ/mol higher.

Topological ordering in liquid UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benmore, C. J.; Skinner, L. B.; Lee, B.

2015-12-10

A molecular dynamics model of liquid UO2 that is in good agreement with recent high-energy x-ray diffraction data has been analyzed using the Bhatia–Thornton formalism. A pre-peak appears in the topological structure factor S NN(Q) at Q = 1.85(1)Å-1 which is not present in the more common, element specific Faber–Ziman partial structure factors. A radical Voronoi tessellation of the 3D molecular dynamics model shows the presence of a wide distribution of clusters, consistent with presence of highly mobile oxygen atoms. However, 4-fold Voronoi polyhedra (n 4) are found to dominate the structure and the majority of clusters can be describedmore » by the distribution n 3 ≤ n 4 ≥ n 5. It is argued that an open network of 4-fold Voronoi polyhedra could explain the origin of the pre-peak in S NN(Q) and the topological ordering observed in liquid UO2.« less

Local structure and charge distribution in the UO(2)-U(4)O(9) system.

PubMed

Conradson, Steven D; Manara, Dario; Wastin, Franck; Clark, David L; Lander, Gerard H; Morales, Luis A; Rebizant, Jean; Rondinella, Vincenzo V

2004-11-01

Analysis of X-ray absorption fine structure spectra of UO(2+x) for x = 0-0.20 (UO(2)--U(4)O(9)) reveals that the adventitious O atoms are incorporated as oxo groups with U--O distances of 1.74 A, most likely associated with U(VI), that occur in clusters so that the UO(2) fraction of the material largely remains intact. In addition to the formation of some additional longer U--O bonds, the U sublattice consists of an ordered portion that displays the original U--U distance and a spectroscopically silent, glassy part. This is very different from previous models derived from neutron diffraction that maintained long U--O distances and high U--O coordination numbers. UO(2+x) also differs from PuO(2+x) in its substantially shorter An-oxo distances and no sign of stable coordination with H(2)O and its hydrolysis products.

Richland five-year O2 R and D Program. Integrated site operation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1966-07-11

The technical feasibility of using an electrolytic reduction process to reduce metal scrap and oxide to usable uranium metal is being studied. The incentives for using electrolytic reduction at Richland may be summarized as follows: (1) reduce the unit and total costs of producing plutonium; (2) increase the flexibility of the Richland reactors for producing isotopes, particularly U-236; and (3) simplify the present fuel cycle complex. The scope of the mission is limited to the evaluation of hollow extruded I and E cores, the evaluation of electro-reduced uranium, an investigation of the solution rate of UO{sub 2} in the electrolyte,more » and small-scale irradiations of UO{sub 2} fuels in the N and K Reactors. Progress during FY 1966 is summarized.« less

The effect of fuel chemistry on UO2 dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Casella, Amanda; Hanson, Brady; Miller, William

2016-08-01

The dissolution rate of both unirradiated UO2 and used nuclear fuel has been studied by numerous countries as part of the performance assessment of proposed geologic repositories. In the scenario of waste package failure and groundwater infiltration into the fuel, the effects of variables such as temperature, dissolved oxygen, and water and fuel chemistry on the dissolution rates of the fuel are necessary to provide a quantitative estimate of the potential release over geologic time frames. The primary objective of this research was to determine the influence these parameters have on the dissolution rate of unirradiated UO2 under repository conditionsmore » and compare them to the rates predicted by current dissolution models. Both unirradiated UO2 and UO2 doped with varying concentrations of Gd2O3, to simulate used fuel composition after long time periods where radiolysis has minor contributions to dissolution, were examined. In general, a rise in temperature increased the dissolution rate of UO2 and had a larger effect on pure UO2 than on those doped with Gd2O3. Oxygen dependence was observed in the UO2 samples with no dopant and increased as the temperature rose; in the doped fuels less dependence was observed. The addition of gadolinia into the UO2 matrix showed a significant decrease in the dissolution rate. The matrix stabilization effect resulting from the dopant proved even more beneficial in lowering the dissolution rate at higher temperatures and dissolved O2 concentrations in the leachate where the rates would typically be elevated.« less

Supplying materials needed for grain growth characterizations of nano-grained UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Kun; Miao, Yinbin; Yun, Di

2015-09-30

This activity is supported by the US Nuclear Energy Advanced Modeling and Simulation (NEAMS) Fuels Product Line (FPL) and aims at providing experimental data for the validation of the mesoscale simulation code MARMOT. MARMOT is a mesoscale multiphysics code that predicts the coevolution of microstructure and properties within reactor fuel during its lifetime in the reactor. It is an important component of the Moose-Bison-Marmot (MBM) code suite that has been developed by Idaho National Laboratory (INL) to enable next generation fuel performance modeling capability as part of the NEAMS Program FPL. In order to ensure the accuracy of the microstructuremore » based materials models being developed within the MARMOT code, extensive validation efforts must be carried out. In this report, we summarize our preliminary synchrotron radiation experiments at APS to determine the grain size of nanograin UO 2. The methodology and experimental setup developed in this experiment can directly apply to the proposed in-situ grain growth measurements. The investigation of the grain growth kinetics was conducted based on isothermal annealing and grain growth characterization as functions of duration and temperature. The kinetic parameters such as activation energy for grain growth for UO 2 with different stoichiometry are obtained and compared with molecular dynamics (MD) simulations.« less

The thermodynamic properties of gaseous UO2(OH)2

NASA Astrophysics Data System (ADS)

Konings, R. J. M.; Kovács, A.; Beneš, O.

2017-12-01

Quantum chemical calculations of the molecular properties of the UO2(OH)2 molecule are presented. From the results the thermodynamic properties of this gaseous species have been calculated, and these have been used to re-evaluate the existing literature study on the volatilization of U3O8 in steam, allowing to derive the enthalpy of formation of the UO2(OH)2 molecule.

Syntheses and crystal structures of two topologically related modifications of Cs(2)[(UO(2))(2)(MoO(4))(3)].

PubMed

Krivovichev, S V; Cahill, C L; Burns, P C

2002-01-14

Two polymorphs of Cs(2)(UO(2))(2)(MoO(4))(3) have been synthesized by hydrothermal (alpha-phase) and high-temperature (beta-phase) routes. Both were characterized by single-crystal X-ray diffraction: alpha-Cs(2)(UO(2))(2)(MoO(4))(3), orthorhombic, Pna2(1), a = 20.4302(15) A, b = 8.5552(7) A, c = 9.8549(7) A, Z = 4; beta-Cs(2)(UO(2))(2)(MoO(4))(3), tetragonal, P4(2)/n, a = 10.1367(8) A, c = 16.2831(17) A, Z = 4. The structures of both phases consist of linked UO(7) pentagonal bipyramids and MoO(4) tetrahedra: alpha-Cs(2)(UO(2))(2)(MoO(4))(3) is a framework compound with large channels parallel to the c axis. Two cesium sites are located in these channels and are coordinated by 8 and 10 oxygen atoms. The structure of beta-Cs(2)(UO(2))(2)(MoO(4))(3) contains corrugated [(UO(2))(2)(MoO(4))(3)] sheets that are parallel to (001). The cesium cations are located between the sheets and are coordinated by eight oxygen atoms. The structures are topologically related; both can be described in terms of chains of 5-connected UO(7) pentagonal bipyramids and 3- and 4-connected MoO(4) tetrahedra.

Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

PubMed

Cao, Zhiji; Balasubramanian, K

2009-10-28

Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

Dissolution of Biogenic and Synthetic UO2 under Varied Reducing Conditions

PubMed Central

ULRICH, KAI – UWE; SINGH, ABHAS; SCHOFIELD, ELEANOR J.; BARGAR, JOHN R.; VEERAMANI, HARISH; SHARP, JONATHAN O.; LATMANI, RIZLAN BERNIER -; GIAMMAR, DANIEL E.

2008-01-01

The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles’ surface free energy, structural defects, and compositional variability in analogy to abiotic UO2+x (0 ≤ x ≤ 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00. Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases. PMID:18754482

UO(2) 2+ speciation determines uranium toxicity and bioaccumulation in an environmental Pseudomonas sp. isolate.

PubMed

Vanengelen, Michael R; Field, Erin K; Gerlach, Robin; Lee, Brady D; Apel, William A; Peyton, Brent M

2010-04-01

In the present study, experiments were performed to investigate how representative cellulosic breakdown products, when serving as growth substrates under aerobic conditions, affect hexavalent uranyl cation (UO(2) (2+)) toxicity and bioaccumulation within a Pseudomonas sp. isolate (designated isolate A). Isolate A taken from the Cold Test Pit South (CTPS) region of the Idaho National Laboratory (INL), Idaho Falls, ID, USA. The INL houses low-level uranium-contaminated cellulosic material and understanding how this material, and specifically its breakdown products, affect U-bacterial interactions is important for understanding UO(2) (2+) fate and mobility. Toxicity was modeled using a generalized Monod expression. Butyrate, dextrose, ethanol, and lactate served as growth substrates. The potential contribution of bicarbonate species present in high concentrations was also investigated and compared with toxicity and bioaccumulation patterns seen in low-bicarbonate conditions. Isolate A was significantly more sensitive to UO(2) (2+) and accumulated significantly more UO(2) (2+) in low-bicarbonate concentrations. In addition, UO(2) (2+) growth inhibition and bioaccumulation varied depending on the growth substrate. In the presence of high bicarbonate concentrations, sensitivity to UO(2) (2+) inhibition was greatly mitigated, and did not vary between the four substrates tested. The extent of UO(2) (2+) accumulation was also diminished. The observed patterns were related to UO(2) (2+) aqueous complexation, as predicted by MINTEQ (ver. 2.52) (Easton, PA, USA). In the low- bicarbonate medium, the presence of positively charged and unstable UO(2) (2+)-hydroxide complexes explained both the greater sensitivity of isolate A to UO(2) (2+), and the ability of isolate A to accumulate significant amounts of UO(2) (2+). The exclusive presence of negatively charged and stable UO(2) (2+)-carbonate complexes in the high bi-carbonate medium explained the diminished sensitivity of

Improving Jet Reactor Configuration for Production of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Povitsky, Alex

2000-01-01

The jet mixing reactor has been proposed for the industrial production of fullerene carbon nanotubes. Here we study the flowfield of this reactor using the SIMPLER algorithm. Hot peripheral jets are used to enhance heating of the central jet by mixing with the ambiance of reactor. Numerous configurations of peripheral jets with various number of jets, distance between nozzles, angles between the central jet and a peripheral jets, and twisted configuration of nozzles are considered. Unlike the previous studies of jet mixing, the optimal configuration of peripheral jets produces strong non-uniformity of the central jet in a cross-section. The geometrical shape of reactor is designed to obtain a uniform temperature of a catalyst.

A charge-optimized many-body potential for the U-UO2-O2 system

NASA Astrophysics Data System (ADS)

Li, Yangzhong; Liang, Tao; Sinnott, Susan B.; Phillpot, Simon R.

2013-12-01

Building on previous charge-optimized many-body (COMB) potentials for metallic α-U and gaseous O2, we have developed a new potential for UO2, which also allows the simulation of U-UO2-O2 systems. The UO2 lattice parameter, elastic constants and formation energies of stoichiometric and non-stoichiometric intrinsic defects are well reproduced. Moreover, this is the first rigid-ion potential that produces the correct deviation of the Cauchy relation, as well as the first classical interatomic potential that is able to determine the defect energies of non-stoichiometric intrinsic point defects in UO2 with an appropriate reference state. The oxygen molecule interstitial in the α-U structure is shown to decompose, with some U-O bonds approaching the natural bond length of perfect UO2. Finally, we demonstrate the capability of this COMB potential to simulate a complex system by performing a simulation of the α-U + O2 → UO2 phase transformation. We also identify a possible mechanism for uranium oxidation and the orientation of the resulting fluorite UO2 structure relative to the coordinate system of orthorhombic α-U.

In-situ TEM observation of nano-void formation in UO2 under irradiation

NASA Astrophysics Data System (ADS)

Sabathier, C.; Martin, G.; Michel, A.; Carlot, G.; Maillard, S.; Bachelet, C.; Fortuna, F.; Kaitasov, O.; Oliviero, E.; Garcia, P.

2014-05-01

Transmission electron microscopy (TEM) observations of UO2 polycrystals irradiated in situ with 4 MeV Au ions were performed at room temperature (RT) to better understand the mechanisms of cavity and ultimately fission products nucleation in UO2. Experiments were carried out at the JANNuS Orsay facility that enables in situ ion irradiations inside the microscope to be carried out. The majority of 4 MeV gold ions were transmitted through the thin foil, and the induced radiation defects were investigated by TEM. Observations showed that nano-void formation occurs at ambient temperature in UO2 thin foils irradiated with energetic heavy ions under an essentially nuclear energy loss regime. The diameter and density of nano-objects were measured as a function of the gold irradiation dose at RT. A previous paper has also revealed a similar nano-object population after a Xe implantation performed at 390 keV at 870 K. The nano-object density was modelled using simple concepts derived from Classical Molecular Dynamics simulations. The results are in good agreement, which suggests a mechanism of heterogeneous nucleation induced by energetic cascade overlaps. This indicates that nano-void formation mechanism is controlled by radiation damage. Such nanovoids are likely to act as sinks for mobile fission products during reactor operation.

Summary report on UO 2 thermal conductivity model refinement and assessment studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang-Yang; Cooper, Michael William Donald; Mcclellan, Kenneth James

Uranium dioxide (UO 2) is the most commonly used fuel in light water nuclear reactors and thermal conductivity controls the removal of heat produced by fission, therefore, governing fuel temperature during normal and accident conditions. The use of fuel performance codes by the industry to predict operational behavior is widespread. A primary source of uncertainty in these codes is thermal conductivity, and optimized fuel utilization may be possible if existing empirical models were replaced with models that incorporate explicit thermal conductivity degradation mechanisms during fuel burn-up. This approach is able to represent the degradation of thermal conductivity due to eachmore » individual defect type, rather than the overall burn-up measure typically used which is not an accurate representation of the chemical or microstructure state of the fuel that actually governs thermal conductivity and other properties. To generate a mechanistic thermal conductivity model, molecular dynamics (MD) simulations of UO 2 thermal conductivity including representative uranium and oxygen defects and fission products are carried out. These calculations employ a standard Buckingham type interatomic potential and a potential that combines the many-body embedded atom method potential with Morse-Buckingham pair potentials. Potential parameters for UO 2+x and ZrO 2 are developed for the latter potential. Physical insights from the resonant phonon-spin scattering mechanism due to spins on the magnetic uranium ions have been introduced into the treatment of the MD results, with the corresponding relaxation time derived from existing experimental data. High defect scattering is predicted for Xe atoms compared to that of La and Zr ions. Uranium defects reduce the thermal conductivity more than oxygen defects. For each defect and fission product, scattering parameters are derived for application in both a Callaway model and the corresponding high-temperature model typically used in fuel

Fabrication of micro-cell UO2-Mo pellet with enhanced thermal conductivity

NASA Astrophysics Data System (ADS)

Kim, Dong-Joo; Rhee, Young Woo; Kim, Jong Hun; Kim, Keon Sik; Oh, Jang Soo; Yang, Jae Ho; Koo, Yang-Hyun; Song, Kun-Woo

2015-07-01

As one of accident tolerant fuel pellets which should have features of good thermal conductivity and high fission product retention, a micro-cell UO2-Mo pellet has been studied in the aspect of fabrication and thermal property. It was intended to develop the compatible process with conventional UO2 pellet fabrication process. The effects of processing parameters such as the size and density of UO2 granule and the size of Mo powder have been studied to produce sound and dense pellet with completely connected uniform Mo cell-walls. The micro-cell UO2-Mo pellet consists of many Mo micro-cells and UO2 in them. The thermal conductivity of the micro-cell UO2-Mo pellet was measured and compared to those of the UO2 pellet and the UO2-Mo pellet with dispersed form of Mo particles. The thermal conductivity of the micro-cell UO2-Mo pellet was much enhanced and was found to be influenced by the Mo volumetric fraction and pellet integrity. A continuous Mo micro-cell works as a heat conducting channel in the pellet, greatly enhancing the thermal conductivity of the micro cell UO2-Mo pellet.

Evaluation of B&W UO2/ThO2 VIII experimental core: criticality and thermal disadvantage factor analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carlo Parisi; Emanuele Negrenti

2017-02-01

In the framework of the OECD/NEA International Reactor Physics Experiment (IRPHE) Project, an evaluation of core VIII of the Babcock & Wilcox (B&W) Spectral Shift Control Reactor (SSCR) critical experiment program was performed. The SSCR concept, moderated and cooled by a variable mixture of heavy and light water, envisaged changing of the thermal neutron spectrum during the operation to encourage breeding and to sustain the core criticality. Core VIII contained 2188 fuel rods with 93% enriched UO2-ThO2 fuel in a moderator mixture of heavy and light water. The criticality experiment and measurements of the thermal disadvantage factor were evaluated.

Excited States and Luminescent Properties of UO 2F 2 and Its Solvated Complexes in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Jing; Wang, Zheming; Pan, Duoqiang

2014-07-21

The electronic absorption and emission spectra of free UO 2F 2 and its water solvated complexes below 32 000 cm –1 are investigated at the levels of ab initio CASPT2 and CCSD(T) with inclusion of scalar relativistic and spin–orbit coupling effects. The influence of the water coordination on the electronic spectra of UO 2F 2 is explored by investigating the excited states of solvated complexes (H 2O) nUO 2F 2 (n = 1–3). In these uranyl complexes, water coordination is found to have appreciable influence on the 3Δ (Ω = 1 g) character of the luminescent state and on themore » electronic spectral shape. The simulated luminescence spectral curves based on the calculated spectral parameters of (H 2O) nUO 2F 2 from CCSD(T) approach agree well with experimental spectra in aqueous solution at both near-liquid-helium temperature and room temperature. The possible luminescence spectra of free UO 2F 2 in gas phase are predicted on the basis of CASPT2 and CCSD(T) results, respectively, by considering three symmetric vibration modes. Finally, the effect of competition between spin–orbit coupling and ligand field repulsion on the luminescent state properties is discussed.« less

Chelation of UO(2)(2+) by vitamin B6 complex derivatives: synthesis and characterization of [UO2(beta-pyracinide)2(H2O)] and [UO2(Pyr2en)DMSO]Cl2{Pyr2en=N,N'-ethylenebis(pyridoxylideneiminato)}. A useful modeling of assimilation of uranium by living beings.

PubMed

Back, Davi Fernando; de Oliveira, Gelson Manzoni; Lang, Ernesto Schulz

2006-10-01

The vitamin B(6) derivatives 4-pyridoxic acid (anionic) and the Schiff base N,N'-ethylenebis(pyridoxylideneiminato) react with UO(2)(NO(3))(2) * 6H(2)O to give [UO(2)(beta-pyracinide)(2)(H(2)O)] (beta-pyracin=4-pyridoxic acid) and [UO(2)(Pyr(2)en)DMSO]Cl(2)(Pyr(2)en=N,N'-ethylenebis(pyridoxylideneiminato); DMSO=dimethyl sulfoxide). In both compounds the two uranyl oxo ligands set the axis of distorted pentagonal bipyramides. The ability of vitamin B(6) derivatives to react with UO(2)(2+) allowing the chelation of one uranium atom represents a very specific model of assimilation of uranium by living beings. It could also explain the serious damages caused by heavy or radioactive metals like uranium since their complexation "in vivo" by enzymatic systems like pyridoxal phosphate-containing enzymes would lead to a modification of the prosthetic groups of the metalloenzymes with loss of their catalytic activities.

Non-Destructive Characterization of UO2+x Nuclear Fuels

DOE PAGES

Pokharel, Reeju; Brown, Donald W.; Clausen, Bjørn; ...

2017-10-27

This article describes the effect of fabrication conditions on as-sintered microstructures of various stoichiometric ratios of uranium dioxide, UO 2+x, with the aim of enhancing the understanding of fabrication process and developing and validating a predictive microstructurebased model for fuel performance. We demonstrate the ability of novel, non-destructive methods such as near-field high-energy X-ray diffraction microscopy (nf-HEDM) and micro-computed tomography (μ-CT) to probe bulk samples of high-Z materials by non-destructively characterizing three samples: UO 2.00, UO 2.11, and UO 2.16, which were sintered at 1450°C for 4 hours. The measured 3D microstructures revealed that grain size and porosity were influencedmore » by deviation from stoichiometry.« less

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

Status of Fuel Development and Manufacturing for Space Nuclear Reactors at BWX Technologies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carmack, W.J.; Husser, D.L.; Mohr, T.C.

2004-02-04

New advanced nuclear space propulsion systems will soon seek a high temperature, stable fuel form. BWX Technologies Inc (BWXT) has a long history of fuel manufacturing. UO2, UCO, and UCx have been fabricated at BWXT for various US and international programs. Recent efforts at BWXT have focused on establishing the manufacturing techniques and analysis capabilities needed to provide a high quality, high power, compact nuclear reactor for use in space nuclear powered missions. To support the production of a space nuclear reactor, uranium nitride has recently been manufactured by BWXT. In addition, analytical chemistry and analysis techniques have been developedmore » to provide verification and qualification of the uranium nitride production process. The fabrication of a space nuclear reactor will require the ability to place an unclad fuel form into a clad structure for assembly into a reactor core configuration. To this end, BWX Technologies has reestablished its capability for machining, GTA welding, and EB welding of refractory metals. Specifically, BWX Technologies has demonstrated GTA welding of niobium flat plate and EB welding of niobium and Nb-1Zr tubing. In performing these demonstration activities, BWX Technologies has established the necessary infrastructure to manufacture UO2, UCx, or UNx fuel, components, and complete reactor assemblies in support of space nuclear programs.« less

ON THE REACTION OF COMPONENETS IN MeNO$sub 3$-UO$sub 2$(NO$sub 3$)$sub 2$- H$sub 2$O TYPE SYSTEMS (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yakimov, M.A.; Nosova, N.F.; Degtyarev, A.Ya.

1963-01-01

Solubility in ternary systems TlNO/sub 3/--UO/sub 2/(NO/sub 3/)/sub 2/-- H/sub 2/ O and CsNO/sub 3/--UO/sub 2/(NO/sub 3/)/sub 2/--H/sub 2/O at 0 to 25 c- C was studi ed by the isothermal method. The first system did not form solid phase compounds; the second system formed two compounds Cs/sub 2/UO/ sub 2/(NO/sub 3/)/sub 4/ and CsUO/sub 2/(NO/sub 3/)/sub 3/ at 25 c- and of water vapor pressure over the systems at 25 c- showed that water activity in the ternary systems at certain concentrations does not exceed the water activity in binary uranyl nitratewater system (at identical uranyl nitrate concentrations) confirmingmore » the observed complex formation in the solution. The mechanism of complex formation was analyzed and expanded for alkali metal - metal salt-complexing agent water systems. (R.V.J.)« less

Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

DOE PAGES

Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

2013-11-11

Our study demonstrates a direct electrodeposition of UO 2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO 2(NTf 2) 2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM +NTf 2 –). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO 2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. Themore » UO 2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).« less

Thermal reactions of uranium metal, UO 2, U 3O 8, UF 4, and UO 2F 2 with NF 3 to produce UF 6

NASA Astrophysics Data System (ADS)

McNamara, Bruce; Scheele, Randall; Kozelisky, Anne; Edwards, Matthew

2009-11-01

This paper demonstrates that NF 3 fluorinates uranium metal, UO 2, UF 4, UO 3, U 3O 8, and UO 2F 2·2H 2O to produce the volatile UF 6 at temperatures between 100 and 550 °C. Thermogravimetric and differential thermal analysis reaction profiles are described that reflect changes in the uranium fluorination/oxidation state, physiochemical effects, and instances of discrete chemical speciation. Large differences in the onset temperatures for each system investigated implicate changes in mode of the NF 3 gas-solid surface interaction. These studies also demonstrate that NF 3 is a potential replacement fluorinating agent in the existing nuclear fuel cycle and in actinide volatility reprocessing.

Onset conditions for flash sintering of UO 2

DOE PAGES

Raftery, Alicia M.; Pereira da Silva, João Gustavo; Byler, Darrin D.; ...

2017-06-22

In this paper, flash sintering was demonstrated on stoichiometric and non-stoichiometric uranium dioxide pellets at temperatures ranging from room temperature (26°C) up to 600°C. The onset conditions for flash sintering were determined for three stoichiometries (UO 2.00, UO 2.08, and UO 2.16) and analyzed against an established thermal runaway model. The presence of excess oxygen was found to enhance the flash sintering onset behavior of uranium dioxide, lowering the field required to flash and shortening the time required for a flash to occur. Finally, the results from this study highlight the effect of stoichiometry on the flash sintering behavior ofmore » uranium dioxide and will serve as the foundation for future studies on this material.« less

Onset conditions for flash sintering of UO2

NASA Astrophysics Data System (ADS)

Raftery, Alicia M.; Pereira da Silva, João Gustavo; Byler, Darrin D.; Andersson, David A.; Uberuaga, Blas P.; Stanek, Christopher R.; McClellan, Kenneth J.

2017-09-01

In this work, flash sintering was demonstrated on stoichiometric and non-stoichiometric uranium dioxide pellets at temperatures ranging from room temperature (26 °C) up to 600 °C . The onset conditions for flash sintering were determined for three stoichiometries (UO2.00, UO2.08, and UO2.16) and analyzed against an established thermal runaway model. The presence of excess oxygen was found to enhance the flash sintering onset behavior of uranium dioxide, lowering the field required to flash and shortening the time required for a flash to occur. The results from this study highlight the effect of stoichiometry on the flash sintering behavior of uranium dioxide and will serve as the foundation for future studies on this material.

Use of UO 2 films for electrochemical studies

NASA Astrophysics Data System (ADS)

Miserque, F.; Gouder, T.; Wegen, D. H.; Bottomley, P. D. W.

2001-10-01

UO 2 films have been prepared by dc reactive sputtering of a uranium metal target in an Ar/O 2 atmosphere. We have used the films deposited on gold substrates as working electrodes for electrochemical investigations as simulating the surfaces of fuel pellets. Film composition was determined by photoelectron spectroscopy (XPS and UPS) and X-ray diffraction (XRD). The oxide stoichiometry as a function of deposition conditions was determined and the appropriate conditions for UO 2.0 formation established. AC impedance and cyclic voltammetry measurements were performed. A double RC electrical equivalent circuit was used to fit the data from impedance measurements, similar to those used in unirradiated UO 2 or spent fuel pellets. However due to the porosity or adhesion defects on the thin films that permitted a direct contact between the solution and the gold substrate, we were obliged to add a contribution simulating the water-gold system. Cyclic voltammetry measurements show the influence of pH on the dissolution mechanism. Alkaline solutions permit the formation of an oxidised layer (UO 2.33) which is not present in the acidic solutions. In both pH=2 and pH=6 solutions, a U VI species layer is formed.

Strong electron correlation in UO{sub 2}{sup −}: A photoelectron spectroscopy and relativistic quantum chemistry study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wei-Li; Jian, Tian; Lopez, Gary V.

2014-03-07

The electronic structures of actinide systems are extremely complicated and pose considerable challenges both experimentally and theoretically because of significant electron correlation and relativistic effects. Here we report an investigation of the electronic structure and chemical bonding of uranium dioxides, UO{sub 2}{sup −} and UO{sub 2}, using photoelectron spectroscopy and relativistic quantum chemistry. The electron affinity of UO{sub 2} is measured to be 1.159(20) eV. Intense detachment bands are observed from the UO{sub 2}{sup −} low-lying (7sσ{sub g}){sup 2}(5fϕ{sub u}){sup 1} orbitals and the more deeply bound O2p-based molecular orbitals which are separated by a large energy gap from themore » U-based orbitals. Surprisingly, numerous weak photodetachment transitions are observed in the gap region due to extensive two-electron transitions, suggesting strong electron correlations among the (7sσ{sub g}){sup 2}(5fϕ{sub u}){sup 1} electrons in UO{sub 2}{sup −} and the (7sσ{sub g}){sup 1}(5fϕ{sub u}){sup 1} electrons in UO{sub 2}. These observations are interpreted using multi-reference ab initio calculations with inclusion of spin-orbit coupling. The strong electron correlations and spin-orbit couplings generate orders-of-magnitude more detachment transitions from UO{sub 2}{sup −} than expected on the basis of the Koopmans’ theorem. The current experimental data on UO{sub 2}{sup −} provide a long-sought opportunity to arbitrating various relativistic quantum chemistry methods aimed at handling systems with strong electron correlations.« less

K 2x Sn 4-x S 8-x (x = 0.65–1): a new metal sulfide for rapid and selective removal of Cs + , Sr 2+ and UO 2 2+ ions

DOE PAGES

Sarma, Debajit; Malliakas, Christos D.; Subrahmanyam, K. S.; ...

2015-10-27

The fission of uranium produces radionuclides, 137Cs and 90Sr, which are major constituents of spent nuclear fuel. The half-life of 137Cs and 90Sr is nearly 30 years and thus that makes them harmful to human life and the environment. The selective removal of these radionuclides in the presence of high salt concentrations from industrial nuclear waste is necessary for safe storage. We report the synthesis and crystal structure of K 2xSn 4-xS 8-x (x = 0.65–1, KTS-3) a material which exhibits excellent Cs +, Sr 2+ and UO 2 2+ ion exchange properties in varying conditions. Furthermore, the compound adoptsmore » a layered structure which consists of exchangeable potassium ions sandwiched between infinite layers of octahedral and tetrahedral tin centers. K 2xSn 4-xS 8-x (x = 0.65–1, KTS-3) crystallizes in the monoclinic space group P2 1/c with cell parameters a = 13.092(3) Å, b = 16.882(2) Å, c = 7.375(1) Å and β = 98.10(1)°. Refinement of the single crystal diffraction data revealed the presence of Sn vacancies in the tetrahedra that are long range ordered. The interlayer potassium ions of KTS-3 can be exchanged for Cs +, Sr 2+ and UO 2 2+. KTS-3 exhibits rapid and efficient ion exchange behavior in a broad pH range. The distribution coefficients (K d) for KTS-3 are high for Cs + (5.5 × 10 4), Sr 2+ (3.9 × 10 5) and UO 2 2+ (2.7 × 10 4) at neutral pH (7.4, 6.9, 5.7 ppm Cs +, Sr 2+ and UO 2 2+, respectively; V/m ~ 1000 mL g -1). KTS-3 exhibits impressive Cs +, Sr 2+ and UO 2 2+ ion exchange properties in high salt concentration and over a broad pH range, which coupled with the low cost, environmentally friendly nature and facile synthesis underscores its potential in treating nuclear waste.« less

Method for producing UO$sub 2$ loaded refractory metals

DOEpatents

Baker, R.D.; Hayter, S.W.; Lewis, H.D.

1973-12-11

A finely divided dispersion of UO/sub 2/ in tungsten or molybdenum is prepared by co-precipitating the metals from mixed aqueous solution with oxine. The co-precipitate thus formed is separated from the solution, dried, calcined, and finally reduced to UO/sub 2/ and refractory metal. (Official Gazette)

PROCESS FOR THE PRODUCTION OF AN ACTIVATED FORM OF UO$sub 2$

DOEpatents

Polissar, M.J.

1957-09-24

A process for producing a highly active form of UO/sub 2/ characterized both by rapid oxidation in air and by rapid chlorination with CCl/sub 4/ vapor at an elevated temperature is reported. In accordance with the process, commercial UO/sub 2/, is subjected to a series of oxidation-reduction operations to produce a form of UC/sub 2/ of enhanced reactivity. By treatimg commercial UO/sub 2/ at a temperature between 335 and 485 deg C with methane, then briefly with an oxygen containing gas and followimg this by a second treatment with a methane containing gas, the original relatively stable charge of UO/sub 2/ will be transformed into an active form of UO/sub 2/.

Methodology for Producing a Uniform Distribution of UO2 in a Tungsten Matrix

NASA Technical Reports Server (NTRS)

Tucker, Dennis S.; O'Conner, Andrew; Hickman, Rickman; Broadway, Jeramie; Belancik, Grace

2015-01-01

Current work at NASA's Marshall Space Flight Center (MSFC) is focused on the development CERMET fuel materials for Nuclear Thermal Propulsion (NTP). The CERMETs consist of uranium dioxide (UO2) fuel particles embedded in a tungsten (W) metal matrix. Initial testing of W-UO2 samples fabricated from fine angular powders performed reasonably well, but suffered from significant fuel loss during repeated thermal cycling due to agglomeration of the UO2 (1). The blended powder mixtures resulted in a non-uniform dispersion of the UO2 particles in the tungsten matrix, which allows rapid vaporization of the interconnected UO2 from the sample edges into the bulk material. Also, the angular powders create areas of stress concentrations due to thermal expansion mismatch, which eventually cracks the tungsten matrix. Evenly coating spherical UO2 particles with chemical vapor deposited (CVD) tungsten prior to consolidation was previously demonstrated to provide improved performance. However, the CVD processing technology is expensive and not currently available. In order to reduce cost and enhance performance, a powder coating process has been developed at MSFC to produce a uniform distribution of the spherical UO2 particles in a tungsten matrix. The method involves utilization of a polyethylene binder during mixing which leads to fine tungsten powders clinging to the larger UO2 spherical particles. This process was developed using HfO2 as a surrogate for UO2. Enough powder was mixed to make 8 discs (2cm diameter x 8mm thickness) using spark plasma sintering. A uniaxial pressure of 50 MPa was used at four different temperatures (2 samples at each temperature). The first two samples were heated to 1400C and 1500C respectively for 5 minutes. Densities for these samples were less than 85% of theoretical, so the time at temperature was increased to 20 minutes for the remaining samples. The highest densities were achieved for the two samples sintered at 1700C (approx. 92% of

XPS studies of UO 2 oxidation by alpha radiolysis of water at 100°C

NASA Astrophysics Data System (ADS)

Sunder, S.; Boyer, G. D.; Miller, N. H.

1990-12-01

The effect of alpha radiolysis of water on the oxidation and dissolution of UO 2 was studied at 100°C as a function of alpha-field strength and water chemistry using X-ray photoelectron spectroscopy. In N 2-purged solutions the oxidation of UO 2 increases with the strength of the alpha flux; an alpha flux greater than or equal to that from a 250-μ Ci americium-241 source leads to oxidation of UO 2 beyond the UO 2.33 (U 3O 7) stage, and an alpha flux equal to that from a 5-μ Ci source does not result in UO 2 oxidation beyond the UO 2.33 stage. The presence of dissolved H 2 in water, at a concentration ≥ 1.6 × 10 -4moldm-3, reduces the oxidation and dissolution of UO 2 due to alpha radiolysis at temperatures ≥ 100° C. It is concluded that the radiolysis of groundwater at ~ 100°C, due to the alpha flux associated with used CANDU fuel, is unlikely to make a significant contribution to its oxidative dissolution in the geological disposal vault planned in the Canadian Nuclear Fuel Waste Management Program. CANada Deuterium Uranium. Registered trademark.

UO 2 Particle Standards: Synthesis, Purification & Planchet Preparation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barrett, Christopher A.; Anheier, Norman C.

2016-03-31

The IAEA has previously indicated its desire for reliable provision of suitable reference materials in support of environmental sample analysis and sustained advancement at the Department of Safeguards, as laid out in the Long Term R&D plan (LTRD 10.1 & 10.2). In a recent meeting between NPAC, the IAEA and PNNL, this pressing need was directly outlined by the IAEA as having two main objectives. The first pertains to current operations, such as instrument calibrations and evaluation of bias across the Network of Analytical Laboratories and requires particles on the order of 300-500 nm in diameter. The second need formore » particle reference material would directly support the IAEA’s ongoing R&D efforts and calls for smaller particles ranging from 50 -100 nm in size. As such, the IAEA has expressed a great deal of interest in the newly established synthesis capabilities at PNNL, initially cultivated through a PNNL LDRD project to address the particle-standards shortcomings for uranium oxide material. The joint meeting concluded with a request by the IAEA for 1-2 planchet samples containing PNNL’s UO 2 particulate material, to be delivered in the near-term. This report outlines the steps taken to meet that request and includes some basic characteristics of the samples sent to the IAEA.« less

$sup 18$O enrichment process in UO$sub 2$F$sub 2$ utilizing laser light

DOEpatents

DePoorter, G.L.; Rofer-DePoorter, C.K.

1975-12-01

Photochemical reaction induced by laser light is employed to separate oxygen isotopes. A solution containing UO$sub 2$F$sub 2$, HF, H$sub 2$O and a large excess of CH$sub 3$OH is irradiated with laser light of appropriate wavelength to differentially excite the UO$sub 2$$sup 2+$ ions containing $sup 16$O atoms and cause a reaction to proceed in accordance with the reaction 2 UO$sub 2$F$sub 2$ + CH$sub 3$OH + 4 HF $Yields$ 2 UF$sub 4$ down arrow + HCOOH + 3 H$sub 2$O. Irradiation is discontinued when about 10 percent of the UO$sub 2$F$sub 2$ has reacted, the UF$sub 4$ is filtered from the reaction mixture and the residual CH$sub 3$OH and HF plus the product HCOOH and H$sub 2$O are distilled away from the UO$sub 2$F$sub 2$ which is thereby enriched in the $sup 18$O isotope, or the solution containing the UO$sub 2$F$sub 2$ may be photochemically processed again to provide further enrichment in the $sup 18$O isotope.

Resolution of 1-n-butyl-3-methyl-3-phospholene 1-oxide with TADDOL derivatives and calcium salts of O,O'-Dibenzoyl-(2R,3R)- or O,O'-di-p-toluoyl-(2R,3R)-tartaric acid.

PubMed

Bagi, Péter; Fekete, András; Kállay, Mihály; Hessz, Dóra; Kubinyi, Miklós; Holczbauer, Tamás; Czugler, Mátyás; Fogassy, Elemér; Keglevich, György

2014-03-01

The resolution methods applying (-)-(4R,5R)-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyldioxolane ("TADDOL"), (-)-(2R,3R)-α,α,α',α'-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol ("spiro-TADDOL"), as well as the acidic and neutral Ca(2+) salts of (-)-O,O'-dibenzoyl- and (-)-O,O'-di-p-toluoyl-(2R,3R)-tartaric acid were extended for the preparation of 1-n-butyl-3-methyl-3-phospholene 1-oxide in optically active form. In one case, the intermediate diastereomeric complex could be identified by single-crystal X-ray analysis. The absolute P-configuration of the enantiomers of the phospholene oxide was also determined by comparing the experimentally obtained and calculated CD spectra. © 2014 Wiley Periodicals, Inc.

Modeling the UO2 ex-AUC pellet process and predicting the fuel rod temperature distribution under steady-state operating condition

NASA Astrophysics Data System (ADS)

Hung, Nguyen Trong; Thuan, Le Ba; Thanh, Tran Chi; Nhuan, Hoang; Khoai, Do Van; Tung, Nguyen Van; Lee, Jin-Young; Jyothi, Rajesh Kumar

2018-06-01

Modeling uranium dioxide pellet process from ammonium uranyl carbonate - derived uranium dioxide powder (UO2 ex-AUC powder) and predicting fuel rod temperature distribution were reported in the paper. Response surface methodology (RSM) and FRAPCON-4.0 code were used to model the process and to predict the fuel rod temperature under steady-state operating condition. Fuel rod design of AP-1000 designed by Westinghouse Electric Corporation, in these the pellet fabrication parameters are from the study, were input data for the code. The predictive data were suggested the relationship between the fabrication parameters of UO2 pellets and their temperature image in nuclear reactor.

Gas-phase reactions of uranate ions, UO(2)(-), UO(3)(-), UO(4)(-), and UO(4)H(-), with methanol: a convergence of experiment and theory.

PubMed

Michelini, Maria Del Carmen; Marçalo, Joaquim; Russo, Nino; Gibson, John K

2010-04-19

Bimolecular reactions of uranium oxide molecular anions with methanol have been studied experimentally, by Fourier transform ion cyclotron resonance mass spectrometry, and computationally, by density functional theory (DFT). The primary goals were to provide fundamental insights into mechanistic and structural details of model reactions of uranium oxides with organics, and to examine the validity of theoretical modeling of these types of reactions. The ions UO(3)(-), UO(4)(-), and UO(4)H(-) each reacted with methanol to give a singular product; the primary products each exhibited sequential reactions with two additional methanol molecules to again give singular products. The observed reactions were elimination of water, formaldehyde, or hydrogen, and in one case addition of a methanol molecule. The potential energy profiles were computed for each reaction, and isotopic labeling experiments were performed to probe the validity of the computed mechanisms and structures-in each case where the experiments could be compared with the theory there was concurrence, clearly establishing the efficacy of the employed DFT methodologies for these and related reaction systems. The DFT results were furthermore in accord with the surprisingly inert nature of UO(2)(-). The results provide a basis to understand mechanisms of key reactions of uranium oxides with organics, and a foundation to extend DFT methodologies to more complex actinide systems which are not amenable to such direct experimental studies.

XPS study of the surface chemistry of UO2 (111) single crystal film

NASA Astrophysics Data System (ADS)

Maslakov, Konstantin I.; Teterin, Yury A.; Popel, Aleksej J.; Teterin, Anton Yu.; Ivanov, Kirill E.; Kalmykov, Stepan N.; Petrov, Vladimir G.; Springell, Ross; Scott, Thomas B.; Farnan, Ian

2018-03-01

A (111) air-exposed surface of UO2 thin film (150 nm) on (111) YSZ (yttria-stabilized zirconia) before and after the Ar+ etching and subsequent in situ annealing in the spectrometer analytic chamber was studied by XPS technique. The U 5f, U 4f and O 1s electron peak intensities were employed for determining the oxygen coefficient kO = 2 + x of a UO2+x oxide on the surface. It was found that initial surface (several nm) had kO = 2.20. A 20 s Ar+ etching led to formation of oxide UO2.12, whose composition does not depend significantly on the etching time (up to 180 s). Ar+ etching and subsequent annealing at temperatures 100-380 °C in vacuum was established to result in formation of stable well-organized structure UO2.12 reflected in the U 4f XPS spectra as high intensity (∼28% of the basic peak) shake-up satellites 6.9 eV away from the basic peaks, and virtually did not change the oxygen coefficient of the sample surface. This agrees with the suggestion that a stable (self-assembling) phase with the oxygen coefficient kO ≈ 2.12 forms on the UO2 surface.

PUREX/UO{sub 3} deactivation project management plan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Washenfelder, D.J.

1993-12-01

From 1955 through 1990, the Plutonium-Uranium Extraction Plant (PUREX) provided the United States Department of Energy Hanford Site with nuclear fuel reprocessing capability. It operated in sequence with the Uranium Trioxide (UO{sub 3}) Plant, which converted the PUREX liquid uranium nitrate product to solid UO{sub 3} powder. Final UO{sub 3} Plant operation ended in 1993. In December 1992, planning was initiated for the deactivation of PUREX and UO{sub 3} Plant. The objective of deactivation planning was to identify the activities needed to establish a passively safe, environmentally secure configuration at both plants, and ensure that the configuration could be retainedmore » during the post-deactivation period. The PUREX/UO{sub 3} Deactivation Project management plan represents completion of the planning efforts. It presents the deactivation approach to be used for the two plants, and the supporting technical, cost, and schedule baselines. Deactivation activities concentrate on removal, reduction, and stabilization of the radioactive and chemical materials remaining at the plants, and the shutdown of the utilities and effluents. When deactivation is completed, the two plants will be left unoccupied and locked, pending eventual decontamination and decommissioning. Deactivation is expected to cost $233.8 million, require 5 years to complete, and yield $36 million in annual surveillance and maintenance cost savings.« less

Complete reduction of high-density UO2 to metallic U in molten Li2O-LiCl

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Lee, Jeong

2017-10-01

The large size and high density of spent fuel pellets make it difficult to use the pellets directly in electrolytic reduction (also called as oxide reduction, OR) for pyroprocessing owing to the slow diffusion of molten Li2O-LiCl salt electrolyte into the pellets. In this study, we investigated complete OR of high-density UO2 to metallic U without any remaining UO2. Only partial reductions near the surface of high-density UO2 pellets were observed under operation conditions employing fast electrolysis rate that allowed previously complete reduction of low-density UO2 pellets. Complete reduction of high-density UO2 pellets was observed at fast electrolysis rate when the pellet size was reduced. The complete reduction of high-density UO2 pellets without size reduction was achieved at slow electrolysis rate, which allowed sufficient chemical reduction of UO2 with the lithium metal generated by the cathode reaction.

Molten salt flux synthesis and crystal structure of a new open-framework uranyl phosphate Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}: Spectroscopic characterization and cationic mobility studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagoubi, S., E-mail: said.yagoubi@cea.fr; Renard, C.; Abraham, F.

2013-04-15

The reaction of triuranyl diphosphate tetrahydrate precursor (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} with a CsI flux at 750 °C yields a yellow single crystals of new compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. The crystal structure (monoclinic, space group C2/c, a=13.6261 (13) Å, b=8.1081(8) Å, c=12.3983(12) Å, β=114.61(12)°, V=1245.41(20) Å{sup 3} with Z=4) has been solved using direct methods and Fourier difference techniques. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R1=0.028 and wR2=0.071 for 79 parameters and 1352 independent reflections with I≥2σ(I) collected on a BRUKER AXS diffractometer with MoKα radiation and a charge-coupledmore » device detector. The crystal structure is built by two independent uranium atoms in square bipyramidal coordination, connected by two opposite corners to form infinite chains {sup 1}{sub ∞}[UO{sub 5}] and by one phosphorus atom in a tetrahedral environment PO{sub 4}. The two last entities {sup 1}{sub ∞}[UO{sub 5}] and PO{sub 4} are linked by sharing corners to form a three-dimensional structure presenting different types of channels occupied by Cs{sup +} alkaline cations. Their mobility within the tunnels were studied between 280 and 800 °C and compared with other tunneled uranyl minerals. The infrared spectrum shows a good agreement with the values inferred from the single crystal structure analysis of uranyl phosphate compound. - Graphical abstract: Arrhenius plot of the electrical conductivity of tunneled compounds Cs{sub 3}U{sub 2}PO{sub 10} and CsU{sub 2}Nb{sub 2}O{sub 11.5}. Highlights: ► The reaction of (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} in excess of molten CsI leads to single-crystals of new tunneled compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. ► Ionic conductivity measurements and crystal structure analysis indicate a strong connection of the Cs{sup +} cations to the tunnels. ► A low symmetry in Cs{sub 3

UO(2) Oxidative Corrosion by Nonclassical Diffusion.

PubMed

Stubbs, Joanne E; Chaka, Anne M; Ilton, Eugene S; Biwer, Craig A; Engelhard, Mark H; Bargar, John R; Eng, Peter J

2015-06-19

Using x-ray scattering, spectroscopy, and density-functional theory, we determine the structure of the oxidation front when a UO(2) (111) surface is exposed to oxygen at ambient conditions. In contrast to classical diffusion and previously reported bulk UO(2+x) structures, we find oxygen interstitials order into a nanoscale superlattice with three-layer periodicity and uranium in three oxidation states: IV, V, and VI. This oscillatory diffusion profile is driven by the nature of the electron transfer process, and has implications for understanding the initial stages of oxidative corrosion in materials at the atomistic level.

Safety Criticality Standards Using the French CRISTAL Code Package: Application to the AREVA NP UO{sub 2} Fuel Fabrication Plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doucet, M.; Durant Terrasson, L.; Mouton, J.

2006-07-01

Criticality safety evaluations implement requirements to proof of sufficient sub critical margins outside of the reactor environment for example in fuel fabrication plants. Basic criticality data (i.e., criticality standards) are used in the determination of sub critical margins for all processes involving plutonium or enriched uranium. There are several criticality international standards, e.g., ARH-600, which is one the US nuclear industry relies on. The French Nuclear Safety Authority (DGSNR and its advising body IRSN) has requested AREVA NP to review the criticality standards used for the evaluation of its Low Enriched Uranium fuel fabrication plants with CRISTAL V0, the recentlymore » updated French criticality evaluation package. Criticality safety is a concern for every phase of the fabrication process including UF{sub 6} cylinder storage, UF{sub 6}-UO{sub 2} conversion, powder storage, pelletizing, rod loading, assembly fabrication, and assembly transportation. Until 2003, the accepted criticality standards were based on the French CEA work performed in the late seventies with the APOLLO1 cell/assembly computer code. APOLLO1 is a spectral code, used for evaluating the basic characteristics of fuel assemblies for reactor physics applications, which has been enhanced to perform criticality safety calculations. Throughout the years, CRISTAL, starting with APOLLO1 and MORET 3 (a 3D Monte Carlo code), has been improved to account for the growth of its qualification database and for increasing user requirements. Today, CRISTAL V0 is an up-to-date computational tool incorporating a modern basic microscopic cross section set based on JEF2.2 and the comprehensive APOLLO2 and MORET 4 codes. APOLLO2 is well suited for criticality standards calculations as it includes a sophisticated self shielding approach, a P{sub ij} flux determination, and a 1D transport (S{sub n}) process. CRISTAL V0 is the result of more than five years of development work focusing on

METHOD FOR DECONTAMINATION OF REACTOR SOLUTIONS

DOEpatents

Maraman, W.J.; Baxman, H.R.; Baker, R.D.

1959-05-01

A process for U recovery from phosphate fuel solutions is described. To fuel solution drawn from the reactor is added Fe(NO/sub 3/)/sub 3/ which destroys the U complex and forms ferric phosphate complex. The UO/sub 2/(NO/sub 3/)/sub 2/ formed is extracted into TBP-kerosene in a countercurrent column. The TBP contalning UO/sub 2/(NO/sub 3/)/sub 2/ is further purified by an aqueous Al(NO/ sub 3/)/sub 3/ scrub solution. The pregnant solution then goes to an H/sub 3/PO/ sub 4/ stripping and kerosene washing column. The H/sub 3/PO/sub 4/--uranyl phosphate solution is separated at the bottom and boiled to remove HNO/sub 3/ then diluted to fuel solution make-up strength. (T.R.H.)

Adsorptive features of polyacrylamide-apatite composite for Pb2+, UO(2)2+ and Th4+.

PubMed

Ulusoy, Ulvi; Akkaya, Recep

2009-04-15

Micro-composite of polyacrylamide (PAA) and apatite (Apt) was prepared by direct polymerization of acrylamide in a suspension of Apt and characterized by means of FT-IR, XRD, SEM and BET analysis. The adsorptive features of PAA-Apt and Apt were then investigated for Pb(2+), UO(2)(2+) and Th(4+) in view of dependency on ion concentration, temperature, kinetics, ion selectivity and reusability. Experimentally obtained isotherms were evaluated with reference to Langmuir, Freundlich and Dubinin-Radushkevich (DR) models. Apt in PAA-Apt had higher adsorption capacity (0.81, 1.27 and 0.69 mol kg(-1)) than bare Apt (0.28, 0.41 and 1.33 mol kg(-1)) for Pb(2+) and Th(4+), but not for UO(2)(2+). The affinity to PAA-Apt increased for Pb(2+) and UO(2)(2+) but not changed for Th(4+). The values of enthalpy and entropy changed were positive for all ions for both Apt and PAA-Apt. Free enthalpy change was DeltaG<0. Well compatibility of adsorption kinetics to the pseudo-second-order model predicated that the rate-controlling step was a chemical sorption. This was consistent with the free energy values derived from DR model. The reusability tests for Pb(2+) for five uses proved that the composite was reusable to provide a mean adsorption of 53.2+/-0.7% from 4x10(-3)M Pb(2+) solution and complete recovery of the adsorbed ion was possible (98+/-1%). The results of this investigation suggested that the use of Apt in the micro-composite form with PAA significantly enhanced the adsorptive features of Apt.

Uranium migration in spark plasma sintered W/UO2 CERMETS

NASA Astrophysics Data System (ADS)

Tucker, Dennis S.; Wu, Yaqiao; Burns, Jatuporn

2018-03-01

W/UO2 CERMET samples were sintered in a Spark Plasma Sintering (SPS) furnace at various temperature under vacuum and pressure. High Resolution Transmission Electron Microscopy (HRTEM) with Energy Dispersive Spectroscopy (EDS) was performed on the samples to determine interface structures and uranium diffusion from the UO2 particles into the tungsten matrix. Local Electrode Atom Probe (LEAP) was also performed to determine stoichiometry of the UO2 particles. It was seen that uranium diffused approximately 10-15 nm into the tungsten matrix. This is explained in terms of production of oxygen vacancies and Fick's law of diffusion.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE PAGES

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang; ...

2016-05-19

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Theoretical investigation of thermodynamic stability and mobility of the oxygen vacancy in ThO 2 –UO 2 solid solutions

DOE PAGES

Liu, B.; Aidhy, D. S.; Zhang, Y.; ...

2014-10-16

The thermodynamic stability and the migration energy barriers of oxygen vacancies in ThO 2 –UO 2 solid solutions are investigated by density functional theory calculations. In pure ThO 2, the formation energy of oxygen vacancy is 7.58 eV and 1.46 eV under O rich and O poor conditions, respectively, while its migration energy barrier is 1.97 eV. The addition of UO 2 into ThO 2 significantly decreases the energetics of formation and migration of the oxygen vacancy. Among the range of UO 2-ThO 2 solid solutions studied in this work, UO 2 exhibits the lowest formation energy (5.99 eV andmore » -0.13 eV under O rich and O poor conditions, respectively) and Th 0.25U0 .75O 2 exhibits the lowest migration energy barrier (~ 1 eV). Moreover, by considering chemical potential, the phase diagram of oxygen vacancy as a function of both temperature and oxygen partial pressure is shown, which could help to gain experimental control over oxygen vacancy concentration.« less

Photochemical reduction of UO(2)(2+) in the presence of alcohol studied by density functional theory calculations.

PubMed

Tsushima, Satoru

2009-06-01

A well-known photochemical process of U(VI)O(2)(2+) reduction to U(V)O(2)(+) in the presence of alcohols was studied by density functional theory (DFT) calculations. It was found that the first process which takes place is a photoexcitation of the ground-state UO(2)(2+) to the triplet excited state (*UO(2)(2+)) followed by a significant shortening of the *UO(2)(2+)-to-alcohol O(ax)-H distance. A charge transfer from *UO(2)(2+) to alcohol and hydrogen abstraction takes place in the following step. Consequently, U(VI)O(2)(2+) gets reduced to U(V)O(OH)(2+). The photochemical byproduct RCHOH acts further as a reducing agent toward UO(2)(2+) to yield UO(2)(+) and RCHO (aldehyde). Only a combination of these two reactions can explain a high quantum yield of this reaction. In the absence of alcohol, the lowest-lying triplet state exhibits a different character, and photoreduction is unlikely to take place via the same mechanism. The present results agree well with recent experimental finding [J. Am. Chem. Soc. 2006, 128, 14024] and supports the idea that the O(ax)-H linkage between UO(2)(2+) and the solvent molecule is the key to the photochemical reduction process.

SINGLE-STEP CONVERSION OF UO$sub 3$ TO UF$sub 4$

DOEpatents

Moore, J.E.

1960-07-12

A description is given of the preparation of uranium tetrafluoride by reacting a hexavalent uranium compound with a pclysaccharide and gaseous hydrogen fluoride at an elevated temperature. Uranium trioxide and starch are combined with water to form a doughy mixture. which is extruded into pellets and dried. The pellets are then contacted with HF at a temperature from 500 to 700 deg C in a moving bed reactor to prcduce UF/sub 4/. Reduction of the hexavalent uranium to UO/sub 2/ and conversion of the UO/sub 2/ to UF/sub 4/ are accomplished simultaneously in this process.

Functionalized UO[sub 2] salenes. Neutral receptors for anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudkevich, D.M.; Verboom, W.; Brzozka, Z.

1994-05-18

A novel class of neutral receptors for anions that contain a unique combination of an immobilized Lewis acidic binding site (UO[sub 2][sup 2+]) and additional amide C(O)NH groups, which can form a favorable H-bond with a coordinated anion guest, has been developed. The unique combination of a Lewis acidic UO[sub 2] center and amide C(O)NH groups in one receptor leads to highly specific H[sub 2]PO[sub 4[sup [minus

Adsorption characteristics of UO(2)(2+) and Th(4+) ions from simulated radioactive solutions onto chitosan/clinoptilolite sorbents.

PubMed

Humelnicu, Doina; Dinu, Maria Valentina; Drăgan, Ecaterina Stela

2011-01-15

Adsorption features of UO(2)(2+) and Th(4+) ions from simulated radioactive solutions onto a novel chitosan/clinoptilolite (CS/CPL) composite as beads have been investigated compared with chitosan cross-linked with epichlorohydrin. The effects of contact time, the initial metal ion concentration, sorbent mass and temperature on the adsorption capacity of the CS-based sorbents were investigated. The adsorption kinetics was well described by the pseudo-second order equation, and the adsorption isotherms were better fitted by the Sips model. The maximum experimental adsorption capacities were 328.32 mg Th(4+)/g composite, and 408.62 mg UO(2)(2+)/g composite. The overall adsorption tendency of CS/CPL composite toward UO(2)(2+) and Th(4+) radiocations in the presence of Cu(2+), Fe(2+) and Al(3+), under competitive conditions, followed the order: Cu(2+)>UO(2)(2+)>Fe(2+)>Al(3+), and Cu(2+)>Th(4+)>Fe(2+)>Al(3+), respectively. The negative values of Gibbs free energy of adsorption indicated the spontaneity of the adsorption of radioactive ions on both the CS/CPL composite and the cross-linked CS. The desorption level of UO(2)(2+) from the composite CS/CPL, by using 0.1M Na(2)CO(3), was around 92%, and that of Th(4+) ions, performed by 0.1M HCl, was around 85%, both values being higher than the desorption level of radiocations from the cross-linked CS, which were 89% and 83%, respectively. Copyright © 2010 Elsevier B.V. All rights reserved.

Creaming enhancement in a liter scale ultrasonic reactor at selected transducer configurations and frequencies.

PubMed

Juliano, Pablo; Temmel, Sandra; Rout, Manoj; Swiergon, Piotr; Mawson, Raymond; Knoerzer, Kai

2013-01-01

Recent research has shown that high frequency ultrasound (0.4-3 MHz), can enhance milkfat separation in small scale systems able to treat only a few milliliters of sample. In this work, the effect of ultrasonic standing waves on milkfat creaming was studied in a 6L reactor and the influence of different frequencies and transducer configurations in direct contact with the fluid was investigated. A recombined coarse milk emulsion with fat globules stained with oil-red-O dye was selected for the separation trials. Runs were performed with one or two transducers placed in vertical (parallel or perpendicular) and horizontal positions (at the reactor base) at 0.4, 1 and/or 2 MHz (specific energy 8.5 ± 0.6 kJ/kg per transducer). Creaming behavior was assessed by measuring the thickness of the separated cream layer. Other methods supporting this assessment included the measurement of fat content, backscattering, particle size distribution, and microscopy of samples taken at the bottom and top of the reactor. Most efficient creaming was found after treatment at 0.4 MHz in single and double vertical transducer configurations. Among these configurations, a higher separation rate was obtained when sonicating at 0.4 MHz in a vertical perpendicular double transducer setup. The horizontal transducer configuration promoted creaming at 2 MHz only. Fat globule size increase was observed when creaming occurred. This research highlights the potential for enhanced separation of milkfat in larger scale systems from selected transducer configurations in contact with a dairy emulsion, or emulsion splitting in general. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermodynamics of fission products in UO(2 ± x).

PubMed

Nerikar, P V; Liu, X-Y; Uberuaga, B P; Stanek, C R; Phillpot, S R; Sinnott, S B

2009-10-28

The stabilities of selected fission products-Xe, Cs, and Sr-are investigated as a function of non-stoichiometry x in UO(2 ± x). In particular, density functional theory (DFT) is used to calculate the incorporation and solution energies of these fission products at the anion and cation vacancy sites, at the divacancy, and at the bound Schottky defect. In order to reproduce the correct insulating state of UO(2), the DFT calculations are performed using spin polarization and with the Hubbard U term. In general, higher charge defects are more soluble in the fuel matrix and the solubility of fission products increases as the hyperstoichiometry increases. The solubility of fission product oxides is also explored. Cs(2)O is observed as a second stable phase and SrO is found to be soluble in the UO(2) matrix for all stoichiometries. These observations mirror experimentally observed phenomena.

Using R in Taverna: RShell v1.2

PubMed Central

Wassink, Ingo; Rauwerda, Han; Neerincx, Pieter BT; Vet, Paul E van der; Breit, Timo M; Leunissen, Jack AM; Nijholt, Anton

2009-01-01

Background R is the statistical language commonly used by many life scientists in (omics) data analysis. At the same time, these complex analyses benefit from a workflow approach, such as used by the open source workflow management system Taverna. However, Taverna had limited support for R, because it supported just a few data types and only a single output. Also, there was no support for graphical output and persistent sessions. Altogether this made using R in Taverna impractical. Findings We have developed an R plugin for Taverna: RShell, which provides R functionality within workflows designed in Taverna. In order to fully support the R language, our RShell plugin directly uses the R interpreter. The RShell plugin consists of a Taverna processor for R scripts and an RShell Session Manager that communicates with the R server. We made the RShell processor highly configurable allowing the user to define multiple inputs and outputs. Also, various data types are supported, such as strings, numeric data and images. To limit data transport between multiple RShell processors, the RShell plugin also supports persistent sessions. Here, we will describe the architecture of RShell and the new features that are introduced in version 1.2, i.e.: i) Support for R up to and including R version 2.9; ii) Support for persistent sessions to limit data transfer; iii) Support for vector graphics output through PDF; iv)Syntax highlighting of the R code; v) Improved usability through fewer port types. Our new RShell processor is backwards compatible with workflows that use older versions of the RShell processor. We demonstrate the value of the RShell processor by a use-case workflow that maps oligonucleotide probes designed with DNA sequence information from Vega onto the Ensembl genome assembly. Conclusion Our RShell plugin enables Taverna users to employ R scripts within their workflows in a highly configurable way. PMID:19607662

Configurational Reassignment and Improved Preparation of the Competitive IL-6 Receptor Antagonist 20R,21R-Epoxyresibufogenin-3-formate

PubMed Central

Boos, Terrence L.; Cheng, Kejun; Greiner, Elisabeth; Deschamps, Jeffrey R.; Jacobson, Arthur E.; Rice, Kenner C.

2012-01-01

20R,21R-Epoxyresibufogenin-3-formate (1) and 20S,21S-epoxyresibufogenin-3-formate (2) were synthesized from commercial resibufogenin (3) using known procedures. The major product (1) was dextrorotatory, as was the major product from the reported synthesis of epoxyresibufogenin-3-formate; however, the literature (+)-compound was assigned the 20S,21S-configuration based on NMR data. We have now unequivocally determined, using single-crystal X-ray structure analyses of the major and minor products of the synthesis and of their derivatives, that the major product from the synthesis was (+)-20R,21R-epoxyresibufogenin-3-formate (1). Our minor synthetic product was determined to have the (-)-20S,21S-configuration (2). The (+)-20R,21R-compound 1 has been found to have high affinity for the IL-6 receptor and to act as an IL-6 antagonist. A greatly improved synthesis of 1 was achieved through oxidation of preformed resibufogenin-3-formate. This has enabled us to prepare, from the very expensive commercial resibufogenin, considerably larger quantities of 1, the only known non-peptide small molecule IL-6 antagonist. PMID:22360661

Adaptive Algorithm for Aircraft Configuration in Turbulent Flow

DTIC Science & Technology

1992-11-25

8217), + a2 (APO) (bUo)),2 + r4 (1 - APO) (bUO), (27) AP is the pressure switch chat is used to turn the shock smoothing and the background smoothing on at...the appropriate regions. For any node 0, the pressure switch is computed as (APo)= E𔃻=1 (PN()- PO) (28) zF:,’ + PO) the summation is over all the edges...that share the node 0. The pressure switch is normalized by the maximum value over the domain so that 0 < AP < 1. When evaluated as above, AP has a

Simulations of Xe and U diffusion in UO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders D.; Vyas, Shyam; Tonks, Michael R.

2012-09-10

Diffusion of xenon (Xe) and uranium (U) in UO{sub 2} is controlled by vacancy mechanisms and under irradiation the formation of mobile vacancy clusters is important. Based on the vacancy and cluster diffusion mechanisms established from density functional theory (DFT) calculations, we derive continuum thermodynamic and diffusion models for Xe and U in UO{sub 2}. In order to capture the effects of irradiation, vacancies (Va) are explicitly coupled to the Xe and U dynamics. Segregation of defects to grain boundaries in UO{sub 2} is described by combining the bulk diffusion model with models of the interaction between Xe atoms andmore » vacancies with grain boundaries, which were derived from atomistic calculations. The diffusion and segregation models were implemented in the MOOSE-Bison-Marmot (MBM) finite element (FEM) framework and the Xe/U redistribution was simulated for a few simple microstructures.« less

Near Surface Stoichiometry in UO 2 : A Density Functional Theory Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Jianguo; Valderrama, Billy; Henderson, Hunter B.

2015-01-01

The mechanisms of oxygen stoichiometry variation in UO 2at different temperature and oxygen partial pressure are important for understanding the dynamics of microstructure in these crystals. However, very limited experimental studies have been performed to understand the atomic structure of UO 2near surface and defect effects of near surface on stoichiometry in which the system can exchange atoms with the external reservoir. In this study, the near (110) surface relaxation and stoichiometry in UO 2have been studied with density functional theory (DFT) calculations. On the basis of the point-defect model (PDM), a general expression for the near surface stoichiometric variationmore » is derived by using DFT total-energy calculations and atomistic thermodynamics, in an attempt to pin down the mechanisms of oxygen exchange between the gas environment and defected UO 2. By using the derived expression, it is observed that, under poor oxygen conditions, the stoichiometry of near surface is switched from hyperstoichiometric at 300 K with a depth around 3 nm to near-stoichiometric at 1000 K and hypostoichiometric at 2000 K. Furthermore, at very poor oxygen concentrations and high temperatures, our results also suggest that the bulk of the UO 2prefers to be hypostoichiometric, although the surface is near-stoichiometric.« less

Near surface stoichiometry in UO 2: A density functional theory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Jianguo; Valderrama, Billy; Henderson, Hunter B.

2015-08-01

The mechanisms of oxygen stoichiometry variation in UO 2 at different temperature and oxygen partial pressure are important for understanding the dynamics of microstructure in these crystals. However, very limited experimental studies have been performed to understand the atomic structure of UO 2 near surface and defect effects of near surface on stoichiometry in which the system can exchange atoms with the external reservoir. In this study, the near (110) surface relaxation and stoichiometry in UO 2 have been studied with density functional theory (DFT) calculations. On the basis of the point-defect model (PDM), a general expression for the nearmore » surface stoichiometric variation is derived by using DFT total-energy calculations and atomistic thermodynamics, in an attempt to pin down the mechanisms of oxygen exchange between the gas environment and defected UO 2. By using the derived expression, it is observed that, under poor oxygen conditions, the stoichiometry of near surface is switched from hyperstoichiometric at 300 K with a depth around 3 nm to near-stoichiometric at 1000 K and hypostoichiometric at 2000 K. Furthermore, at very poor oxygen concentrations and high temperatures, our results also suggest that the bulk of the UO 2 prefers to be hypostoichiometric, although the surface is near-stoichiometric.« less

Thermodynamic and kinetic aspects of UO 2 fuel oxidation in air at 400-2000 K

NASA Astrophysics Data System (ADS)

Taylor, Peter

2005-09-01

Most nuclear fuel oxidation research has addressed either low-temperature (<700 K) air oxidation related to fuel storage or high-temperature (>1500 K) steam oxidation linked to reactor safety. This paper attempts to unify modelling for air oxidation of UO 2 fuel over a wide range of temperature, and thus to assist future improvement of the ASTEC code, co-developed by IRSN and GRS. Phenomenological correlations for different temperature ranges distinguish between oxidation on the scale of individual grains to U 3O 7 and U 3O 8 below ˜700 K and individual fragments to U 3O 8 via UO 2+ x and/or U 4O 9 above ˜1200 K. Between about 700 and 1200 K, empirical oxidation rates slowly decline as the U 3O 8 product becomes coarser-grained and more coherent, and fragment-scale processes become important. A more mechanistic approach to high-temperature oxidation addresses questions of oxygen supply, surface reaction kinetics, thermodynamic properties, and solid-state oxygen diffusion. Experimental data are scarce, however, especially at low oxygen partial pressures and high temperatures.

Stability and migration of large oxygen clusters in UO(2+x): density functional theory calculations.

PubMed

Andersson, D A; Espinosa-Faller, F J; Uberuaga, B P; Conradson, S D

2012-06-21

Using ab initio molecular dynamics simulations and nudged elastic band calculations we examine the finite temperature stability, transition pathways, and migration mechanisms of large oxygen clusters in UO(2+x). Here we specifically consider the recently proposed split quad-interstitial and cuboctahedral oxygen clusters. It is shown that isolated cuboctahedral clusters may transform into more stable configurations that are closely linked to the split quad-interstitial. The split quad-interstitial is stable with respect to single interstitials occupying the empty octahedral holes of the UO(2) lattice. In order to better understand discrepancies between theory and experiments, the simulated atomic pair distribution functions for the split quad-interstitial structures are analyzed with respect to the distribution function for U(4)O(9) previously obtained from neutron diffraction data. Our nudged elastic band calculations suggest that the split quad-interstitial may migrate by translating one of its constituent di-interstitial clusters via a barrier that is lower than the corresponding barrier for individual interstitials, but higher than the barrier for the most stable di-interstitial cluster.

Multi-reactor power system configurations for multimegawatt nuclear electric propulsion

NASA Technical Reports Server (NTRS)

George, Jeffrey A.

1991-01-01

A modular, multi-reactor power system and vehicle configuration for piloted nuclear electric propulsion (NEP) missions to Mars is presented. Such a design could provide enhanced system and mission reliability, allowing a comfortable safety margin for early manned flights, and would allow a range of piloted and cargo missions to be performed with a single power system design. Early use of common power modules for cargo missions would also provide progressive flight experience and validation of standardized systems for use in later piloted applications. System and mission analysis are presented to compare single and multi-reactor configurations for piloted Mars missions. A conceptual design for the Hydra modular multi-reactor NEP vehicle is presented.

Recovery of UO[sub 2]/PuO[sub 2] in IFR electrorefining process

DOEpatents

Tomczuk, Z.; Miller, W.E.

1994-10-18

A process is described for converting PuO[sub 2] and UO[sub 2] present in an electrorefiner to the chlorides, by contacting the PuO[sub 2] and UO[sub 2] with Li metal in the presence of an alkali metal chloride salt substantially free of rare earth and actinide chlorides for a time and at a temperature sufficient to convert the UO[sub 2] and PuO[sub 2] to metals while converting Li metal to Li[sub 2]O. Li[sub 2]O is removed either by reducing with rare earth metals or by providing an oxygen electrode for transporting O[sub 2] out of the electrorefiner and a cathode, and thereafter applying an emf to the electrorefiner electrodes sufficient to cause the Li[sub 2]O to disassociate to O[sub 2] and Li metal but insufficient to decompose the alkali metal chloride salt. The U and Pu and excess lithium are then converted to chlorides by reaction with CdCl[sub 2].

Recovery of UO.sub.2 /Pu O.sub.2 in IFR electrorefining process

DOEpatents

Tomczuk, Zygmunt; Miller, William E.

1994-01-01

A process for converting PuO.sub.2 and UO.sub.2 present in an electrorefiner to the chlorides, by contacting the PuO.sub.2 and UO.sub.2 with Li metal in the presence of an alkali metal chloride salt substantially free of rare earth and actinide chlorides for a time and at a temperature sufficient to convert the UO.sub.2 and PuO.sub.2 to metals while converting Li metal to Li.sub.2 O. Li.sub.2 O is removed either by reducing with rare earth metals or by providing an oxygen electrode for transporting O.sub.2 out of the electrorefiner and a cathode, and thereafter applying an emf to the electrorefiner electrodes sufficient to cause the Li.sub.2 O to disassociate to O.sub.2 and Li metal but insufficient to decompose the alkali metal chloride salt. The U and Pu and excess lithium are then converted to chlorides by reaction with CdCl.sub.2.

Speciation of residual carbon contained in UO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ziouane, Yannis; Arab-Chapelet, Bénédicte; Tamain, Christelle

2016-12-15

UO{sub 2} powders were synthesized thanks to oxalic precipitation (platelet morphology) and sol-gel route and completely characterized. A secondary phase was found depending on the calcination atmospheres. This phase has been identified by Raman spectroscopy as graphitic material (i.e. carbon-based secondary compound) and quantified by thermogravimetric analyses. Its amount varies with the calcination atmosphere. The presence of this secondary phase has no significant effect on the lattice parameter and its specific surface area. - Graphical abstract: Figure 2: Raman spectroscopy of the three UO{sub 2} powders and of the dissolution residues.

Density functional theory calculations of UO2 oxidation: evolution of UO(2+x), U4O(9-y), U3O7, and U3O8.

PubMed

Andersson, D A; Baldinozzi, G; Desgranges, L; Conradson, D R; Conradson, S D

2013-03-04

Formation of hyperstoichiometric uranium dioxide, UO2+x, derived from the fluorite structure was investigated by means of density functional theory (DFT) calculations. Oxidation was modeled by adding oxygen atoms to UO2 fluorite supercells. For each compound ab initio molecular dynamics simulations were performed to allow the ions to optimize their local geometry. A similar approach was used for studying the reduction of U3O8. In agreement with the experimental phase diagram we identify stable line compounds at the U4O9-y and U3O7 stoichiometries. Although the transition from fluorite to the layered U3O8 structure occurs at U3O7 (UO2.333) or U3O7.333 (UO2.444), our calculated low temperature phase diagram indicates that the fluorite derived compounds are favored up to UO2.5, that is, as long as the charge-compensation for adding oxygen atoms occurs via formation of U(5+) ions, after which the U3O8-y phase becomes more stable. The most stable fluorite UO2+x phases at low temperature (0 K) are based on ordering of split quad-interstitial oxygen clusters. Most existing crystallographic models of U4O9 and U3O7, however, apply the cuboctahedral cluster. To better understand these discrepancies, the new structural models are analyzed in terms of existing neutron diffraction data. DFT calculations were also performed on the experimental cuboctahedral based U4O9-y structure, which enable comparisons between the properties of this phase with the quad-interstitial ones in detail.

Modelling oxygen self-diffusion in UO 2 under pressure

DOE PAGES

Cooper, Michael William D.; Grimes, R. W.; Fitzpatrick, M. E.; ...

2015-10-22

Access to values for oxygen self-diffusion over a range of temperatures and pressures in UO 2 is important to nuclear fuel applications. Here, elastic and expansivity data are used in the framework of a thermodynamic model, the cBΩ model, to derive the oxygen self-diffusion coefficient in UO 2 over a range of pressures (0–10 GPa) and temperatures (300–1900 K). Furthermore, the significant reduction in oxygen self-diffusion as a function of increasing hydrostatic pressure, and the associated increase in activation energy, is identified.

Optimization of hydraulic shear parameters and reactor configuration in the aerobic granular sludge process.

PubMed

Zhu, Liang; Zhou, Jiaheng; Yu, Haitian; Xu, Xiangyang

2015-01-01

The hydraulic shear acts as an important selection pressure in aerobic sludge granulation. The effects of the hydraulic shear rate and reactor configuration on structural characteristics of aerobic granule in view of the hydromechanics. The hydraulic shear analysis was proposed to overcome the limitation of using superficial gas velocity (SGV) to express the hydraulic shear stress. Results showed that the stronger hydraulic shear stress with SGV above 2.4 cm s(-1) promoted the microbial aggregation, and favoured the structural stability of the granular sludge. According to the hydraulic shear analysis, the total shear rate reached (0.56-2.31)×10(5) s(-1) in the granular reactor with a larger ratio of height to diameter (H/D), and was higher than that in the reactor with smaller H/D, where the sequencing airlift bioreactor with smaller H/D had a high total shear rate under the same SGV. Results demonstrated that the granular reactor could provide a stronger hydraulic shear stress which promotes the formation and structural stability of aerobic granules.

Chemical reactivity of CVC and CVD SiC with UO2 at high temperatures

NASA Astrophysics Data System (ADS)

Silva, Chinthaka M.; Katoh, Yutai; Voit, Stewart L.; Snead, Lance L.

2015-05-01

Two types of silicon carbide (SiC) synthesized using two different vapor deposition processes were embedded in UO2 pellets and evaluated for their potential chemical reaction with UO2. While minor reactivity between chemical-vapor-composited (CVC) SiC and UO2 was observed at comparatively low temperatures of 1100 and 1300 °C, chemical-vapor-deposited (CVD) SiC did not show any such reactivity. However, both CVD and CVC SiCs showed some reaction with UO2 at a higher temperature (1500 °C). Elemental maps supported by phase maps obtained using electron backscatter diffraction indicated that CVC SiC was more reactive than CVD SiC at 1500 °C. Furthermore, this investigation indicated the formation of uranium carbides and uranium silicide chemical phases such as UC, USi2, and U3Si2 as a result of SiC reaction with UO2.

A novel design of reactive distillation configuration for 2-methoxy-2-methylheptane process

NASA Astrophysics Data System (ADS)

Hussain, Arif; Qyyum, Muhammad Abdul; Quang Minh, Le; Jimin, Hong; Lee, Moonyong

2017-11-01

The study aims to reveal the possibility of reactive distillation (RD) in the 2-methoxy-2-methylheptane (MMH) production process. MMH is getting more industrial and academic interests as a gasoline additive to replace methyl tert-butyl ether. Traditionally, MMH is obtained by carrying out the reaction in the reactor followed by three distillation columns. The high yield of MMH could be achieved by keeping the large reactor size or by using the large excess of 2-methyl-1-heptene (MH). Both former and latter strategies are associated with the high capital and operating costs. To solve these problems, this study proposed an innovative RD configuration to take synergistic benefits of reaction and separation involved. This innovative RD configuration allows the production of MMH with significantly lower capital, operating and total annual costs. For desired MMH yield, the result demonstrates that the proposed RD configuration can reduce energy, capital, and total annual costs up to 7.7, 31.3, and 17.1%, respectively, compared to a conventional process. Furthermore, the influence of some important design parameters on the RD column performance was also explored to overcome the temperature limitation of acid resin catalyst inside the reactive zone of the RD column.

Irradiation effects in UO2 and CeO2

NASA Astrophysics Data System (ADS)

Ye, Bei; Oaks, Aaron; Kirk, Mark; Yun, Di; Chen, Wei-Ying; Holtzman, Benjamin; Stubbins, James F.

2013-10-01

Single crystal CeO2, as a surrogate material to UO2, was irradiated with 500 keV xenon ions at 800 °C while being observed using in situ transmission electron microscopy (TEM). Experimental results show the formation and growth of defect clusters including dislocation loops and cavities as a function of increasing atomic displacement dose. At high dose, the dislocation loop structure evolves into an extended dislocation line structure, which appears to remain stable to the high dose levels examined in this study. A high concentration of cavities was also present in the microstructure. Despite high atomic displacement doses, the specimen remained crystalline to a cumulated dose of 5 × 1015 ions/cm2, which is consistent with the known stability of the fluorite structure under high dose irradiation. Kinetic Monte Carlo calculations show that oxygen mobility is substantially higher in hypo-stoichiometric UO2/CeO2 than hyper-stoichiometric systems. This result is consistent with the ability of irradiation damage to recover even at intermediate irradiation temperatures.

Multiple Irradiation Capsule Experiment (MICE)-3B Irradiation Test of Space Fuel Specimens in the Advanced Test Reactor (ATR) - Close Out Documentation for Naval Reactors (NR) Information

DOE Office of Scientific and Technical Information (OSTI.GOV)

M. Chen; CM Regan; D. Noe

2006-01-09

Few data exist for UO{sub 2} or UN within the notional design space for the Prometheus-1 reactor (low fission rate, high temperature, long duration). As such, basic testing is required to validate predictions (and in some cases determine) performance aspects of these fuels. Therefore, the MICE-3B test of UO{sub 2} pellets was designed to provide data on gas release, unrestrained swelling, and restrained swelling at the upper range of fission rates expected for a space reactor. These data would be compared with model predictions and used to determine adequacy of a space reactor design basis relative to fission gas releasemore » and swelling of UO{sub 2} fuel and to assess potential pellet-clad interactions. A primary goal of an irradiation test for UN fuel was to assess performance issues currently associated with this fuel type such as gas release, swelling and transient performance. Information learned from this effort may have enabled use of UN fuel for future applications.« less

Chemical reactivity of CVC and CVD SiC with UO 2 at high temperatures

DOE PAGES

Silva, Chinthaka M.; Katoh, Yutai; Voit, Stewart L.; ...

2015-02-11

Two types of silicon carbide (SiC) synthesized using two different vapor deposition processes were embedded in UO 2 pellets and evaluated for their potential chemical reaction with UO 2. While minor reactivity between chemical-vapor-composited (CVC) SiC and UO 2 was observed at comparatively low temperatures of 1100 and 1300 C, chemical-vapor-deposited (CVD) SiC did not show any such reactivity, according to microstructural investigations. But, both CVD and CVC SiCs showed some reaction with UO 2 at a higher temperature (1500 C). Elemental maps supported by phase maps obtained using electron backscatter diffraction indicated that CVC SiC was more reactive thanmore » CVD SiC at 1500 C. Moreover, this investigation indicated the formation of uranium carbides and uranium silicide chemical phases such as UC, USi 2, and U 3Si 2 as a result of SiC reaction with UO 2.« less

Catalysis of aptamer-modified AuPd nanoalloy probe and its application to resonance scattering detection of trace UO(2)2+.

PubMed

Liang, Aihui; Zhang, Yi; Fan, Yanyan; Chen, Chunqiang; Wen, Guiqing; Liu, Qingye; Kang, Caiyan; Jiang, Zhiliang

2011-08-01

AuPd nanoalloy and nanopalladium with a diameter of 5 nm were prepared, using sodium citrate as the stabilizing agent and NaBH(4) as the reductant. The nanocatalyst containing palladium on the surface exhibited a strong catalytic effect on the slow NiP particle reaction between NiCl(2) and NaH(2)PO(2), and the NiP particle system showed a resonance scattering (RS) peak at 508 nm. The RS results showed that the Pd atom on AuPd nanoalloy surface is the catalytic center. Combining the aptamer cracking reaction of double-stranded DNA (dsDNA)-UO(2)(2+), AuPd nanoalloy aggregation, and AuPd nanoalloy catalysis, both AuPd nanoalloy RS probe and AuPd nanoalloy catalytic RS assays were developed for the determination of 40-250 pmol L(-1) UO(2)(2+) and 5.0-50 pmol L(-1) UO(2)(2+), respectively. This journal is © The Royal Society of Chemistry 2011

Experimental evaluation of thermal ratcheting behavior in UO2 fuel elements

NASA Technical Reports Server (NTRS)

Phillips, W. M.

1973-01-01

The effects of thermal cycling of UO2 at high temperatures has been experimentally evaluated to determine the rates of distortion of UO2/clad fuel elements. Two capsules were rested in the 1500 C range, one with a 50 C thermal cycle, the other with a 100 C thermal cycle. It was observed that eight hours at the lower cycle temperature produced sufficient UO2 redistribution to cause clad distortion. The amount of distortion produced by the 100 C cycle was less than double that produced by the 50 C, indicating smaller thermal cycles would result in clad distortion. An incubation period was observed to occur before the onset of distortion with cycling similar to fuel swelling observed in-pile at these temperatures.

Electrochemical and spectroelectrochemical studies on UO(2)(saloph)L (saloph = N,N'-disalicylidene-o-phenylenediaminate, L=dimethyl sulfoxide or N,N-dimethylformamide).

PubMed

Mizuoka, Koichiro; Kim, Seong-Yun; Hasegawa, Miki; Hoshi, Toshihiko; Uchiyama, Gunzo; Ikeda, Yasuhisa

2003-02-24

To examine properties of pentavalent uranium, U(V), we have carried out electrochemical and spectroelectrochemical studies on UO(2)(saloph)L [saloph = N,N'-disalicylidene-o-phenylenediaminate, L = dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF)]. The electrochemical reactions of UO(2)(saloph)L complexes in L were found to occur quasireversibly. The reduction processes of UO(2)(saloph)L complexes were followed spectroelectrochemically by using an optical transparent thin layer electrode cell. It was found that the absorption spectra measured at the applied potentials from 0 to -1.650 V versus ferrocene/ferrocenium ion redox couple (Fc/Fc(+)) for UO(2)(saloph)DMSO in DMSO have clear isosbestic points and that the evaluated electron stoichiometry equals 1.08. These results indicate that the reduction product of UO(2)(saloph)DMSO is [U(V)O(2)(saloph)DMSO](-), which is considerably stable in DMSO. Furthermore, it was clarified that the absorption spectrum of the [U(V)O(2)(saloph)DMSO](-) complex has a very small molar absorptivity in the visible region and characteristic absorption bands due to the 5f(1) orbital at around 750 and 900 nm. For UO(2)(saloph)DMF in DMF, the clear isosbestic points were not observed in the similar spectral changes. It is proposed that the UO(2)(saloph)DMF complex is reduced to [U(V)O(2)(saloph)DMF](-) accompanied by the dissociation of DMF as a successive reaction. The formal redox potentials of UO(2)(saloph)L in L (E(0), vs Fc/Fc(+)) for U(VI)/U(V) couple were determined to be -1.550 V for L = DMSO and -1.626 V for L = DMF.

Effect of the ZrCl4 concentration in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt and the electrolysis current density on the quantitative composition of UO2-ZrO2 cathode deposits. Calculation and experiment

NASA Astrophysics Data System (ADS)

Krotov, V. E.; Filatov, E. C.

2014-08-01

A method is proposed for calculating the ZrO2 content in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt. Based on the known composition of a UO2-ZrO2 cathode deposit, the content is calculated at current densities of 0.08-0.63 A/cm2 and ZrCl4 concentrations of 0-12.3 wt %. The calculated and experimental ZrO2 contents in UO2-ZrO2 cathode deposits are in qualitative and adequate quantitative agreement.

Numerical characterization of micro-cell UO2sbnd Mo pellet for enhanced thermal performance

NASA Astrophysics Data System (ADS)

Lee, Heung Soo; Kim, Dong-Joo; Kim, Sun Woo; Yang, Jae Ho; Koo, Yang-Hyun; Kim, Dong Rip

2016-08-01

Metallic micro-cell UO2 pellet with high thermal conductivity has received attention as a promising accident-tolerant fuel. Although experimental demonstrations have been successful, studies on the potency of current metallic micro-cell UO2 fuels for further enhancement of thermal performance are lacking. Here, we numerically investigated the thermal conductivities of micro-cell UO2sbnd Mo pellets in terms of the amount of Mo content, the unit cell size, and the aspect ratio of the micro-cells. The results showed good agreement with experimental measurements, and more importantly, indicated the importance of optimizing the unit cell geometries of the micro-cell pellets for greater increases in thermal conductivity. Consequently, the micro-cell UO2sbnd Mo pellets (5 vol% Mo) with modified geometries increased the thermal conductivity of the current UO2 pellets by about 2.5 times, and lowered the temperature gradient within the pellets by 62.9% under a linear heat generation rate of 200 W/cm.

Facile Reductive Silylation of UO22+ to Uranium(IV) Chloride.

PubMed

Kiernicki, John J; Zeller, Matthias; Bart, Suzanne C

2017-01-19

General reductive silylation of the UO 2 2+ cation occurs readily in a one-pot, two-step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO 2 X 2 (L) 2 (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R 3 Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R 3 SiO) 2 UX 2 (L) 2 in high yields. Support is included for the key step in the process, reduction of U VI to U V . This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl 4 or two equivalents of Me 2 SiCl 2 results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Processing and microstructural characterisation of a UO2-based ceramic for disposal studies on spent AGR fuel

NASA Astrophysics Data System (ADS)

Hiezl, Z.; Hambley, D. I.; Padovani, C.; Lee, W. E.

2015-01-01

Preparation and characterisation of a Simulated Spent Nuclear Fuel (SIMFuel), which replicates the chemical state and microstructure of Spent Nuclear Fuel (SNF) discharged from a UK Advanced Gas-cooled Reactor (AGR) after a cooling time of 100 years is described. Given the relatively small differences in radionuclide inventory expected over longer time periods, the SIMFuel studied in this work is expected to be also representative of spent fuel after significantly longer periods (e.g. 1000 years). Thirteen stable elements were added to depleted UO2 and sintered to simulate the composition of fuel pellets after burn-ups of 25 and 43 GWd/tU and, as a reference, pure UO2 pellets were also investigated. The fission product distribution was calculated using the FISPIN code provided by the UK National Nuclear Laboratory. SIMFuel pellets were up to 92% dense and during the sintering process in H2 atmosphere Mo-Ru-Rh-Pd metallic precipitates and grey-phase ((Ba, Sr)(Zr, RE) O3 oxide precipitates) formed within the UO2 matrix. These secondary phases are present in real PWR and AGR SNF. Metallic precipitates are generally spherical and have submicron particle size (0.8 ± 0.7 μm). Spherical oxide precipitates in SIMFuel measured up to 30 μm in diameter, but no data were available in the public domain to compare this to AGR SNF. The grain size of actual AGR SNF (∼ 3-30 μm) is larger than that measured in AGR SIMFuel (∼ 2-5 μm).

Raman spectroscopic studies of defect structures and phase transition in hyper-stoichiometric UO(2+x).

PubMed

He, Heming; Shoesmith, David

2010-07-28

A method to determine the defect structures in hyper-stoichiometric UO(2+x) using a combination of XRD and Raman spectroscopy has been developed. A sequence of phase transitions, from cubic to tetragonal symmetry, occurs with increasing degree of non-stoichiometry. This sequence proceeds from a cubic phase through an intermediate t''-type tetragonal (axial ratio c/a = 1) phase to a final t-type tetragonal (c/a not = 1) phase. Four distinct structural defect regions can be identified in the stoichiometry range, UO(2) to U(3)O(7): (i) a random point defect structure (x (in UO(2+x)) < or = 0.05); (ii) a non-stoichiometry region (0.05 < or = x < or = 0.15) over which point defects are gradually eliminated and replaced by the Willis 2:2:2 cluster; (iii) a mixture of Willis and cuboctahedral clusters (0.15 < or = x < or = 0.23); (iv) the cuboctahedral cluster (x > or = 0.23). The geometry and steric arrangement of these defects is primarily determined by the concentration of the excess-oxygen interstitials.

Effect of point defects on the thermal conductivity of UO2: molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang-Yang; Stanek, Christopher Richard; Andersson, Anders David Ragnar

2015-07-21

The thermal conductivity of uranium dioxide (UO 2) fuel is an important materials property that affects fuel performance since it is a key parameter determining the temperature distribution in the fuel, thus governing, e.g., dimensional changes due to thermal expansion, fission gas release rates, etc. [1] The thermal conductivity of UO 2 nuclear fuel is also affected by fission gas, fission products, defects, and microstructural features such as grain boundaries. Here, molecular dynamics (MD) simulations are carried out to determine quantitatively, the effect of irradiation induced point defects on the thermal conductivity of UO 2, as a function of defectmore » concentrations, for a range of temperatures, 300 – 1500 K. The results will be used to develop enhanced continuum thermal conductivity models for MARMOT and BISON by INL. These models express the thermal conductivity as a function of microstructure state-variables, thus enabling thermal conductivity models with closer connection to the physical state of the fuel [2].« less

Electronic transport in pure and doped UO2

NASA Astrophysics Data System (ADS)

Massih, A. R.

2017-12-01

The thermoelectric properties of pure and doped UO2, namely the thermal and electrical conductivities and the thermopower, are assessed. We adopt the small polaron theory of the Mott type insulators, wherein the charge carriers, the electron and hole on the U3+ and U5+ ions, are treated as small polarons. For the thermal conductivity, the small polaron theory is applicable at temperatures above 1500 K. A review of the experimental data on the temperature dependence of the aforementioned transport properties is made. The data include UO2 with dopants such as Cr2O3, Gd2O3, Y2O3 and Nb2O5. We compare the applications of the theory with the data. Two limiting regimes, adiabatic and nonadiabatic, with the ensuing expressions for the conductivities and the thermoelectric power are considered. We discuss both the merits and shortcomings of the putative small polaron model and the simplification thereof as applied to pure and doped uranium dioxide.

Coordination trends in alkali metal crown ether uranyl halide complexes: the series [A(crown)]2[UO(2)X(4)] where A=Li, Na, K and X=Cl, Br.

PubMed

Danis, J A; Lin, M R; Scott, B L; Eichhorn, B W; Runde, W H

2001-07-02

UO(2)(C(2)H(3)O(2))(2).2H(2)O reacts with AX or A(C(2)H(3)O(2) or ClO(4)) (where A = Li, Na, K; X = Cl, Br) and crown ethers in HCl or HBr aqueous solutions to give the sandwich-type compounds [K(18-crown-6)](2)[UO(2)Cl(4)] (1), [K(18-crown-6)](2)[UO(2)Br(4)] (2), [Na(15-crown-5)](2)[UO(2)Cl(4)] (3), [Na(15-crown-5)](2)[UO(2)Br(4)] (4), [Li(12-crown-4)](2)[UO(2)Cl(4)] (5), and [Li(12-crown-4)](2)[UO(2)Br(4)] (6). The compounds have been characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and Raman spectroscopy. The [UO(2)X(4)](2-) ions coordinate to two [A(crown)](+) cations through the four halides only (2), through two halides only (3), through the two uranyl oxygens and two halides (3, 4), or through the two uranyl oxygen atoms only (5, 6). Raman spectra reveal nu(U-O) values that correlate with expected trends. The structural trends are discussed within the context of classical principles of hard-soft acid-base theory.

First-principles study of defects and phase transition in UO(2).

PubMed

Yu, Jianguo; Devanathan, Ram; Weber, William J

2009-10-28

Defect properties and phase transition in UO(2) have been studied from first principles by the all-electron projector-augmented-wave (PAW) method. The generalized gradient approximation with empirical self-interaction correction, (GGA)+U, formalism has been used to account for the strong on-site Coulomb repulsion among the localized U 5f electrons. The Hubbard parameter U(eff), magnetic ordering, chemical potential and heat of formation have been systematically examined. By choosing an appropriate U(eff) = 3.0 eV it is possible to consistently describe structural properties of UO(2) and model the phase transition processes. The phase transition pressure for UO(2) is about 20 GPa, which is less than the experimental value of 42 GPa but better than the LDA+U value of 7.8 GPa. Meanwhile our results for the formation energies of intrinsic defects partly confirm earlier calculations for the intrinsic charge neutral defects but reveal large variations depending on the determination of the chemical potential and whether the environment is O-rich or U-rich. Moreover, the results for extrinsic defects of Xe, which are representative of mobile insoluble fission product in UO(2), are consistent with experimental data in which Xe prefers to be trapped by Schottky defects.

Applying design principles to fusion reactor configurations for propulsion in space

NASA Technical Reports Server (NTRS)

Carpenter, Scott A.; Deveny, Marc E.; Schulze, Norman R.

1993-01-01

The application of fusion power to space propulsion requires rethinking the engineering-design solution to controlled-fusion energy. Whereas the unit cost of electricity (COE) drives the engineering-design solution for utility-based fusion reactor configurations; initial mass to low earth orbit (IMLEO), specific jet power (kW(thrust)/kg(engine)), and reusability drive the engineering-design solution for successful application of fusion power to space propulsion. We applied three design principles (DP's) to adapt and optimize three candidate-terrestrial-fusion-reactor configurations for propulsion in space. The three design principles are: provide maximum direct access to space for waste radiation, operate components as passive radiators to minimize cooling-system mass, and optimize the plasma fuel, fuel mix, and temperature for best specific jet power. The three candidate terrestrial fusion reactor configurations are: the thermal barrier tandem mirror (TBTM), field reversed mirror (FRM), and levitated dipole field (LDF). The resulting three candidate space fusion propulsion systems have their IMLEO minimized and their specific jet power and reusability maximized. We performed a preliminary rating of these configurations and concluded that the leading engineering-design solution to space fusion propulsion is a modified TBTM that we call the Mirror Fusion Propulsion System (MFPS).

On the Role of the Electrical Field in Spark Plasma Sintering of UO2+x

NASA Astrophysics Data System (ADS)

Tyrpekl, Vaclav; Naji, Mohamed; Holzhäuser, Michael; Freis, Daniel; Prieur, Damien; Martin, Philippe; Cremer, Bert; Murray-Farthing, Mairead; Cologna, Marco

2017-04-01

The electric field has a large effect on the stoichiometry and grain growth of UO2+x during Spark Plasma Sintering. UO2+x is gradually reduced to UO2.00 as a function of sintering temperature and time. A gradient in the oxidation state within the pellets is observed in intermediate conditions. The shape of the gradient depends unequivocally on the direction of the electrical field. The positive surface of the pellet shows a higher oxidation state compared to the negative one. An area with larger grain size is found close to the positive electrode, but not in contact with it. We interpret these findings with the redistribution of defects under an electric field, which affect the stoichiometry of UO2+x and thus the cation diffusivity. The results bear implications for understanding the electric field assisted sintering of UO2 and non-stoichiometric oxides in general.

On the Role of the Electrical Field in Spark Plasma Sintering of UO2+x

PubMed Central

Tyrpekl, Vaclav; Naji, Mohamed; Holzhäuser, Michael; Freis, Daniel; Prieur, Damien; Martin, Philippe; Cremer, Bert; Murray-Farthing, Mairead; Cologna, Marco

2017-01-01

The electric field has a large effect on the stoichiometry and grain growth of UO2+x during Spark Plasma Sintering. UO2+x is gradually reduced to UO2.00 as a function of sintering temperature and time. A gradient in the oxidation state within the pellets is observed in intermediate conditions. The shape of the gradient depends unequivocally on the direction of the electrical field. The positive surface of the pellet shows a higher oxidation state compared to the negative one. An area with larger grain size is found close to the positive electrode, but not in contact with it. We interpret these findings with the redistribution of defects under an electric field, which affect the stoichiometry of UO2+x and thus the cation diffusivity. The results bear implications for understanding the electric field assisted sintering of UO2 and non-stoichiometric oxides in general. PMID:28422164

[(S)-1-Carbamoylethyl]bis(dimethylglyoximato-kappa2N,N')[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato-kappa2N,N')[(R)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III) monohydrate.

PubMed

Orisaku, Keiko Komori; Hagiwara, Mieko; Ohgo, Yoshiki; Arai, Yoshifusa; Ohgo, Yoshiaki

2005-04-01

The title complexes, [Co(C3H6NO)(C4H7N2O2)2(C8H11N)] and [Co(C4H8NO)(C4H7N2O2)2(C8H11N)].H2O, were resolved from [(RS)-1-carbamoylethyl]bis(dimethylglyoximato)[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato)[(RS)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III), respectively, and their crystal structures were determined in order to reveal the absolute configuration of the major enantiomer produced in the photoisomerization of each series of 2-carbamoylethyl and 2-(N-methylcarbamoyl)ethyl cobaloxime complexes.

Development Status of a CVD System to Deposit Tungsten onto UO2 Powder via the WCI6 Process

NASA Technical Reports Server (NTRS)

Mireles, O. R.; Kimberlin, A.; Broadway, J.; Hickman, R.

2014-01-01

Nuclear Thermal Propulsion (NTP) is under development for deep space exploration. NTP's high specific impulse (> 850 second) enables a large range of destinations, shorter trip durations, and improved reliability. W-60vol%UO2 CERMET fuel development efforts emphasize fabrication, performance testing and process optimization to meet service life requirements. Fuel elements must be able to survive operation in excess of 2850 K, exposure to flowing hydrogen (H2), vibration, acoustic, and radiation conditions. CTE mismatch between W and UO2 result in high thermal stresses and lead to mechanical failure as a result UO2 reduction by hot hydrogen (H2) [1]. Improved powder metallurgy fabrication process control and mitigated fuel loss can be attained by coating UO2 starting powders within a layer of high density tungsten [2]. This paper discusses the advances of a fluidized bed chemical vapor deposition (CVD) system that utilizes the H2-WCl6 reduction process.

Thermal transport in UO 2 with defects and fission products by molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang-Yang; Cooper, Michael William Donald; Mcclellan, Kenneth James

2015-10-14

The importance of the thermal transport in nuclear fuel has motivated a wide range of experimental and modelling studies. In this report, the reduction of thermal transport in UO 2 due to defects and fission products has been investigated using non-equilibrium MD simulations, with two sets of empirical potentials for studying the degregation of UO 2 thermal conductivity including a Buckingham type interatomic potential and a recently developed EAM type interatomic potential. Additional parameters for U 5+ and Zr 4+ in UO 2 have been developed for the EAM potential. The thermal conductivity results from MD simulations are then correctedmore » for the spin-phonon scattering through Callaway model formulations. To validate the modelling results, comparison was made with experimental measurements on single crystal hyper-stoichiometric UO 2+x samples.« less

Study of phonons in irradiated epitaxial thin films of UO2

NASA Astrophysics Data System (ADS)

Rennie, S.; Lawrence Bright, E.; Darnbrough, J. E.; Paolasini, L.; Bosak, A.; Smith, A. D.; Mason, N.; Lander, G. H.; Springell, R.

2018-06-01

We report experiments to determine the effect of radiation damage on the phonon spectra of the most common nuclear fuel, UO2. We irradiated thin (˜300 nm) epitaxial films of UO2 with 2.1 MeV He2 + ions to 0.15 displacements per atom and a lattice swelling of Δ a /a ˜0.6 % and then used grazing-incidence inelastic x-ray scattering to measure the phonon spectrum. We succeeded in observing the acoustic modes, both transverse and longitudinal, across the Brillouin zone. The phonon energies, in both the pristine and irradiated samples, are unchanged from those observed in bulk material. On the other hand, the phonon linewidths (inversely proportional to the phonon lifetimes) show a significant broadening when comparing the pristine and irradiated samples. This effect is shown to increase with phonon energy across the Brillouin zone. The decreases in the phonon lifetimes of the acoustic modes are roughly consistent with a 50% reduction in the thermal conductivity.

First-principles molecular dynamics simulation of the Ca 2UO 2(CO 3) 3 complex in water

DOE PAGES

Priest, Chad; Tian, Ziqi; Jiang, De-en

2016-01-22

Recent experiments have shown that the neutral Ca 2UO 2(CO 3) 3 complex is the dominant species of uranium in many uranyl-containing streams. However, the structure and solvation of such a species in water has not been investigated from first principles. Herein we present a first principles molecular dynamics perspective of the Ca 2UO 2(CO 3) 3 complex in water based on density functional theory and Born–Oppenheimer approximation. We find that the Ca 2UO 2(CO 3) 3 complex is very stable in our simulation timeframe for three different concentrations considered and that the key distances from our simulation are inmore » good agreement with the experimental data from extended X-ray absorption fine structure (EXAFS) spectroscopy. More important, we find that the two Ca ions bind differently in the complex, as a result of the hydrogen-bonding network around the whole complex. Furthermore, this finding invites confirmation from time-resolved EXAFS and has implications in understanding the dissociative equilibrium of the Ca 2UO 2(CO 3) 3 complex in water.« less

Temperature dependence of the Raman spectrum of UO2

NASA Astrophysics Data System (ADS)

Elorrieta, J. M.; Bonales, L. J.; Baonza, V. G.; Cobos, J.

2018-05-01

The position of the main spectral features (located at ∼445, ∼575, ∼625, ∼925 and ∼1145 cm-1) in the Raman spectrum of UO2 has been examined from room temperature up to 600 °C. The wavenumber shifts measured for the observed bands have allowed us to obtain the temperature dependence (dω/dT) of the different vibrational modes. Our measurements corroborate the assignment of the band observed at ∼1145 cm-1 to the 2LO overtone. In addition, the temperature dependence of the bandwidths of the T2g and 2LO modes has been analysed.

Numerical study of the effects of lamp configuration and reactor wall roughness in an open channel water disinfection UV reactor.

PubMed

Sultan, Tipu

2016-07-01

This article describes the assessment of a numerical procedure used to determine the UV lamp configuration and surface roughness effects on an open channel water disinfection UV reactor. The performance of the open channel water disinfection UV reactor was numerically analyzed on the basis of the performance indictor reduction equivalent dose (RED). The RED values were calculated as a function of the Reynolds number to monitor the performance. The flow through the open channel UV reactor was modelled using a k-ε model with scalable wall function, a discrete ordinate (DO) model for fluence rate calculation, a volume of fluid (VOF) model to locate the unknown free surface, a discrete phase model (DPM) to track the pathogen transport, and a modified law of the wall to incorporate the reactor wall roughness effects. The performance analysis was carried out using commercial CFD software (ANSYS Fluent 15.0). Four case studies were analyzed based on open channel UV reactor type (horizontal and vertical) and lamp configuration (parallel and staggered). The results show that lamp configuration can play an important role in the performance of an open channel water disinfection UV reactor. The effects of the reactor wall roughness were Reynolds number dependent. The proposed methodology is useful for performance optimization of an open channel water disinfection UV reactor. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ synchrotron investigation of grain growth behavior of nano-grained UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miao, Yinbin; Yao, Tiankai; Lian, Jie

Here, we report on the study of grain growth kinetics in nano-grained UO 2 samples. Dense nano-grained UO 2 samples with well-controlled stoichiometry and grain size were fabricated using the spark plasma sintering technique. To determine the grain growth kinetics at elevated temperatures, a synchrotron wide-angle X-ray scattering (WAXS) study was performed in situ to measure the real-time grain size evolution based on the modified Williamson-Hall analysis. The unique grain growth kinetics of nanocrystalline UO 2 at 730 °C and 820 °C were observed and explained by the difference in mobility of various grain boundaries.

In situ synchrotron investigation of grain growth behavior of nano-grained UO 2

DOE PAGES

Miao, Yinbin; Yao, Tiankai; Lian, Jie; ...

2017-01-09

Here, we report on the study of grain growth kinetics in nano-grained UO 2 samples. Dense nano-grained UO 2 samples with well-controlled stoichiometry and grain size were fabricated using the spark plasma sintering technique. To determine the grain growth kinetics at elevated temperatures, a synchrotron wide-angle X-ray scattering (WAXS) study was performed in situ to measure the real-time grain size evolution based on the modified Williamson-Hall analysis. The unique grain growth kinetics of nanocrystalline UO 2 at 730 °C and 820 °C were observed and explained by the difference in mobility of various grain boundaries.

An investigation into the feasibility of thorium fuels utilization in seed-blanket configurations for TRIGA PUSPATI Reactor (RTP)

NASA Astrophysics Data System (ADS)

Damahuri, Abdul Hannan Bin; Mohamed, Hassan; Aziz Mohamed, Abdul; Idris, Faridah

2018-01-01

Thorium is one of the elements that needs to be explored for nuclear fuel research and development. One of the popular core configurations of thorium fuel is seed-blanket configuration or also known as Radkowsky Thorium Fuel concept. The seed will act as a supplier of neutrons, which will be placed inside of the core. The blanket, on the other hand, is the consumer of neutrons that is located at outermost of the core. In this work, a neutronic analysis of seed-blanket configuration for the TRIGA PUSPATI Reactor (RTP) is carried out using Monte Carlo method. The reactor, which has been operated since 1982 use uranium zirconium hydride (U-ZrH1.6) as the fuel and have multiple uranium weight which are 8.5, 12 and 20 wt.%. The pool type reactor is one and only research reactor that located in Malaysia. The design of core included the Uranium Zirconium Hydride located at the centre of the core that will act as the seed to supply neutron. The thorium oxide that will act as blanket situated outside of seed region will receive neutron to transmute 232Th to 233U. The neutron multiplication factor or criticality of each configuration is estimated. Results show that the highest initial criticality achieved is 1.30153.

Molecular dynamics simulation of thermal transport in UO 2 containing uranium, oxygen, and fission-product defects

DOE PAGES

Liu, Xiang -Yang; Cooper, Michael William D.; McClellan, Kenneth James; ...

2016-10-25

Uranium dioxide (UO 2) is the most commonly used fuel in light-water nuclear reactors and thermal conductivity controls the removal of heat produced by fission, thereby governing fuel temperature during normal and accident conditions. The use of fuel performance codes by the industry to predict operational behavior is widespread. A primary source of uncertainty in these codes is thermal conductivity, and optimized fuel utilization may be possible if existing empirical models are replaced with models that incorporate explicit thermal-conductivity-degradation mechanisms during fuel burn up. This approach is able to represent the degradation of thermal conductivity due to each individual defectmore » type, rather than the overall burn-up measure typically used, which is not an accurate representation of the chemical or microstructure state of the fuel that actually governs thermal conductivity and other properties. To generate a mechanistic thermal conductivity model, molecular dynamics (MD) simulations of UO 2 thermal conductivity including representative uranium and oxygen defects and fission products are carried out. These calculations employ a standard Buckingham-type interatomic potential and a potential that combines the many-body embedded-atom-method potential with Morse-Buckingham pair potentials. Potential parameters for UO 2+x and ZrO 2 are developed for the latter potential. Physical insights from the resonant phonon-spin-scattering mechanism due to spins on the magnetic uranium ions are introduced into the treatment of the MD results, with the corresponding relaxation time derived from existing experimental data. High defect scattering is predicted for Xe atoms compared to that of La and Zr ions. Uranium defects reduce the thermal conductivity more than oxygen defects. For each defect and fission product, scattering parameters are derived for application in both a Callaway model and the corresponding high-temperature model typically used in fuel

Molecular dynamics simulation of thermal transport in UO 2 containing uranium, oxygen, and fission-product defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang -Yang; Cooper, Michael William D.; McClellan, Kenneth James

Uranium dioxide (UO 2) is the most commonly used fuel in light-water nuclear reactors and thermal conductivity controls the removal of heat produced by fission, thereby governing fuel temperature during normal and accident conditions. The use of fuel performance codes by the industry to predict operational behavior is widespread. A primary source of uncertainty in these codes is thermal conductivity, and optimized fuel utilization may be possible if existing empirical models are replaced with models that incorporate explicit thermal-conductivity-degradation mechanisms during fuel burn up. This approach is able to represent the degradation of thermal conductivity due to each individual defectmore » type, rather than the overall burn-up measure typically used, which is not an accurate representation of the chemical or microstructure state of the fuel that actually governs thermal conductivity and other properties. To generate a mechanistic thermal conductivity model, molecular dynamics (MD) simulations of UO 2 thermal conductivity including representative uranium and oxygen defects and fission products are carried out. These calculations employ a standard Buckingham-type interatomic potential and a potential that combines the many-body embedded-atom-method potential with Morse-Buckingham pair potentials. Potential parameters for UO 2+x and ZrO 2 are developed for the latter potential. Physical insights from the resonant phonon-spin-scattering mechanism due to spins on the magnetic uranium ions are introduced into the treatment of the MD results, with the corresponding relaxation time derived from existing experimental data. High defect scattering is predicted for Xe atoms compared to that of La and Zr ions. Uranium defects reduce the thermal conductivity more than oxygen defects. For each defect and fission product, scattering parameters are derived for application in both a Callaway model and the corresponding high-temperature model typically used in fuel

Mineralization and defluoridation of 2,2,3,3-tetrafluoro -1-propanol (TFP) by UV oxidation in a novel three-phase fluidized bed reactor (3P-FBR).

PubMed

Shih, Yu-Jen; Tsai, Meng-Tso; Huang, Yao-Hui

2013-05-01

2,2,3,3-Tetrafluoro-1-propanol (TFP, C3H4F4O, M.W. = 132.06) is extensively used as the solvent in CD-R and DVD-R fabrication. Since it has a fluorinated alky-chain configuration and is non-biodegradable, its treatment by conventional oxidation methods is typically very inefficient. In this work, novel three-phase fluidized bed reactor (3P-FBR, 7.5 cm in diameter, 50 cm high) that combines photo oxidation (UV/H2O2, one of AOPs (Advanced Oxidation Process) and adsorption (BT5 iron oxide as adsorbent) processes is designed for mineralizing and defluorinizing TFP wastewater. The experimental results reveal that TFP can be efficiently mineralized, and the BT5 that is circulated by aeration in the 3P-FBR system can remove the released fluoride ions in the reaction period. Irradiation with 254 nm UV and a 10 mM H2O2 dose yield a TOC removal of TFP (1.39 mM, equivalent to an initial TOC of 50 ppm) of over 99.95% in 2 h, and 99% of fluoride was removed by BT5 with an adsorption capacity of 24.1 mg-F g(-1). Copyright © 2013 Elsevier Ltd. All rights reserved.

High temperature redox reactions with uranium: Synthesis and characterization of Cs(UO{sub 2})Cl(SeO{sub 3}), Rb{sub 2}(UO{sub 2}){sub 3}O{sub 2}(SeO{sub 3}){sub 2}, and RbNa{sub 5}U{sub 2}(SO{sub 4}){sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babo, Jean-Marie; Department of Civil and Environmental Engineering and Earth Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556; Albrecht-Schmitt, Thomas E., E-mail: talbrechtschmitt@gmail.com

2013-10-15

Cs(UO{sub 2})Cl(SeO{sub 3}) (1), Rb{sub 2}(UO{sub 2}){sub 3}O{sub 2}(SeO{sub 3}){sub 3} (2), and RbNa{sub 5}U{sub 2}(SO{sub 4}){sub 7} (3) single crystals were synthesized using CsCl, RbCl, and a CuCl/NaCl eutectic mixture as fluxes, respectively. Their lattice parameters and space groups are as follows: P2{sub 1}/n (a=6.548(1) Å, b=11.052(2) Å, c=10.666(2) Å and β=93.897(3)°), P1{sup ¯} (a=7.051(2) Å, b=7.198(2) Å, c=8.314(2) Å, α=107.897(3)°, β=102.687(3)° and γ=100.564(3)°) and C2/c (a=17.862(4) Å, b=6.931(1) Å, c=20.133(4) Å and β=109.737(6)°. The small anionic building units found in these compounds are SeO{sub 3}{sup 2−} and SO{sub 4}{sup 2−} tetrahedra, oxide, and chloride. The crystal structure ofmore » the first compound is composed of [(UO{sub 2}){sub 2}Cl{sub 2}(SeO{sub 3}){sub 2}]{sup 2−} chains separated by Cs{sup +} cations. The structure of (2) is constructed from [(UO{sub 2}){sub 3}O{sub 11}]{sup 16−} chains further connected through selenite units into layers stacked perpendicularly to the [0 1 0] direction, with Rb{sup +} cations intercalating between them. The structure of compound (3) is made of uranyl sulfate layers formed by edge and vertex connections between dimeric [U{sub 2}O{sub 16}] and [SO{sub 4}] polyhedra. These layers contain unusual sulfate–metal connectivity as well as large voids. - Graphical abstract: A new family of uranyl selenites and sulfates has been prepared by high-temperature redox reactions. This compounds display new bonding motifs. Display Omitted - Highlights: • Low-dimensional Uranyl Oxoanion compounds. • Conversion of U(IV) to U(VI) at high temperatures. • Dimensional reduction by both halides and stereochemically active lone-pairs.« less

MARMOT simulations of Xe segregation to grain boundaries in UO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders D.; Tonks, Michael; Casillas, Luis

2012-06-20

Diffusion of Xe and U in UO{sub 2} is controlled by vacancy mechanisms and under irradiation the formation of mobile vacancy clusters is important. We derive continuum thermodynamic and diffusion models for Xe and U in UO{sub 2} based on the vacancy and cluster diffusion mechanisms established from recent density functional theory (DFT) calculations. Segregation of defects to grain boundaries in UO{sub 2} is described by combining the diffusion model with models of the interaction between Xe atoms and vacancies with grain boundaries derived from separate atomistic calculations. The diffusion and segregation models are implemented in the MOOSE/MARMOT (MBM) finitemore » element (FEM) framework and we simulate Xe redistribution for a few simple microstructures. In this report we focus on segregation to grain boundaries. The U or vacancy diffusion model as well as the coupled diffusion of vacancies and Xe have also been implemented, but results are not included in this report.« less

Neutron diffraction study of the in situ oxidation of UO(2).

PubMed

Desgranges, Lionel; Baldinozzi, Gianguido; Rousseau, Gurvan; Nièpce, Jean-Claude; Calvarin, Gilbert

2009-08-17

This paper discusses uranium oxide crystal structure modifications that are observed during the low-temperature oxidation which transforms UO(2) into U(3)O(8). The symmetries and the structural parameters of UO(2), beta-U(4)O(9), beta-U(3)O(7), and U(3)O(8) were determined by refining neutron diffraction patterns on pure single-phase samples. Neutron diffraction patterns were also collected during the in situ oxidation of powder samples at 483 K. The lattice parameters and relative ratios of the four pure phases were measured during the progression of the isothermal oxidation. The transformation of UO(2) into U(3)O(8) involves a complex modification of the oxygen sublattice and the onset of complex superstructures for U(4)O(9) and U(3)O(7), associated with regular stacks of complex defects known as cuboctahedra, which consist of 13 oxygen atoms. The kinetics of the oxidation process are discussed on the basis of the results of the structural analysis.

Modelling the radiolytic corrosion of α-doped UO2 and spent nuclear fuel

NASA Astrophysics Data System (ADS)

Liu, Nazhen; Qin, Zack; Noël, James J.; Shoesmith, David W.

2017-10-01

A model previously developed to predict the corrosion rate of spent fuel (UO2) inside a failed waste container has been adapted to simulate the rates measured on a wide range of α-doped UO2 and spent fuel specimens. This simulation confirms the validity of the model and demonstrates that the steady-state corrosion rate is controlled by the radiolytic production of H2O2 (which has been shown to be the primary oxidant driving fuel corrosion), irrespective of the reactivity of the UO2 matrix. The model was then used to determine the consequences of corrosion inside a failed container resealed by steel corrosion products. The possible accumulation of O2, produced by H2O2 decomposition, was found to accelerate the corrosion rate in a closed system. However, the simultaneous accumulation of radiolytic H2, which is activated as a reductant on the noble metal (ε) particles in the spent fuel, rapidly overcame this acceleration leading to the eventual suppression of the corrosion rate to insignificant values. Calculations also showed that, while the radiation dose rate, the H2O2 decomposition ratio, and the surface coverage of ε particles all influenced the short term corrosion rate, the influence of the radiolytically produced H2 was the overwhelming influence in reducing the rate to negligible level (i.e., <10-20 mol m-2 s-1).

Fusion Ash Separation in the Princeton Field-Reversed Configuration Reactor

NASA Astrophysics Data System (ADS)

Abbate, Joseph; Yeh, Meagan; McGreivy, Nick; Cohen, Samuel

2016-10-01

The Princeton Field-Reversed Configuration (PFRC) concept relies on low-neutron production by D-3He fusion to enable small, safe nuclear-fusion reactors to be built, an approach requiring rapid and efficient extraction of fusion ash and energy produced by D-3He fusion reactions. The ash exhaust stream would contain energetic (0.1-1 MeV) protons, T, 3He, and 4He ions and nearly 1e5 cooler (ca. 100 eV) D ions. The T extracted from the reactor would be a valuable fusion product in that it decays into 3He, which could be used as fuel. If the T were not extracted it would be troublesome because of neutron production by the D-T reaction. This paper discusses methods to separate the various species in a PFRC reactor's exhaust stream. First, we discuss the use of curved magnetic fields to separate the energetic from the cool components. Then we discuss exploiting material properties, specifically reflection, sputtering threshold, and permeability, to allow separation of the hydrogen from the helium isotopes. DOE Contract Number DE-AC02-09CH11466.

Investigation of Oxygen Diffusion in Irradiated UO2 with MD Simulation

NASA Astrophysics Data System (ADS)

Günay, Seçkin D.

2016-11-01

In this study, irradiated UO2 is analyzed by atomistic simulation method to obtain diffusion coefficient of oxygen ions. For this purpose, a couple of molecular dynamics (MD) supercells containing Frenkel, Schottky, vacancy and interstitial types for both anion and cation defects is constructed individually. Each of their contribution is used to calculate the total oxygen diffusion for both intrinsic and extrinsic ranges. The results display that irradiation-induced defects contribute the most to the overall oxygen diffusion at temperatures below 800-1,200 K. This result is quite sensible because experimental data shows that, from room temperature to about 1,500 K, irradiation-induced swelling decreases and irradiated UO2 lattice parameter is gradually recovered because defects annihilate each other. Another point is that, concentration of defects enhances the irradiation-induced oxygen diffusion. Irradiation type also has the similar effect, namely oxygen diffusion in crystals irradiated with α-particles is more than the crystals irradiated with neutrons. Dynamic Frenkel defects dominate the oxygen diffusion data above 1,500—1,800 K. In all these temperature ranges, thermally induced Frenkel defects make no significant contribution to overall oxygen diffusion.

Determination of successive complexation constants in an ionic liquid: complexation of UO(2)(2+) with NO(3)(-) in C(4)-mimTf(2)N studied by UV-Vis spectroscopy.

PubMed

Georg, Sylvia; Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde; Petitjean, Laetitia; Picquet, Michel; Solov'ev, Vitaly

2010-04-01

The complexation of UO(2)(2+) with NO(3)(-) has been investigated in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by UV-vis spectroscopy at T = 18.5 degrees C. The complexation is evidenced through the appearance of four peaks at 425, 438, 453, and 467 nm. EXAFS data indicate that the trinitrato complex, UO(2)(NO(3))(3)(-), is dominating the speciation for a reagent ratio of [NO(3)(-)]/[UO(2)(2+)] > 3. Assuming three successive complexation steps, the conditional stability constants are calculated, the individual absorption spectra are derived, and a speciation plot is presented.

Local structure in solid solutions of stabilised zirconia with actinide dioxides (UO{sub 2}, NpO{sub 2})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walter, Marcus, E-mail: marcus.walter@vkta.d; Somers, Joseph; Bouexiere, Daniel

2011-04-15

The local structure of (Zr,Lu,U)O{sub 2-x} and (Zr,Y,Np)O{sub 2-x} solid solutions has been investigated by extended X-ray absorption fine structure (EXAFS). Samples were prepared by mixing reactive (Zr,Lu)O{sub 2-x} and (Zr,Y)O{sub 2-x} precursor materials with the actinide oxide powders, respectively. Sintering at 1600 {sup o}C in Ar/H{sub 2} yields a fluorite structure with U(IV) and Np(IV). As typical for stabilised zirconia the metal-oxygen and metal-metal distances are characteristic for the different metal ions. The bond lengths increase with actinide concentration, whereas highest adaptation to the bulk stabilised zirconia structure was observed for U---O and Np---O bonds. The Zr---O bond showsmore » only a slight increase from 2.14 A at 6 mol% actinide to 2.18 A at infinite dilution in UO{sub 2} and NpO{sub 2}. The short interatomic distance between Zr and the surrounding oxygen and metal atoms indicate a low relaxation of Zr with respect to the bulk structure, i.e. a strong Pauling behaviour. -- Graphical abstract: Metal-oxygen bond distances in (Zr,Lu,U)O{sub 2-x} solid solutions with different oxygen vacancy concentrations (Lu/Zr=1 and Lu/Zr=0.5). Display Omitted Research Highlights: {yields} EXAFS indicates high U and Np adaption to the bulk structure of stabilised zirconia. {yields} Zr---O bond length is 2.18 A at infinite Zr dilution in UO{sub 2} and NpO{sub 2}. {yields} Low relaxation (strong Pauling behaviour) of Zr explains its low solubility in UO{sub 2}.« less

Estimated critical conditions for UO{sub 2}F{sub 2}--H{sub 2}O systems in fully water-reflected spherical geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jordan, W.C.; Turner, J.C.

1992-12-01

The purpose of this report is to document reference calculations performed using the SCALE-4.0 code system to determine the critical parameters of UO{sub 2}F{sub 2}-H{sub 2}O spheres. The calculations are an extension of those documented in ORNL/CSD/TM-284. Specifically, the data for low-enriched UO{sub 2}F{sub 2}-H{sub 2}O spheres have been extended to highly enriched uranium. These calculations, together with those reported in ORNL/CSD/TM-284, provide a consistent set of critical parameters (k{sub {infinity}}, volume, mass, mass of water) for UO{sub 2}F{sub 2} and water over the full range of enrichment and moderation ratio.

UO2 fuel pellets fabrication via Spark Plasma Sintering using non-standard molybdenum die

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Shichalin, O. O.; Mironenko, A. Yu; Tananaev, I. G.; Avramenko, V. A.; Sergienko, V. I.

2018-02-01

The article investigates spark plasma sintering (SPS) of commercial uranium dioxide (UO2) powder of ceramic origin into highly dense fuel pellets using non-standard die instead of usual graphite die. An alternative and formerly unknown method has been suggested to fabricate UO2 fuel pellets by SPS for excluding of typical problems related to undesirable carbon diffusion. Influence of SPS parameters on chemical composition and quality of UO2 pellets has been studied. Also main advantages and drawbacks have been revealed for SPS consolidation of UO2 in non-standard molybdenum die. The method is very promising due to high quality of the final product (density 97.5-98.4% from theoretical, absence of carbon traces, mean grain size below 3 μm) and mild sintering conditions (temperature 1100 ºC, pressure 141.5 MPa, sintering time 25 min). The results are interesting for development and probable application of SPS in large-scale production of nuclear ceramic fuel.

Carbon monoxide reaction with UO2(111) single crystal surfaces: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Senanayake, S. D.; Soon, A.; Kohlmeyer, A.; Söhnel, T.; Idriss, H.

2005-07-01

The reaction of CO has been investigated on the surfaces of UO2(111) single crystal. Over the stoichiometric surface CO does not adsorb at 300 K and no further reaction is noticed. Over UO2-x (prepared by Ar+ bombardment), CO molecules adsorb and in presence of traces of H2 they couple to form acetylene molecules that desorb in two temperature domains during temperature programmed desorption (TPD). In the presence of excess H2 the coupling product is found to be ethylene. X-ray photoelectron spectroscopy (XPS) of the core level shows the presence of an U 4f line at 377 eV on the UO2-x surface, attributed to U metal. This line disappears upon CO adsorption (5 L and above) at 300 K indicating oxidation of U metal atoms by O from dissociatively adsorbed CO. XPS C 1s shows that the only C containing species formed is carbide. Computation of a α-U metal 2d-periodic slab was also conducted using plane-wave pseudopotential in the density functional theoretical framework. Two modes of CO adsorption were considered: molecular and dissociative. The dissociative adsorption was found more energetically favoured by 0.46 eV. From TPD, XPS and computation results it is strongly suggested that CO is dissociatively adsorbed on UO2-x and that a stable U-C species is formed at 300 K.

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Comparative performance of fixed-film biological filters: Application of reactor theory

USGS Publications Warehouse

Watten, B.J.; Sibrell, P.L.

2006-01-01

high levels of the latter reduces the effective reactor utilization rate (%) defined here as (RNavg/RNmax)100 where RNavg is the mean reactive nitrogen concentration ([NH4-N] + [NO2-N]) within the reactor, and RNmax represents the feed concentration of the same. Low utilization rates provide a hedge against unexpected increases in substrate loading and reduce water pumping requirements but force use of elevated reactor volumes. Further ?? effects on R1 and R2 can be reduced through use of a tanks-in-series versus a single mixed-flow reactor configuration and by improving the solids removal efficiency of microscreen treatment.

In situ ligand synthesis with the UO22+ cation under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Frisch, Mark; Cahill, Christopher L.

2007-09-01

A novel uranium (VI) coordination polymer, (UO 2) 2(C 2O 4)(C 5H 6NO 3) 2 ( 1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/ c, a=22.541(6) Å, b=5.7428(15) Å, c=15.815(4) Å, β=119.112(4)°, Z=4, R1=0.0237, w R2=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO 2 to form the oxalate linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C 2O 4)· nH 2O; 0⩽ n⩽1) and a known uranyl oxalate [(UO 2) 2(C 2O 4)(OH) 2(H 2O) 2·H 2O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state.

Design, fabrication, and testing of an external fuel (UO2), full-length thermionic converter

NASA Technical Reports Server (NTRS)

Schock, A.; Raab, B.

1971-01-01

The development of a full-length external-fuel thermionic converter for in-pile testing is described. The development program includes out-of-pile performance testing of the fully fueled-converter, using RF-induction heating, before its installation in the in-pile test capsule. The external-fuel converter is cylindrical in shape, and consists of an inner, centrally cooled collector, and an outer emitter surrounded by nuclear fuel. The term full-length denotes that the converter is long enough to extend over the full height of the reactor core. Thus, the converter is not a scaled-down test device, but a full-scale fuel element of the thermionic reactor. The external-fuel converter concept permits a number of different design options, particularly with respect to the fuel composition and shape, and the collector cooling arrangement. The converter described was developed for the Jet Propulsion Laboratory, and is based on their concept for a thermionic reactor with uninsulated collector cooling as previously described. The converter is double-ended, with through-flow cooling, and with ceramic seals and emitter and collector power take-offs at both ends. The design uses a revolver-shaped tungsten emitter body, with the central emitter hole surrounded by six peripheral fuel holes loaded with cylindrical UO2 pellets.

IEA-R1 Nuclear Research Reactor: 58 Years of Operating Experience and Utilization for Research, Teaching and Radioisotopes Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cardenas, Jose Patricio Nahuel; Filho, Tufic Madi; Saxena, Rajendra

IEA-R1 research reactor at the Instituto de Pesquisas Energeticas e Nucleares (Nuclear and Energy Research Institute) IPEN, Sao Paulo, Brazil is the largest power research reactor in Brazil, with a maximum power rating of 5 MWth. It is being used for basic and applied research in the nuclear and neutron related sciences, for the production of radioisotopes for medical and industrial applications, and for providing services of neutron activation analysis, real time neutron radiography, and neutron transmutation doping of silicon. IEA-R1 is a swimming pool reactor, with light water as the coolant and moderator, and graphite and beryllium as reflectors.more » The reactor was commissioned on September 16, 1957 and achieved its first criticality. It is currently operating at 4.5 MWth with a 60-hour cycle per week. In the early sixties, IPEN produced {sup 131}I, {sup 32}P, {sup 198}Au, {sup 24}Na, {sup 35}S, {sup 51}Cr and labeled compounds for medical use. During the past several years, a concerted effort has been made in order to upgrade the reactor power to 5 MWth through refurbishment and modernization programs. One of the reasons for this decision was to produce {sup 99}Mo at IPEN. The reactor cycle will be gradually increased to 120 hours per week continuous operation. It is anticipated that these programs will assure the safe and sustainable operation of the IEA-R1 reactor for several more years, to produce important primary radioisotopes {sup 99}Mo, {sup 125}I, {sup 131}I, {sup 153}Sm and {sup 192}Ir. Currently, all aspects of dealing with fuel element fabrication, fuel transportation, isotope processing, and spent fuel storage are handled by IPEN at the site. The reactor modernization program is slated for completion by 2015. This paper describes 58 years of operating experience and utilization of the IEA-R1 research reactor for research, teaching and radioisotopes production. (authors)« less

(2R,1'S,2'R)- and (2S,1'S,2'R)-3-[2-Mono(di,tri)fluoromethylcyclopropyl]alanines and their incorporation into hormaomycin analogues

PubMed Central

Kozhushkov, Sergei I; Yufit, Dmitrii S; Grosse, Christian; Kaiser, Marcel

2014-01-01

Summary Efficient and scalable syntheses of enantiomerically pure (2R,1'S,2'R)- and (2S,1'S,2'R)-3-[2-mono(di,tri)fluoromethylcyclopropyl]alanines 9a–c, as well as allo-D-threonine (4) and (2S,3R)-β-methylphenylalanine (3), using the Belokon' approach with (S)- and (R)-2-[(N-benzylprolyl)amino]benzophenone [(S)- and (R)-10] as reusable chiral auxiliaries have been developed. Three new fluoromethyl analogues of the naturally occurring octadepsipeptide hormaomycin (1) with (fluoromethylcyclopropyl)alanine moieties have been synthesized and subjected to preliminary tests of their antibiotic activity. PMID:25550751

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Na; Klepov, Vladislav V.; Villa, Eric M.

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O (α-, β-RbUAs) and the anhydrous phase Rb[UO2(AsO3OH)(AsO2(OH)2)] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions.

Effect of Al(OH)3 on the sintering of UO2-Gd2O3 fuel pellets with addition of U3O8 from recycle

NASA Astrophysics Data System (ADS)

dos Santos, Lauro Roberto; Durazzo, Michelangelo; Urano de Carvalho, Elita Fontenele; Riella, Humberto Gracher

2017-09-01

The incorporation of gadolinium as burnable poison directly into nuclear fuel is important for reactivity compensation, which enables longer fuel cycles. The function of the burnable poison fuel is to control the neutron population in the reactor core during its startup and the beginning of the fuel burning cycle to extend the use of the fuel. The implementation of UO2-Gd2O3 poisoned fuel in Brazil has been proposed according to the future requirements established for the Angra-2 nuclear power plant. The UO2 powder used is produced from the Ammonium Uranyl Carbonate (AUC). The incorporation of Gd2O3 powder directly into the AUC-derived UO2 powder by dry mechanical blending is the most attractive process, because of its simplicity. Nevertheless, processing by this method leads to difficulties while obtaining sintered pellets with the minimum required density. The cause of the low densities is the bad sintering behavior of the UO2-Gd2O3 mixed fuel, which shows a blockage in the sintering process that hinders the densification. This effect has been overcome by microdoping of the fuel with small quantities of aluminum. The process for manufacturing the fuel inevitably generates uranium-rich scraps from various sources. This residue is reincorporated into the production process in the form of U3O8 powder additions. The addition of U3O8 also hinders densification in sintering. This study was carried out to investigate the influence of both aluminum and U3O8 additives on the density of fuel pellets after sintering. As the effects of these additives are counterposed, this work studied the combined effect thereof, seeking to find an applicable composition for the production process. The experimental results demonstrated the effectiveness of aluminum, in the form of Al(OH)3, as an additive to promote increase in the densification of the (U,Gd)O2 pellets during sintering, even with high additions of U3O8 recycled from the manufacturing process.

Synthesis, characterization, structural and biological aspects of copper(II) dithiocarbamate complexes - Part II, [Cu{S2CN(Me)(R1)}2], [Cu{S2CN(Me)(R2)}2] and [Cu{S2CN(R3)(R4)}2] {R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH}

NASA Astrophysics Data System (ADS)

Ferreira, Isabella P.; de Lima, Geraldo M.; Paniago, Eucler B.; Takahashi, Jacqueline A.; Krambrock, Klaus; Pinheiro, Carlos B.; Wardell, James L.; Visentin, Lorenzo C.

2013-09-01

Three new copper(II) dithiocarbamates (DTC), [Cu{S2CN(Me)(R1)}2] (1), [Cu{S2CN(Me)(R2)}2] (2) and [Cu{S2CN(R3)(R4)}2] (3) with R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH, have been synthesized and characterized by different spectroscopic techniques. Complexes (1) and (2) display typical EPR spectra for separated Cu(II) centers, and the spectrum of (3) is characteristic of two magnetically coupled Cu(II) ions with S = 1. The X-ray crystallographic determination has shown that complexes (1) and (2) crystallise in the triclinic and monoclinic systems. In addition both complexes are monomers in which the geometry at each Cu(II) is square planar. The in vitro antimicrobial activity of the sodium salts of ligands, and of the Cu(II)-DTC complexes have been screened against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum and Curvularia senegalensis, as well as Gram positive and Gram negative bacteria. Finally, the toxic effects of complexes (1)-(3) were performed using Chlorella vulgaris.

Effect of reactor radiation on the thermal conductivity of TREAT fuel

NASA Astrophysics Data System (ADS)

Mo, Kun; Miao, Yinbin; Kontogeorgakos, Dimitrios C.; Connaway, Heather M.; Wright, Arthur E.; Yacout, Abdellatif M.

2017-04-01

The Transient Reactor Test Facility (TREAT) at the Idaho National Laboratory is resuming operations after more than 20 years in latency in order to produce high-neutron-flux transients for investigating transient-induced behavior of reactor fuels and their interactions with other materials and structures. A parallel program is ongoing to develop a replacement core in which the fuel, historically containing highly-enriched uranium (HEU), is replaced by low-enriched uranium (LEU). Both the HEU and prospective LEU fuels are in the form of UO2 particles dispersed in a graphite matrix, but the LEU fuel will contain a much higher volume of UO2 particles, which may create a larger area of interphase boundaries between the particles and the graphite. This may lead to a higher volume fraction of graphite exposed to the fission fragments escaping from the UO2 particles, and thus may induce a higher volume of fission-fragment damage on the fuel graphite. In this work, we analyzed the reactor-radiation induced thermal conductivity degradation of graphite-based dispersion fuel. A semi-empirical method to model the relative thermal conductivity with reactor radiation was proposed and validated based on the available experimental data. Prediction of thermal conductivity degradation of LEU TREAT fuel during a long-term operation was performed, with a focus on the effect of UO2 particle size on fission-fragment damage. The proposed method can be further adjusted to evaluate the degradation of other properties of graphite-based dispersion fuel.

Synthesis, characterization and biological study on Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide and bis(3-hydroxyimino)butan-2-ylidene)-oxalohydrazide.

PubMed

El-Asmy, A A; El-Gammal, O A; Radwan, H A

2010-09-01

Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide (H(2)L(1)) and oxalyl bis(diacetylmonoxime hydrazone) [its IUPAC name is oxalyl bis(3-hydroxyimino)butan-2-ylidene)oxalohydrazide] (H(4)L(2)) have been synthesized and characterized by partial elemental analysis, spectral (IR; electronic), thermal and magnetic measurements. [Cr(L(1))(H(2)O)(3)(Cl)].H(2)O, [ZrO(HL(1))(2)].C(2)H(5)OH, [UO(2)(L(1))(H(2)O)(2)] [ZrO(H(3)L(2))(Cl)](2).2H(2)O, [HfO(H(3)L(2))(Cl)](2).2H(2)O and [UO(2)(H(2)L(2))].2H(2)O have been suggested. H(2)L(1) behaves as a monobasic or dibasic bidentate ligand while H(4)L(2) acts as a tetrabasic octadentate with the two metal centers. The molecular modeling of the two ligands have been drawn and their molecular parameters were calculated. Examination of the DNA degradation of H(2)L(1) and H(4)L(2) as well as their complexes revealed that direct contact of [ZrO(H(3)L(2))(Cl)](2).2H(2)O or [HfO(H(3)L(2))(Cl)](2).2H(2)O degrading the DNA of Eukaryotic subject. The ligands and their metal complexes were tested against Gram's positive Bacillus thuringiensis (BT) and Gram's negative (Escherichia coli) bacteria. All compounds have small inhibitory effects. Copyright 2010 Elsevier B.V. All rights reserved.

(2R,3S,4R)-3,4-Isopropyl­idenedi­oxy-2-(phenyl­sulfonyl­meth­yl)pyrrolidin-1-ol

PubMed Central

Flores, Mari Fe; Garcia, Pilar; M. Garrido, Narciso; Sanz, Francisca; Diez, David

2012-01-01

The title compound, C14H19NO5S, was prepared by nucleophilic addition of the lithium derivative of methyl­phenyl­sulfone to (3S,4R)-3,4-isopropyl­idene­dioxy­pyrroline 1-oxide. There are four mol­ecules in the asymmetric unit. The crystal structure determination confirms the configuration of the chiral centres as 2R,3S,4R. In the crystal, pairs of O—H⋯N hydrogen bonds link the mol­ecules into dimers. PMID:22904989

Phase equilibria in the UO 2-PuO 2 system under a temperature gradient

NASA Astrophysics Data System (ADS)

Kleykamp, Heiko

2001-04-01

The phase behaviour of U 0.80Pu 0.20O 1.95 was investigated under a steady-state temperature gradient between the solidus and liquidus by a short-time power-to-melt irradiation experiment. The radial U, Pu, Am and O profiles in the fuel pin after redistribution were measured by X-ray microanalysis. During irradiation, an inner fuel melt forms which is separated from the outer solid only by one concentric liquid-solid-phase boundary. The UO 2 concentration increases to 85% and the PuO 2 concentration decreases to 15% on the solid side of the interface. Opposite gradients occur on the liquid side of the interface. The concentration discontinuity is a consequence of the necessary equality of the chemical potentials of UO 2 and PuO 2 on both sides of the phase boundary which corresponds to a 2750°C isotherm. The radial oxygen profile results in an O/(U + Pu) ratio of 2.00 at the fuel surface and 1.92 at the central void of the fuel. The redistribution is caused by the thermal diffusion of oxygen vacancies in the lattice along the temperature gradient. This process is quantified by the heat of transport Q*v which ranges between -10 kJ/mol at the central void and about -230 kJ/mol near the fuel surface.

Ab initio DFT+U study of He atom incorporation into UO(2) crystals.

PubMed

Gryaznov, Denis; Heifets, Eugene; Kotomin, Eugene

2009-09-07

We present and discuss results of the density functional theory (DFT) for perfect UO(2) crystals with He atoms in octahedral interstitial positions therein. We have calculated basic bulk crystal properties and He incorporation energies into the low temperature anti-ferromagnetic UO(2) phase using several exchange-correlation functionals within the spin-polarized local density (LDA) and generalized gradient (GGA) approximations. In all DFT calculations we included the on-site correlation corrections using the Hubbard model (DFT+U approach). We analysed a potential crystalline symmetry reduction from tetragonal down to orthorhombic structure and confirmed the presence of the Jahn-Teller effect in a perfect UO(2). We discuss also the problem of a conducting electronic state arising when He is placed into a tetragonal antiferromagnetic phase of UO(2) commonly used in defect modelling. Consequently, we found a specific monoclinic lattice distortion which allowed us to restore the semiconducting state and properly estimate He incorporation energies. Unlike the bulk properties, the He incorporation energy strongly depends on several factors, including the supercell size, the use of spin polarization, the exchange-correlation functionals and on-site correlation corrections. We compare our results for the He incorporation with the previous shell model and ab initio DFT calculations.

Infrared spectroscopy of extreme coordination: the carbonyls of U(+) and UO(2)(+).

PubMed

Ricks, Allen M; Gagliardi, Laura; Duncan, Michael A

2010-11-17

Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)(8)(+) and UO(2)(CO)(5)(+), with D(4d) square antiprism and D(5h) pentagonal bipyramid structures. Back-bonding in U(CO)(8)(+) causes a red-shifted CO stretch, but back-donation is inefficient for UO(2)(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.

Effect of reactor radiation on the thermal conductivity of TREAT fuel

DOE PAGES

Mo, Kun; Miao, Yinbin; Kontogeorgakos, Dimitrios C.; ...

2017-02-04

The Transient Reactor Test Facility (TREAT) at the Idaho National Laboratory is resuming operations after more than 20 years in latency in order to produce high-neutron-flux transients for investigating transient-induced behavior of reactor fuels and their interactions with other materials and structures. A parallel program is ongoing to develop a replacement core in which the fuel, historically containing highly-enriched uranium (HEU), is replaced by low-enriched uranium (LEU). Both the HEU and prospective LEU fuels are in the form of UO 2 particles dispersed in a graphite matrix, but the LEU fuel will contain a much higher volume of UO 2more » particles, which may create a larger area of interphase boundaries between the particles and the graphite. This may lead to a higher volume fraction of graphite exposed to the fission fragments escaping from the UO 2 particles, and thus may induce a higher volume of fission-fragment damage on the fuel graphite. In this work, we analyzed the reactor-radiation induced thermal conductivity degradation of graphite-based dispersion fuel. A semi-empirical method to model the relative thermal conductivity with reactor radiation was proposed and validated based on the available experimental data. Prediction of thermal conductivity degradation of LEU TREAT fuel during a long-term operation was performed, with a focus on the effect of UO 2 particle size on fission-fragment damage. Lastly, the proposed method can be further adjusted to evaluate the degradation of other properties of graphite-based dispersion fuel.« less

Effect of reactor radiation on the thermal conductivity of TREAT fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Kun; Miao, Yinbin; Kontogeorgakos, Dimitrios C.

The Transient Reactor Test Facility (TREAT) at the Idaho National Laboratory is resuming operations after more than 20 years in latency in order to produce high-neutron-flux transients for investigating transient-induced behavior of reactor fuels and their interactions with other materials and structures. A parallel program is ongoing to develop a replacement core in which the fuel, historically containing highly-enriched uranium (HEU), is replaced by low-enriched uranium (LEU). Both the HEU and prospective LEU fuels are in the form of UO 2 particles dispersed in a graphite matrix, but the LEU fuel will contain a much higher volume of UO 2more » particles, which may create a larger area of interphase boundaries between the particles and the graphite. This may lead to a higher volume fraction of graphite exposed to the fission fragments escaping from the UO 2 particles, and thus may induce a higher volume of fission-fragment damage on the fuel graphite. In this work, we analyzed the reactor-radiation induced thermal conductivity degradation of graphite-based dispersion fuel. A semi-empirical method to model the relative thermal conductivity with reactor radiation was proposed and validated based on the available experimental data. Prediction of thermal conductivity degradation of LEU TREAT fuel during a long-term operation was performed, with a focus on the effect of UO 2 particle size on fission-fragment damage. Lastly, the proposed method can be further adjusted to evaluate the degradation of other properties of graphite-based dispersion fuel.« less

Effect of organic complexing agents on the interactions of Cs(+), Sr(2+) and UO(2)(2+) with silica and natural sand.

PubMed

Reinoso-Maset, Estela; Worsfold, Paul J; Keith-Roach, Miranda J

2013-05-01

Sorption processes play a key role in controlling radionuclide migration through subsurface environments and can be affected by the presence of anthropogenic organic complexing agents found at contaminated sites. The effect of these complexing agents on radionuclide-solid phase interactions is not well known. Therefore the aim of this study was to examine the processes by which EDTA, NTA and picolinate affect the sorption kinetics and equilibria of Cs(+), Sr(2+) and UO2(2+) onto natural sand. The caesium sorption rate and equilibrium were unaffected by the complexing agents. Strontium however showed greater interaction with EDTA and NTA in the presence of desorbed matrix cations than geochemical modelling predicted, with SrNTA(-) enhancing sorption and SrEDTA(2-) showing lower sorption than Sr(2+). Complexing agents reduced UO2(2+) sorption to silica and enhanced the sorption rate in the natural sand system. Elevated concentrations of picolinate reduced the sorption of Sr(2+) and increased the sorption rate of UO2(2+), demonstrating the potential importance of this complexing agent. These experiments provide a direct comparison of the sorption behaviour of Cs(+), Sr(2+) and UO2(2+)onto natural sand and an assessment of the relative effects of EDTA, NTA and picolinate on the selected elements. Copyright © 2013 Elsevier Ltd. All rights reserved.

The thermal conductivity of mixed fuel U xPu 1-xO 2: molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang-Yang; Cooper, Michael William Donald; Stanek, Christopher Richard

2015-10-16

Mixed oxides (MOX), in the context of nuclear fuels, are a mixture of the oxides of heavy actinide elements such as uranium, plutonium and thorium. The interest in the UO 2-PuO 2 system arises from the fact that these oxides are used both in fast breeder reactors (FBRs) as well as in pressurized water reactors (PWRs). The thermal conductivity of UO 2 fuel is an important material property that affects fuel performance since it is the key parameter determining the temperature distribution in the fuel, thus governing, e.g., dimensional changes due to thermal expansion, fission gas release rates, etc. Formore » this reason it is important to understand the thermal conductivity of MOX fuel and how it differs from UO 2. Here, molecular dynamics (MD) simulations are carried out to determine quantitatively, the effect of mixing on the thermal conductivity of U xPu 1-xO 2, as a function of PuO 2 concentrations, for a range of temperatures, 300 – 1500 K. The results will be used to develop enhanced continuum thermal conductivity models for MARMOT and BISON by INL. These models express the thermal conductivity as a function of microstructure state-variables, thus enabling thermal conductivity models with closer connection to the physical state of the fuel.« less

Charge distribution and local structure and speciation in the UO 2+x and PuO 2+x binary oxides for x⩽0.25

NASA Astrophysics Data System (ADS)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Webster Keogh, D.; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Drew Tait, C.; Kirk Veirs, D.; Villella, Phillip M.; Wastin, Franck

2005-02-01

The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO 2+x (0.00⩽ x⩽0.20) and PuO 2+x/PuO 2+x-y(OH) 2y· zH 2O have been determined by U/Pu L III XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75 Å) U-O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO 2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO 2+x system, which does not show a separate phase at its x=0.25 endpoint, also displays (1) oxo groups at longer 1.9 Å distances consistent with Pu(V+ δ), (2) a multisite Pu-O distribution even when x is close to zero indicative of the formation of stable species with H 2O and its hydrolysis products with O 2-, and (3) a highly disordered, spectroscopically invisible Pu-Pu component. The structure and bonding in AnO 2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Na; Klepov, Vladislav V.; Villa, Eric M.

2014-07-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three differentmore » layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.« less

Reinvestigation of the uranium(3.5+) rare-earth oxysulfides "(UO)2LnS3" (Ln = Yb, Y).

PubMed

Jin, Geng Bang; Choi, Eun Sang; Ibers, James A

2009-09-07

Dark-red square plates of the previously reported compounds "(UO)(2)LnS(3)" (Ln = Yb, Y) have been synthesized by solid-state reactions of UOS and YbS or Y(2)S(3) with Sb(2)S(3) as a flux at 1273 K. The structure of these isotypic compounds was reinvestigated by single-crystal X-ray diffraction methods and an inductively coupled plasma experiment. The actual formula of "(UO)(2)LnS(3)" (Ln = Yb, Y) is (U(0.5)Ln(0.5)O)(2)LnS(3), that is, ULn(2)O(2)S(3), which can be charge-balanced with U(4+) and Ln(3+). The layered structure comprises (U/Ln)O(4)S(4) square antiprisms alternating with LnS(6) octahedra. U and Ln1 atoms disorder on the eight-coordinate metal position, but Ln2 atoms occupy the six-coordinate metal position exclusively. UYb(2)O(2)S(3) is a modified Curie-Weiss paramagnet between 293 and 32 K, below which part of the paramagnetic moments go through a possible ferromagnetic transition. The band gaps of ULn(2)O(2)S(3) (Ln = Yb, Y) are around 2 eV.

Advances in the Development of a WCl6 CVD System for Coating UO2 Powders with Tungsten

NASA Technical Reports Server (NTRS)

Mireles, Omar R.; Tieman, Alyssa; Broadway, Jeramie; Hickman, Robert

2013-01-01

W-UO2 CERMET fuels are under development to enable Nuclear Thermal Propulsion (NTP) for deep space exploration. Research efforts with an emphasis on fuel fabrication, testing, and identification of potential risks is underway. One primary risk is fuel loss due to CTE mismatch between W and UO2 and the grain boundary structure of W particles resulting in higher thermal stresses. Mechanical failure can result in significant reduction of the UO2 by hot hydrogen. Fuel loss can be mitigated if the UO2 particles are coated with a layer of high density tungsten before the consolidation process. This paper discusses the work to date, results, and advances of a fluidized bed chemical vapor deposition (CVD) system that utilizes the H2-WCl6 reduction process. Keywords: Space, Nuclear, Thermal, Propulsion, Fuel, CERMET, CVD, Tungsten, Uranium

Analysis of the vibrational frequencies of the UO/sup 2 +//sub 2/ ion in complexes containing acido-ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobets, L.V.; Umreiko, D.S.

1986-02-01

This paper presents an analysis of the vibrational frequencies of the UO/sup 2 +//sub 2/ ion in its complexes with acido-ligands that shows that in the series of the compounds indicated the correlation of UO/sup 2 +//sub 2/ with the nature of the anions and in particular with their basicity is limited in nature and may not be considered without taking account of the specific structures. If neutral ligands are present in the complexes, the situation is probably even more complicated.

Structural, spectroscopic and thermal characterization of 2-tert-butylaminomethylpyridine-6-carboxylic acid methylester and its Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) complexes.

PubMed

Mohamed, Gehad G; El-Gamel, Nadia E A

2005-04-01

Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) complexes with the ligand 2-tert-butylaminomethylpyridine-6-carboxylic acid methylester (HL(2)) have been prepared and characterized by elemental analyses, molar conductance, magnetic moment, thermal analysis and spectral data. 1:1 M:HL(2) complexes, with the general formula [M(HL(2))X(2)].nH(2)O (where M = Co(II) (X = Cl, n = 0), Ni(II) (X = Cl, n = 3), Cu(II) (grey colour, X = AcO, n = 1), Cu(II) (yellow colour, X = Cl, n = 0) and Zn(II) (X = Br, n = 0). In addition, the Fe(III) and UO(2)(II) complexes of the type 1:2 M:HL(2) and with the formulae [Fe(L(2))(2)]Cl and [UO(2)(HL(2))(2)](NO(3))(2) are prepared. From the IR data, it is seen that HL(2) ligand behaves as a terdentate ligand coordinated to the metal ions via the pyridyl N, carboxylate O and protonated NH group; except the Fe(III) complex, it coordinates via the deprotonated NH group. This is supported by the molar conductance data, which show that all the complexes are non-electrolytes, while the Fe(III) and UO(2)(II) complexes are 1:1 electrolytes. IR and H1-NMR spectral studies suggest a similar behaviour of the Zn(II) complex in solid and solution states. From the solid reflectance spectral data and magnetic moment measurements, the complexes have a trigonal bipyramidal (Co(II), Ni(II), Cu(II) and Zn(II) complexes) and octahedral (Fe(III), UO(2)(II) complexes) geometrical structures. The thermal behaviour of the complexes is studied and the different dynamic parameters are calculated applying Coats-Redfern equation.

PRODUCCION DE PLACAS DELGADAS DE UO$sub 2$ INFORME NO. 71. (Production of Thin Plates of UO$sub 2$. Report No. 71)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koll, H.; Carrea, A.J.

1962-01-01

The effect of some parameters on the fabrication of thin plates of UO/ sub 2/ by the sintering process is studied. Compacting pressures of 0.25 to 2 ton/cm/sub 2/, temperatures from 1100 to 1400 deg C, and sintering times from 1 to 3 hrs were used to determine the optimum values of these parameters. An analysis of the effect of the lubricant during the compression showed that the results were improved by the substitution of polyethylene glycol types for steric types, as the former were more easily removed from the compact and did not attack the UO/sub 2/ during sintering.more » Fracture during compression and extraction was studied. The compression law for the powder was determined, and the valid ity of the Bal'shin law was proved. The furnace atmospher is of importance to the sintered product. Two types of atmosphere were analyzed ---neutral atmosphere during sintering with final reduction in hydrogen and slightly reducing atmosphere during the entire process. An analysis of the effects on the final density and porosity showed that adding 3% H/sub 2/ to Ar produced good density and a stoichiometric oxide in the final product. It was shown that density is not a sufficient measurement to evaluate the degree of sintering. Only the combined use of density and porosity give a good evaluation. The compression pressure has a great effect on the pore size and distribution in the sintered product. Best results are obtained with high pressures, which gives small uniformly distributed pores. A metallographic study was made to determine the relation between pore size and distribution and the process parameters. Compact zones'' were observed with mean diameter from 1 to 2 mm with very reduced porosity. These zones had better hardness and resistance to corrosion and chemical attack than the rest of the material. (tr-auth)« less

Single-Chip T/R Module for 1.2 GHz

NASA Technical Reports Server (NTRS)

Moussessian, Alina; Mojarradi, Mohammad; Johnson, Travis; Davis, John; Grigorian, Edwin; Hoffman, James; Caro, Edward; Kuhn, William

2006-01-01

control line RX/TX (raised bar) is high, causing the field-effect transistor (FET) switch S1 to be closed, forming a parallel resonant tank circuit L1||C1. This circuit presents high impedance to the left of the antenna, so that the received signal is coupled to the LNA. At the same time, FET switches S2 and S3 are open, so that C2 is removed from the circuit (except for a small parasitic capacitance). The combination of L2 and C3 forms a matching network that transforms the antenna impedance of 50 ohms to a higher value from the perspective of the LNA input terminal. This transformation of impedance improves LNA noise figure by increasing the received voltage delivered to the input transistor. This allows lower transconductance and therefore a smaller transistor, which makes it possible to design the CMOS LNA for low power consumption. During transmission, the voltage on control line RX/TX (raised bar) is low, causing switch S1 to be open. In this configuration, the combination of L1 and C1 transforms the antenna impedance to a lower value from the perspective of the PA. This low impedance is helpful in producing a relatively high output power compatible with the low CMOS operating potential. At the same time, switches S2 and S3 are closed, forming the parallel resonant tank circuit L2||C2. This circuit presents high impedance to the right of the antenna, directing the PA output signal to the antenna and away from the LNA. During this time, S3 presents a short circuit across the LNA input terminals to guarantee that the voltage seen by the LNA is small enough to prevent damage.

Volumetric properties under pressure for 1,2-dichlorofluoroethane (R141), 1-fluoro-1,1,2-trichloroethane (R131a), and 1,2-dichloro-1,1-difluoroethane (R132b)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malhotra, R.; Woolf, L.A.

1997-01-01

The effect of pressure on the volume of R141, R131, and R132b is reported as volume ratios (the volume under pressure relative to its value at atmospheric pressure) at six temperatures covering the range 278.15 to 338.13 K and pressures up to 380 MPa for R141 and R131a. For R132b the same temperature range has been used, but above its normal boiling point experimental arrangements have limited maximum pressures to below 300 MPa, with some loss of accuracy. Densities have been measured at atmospheric pressure for each liquid. The experimental data have been used to calculate isothermal compressibilities, thermal expansivities,more » and internal pressures; the change in isobaric heat capacity from its value at atmospheric pressure has also been estimated. The volume ratios for all three compounds can be represented by a version of the Tait equation based on previously reported data for 1,2-dichloroethane and 1,1,2-trichloroethane with the inclusion of allowances of the substitution in the former of chlorine or fluorine for the hydrogens on one of the carbons.« less

Estimated critical conditions for UO[sub 2]F[sub 2]--H[sub 2]O systems in fully water-reflected spherical geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jordan, W.C.; Turner, J.C.

1992-12-01

The purpose of this report is to document reference calculations performed using the SCALE-4.0 code system to determine the critical parameters of UO[sub 2]F[sub 2]-H[sub 2]O spheres. The calculations are an extension of those documented in ORNL/CSD/TM-284. Specifically, the data for low-enriched UO[sub 2]F[sub 2]-H[sub 2]O spheres have been extended to highly enriched uranium. These calculations, together with those reported in ORNL/CSD/TM-284, provide a consistent set of critical parameters (k[sub [infinity

A ``NEW'' Solid-Core Reactor Fuel Form that Maximizes the Performance of Nuclear Thermal and Electric Rockets

NASA Astrophysics Data System (ADS)

Rom, Frank E.; Finnegan, Patrick M.

1994-07-01

The ``NEW'' solid-core fuel form is the old Vapor Transport (VT) fuel pin investigated at NASA about 30 years ago. It is simply a tube sealed at both ends partially filled with UO2. During operation the UO2 forms an annular layer on the inside of the tube by vaporization and condensation. This form is an ideal structure for overall strength and retention of fission products. All of the structural material lies between the fuel (including fission products) and the reactor coolant. The isothermal inside fuel surface temperature that results from the vaporization and condensation of fuel during operation eliminates hotspots, significantly increasing the design fuel pin surface temperature. For NTP, W-UO2 fuel pins yield higher operating temperatures than for other fuel forms, because W has about a ten-fold lower vaporization rate compared to any other known material. The use of perigee propulsion using W-UO2 fuel pins can result in a more than ten-fold reduction in reactor power. Lower reactor power, together with zero fission product release potential, and the simplicity of fabrication of VT fuel pins should greatly simplify and reduce the cost of development of NTP. For NEP, VT fuel pins can increase fast neutron spectrum reactor life with no fission product release. Thermal spectrum NEP reactors using W184 or Mo VT fuel pins, with only small amounts of high neutron absorbing additives, offer benefits because of much lower fissionable fuel requirements. The VT fuel pin has application to commercial power reactors with similar benefits.

Comparative studies of mononuclear Ni(II) and UO2(II) complexes having bifunctional coordinated groups: Synthesis, thermal analysis, X-ray diffraction, surface morphology studies and biological evaluation

NASA Astrophysics Data System (ADS)

Fahem, Abeer A.

2012-03-01

Two Schiff base ligands derived from condensation of phthalaldehyde and o-phenylenediamine in 1:2 (L1) and 2:1 (L2) having bifunctional coordinated groups (NH2 and CHO groups, respectively) and their metal complexes with Ni(II) and UO2(II) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibilities and spectral data (IR, 1H NMR, mass and solid reflectance) as well as thermal, XRPD and SEM analysis. The formula [Ni(L1)Cl2]·2.5H2O, [UO2(L1)(NO3)2]·2H2O, [Ni(L2)Cl2]·1.5H2O and [UO2(L2)(NO3)2] have been suggested for the complexes. The vibrational spectral data show that the ligands behave as neutral ligands and coordinated to the metal ions in a tetradentate manner. The Ni(II) complexes are six coordinate with octahedral geometry and the ligand field parameters: Dq, B, β and LFSE were calculated while, UO2(II) complexes are eight coordinate with dodecahedral geometry and the force constant, FUsbnd O and bond length, RUsbnd O were calculated. The thermal decomposition of complexes ended with metal chloride/nitrate as a final product and the highest thermal stability is displayed by [UO2(L2)(NO3)2] complex. The X-ray powder diffraction data revealed the formation of nano sized crystalline complexes. The SEM analysis provides the morphology of the synthesized compounds and SEM image of [UO2(L2)(NO3)2] complex exhibits nano rod structure. The growth-inhibiting potential of the ligands and their complexes has been assessed against a variety of bacterial and fungal strains.

Microscopic structure of liquid 1-1-1-2-tetrafluoroethane (R134a) from Monte Carlo simulation.

PubMed

Do, Hainam; Wheatley, Richard J; Hirst, Jonathan D

2010-10-28

1-1-1-2-tetrafluoroethane (R134a) is one of the most commonly used refrigerants. Its thermophysical properties are important for evaluating the performance of refrigeration cycles. These can be obtained via computer simulation, with an insight into the microscopic structure of the liquid, which is not accessible to experiment. In this paper, vapour-liquid equilibrium properties of R134a and its liquid microscopic structure are investigated using coupled-decoupled configurational-bias Monte Carlo simulation in the Gibbs ensemble, with a recent potential [J. Phys. Chem. B 2009, 113, 178]. We find that the simulations agree well with the experimental data, except at the vicinity of the critical region. Liquid R134a packs like liquid argon, with a coordination number in the first solvation shell of 12 at 260 K. The nearest neighbours prefer to be localized in three different spaces around the central molecule, in such a manner that the dipole moments are in a parallel alignment. Analysis of the pair interaction energy shows clear association of R134a molecules, but no evidence for C-HF type hydrogen bonding is found. The above findings should be of relevance to a broad range of fluoroalkanes.

Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

PubMed

Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

2010-06-28

With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

Manufacture of a UO2-Based Nuclear Fuel with Improved Thermal Conductivity with the Addition of BeO

NASA Astrophysics Data System (ADS)

Garcia, Chad B.; Brito, Ryan A.; Ortega, Luis H.; Malone, James P.; McDeavitt, Sean M.

2017-12-01

The low thermal conductivity of oxide nuclear fuels is a performance-limiting parameter. Enhancing this property may provide a contribution toward establishing accident-tolerant fuel forms. In this study, the thermal conductivity of UO2 was increased through the fabrication of ceramic-ceramic composite forms with UO2 containing a continuous BeO matrix. Fuel with a higher thermal conductivity will have reduced thermal gradients and lower centerline temperatures in the fuel pin. Lower operational temperatures will reduce fission gas release and reduce fuel restructuring. Additions of BeO were made to UO2 fuel pellets in 2.5, 5, 7.5, and 10 vol pct concentrations with the goals of establishing reliable lab-scale processing procedures, minimizing porosity, and maximizing thermal conductivity. The microstructure was characterized with electron probe microanalysis, and the thermal properties were assessed by light flash analysis and differential scanning calorimetry. Reliable, high-density samples were prepared using compaction pressure between 200 and 225 MPa and sintering times between 4 and 6 hours. It was found that the thermal conductivity of UO2 improved approximately 10 pct for each 1 vol pct BeO added over the measured temperature range 298.15 K to 523.15 K (25 °C to 250 °C) with the maximum observed improvement being ˜ 100 pct, or doubled, at 10 vol pct BeO.

Evaluation of melting point of UO 2 by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Arima, Tatsumi; Idemitsu, Kazuya; Inagaki, Yaohiro; Tsujita, Yuichi; Kinoshita, Motoyasu; Yakub, Eugene

2009-06-01

The melting point of UO 2 has been evaluated by molecular dynamics simulation (MD) in terms of interatomic potential, pressure and Schottky defect concentration. The Born-Mayer-Huggins potentials with or without a Morse potential were explored in the present study. Two-phase simulation whose supercell at the initial state consisted of solid and liquid phases gave the melting point comparable to the experimental data using the potential proposed by Yakub. The heat of fusion was determined by the difference in enthalpy at the melting point. In addition, MD calculations showed that the melting point increased with pressure applied to the system. Thus, the Clausius-Clapeyron equation was verified. Furthermore, MD calculations clarified that an addition of Schottky defects, which generated the local disorder in the UO 2 crystal, lowered the melting point.

ACE H2 Hardware Configuration and Mix Part 1

NASA Image and Video Library

2016-01-04

ISS046e005678 (01/04/2016) ---- ESA (European Space Agency) astronaut Tim Peake works on the Advanced Colloids Experiment 2 (ACE H2) Hardware Configuration and Mix Part 1. Peake sent out a Twitter message with this image: Stirring samples using a bar magnet to turn a tiny metal rod - preparing for today's @ISS_Research. #Principia".

Efficiency of depleted UO2 based semiconductor neutron detectors in direct and indirect configuration—A GEANT4 simulation study

NASA Astrophysics Data System (ADS)

Parida, M. K.; Prabakar, K.; Sundari, S. T.

2018-03-01

In the present work, Monte Carlo simulations using GEANT4 are carried out to estimate the efficiency of semiconductor neutron detectors with depleted UO2 (DUO2) as converter material, in both planar (direct and indirect) and 3D geometry (cylindrical perforation and trenches structure) configurations. The simulations were conducted for neutrons of variable energy viz., thermal (25 meV) and fast (1 to 10 MeV) that were incident on varying thicknesses (0.25 μm to 1000 μm), diameters (1 μm to 9 μm) and widths (1 μm to 9 μm) along with depths (50 μm to 275 μm) of DUO2 for planar, cylindrical perforated and trench structures, respectively. In the case of direct planar detectors, efficiency was found to increase with the thickness of DUO2 and the rate at which efficiency increased was found to follow the macroscopic fission cross section at the corresponding neutron energy. In the case of indirect planar detector, efficiency was lower as compared to direct configuration and was found to saturate beyond a thickness of ~3 μm. This saturation is explained on the basis of mean free path of neutrons in the DUO2 material. For the 3D perforated silicon detectors of cylindrical (trench) geometry, backfilled with DUO2, the efficiency for detection of thermal neutrons ~25 meV and fast neutrons ~ typical energy of 10 MeV was found to be ~0.0159% (~0.0177%) and ~0.0088% (0.0098%), respectively. These efficiency values were two (one) order values higher than planar indirect detector for thermal (fast) neutrons. Histogram plots were also obtained from the GEANT4 simulations to monitor the energy distribution of fission products in planar (direct and indirect) and 3D geometry (cylindrical and trench) configurations. These plots revealed that, for all the detector configurations, the energy deposited by the fission products are higher as compared to the typical gamma ray background. Thus, for detectors with DUO2 as converter material, higher values of low level discriminator

Atropisomeric property of 1-(2,6-difluorobenzyl)-3-[(2R)-amino-2-phenethyl]-5-(2-fluoro-3-methoxyphenyl)-6-methyluracil.

PubMed

Tucci, Fabio C; Hu, Tao; Mesleh, Michael F; Bokser, Allan; Allsopp, Eric; Gross, Timothy D; Guo, Zhiqiang; Zhu, Yun-Fei; Struthers, R Scott; Ling, Nicholas; Chen, Chen

2005-11-01

1-(2,6-Difluorobenzyl)-3-[(2R)-amino-2-phenethyl]-5-(2-fluoro-3-methoxyphenyl)-6-methyluracil (6), a potent and orally active antagonist of the human gonadotropin-releasing hormone receptor, exists as a pair of atropisomers in solution, which was detected by NMR spectroscopy, and separable by HPLC. In addition to a (R)-configured benzylamine, there is a second stereogenic element due to the presence of a chiral axis between the substituted 5-phenyl group and the uracil core. The rate constant of the interconversion (k = 5.07 x 10(-5) s(-1)) of these two atropisomers was determined by proton NMR analysis of a diastereoisomer-enriched sample in aqueous solution at 25 degrees C, and the corresponding Gibbs free energy DeltaG(#) of rotation barrier (97.4 kJ mol(-1)) was calculated using the Eyring equation. The diastereoisomer half-life at physiological temperature (37 degrees C) in aqueous media was estimated to be about 46 min. Copyright 2005 Wiley-Liss, Inc.

High density, uniformly distributed W/UO2 for use in Nuclear Thermal Propulsion

NASA Astrophysics Data System (ADS)

Tucker, Dennis S.; Barnes, Marvin W.; Hone, Lance; Cook, Steven

2017-04-01

An inexpensive, quick method has been developed to obtain uniform distributions of UO2 particles in a tungsten matrix utilizing 0.5 wt percent low density polyethylene. Powders were sintered in a Spark Plasma Sintering (SPS) furnace at 1600 °C, 1700 °C, 1750 °C, 1800 °C and 1850 °C using a modified sintering profile. This resulted in a uniform distribution of UO2 particles in a tungsten matrix with high densities, reaching 99.46% of theoretical for the sample sintered at 1850 °C. The powder process is described and the results of this study are given below.

Neutronics Benchmarks for the Utilization of Mixed-Oxide Fuel: Joint U.S./Russian Progress Report for Fiscal Year 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akkurt, H

2001-01-11

In 1967, a series of critical experiments were conducted at the Westinghouse Reactor Evaluation Center (WREC) using mixed-oxide (MOX) PuO{sub 2}-UO{sub 2} and/or UO{sub 2} fuels in various lattices and configurations . These experiments were performed under the joint sponsorship of the Empire State Atomic Development Associates (ESADA) plutonium program and Westinghouse . The purpose of these experiments was to develop experimental data to validate analytical methods used in the design of a plutonium-bearing replacement fuel for water reactors. Three different fuels were used during the experimental program: two MOX fuels and a low-enriched UO{sub 2} fuel. The MOX fuelsmore » were distinguished by their {sup 240}Pu content: 8 wt% {sup 240}Pu and 24 wt% {sup 240}Pu. Both MOX fuels contained 2.0 wt % PuO{sub 2} in natural UO{sub 2} . The UO{sub 2} fuel with 2.72 wt % enrichment was used for comparison with the plutonium data and for use in multiregion experiments.« less

Characterization of Oxygen Defect Clusters in UO2+ x Using Neutron Scattering and PDF Analysis.

PubMed

Ma, Yue; Garcia, Philippe; Lechelle, Jacques; Miard, Audrey; Desgranges, Lionel; Baldinozzi, Gianguido; Simeone, David; Fischer, Henry E

2018-06-18

In hyper-stoichiometric uranium oxide, both neutron diffraction work and, more recently, theoretical analyses report the existence of clusters such as the 2:2:2 cluster, comprising two anion vacancies and two types of anion interstitials. However, little is known about whether there exists a region of low deviation-from-stoichiometry in which defects remain isolated, or indeed whether at high deviation-from-stoichiometry defect clusters prevail that contain more excess oxygen atoms than the di-interstitial cluster. In this study, we report pair distribution function (PDF) analyses of UO 2 and UO 2+ x ( x ≈ 0.007 and x ≈ 0.16) samples obtained from high-temperature in situ neutron scattering experiments. PDF refinement for the lower deviation from stoichiometry sample suggests the system is too dilute to differentiate between isolated defects and di-interstitial clusters. For the UO 2.16 sample, several defect structures are tested, and it is found that the data are best represented assuming the presence of center-occupied cuboctahedra.

Theoretical investigations of geometry, electronic structure and stability of UO(6): octahedral uranium hexoxide and its isomers.

PubMed

Xiao, Hai; Hu, Han-Shi; Schwarz, W H Eugen; Li, Jun

2010-08-26

The existence of a novel octahedral UO(6) complex had been suggested by Pyykko et al. [Pyykko, P.; Runeberg, N.; Straka, M.; Dyall, K. G. Chem. Phys. Lett. 2000, 328, 415]. We have now investigated the stability, the geometric and electronic structures, and the vibrations of various UO(6) molecules, using spin-orbit density functional and scalar-relativistic coupled-cluster approaches. We find four different (meta-)stable species, namely (3)D(2h)-UO(2)(eta(2)-O(2)(*))(2) at lowest energy, (3)C(2v)-UO(4)(*)(eta(2)-O(2)(*)) and (1)D(3)-U(eta(2)-O(2))(3) at medium energies, and (1)O(h)-UO(6) at highest energy. The decay of O(h)-UO(6) occurs via an activated spin-flip mechanism. The UO(6) species correspond to local minima on singlet and triplet energy surfaces and might be trapped in noble gas matrices. Experimentally, the four species might be identified through their vibrational spectra. Uranium is best described as coordinated by oxygen atoms in various oxidation states as oxo O(2-), oxido(1) O(*-), peroxido O(2)(2-), and superoxido O(2)(*-) ligands. The occurrence of monovalent oxygen is remarkable. The resulting characterization of the central ion as U(VI) in all four cases does not fully reflect the electronic differences, nor the "valence-activity" of the U-6p(6) semicore shell.

Xenon migration in UO2 under irradiation studied by SIMS profilometry

NASA Astrophysics Data System (ADS)

Marchand, B.; Moncoffre, N.; Pipon, Y.; Bérerd, N.; Garnier, C.; Raimbault, L.; Sainsot, P.; Epicier, T.; Delafoy, C.; Fraczkiewicz, M.; Gaillard, C.; Toulhoat, N.; Perrat-Mabilon, A.; Peaucelle, C.

2013-09-01

During Pressurized Water Reactor operation, around 25% of the created Fission Products (FP) are Xenon and Krypton. They have a low solubility in the nuclear fuel and can either (i) agglomerate into bubbles which induce mechanical stress in the fuel pellets or (ii) be released from the pellets, increasing the pressure within the cladding and decreasing the thermal conductivity of the gap between pellets and cladding. After fifty years of studies on the nuclear fuel, all mechanisms of Fission Gas Release (FGR) are still not fully understood. This paper aims at studying the FGR mechanisms by decoupling thermal and irradiation effects and by assessing the Xenon behavior for the first time by profilometry. Samples are first implanted with 136Xe at 800 keV corresponding to a projected range of 140 nm. They are then either annealed in the temperature range 1400-1600 °C, or irradiated with heavy energy ions (182 MeV Iodine) at Room Temperature (RT), 600 °C or 1000 °C. Depth profiles of implanted Xenon in UO2 are determined by Secondary Ion Mass Spectrometry (SIMS). It is shown that Xenon is mobile during irradiation at 1000 °C. In contrast, thermal treatments do not induce any Xenon migration process: these results are correlated to the formation of Xenon bubbles observed by Transmission Electron Microscopy. At depths lower than about 40 nm (zone 1), no bubbles are observed, At depths in between 40 nm and 110 nm (zone 2), a large number of small bubbles (around 2 nm in diameter) can be observed. By comparing with the SRIM profile, it appears that this area corresponds to the maximum of the defect profile, The third zone displays two bubble populations. The first population has the same size than the bubbles present in zone 2. The bubble size of the second population is significantly larger (up to around 10 nm). A STEM micrograph is presented in Fig. 4. It highlights the Xenon bubbles more clearly. It appears that the largest bubbles are located mainly near dislocations

Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

PubMed

Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

2010-02-28

A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

Electronic spectroscopy of UO(2)Cl(2) isolated in solid Ar.

PubMed

Jin, Jin; Gondalia, Raj; Heaven, Michael C

2009-11-12

Laser-induced fluorescence spectra have been recorded for uranyl chloride isolated in a solid Ar matrix. Pulsed excitation was examined using a XeCl excimer laser (308 nm) and a dye laser operating in the 19500-27500 cm-1 range. Several absorption and emission band systems were observed. The emission spectra were characterized by a nearly harmonic vibrational progression with a frequency of 840 cm-1 starting at 20323 cm-1. The electronic absorption spectra were dominated by five harmonic vibrational progressions with frequencies of approximately 710 cm-1. Comparisons with theoretical calculations indicate that all of the transitions observed were associated with the UO2+2 subunit. They involved the promotion of an electron from a bonding orbital to the metal-centered 5f(delta) and 5f(phi) orbitals. Band origins and vibrational constants for five excited states were obtained. Fluorescence was observed from the lowest-energy excited state alone, regardless of the excitation wavelength. The decay curve was found to be biexponential, with characteristic decay lifetimes of 50 and 260 micros.

Methionine Regulates mTORC1 via the T1R1/T1R3-PLCβ-Ca2+-ERK1/2 Signal Transduction Process in C2C12 Cells.

PubMed

Zhou, Yuanfei; Ren, Jiao; Song, Tongxing; Peng, Jian; Wei, Hongkui

2016-10-11

The mammalian target of rapamycin complex 1 (mTORC1) integrates amino acid (AA) availability to support protein synthesis and cell growth. Taste receptor type 1 member (T1R) is a G protein-coupled receptor that functions as a direct sensor of extracellular AA availability to regulate mTORC1 through Ca 2+ stimulation and extracellular signal-regulated kinases 1 and 2 (ERK1/2) activation. However, the roles of specific AAs in T1R1/T1R3-regulated mTORC1 are poorly defined. In this study, T1R1 and T1R3 subunits were expressed in C2C12 myotubes, and l-AA sensing was accomplished by T1R1/T1R3 to activate mTORC1. In response to l-AAs, such as serine (Ser), arginine (Arg), threonine (Thr), alanine (Ala), methionine (Met), glutamine (Gln), and glycine (Gly), Met induced mTORC1 activation and promoted protein synthesis. Met also regulated mTORC1 via T1R1/T1R3-PLCβ-Ca 2+ -ERK1/2 signal transduction. Results revealed a new role for Met-regulated mTORC1 via an AA receptor. Further studies should be performed to determine the role of T1R1/T1R3 in mediating extracellular AA to regulate mTOR signaling and to reveal its mechanism.

Fuel Fabrication and Nuclear Reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karpius, Peter Joseph

2017-02-02

The uranium from the enrichment plant is still in the form of UF 6. UF 6 is not suitable for use in a reactor due to its highly corrosive chemistry as well as its phase diagram. UF 6 is converted into UO 2 fuel pellets, which are in turn placed in fuel rods and assemblies. Reactor designs are variable in moderators, coolants, fuel, performance etc.The dream of energy ‘too-cheap to meter’ is no more, and now the nuclear power industry is pushing ahead with advanced reactor designs.

Electrical and material properties of hydrothermally grown single crystal (111) UO2

NASA Astrophysics Data System (ADS)

Dugan, Christina L.; Peterson, George Glenn; Mock, Alyssa; Young, Christopher; Mann, J. Matthew; Nastasi, Michael; Schubert, Mathias; Wang, Lu; Mei, Wai-Ning; Tanabe, Iori; Dowben, Peter A.; Petrosky, James

2018-04-01

The semiconductor and optical properties of UO2 are investigated. The very long drift carrier lifetimes, obtained from current-voltage I( V) and capacitance-voltage C( V) measurements, along with the well-defined optical properties provide little evidence of an abundance of material defects away from the surface region. Schottky barrier formation may be possible, but very much dependent on the choice of contact and surface stoichiometry and we find that Ohmic contacts are in fact favored. Depth resolved photoemission provided evidence of a chemical shift at the surface. Density functional theory, with the Heyd-Scuseria-Ernzerhof (HSE) functional, indicates a band gap of a 2.19 eV and an anti-ferromagnetic ground state. Ellipsometry measurements indicates at UO2 is relatively isotropic with a band gap of approximately 2.0 eV band gap, consistent with theoretical expectations.

Preparation of UO2, ThO2 and (Th,U)O2 pellets from photochemically-prepared nano-powders

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Čuba, Václav; de Visser-Týnová, Eva; Ekberg, Christian; Persson, Ingmar

2016-02-01

Photochemically-induced preparation of nano-powders of crystalline uranium and/or thorium oxides and their subsequent pelletizing has been investigated. The preparative method was based on the photochemically induced formation of amorphous solid precursors in aqueous solution containing uranyl and/or thorium nitrate and ammonium formate. The EXAFS analyses of the precursors shown that photon irradiation of thorium containing solutions yields a compound with little long-range order but likely "ThO2 like" and the irradiation of uranium containing solutions yields the mixture of U(IV) and U(VI) compounds. The U-containing precursors were carbon free, thus allowing direct heat treatment in reducing atmosphere without pre-treatment in the air. Subsequent heat treatment of amorphous solid precursors at 300-550 °C yielded nano-crystalline UO2, ThO2 or solid (Th,U)O2 solutions with high purity, well-developed crystals with linear crystallite size <15 nm. The prepared nano-powders of crystalline oxides were pelletized without any binder (pressure 500 MPa), the green pellets were subsequently sintered at 1300 °C under an Ar:H2 (20:1) mixture (UO2 and (Th,U)O2 pellets) or at 1600 °C in ambient air (ThO2 pellets). The theoretical density of the sintered pellets varied from 91 to 97%.

Synthesis and structural features of U VI and V IV chelate complexes with (hhmmbH)Cl·H 2O [hhmmb = {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide], a new Schiff base ligand derived from vitamin B6

NASA Astrophysics Data System (ADS)

Back, Davi Fernando; Ballin, Marco Aurélio; de Oliveira, Gelson Manzoni

2009-10-01

The Schiff base ligand {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide hydrochloride monohydrated {(hhmmbH)Cl·H 2O} ( 1) was prepared by reaction of pyridoxine hydrochloride with benzoic acid hydrazide. The reaction of 1 with [VO(acac) 2] and triethylamine yields the neutral vanadium IV complex [VO 2(hhmmb)]·Py ( 2), with a distorted quadratic pyramidal configuration. The Schiff base 1 reacts also with UO 2(NO 3) 2·6H 2O and triethylamine under deprotonation giving the uranium VI cationic complexes [UO 2(hhmmb)(H 2O)Cl] + ( 3) and [UO 2(hhmmb)(CH 3OH)Cl] + ( 4), both showing the classical pentagonal bipyrimidal geometry of UO22+ complexes. The structural features of all compounds are discussed.

Characterization of UO2(2+) binding to osteopontin, a highly phosphorylated protein: insights into potential mechanisms of uranyl accumulation in bones.

PubMed

Qi, Lei; Basset, Christian; Averseng, Olivier; Quéméneur, Eric; Hagège, Agnès; Vidaud, Claude

2014-01-01

Bones are one of the few organs in which uranyl (UO2(2+)) accumulates. This large dioxo-cation displays affinity for carboxylates, phenolates and phosphorylated functional groups in proteins. The noncollagenous protein osteopontin (OPN) plays an important role in bone homeostasis. It is mainly found in the extracellular matrix of mineralized tissues but also in body fluids such as milk, blood and urine. Furthermore, OPN is an intrinsically disordered protein, which, like other proteins of the SIBLING family, contains a polyaspartic acid sequence and numerous patterns of alternating acidic and phosphorylated residues. All these properties led to the hypothesis that this protein could be prone to UO2(2+) binding. In this work, a simple purification procedure enabling highly purified bovine (bOPN) and human OPN (hOPN) to be obtained was developed. Various biophysical approaches were set up to study the impact of phosphorylations on the affinity of OPN for UO2(2+) as well as the formation of stable complexes originating from structural changes induced by the binding of this metal cation. The results obtained suggest a new mechanism of the interaction of UO2(2+) with bone metabolism and a new role for OPN as a metal transporter.

Experimental Demonstration of an Algorithm to Detect the Presence of a Parasitic Satellite

DTIC Science & Technology

2003-03-01

Chile (FASat- Alfa/Bravo), South Africa (UoSAT-3/4/5), Thailand (TMSAT-1), Sin- 1-2 gapore (Merlion payload), and Malaysia (TiungSAT-1). Recently...original configuration. 3.3.1 Hardware. The ground-station computer has been upgraded from the original configuration to a Dell r© Dimension r© Model...1◦/ hr accuracy. This is expected to be a two order of magnitude improvement. It is approximately the same size as the current gyroscope for simple

PRESSURIZED WATER REACTOR PROGRAM TECHNICAL PROGRESS REPORT FOR THE PERIOD MAY 5, 1955 TO JUNE 16, 1955

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

The current PWR plant and core parameters are listed. Resign requirements are briefly summarized for a radiation monitoring system, a fuel handling water system, a coolant purification system, an electrical power distribution system, and component shielding. Results of studies on thermal bowing and stressing of UO/sub 2/ are reported. A graph is presented of reactor power vs. reactor flow for various hot channel conditions. Development of U-- Mo and U-Nb alloys has been stopped because of the recent selection of UO/sub 2/ fuel material for the PWR core and blanket. The fabrication characteristics of UO/sub 2/ powders are being studied.more » Seamless Zircaloy-2 tubing has been tested to determine elastic limits, bursting pressures, and corrosion resistance. Fabrication techniques and tests for corrosion and defects in Zircaloy-clad U-Mo and UO/sub 2/ fuel rods are described. The preparation of UO/sub 2/ by various methods is being studied to determine which method produces a material most suitable for PWR fuel elements. The stability of UO/sub 2/ compacts in high temperature water and steam is being determined. Surface area and density measurements have been performed on samples of UO/sub 2/ powder prepared by various methods. Revelopment work on U-- Mo and U--Nb alloys has included studies of the effect on corrosion behavior of additions to the test water, additions to the alloys, homogenization of the alloys, annealing times, cladding, and fabrication techniques. Data are presented on relaxation in spring materials after exposure to a corrosive environment. Results are reported from loop and autoclave tests on fission product and crud deposition. Results of irradiation and corrosion testing of clad and unclad U--Mo and U-Nh alloys are described. The UO/sub 2/ irradiation program has included studies of dimensional changes, release of fission gases, and activity in the water surrounding the samples. A review of the methods of calculating reactor physics

Mechanism for transient migration of xenon in UO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, X.-Y.; Uberuaga, B. P.; Andersson, D. A.

2011-04-11

In this letter, we report recent work on atomistic modeling of diffusion migration events of the fission gas product xenon in UO{sub 2} nuclear fuel. Under nonequilibrium conditions, Xe atoms can occupy the octahedral interstitial site, in contrast to the thermodynamically most stable uranium substitutional site. A transient migration mechanism involving Xe and two oxygen atoms is identified using basin constrained molecular dynamics employing a Buckingham type interatomic potential. This mechanism is then validated using density functional theory calculations using the nudged elastic band method. An overall reduction in the migration barrier of 1.6-2.7 eV is obtained compared to vacancy-mediatedmore » diffusion on the uranium sublattice.« less

Stellar equilibrium configurations of white dwarfs in the f( R, T) gravity

NASA Astrophysics Data System (ADS)

Carvalho, G. A.; Lobato, R. V.; Moraes, P. H. R. S.; Arbañil, José D. V.; Otoniel, E.; Marinho, R. M.; Malheiro, M.

2017-12-01

In this work we investigate the equilibrium configurations of white dwarfs in a modified gravity theory, namely, f( R, T) gravity, for which R and T stand for the Ricci scalar and trace of the energy-momentum tensor, respectively. Considering the functional form f(R,T)=R+2λ T, with λ being a constant, we obtain the hydrostatic equilibrium equation for the theory. Some physical properties of white dwarfs, such as: mass, radius, pressure and energy density, as well as their dependence on the parameter λ are derived. More massive and larger white dwarfs are found for negative values of λ when it decreases. The equilibrium configurations predict a maximum mass limit for white dwarfs slightly above the Chandrasekhar limit, with larger radii and lower central densities when compared to standard gravity outcomes. The most important effect of f( R, T) theory for massive white dwarfs is the increase of the radius in comparison with GR and also f( R) results. By comparing our results with some observational data of massive white dwarfs we also find a lower limit for λ , namely, λ >- 3× 10^{-4}.

Advanced design concepts in nuclear electric propulsion. [and spacecraft configurations

NASA Technical Reports Server (NTRS)

Peelgren, M. L.; Mondt, J. F.

1974-01-01

Conceptual designs of the nuclear propulsion programs are reported. Major areas of investigation were (1) design efforts on spacecraft configuration and heat rejection subsystem, (2) high-voltage thermionic reactor concepts, and (3) dual-mode spacecraft configuration study.

Substituent effects on the enantioselective retention of anti-HIV 5-aryl-delta 2-1,2,4-oxadiazolines on R,R-DACH-DNB chiral stationary phase.

PubMed

Altomare, C; Cellamare, S; Carotti, A; Barreca, M L; Chimirri, A; Monforte, A M; Gasparrini, F; Villani, C; Cirilli, M; Mazza, F

1996-01-01

A series of racemic 3-phenyl-4-(1-adamantyl)-5-X-phenyl- delta 2-1,2,4-oxadiazo lines (PAdOx) were directly resolved by HPLC using a Pirkle-type stationary phase containing N,N'-(3,5-dinitrobenzoyl)-1(R),2(R)-diaminocyclohexane as chiral selector. The more retained enantiomers have S configuration, as demonstrated by X-ray crystallography and circular dichroism measurements. The influence of aromatic ring substituents on enantioselective retention was quantitatively assessed by traditional linear free energy-related (LFER) equations and comparative molecular field analysis (CoMFA). In good agreement with previous findings, the results from this study indicate that the increase in retention (k') is favoured mainly by the phi-basicity and the hydrophilicity of solute, whereas enantioselectivity (alpha) can be satisfactorily modeled by electronic and bulk parameters or CoMFA descriptors. The LFER equations and CoMFA models gave helpful insights into chiral recognition mechanisms.

Pyroprocessing of Light Water Reactor Spent Fuels Based on an Electrochemical Reduction Technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohta, Hirokazu; Inoue, Tadashi; Sakamura, Yoshiharu

A concept of pyroprocessing light water reactor (LWR) spent fuels based on an electrochemical reduction technology is proposed, and the material balance of the processing of mixed oxide (MOX) or high-burnup uranium oxide (UO{sub 2}) spent fuel is evaluated. Furthermore, a burnup analysis for metal fuel fast breeder reactors (FBRs) is conducted on low-decontamination materials recovered by pyroprocessing. In the case of processing MOX spent fuel (40 GWd/t), UO{sub 2} is separately collected for {approx}60 wt% of the spent fuel in advance of the electrochemical reduction step, and the product recovered through the rare earth (RE) removal step, which hasmore » the composition uranium:plutonium:minor actinides:fission products (FPs) = 76.4:18.4:1.7:3.5, can be applied as an ingredient of FBR metal fuel without a further decontamination process. On the other hand, the electroreduced alloy of high-burnup UO{sub 2} spent fuel (48 GWd/t) requires further decontamination of residual FPs by an additional process such as electrorefining even if RE FPs are removed from the alloy because the recovered plutonium (Pu) is accompanied by almost the same amount of FPs in addition to RE. However, the amount of treated materials in the electrorefining step is reduced to {approx}10 wt% of the total spent fuel owing to the prior UO{sub 2} recovery step. These results reveal that the application of electrochemical reduction technology to LWR spent oxide fuel is a promising concept for providing FBR metal fuel by a rationalized process.« less

Effect of reactor coolant radioactivity upon configuration feasibility for a nuclear electric propulsion vehicle

NASA Technical Reports Server (NTRS)

Soffer, L.; Wright, G. N.

1973-01-01

A preliminary shielding analysis was carried out for a conceptual nuclear electric propulsion vehicle designed to transport payloads from low earth orbit to synchronous orbit. The vehicle employed a thermionic nuclear reactor operating at 1575 kilowatts and generated 120 kilowatts of electricity for a round-trip mission time of 2000 hours. Propulsion was via axially directed ion engines employing 3300 pounds of mercury as a propellant. The vehicle configuration permitted a reactor shadow shield geometry using LiH and the mercury propellant for shielding. However, much of the radioactive NaK reactor coolant was unshielded and in close proximity to the power conditioning electronics. An estimate of the radioactivity of the NaK coolant was made and its unshielded dose rate to the power conditioning equipment calculated. It was found that the activated NaK contributed about three-fourths of the gamma dose constraint. The NaK dose was considered a sufficiently high fraction of the allowable gamma dose to necessitate modifications in configuration.

Development of reactor configurations for an electrofuels platform utilizing genetically modified iron oxidizing bacteria for the reduction of CO2 to biochemicals.

PubMed

Guan, Jingyang; Berlinger, Sarah A; Li, Xiaozheng; Chao, Zhongmou; Sousa E Silva, Victor; Banta, Scott; West, Alan C

2017-03-10

Electrofuels processes are potentially promising platforms for biochemical production from CO 2 using renewable energy. When coupled to solar panels, this approach could avoid the inefficiencies of photosynthesis and there is no competition with food agriculture. In addition, these systems could potentially be used to store intermittent or stranded electricity generated from other renewable sources. Here we develop reactor configurations for continuous electrofuels processes to convert electricity and CO 2 to isobutyric acid (IBA) using genetically modified (GM) chemolithoautotrophic Acidithiobacillus ferrooxidans. These cells oxidize ferrous iron which can be electrochemically reduced. During two weeks of cultivation on ferrous iron, stable cell growth and continuous IBA production from CO 2 were achieved in a process where media was circulated between electrochemical and biochemical rectors. An alternative process with an additional electrochemical cell for accelerated ferrous production was developed, and this system achieved an almost three-fold increase in steady state cell densities, and an almost 4-fold increase in the ferrous iron oxidation rate. Combined, this led to an almost 8-fold increase in the steady state volumetric productivity of IBA up to 0.063±0.012mg/L/h, without a decline in energy efficiency from previous work. Continued development of reactor configurations which can increase the delivery of energy to the genetically modified cells will be required to increase product titers and volumetric productivities. Copyright © 2017 Elsevier B.V. All rights reserved.

Status of French reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ballagny, A.

1997-08-01

The status of French reactors is reviewed. The ORPHEE and RHF reactors can not be operated with a LEU fuel which would be limited to 4.8 g U/cm{sup 3}. The OSIRIS reactor has already been converted to LEU. It will use U{sub 3}Si{sub 2} as soon as its present stock of UO{sub 2} fuel is used up, at the end of 1994. The decision to close down the SILOE reactor in the near future is not propitious for the start of a conversion process. The REX 2000 reactor, which is expected to be commissioned in 2005, will use LEU (exceptmore » if the fast neutrons core option is selected). Concerning the end of the HEU fuel cycle, the best option is reprocessing followed by conversion of the reprocessed uranium to LEU.« less

Integral Inherently Safe Light Water Reactor (I 2S-LWR)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrovic, Bojan; Memmott, Matthew; Boy, Guy

This final report summarizes results of the multi-year effort performed during the period 2/2013- 12/2016 under the DOE NEUP IRP Project “Integral Inherently Safe Light Water Reactors (I 2S-LWR)”. The goal of the project was to develop a concept of a 1 GWe PWR with integral configuration and inherent safety features, at the same time accounting for lessons learned from the Fukushima accident, and keeping in mind the economic viability of the new concept. Essentially (see Figure 1-1) the project aimed to implement attractive safety features, typically found only in SMRs, to a larger power (1 GWe) reactor, to addressmore » the preference of some utilities in the US power market for unit power level on the order of 1 GWe.« less

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs

NASA Astrophysics Data System (ADS)

Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe; Liu, Chiyang; Weng, Ng Seik

2016-11-01

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) under hydrothermal condition. The combination of H3tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO2)2(H2O)4]0.5(tci)2(UO2)4(OH)4·18H2O (1), which contains two distinct UO22+ coordination environments. Four uranyl cations, linked through μ3-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (34.26.3)2(34.46.56.68.73.8). Th3(tci)2O2(OH)2(H2O)3·12H2O (2) generated by the reaction of H3tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers "Th6O4(OH)4" motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (424.64).

Inverse problem of central configurations in the collinear 5-body problem

NASA Astrophysics Data System (ADS)

Davis, Candice; Geyer, Scott; Johnson, William; Xie, Zhifu

2018-05-01

In this paper, we study the inverse problem of collinear central configurations of a 5-body problem: given a collinear configuration q = (-s - 1, -1, r, 1, t + 1) of 5 bodies, does there exist positive masses to make the configuration central? Here we proved the following results: If r = 0 and s = t > 0, there always exist positive masses to make the configuration central and the masses are symmetrical such that m1 = m5, m2 = m4, and m3 is an arbitrary parameter. Specially if r = 0 and s =t =s ¯ , the configuration q =(-s ¯ -1 ,-1,0,1 ,s ¯ +1 ) is always a central configuration for any positive masses 0 < m2 = m4 < ∞ when m1 = m5 are fixed at particular values, which only depend on s ¯ and m3. s ¯ is the unique real root of a fifth order polynomial and numerically s ¯ ≈1.396 812 289 . If r = 0 and s ≠ t > 0, there also always exist positive masses to make the configuration central. For any r ∈ (0, 1) [or r ∈ (-1, 0)], there exist a set E14 (or E25) in the first quadrant of st-plane where every configuration is a central configuration for some positive masses. However, no configuration in the complement of E14 (or E25) is a central configuration for any positive masses.

Gas emission from the UO2 samples, containing fission products and burnable absorber

NASA Astrophysics Data System (ADS)

Kopytin, V. P.; Baranov, V. G.; Burlakova, M. A.; Tenishev, A. V.; Kuzmin, R. S.; Pokrovskiy, S. A.; Mikhalchik, V. V.

2016-04-01

The process gas released from the fuel pellets of uranium fuel during fuel burn-up reduces the thermal conductivity of the rod-shell gap, enhances hydrogen embrittlement of the cladding material, causes it's carbonization, as well as transport processes in the fuel. In this study a technique of investigating the thermal desorption of gases from the UO2 fuel material were perfected in the temperature range 300-2000 K for uniform sample heating rate of 15 K/min in vacuum. The characteristic kinetic dependences are acquired for the gas emission from UO2 samples, containing simulators of fission products (SFP) and the burnable neutron absorber (BNA). Depending on the amount of SFP and BNA contained in the sample thermal desorption gas spectra (TDGS) vary. The composition of emitted gas varies, as well as the number of peaks in the TDGS and the peaks shift to higher temperatures. This indicates that introduction of SFPs and BNA alters the sample material structure and cause the creation of so- called traps which have different bonding energies to the gases. The traps can be a grid of dislocations, voids, and contained in the UO2 matrix SFP and BNA. Similar processes will occur in the fuel pellets in the real conditions of the Nuclear Power Plant as well.

New insight into UO 2F 2 particulate structure by micro-Raman spectroscopy

DOE PAGES

Stefaniak, Elzbieta A.; Darchuk, Larysa; Sapundjiev, Danislav; ...

2013-02-19

Uranyl fluoride particles produced via hydrolysis of uranium hexafluoride have been deposited on different substrates: polished graphite disks, silver foil, stainless steel and gold-coated silicon wafer, and measured with micro-Raman spectroscopy (MRS). All three metallic substrates enhanced the Raman signal delivered by UO 2F 2 in comparison to graphite. The fundamental stretching of the U–O band appeared at 867 cm –1 in case of the graphite substrate, while in case of the others it was shifted to lower frequencies (down to 839 cm –1). All applied metallic substrates showed the expected effect of Raman signal enhancement; however the gold layermore » appeared to be most effective. Lastly, application of new substrates provides more information on the molecular structure of uranyl fluoride precipitation, which is interesting for nuclear safeguards and nuclear environmental analysis.« less

Characterization of cartridge filters from the IEA-R1 Nuclear Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The management of radioactive waste ensures safety to human health and the environment nowadays and for the future, without overwhelming the upcoming generations. The primary characterization of radioactive waste is one of the main steps in the management of radioactive waste. This step permits to choose the best treatment for the radioactive waste before forwarding it to its final disposal. The aim of the present work is the primary characterization of cartridge filters from the IEA-R1 nuclear reactor utilizing gamma-ray spectrometry, and the method of Monte Carlo for calibration. The IEA-R1 is located in the Nuclear and Energy Research Institutemore » (IPEN - CNEN) in the city of Sao Paulo, Brazil. Cartridge filters are used for purification of the cooling water that is pumped through the core of the pool type nuclear research reactors. Once worn out, these filters are replaced and then become radioactive waste. Determination of the radioactive inventory is of paramount importance in the management of such radioactive waste, and one of the main methods for doing so is the gamma-ray spectrometry, which can identify and quantify high energy photon emitters. The technique chosen for the characterization of radioactive waste in the present work is the gamma-ray spectrometry with High purity Germanium (HPGe) detectors. From the energy identified in the experimental spectrum, three radioisotopes were identified in the cartridge filter: {sup 108m}Ag, {sup 110m}Ag, {sup 60}Co. For the estimated activity of the filter, the calibration in efficiency was made utilizing the MCNP4C code of the Monte Carlo method. Such method was chosen because there is no standard source available in the same geometry of the cartridge filter, therefore a simulation had to be developed in order to reach a calibration equation, necessary to estimate the activity of the radioactive waste. The results presented an activity value in the order of MBq for all radioisotopes. (authors)« less

A shadowgraph study of the National Launch System's 1 1/2 stage vehicle configuration and Heavy Lift Launch Vehicle configuration. [Using the Marshall Space Flight Center's 14-Inch Trisonic Wind Tunnel

NASA Technical Reports Server (NTRS)

Pokora, Darlene C.; Springer, Anthony M.

1994-01-01

A shadowgraph study of the National Launch System's (NLS's) 1 1/2 stage and heavy lift launch vehicle (HLLV) configurations is presented. Shadowgraphs are shown for the range of Mach numbers from Mach 0.6 to 5.0 at various angles-of-attack and roll angles. Since the 1 1/2 stage configuration is generally symmetric, no shadowgraphs of any roll angle are shown for this configuration. The major flow field phenomena over the NLS 1 1/2 stage and HLLV configurations are shown in the shadowgraphs. These shadowgraphs are used in the aerothermodynamic analysis of the external flow conditions the launch vehicle would encounter during the ascent stage of flight. The shadowgraphs presented in this study were obtained from configurations tested in the Marshall Space Flight Center's 14-Inch Trisonic Wind Tunnel during 1992.

Thermal property change of MOX and UO2 irradiated up to high burnup of 74 GWd/t

NASA Astrophysics Data System (ADS)

Nakae, Nobuo; Akiyama, Hidetoshi; Miura, Hiromichi; Baba, Toshikazu; Kamimura, Katsuichiro; Kurematsu, Shigeru; Kosaka, Yuji; Yoshino, Aya; Kitagawa, Takaaki

2013-09-01

Thermal property is important because it controls fuel behavior under irradiation. The thermal property change at high burnup of more than 70 GWd/t is examined. Two kinds of MOX fuel rods, which were fabricated by MIMAS and SBR methods, and one referenced UO2 fuel rod were used in the experiment. These rods were taken from the pre-irradiated rods (IFA 609/626, of which irradiation test were carried out by Japanese PWR group) and re-fabricated and re-irradiated in HBWR as IFA 702 by JNES. The specification of fuel corresponds to that of 17 × 17 PWR type fuel and the axially averaged linear heat rates (LHR) of MOX rods are 25 kW/m (BOL of IFA 702) and 20 kW/m (EOL of IFA 702). The axial peak burnups achieved are about 74 GWd/t for both of MOX and UO2. Centerline temperature and plenum gas pressure were measured in situ during irradiation. The measured centerline temperature is plotted against LHR at the position where thermocouples are fixed. The slopes of MOX are corresponded to each other, but that of UO2 is higher than those of MOX. This implies that the thermal conductivity of MOX is higher than that of UO2 at high burnup under the condition that the pellet-cladding gap is closed during irradiation. Gap closure is confirmed by the metallography of the postirradiation examinations. It is understood that thermal conductivity of MOX is lower than that of UO2 before irradiation since phonon scattering with plutonium in MOX becomes remarkable. A phonon scattering with plutonium decreases in MOX when burnup proceeds. Thus, thermal conductivity of MOX becomes close to that of UO2. A reverse phenomenon is observed at high burnup region. The phonon scattering with fission products such as Nd and Zr causes a degradation of thermal conductivity of burnt fuel. It might be speculated that this scattering effect causes the phenomenon and the mechanism is discussed here.

Evaluation of R1-6 gateway treatment alternatives for pedestrian crossings.

DOT National Transportation Integrated Search

2016-02-01

A series of studies evaluated the Gateway configuration of R1-6 in-street signs. A : Gateway configuration consists of an R1-6 sign on the centerline, an R1-6 signs on both edges of : the roadway, and R1-6 signs on the lane lines if it is a multilane...

The defect chemistry of UO2 ± x from atomistic simulations

NASA Astrophysics Data System (ADS)

Cooper, M. W. D.; Murphy, S. T.; Andersson, D. A.

2018-06-01

Control of the defect chemistry in UO2 ± x is important for manipulating nuclear fuel properties and fuel performance. For example, the uranium vacancy concentration is critical for fission gas release and sintering, while all oxygen and uranium defects are known to strongly influence thermal conductivity. Here the point defect concentrations in thermal equilibrium are predicted using defect energies from density functional theory (DFT) and vibrational entropies calculated using empirical potentials. Electrons and holes have been treated in a similar fashion to other charged defects allowing for structural relaxation around the localized electronic defects. Predictions are made for the defect concentrations and non-stoichiometry of UO2 ± x as a function of oxygen partial pressure and temperature. If vibrational entropy is omitted, oxygen interstitials are predicted to be the dominant mechanism of excess oxygen accommodation over only a small temperature range (1265 K-1350 K), in contrast to experimental observation. Conversely, if vibrational entropy is included oxygen interstitials dominate from 1165 K to 1680 K (Busker potential) or from 1275 K to 1630 K (CRG potential). Below these temperature ranges, excess oxygen is predicted to be accommodated by uranium vacancies, while above them the system is hypo-stoichiometric with oxygen deficiency accommodated by oxygen vacancies. Our results are discussed in the context of oxygen clustering, formation of U4O9, and issues for fuel behavior. In particular, the variation of the uranium vacancy concentrations as a function of temperature and oxygen partial pressure will underpin future studies into fission gas diffusivity and broaden the understanding of UO2 ± x sintering.

Fission products and nuclear fuel behaviour under severe accident conditions part 2: Fuel behaviour in the VERDON-1 sample

NASA Astrophysics Data System (ADS)

Geiger, E.; Le Gall, C.; Gallais-During, A.; Pontillon, Y.; Lamontagne, J.; Hanus, E.; Ducros, G.

2017-11-01

Within the framework of the International Source Term Programme (ISTP), the VERDON programme aims at quantifying the source term of radioactive materials in case of a hypothetical severe accident in a light water reactor (LWR). Tests were performed in a new experimental laboratory (VERDON) built in the LECA-STAR facility (CEA Cadarache). The VERDON-1 test was devoted to the study of a high burn-up UO2 fuel and FP releases at very high temperature (≈2873 K) in a reducing atmosphere. Post-test qualitative and quantitative characterisations of the VERDON-1 sample led to the proposal of a scenario explaining the phenomena occurring during the experimental sequence. Hence, the fuel and the cladding may have interacted which led to the melting of UO2-ZrO2 alloy. Although no relocation was observed during the test, it may have been imminent.

A fission-fusion hybrid reactor in steady-state L-mode tokamak configuration with natural uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, Mark; Parker, Ronald R.; Forget, Benoit

2012-06-19

This work develops a conceptual design for a fusion-fission hybrid reactor operating in steady-state L-mode tokamak configuration with a subcritical natural or depleted uranium pebble bed blanket. A liquid lithium-lead alloy breeds enough tritium to replenish that consumed by the D-T fusion reaction. The fission blanket augments the fusion power such that the fusion core itself need not have a high power gain, thus allowing for fully non-inductive (steady-state) low confinement mode (L-mode) operation at relatively small physical dimensions. A neutron transport Monte Carlo code models the natural uranium fission blanket. Maximizing the fission power gain while breeding sufficient tritiummore » allows for the selection of an optimal set of blanket parameters, which yields a maximum prudent fission power gain of approximately 7. A 0-D tokamak model suffices to analyze approximate tokamak operating conditions. This fission blanket would allow the fusion component of a hybrid reactor with the same dimensions as ITER to operate in steady-state L-mode very comfortably with a fusion power gain of 6.7 and a thermal fusion power of 2.1 GW. Taking this further can determine the approximate minimum scale for a steady-state L-mode tokamak hybrid reactor, which is a major radius of 5.2 m and an aspect ratio of 2.8. This minimum scale device operates barely within the steady-state L-mode realm with a thermal fusion power of 1.7 GW. Basic thermal hydraulic analysis demonstrates that pressurized helium could cool the pebble bed fission blanket with a flow rate below 10 m/s. The Brayton cycle thermal efficiency is 41%. This reactor, dubbed the Steady-state L-mode non-Enriched Uranium Tokamak Hybrid (SLEUTH), with its very fast neutron spectrum, could be superior to pure fission reactors in terms of breeding fissile fuel and transmuting deleterious fission products. It would likely function best as a prolific plutonium breeder, and the plutonium it produces could actually be more

A fission-fusion hybrid reactor in steady-state L-mode tokamak configuration with natural uranium

NASA Astrophysics Data System (ADS)

Reed, Mark; Parker, Ronald R.; Forget, Benoit

2012-06-01

This work develops a conceptual design for a fusion-fission hybrid reactor operating in steady-state L-mode tokamak configuration with a subcritical natural or depleted uranium pebble bed blanket. A liquid lithium-lead alloy breeds enough tritium to replenish that consumed by the D-T fusion reaction. The fission blanket augments the fusion power such that the fusion core itself need not have a high power gain, thus allowing for fully non-inductive (steady-state) low confinement mode (L-mode) operation at relatively small physical dimensions. A neutron transport Monte Carlo code models the natural uranium fission blanket. Maximizing the fission power gain while breeding sufficient tritium allows for the selection of an optimal set of blanket parameters, which yields a maximum prudent fission power gain of approximately 7. A 0-D tokamak model suffices to analyze approximate tokamak operating conditions. This fission blanket would allow the fusion component of a hybrid reactor with the same dimensions as ITER to operate in steady-state L-mode very comfortably with a fusion power gain of 6.7 and a thermal fusion power of 2.1 GW. Taking this further can determine the approximate minimum scale for a steady-state L-mode tokamak hybrid reactor, which is a major radius of 5.2 m and an aspect ratio of 2.8. This minimum scale device operates barely within the steady-state L-mode realm with a thermal fusion power of 1.7 GW. Basic thermal hydraulic analysis demonstrates that pressurized helium could cool the pebble bed fission blanket with a flow rate below 10 m/s. The Brayton cycle thermal efficiency is 41%. This reactor, dubbed the Steady-state L-mode non-Enriched Uranium Tokamak Hybrid (SLEUTH), with its very fast neutron spectrum, could be superior to pure fission reactors in terms of breeding fissile fuel and transmuting deleterious fission products. It would likely function best as a prolific plutonium breeder, and the plutonium it produces could actually be more

Plasma induced grafting carboxymethyl cellulose on multiwalled carbon nanotubes for the removal of UO(2)(2+) from aqueous solution.

PubMed

Shao, Dadong; Jiang, Zhongqing; Wang, Xiangke; Li, Jiaxing; Meng, Yuedong

2009-01-29

Carboxymethyl cellulose (CMC) is grafted on multiwalled carbon nanotubes (MWCNT) by using plasma techniques. The CMC grafted MWCNT (MWCNT-g-CMC) is characterized by using Fourier transform infrared spectra (FT-IR), Raman spectra, powder X-ray diffraction (XRD), thermogravimetric analysis (TGA)-differential thermal analysis (DTA), scanning electron microscopy (SEM), and N(2)-BET methods in detail. The application of MWCNT-g-CMC in the removal of UO(2)(2+) from aqueous solution is investigated. MWCNT-g-CMC has much higher sorption ability in the removal of UO(2)(2+) than raw MWCNT. The MWCNT-g-CMC is a suitable material in the preconcentration and solidification of heavy metal ions from large volume of aqueous solutions.

Structural studies of the rhombohedral and orthorhombic monouranates: CaUO{sub 4}, α-SrUO{sub 4}, β-SrUO{sub 4} and BaUO{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murphy, Gabriel; Kennedy, Brendan J., E-mail: kennedyb@chem.usyd.edu.au; Johannessen, Bernt

The structures of some AUO{sub 4} (A=Ca, Sr, or Ba) oxides have been determined using a combination of neutron and synchrotron X-ray diffraction, supported by X-ray absorption spectroscopic measurements at the U L{sub 3}-edge. The smaller Ca cation favours a rhombohedral AUO{sub 4} structure with 8-coordinate UO{sub 8} moieties whilst an orthorhombic structure based on UO{sub 6} groups is found for BaUO{sub 4}. Both the rhombohedral and orthorhombic structures can be stabilised for SrUO{sub 4}. The structural studies suggest that the bonding requirements of the A site cation play a significant role in determining which structure is favoured. In themore » rhombohedral structure, Bond Valence Sums demonstrate the A site is invariably overbonded, which, in the case of rhombohedral α-SrUO{sub 4}, is compensated for by the formation of vacancies in the oxygen sub-lattice. The uranium cation, with its flexible oxidation state, is able to accommodate this by inducing vacancies along its equatorial coordination site as demonstrated by neutron powder diffraction. - Graphical abstract: Diffraction studies of AUO{sub 4} (A = Ca, Sr, or Ba) oxides reveal the importance of the bonding requirements of the A site cation in determining whether the structure is rhombohedral or orthorhombic. - Highlights: • Structures of AUO{sub 4} ( A = Ca Sr, Ba) refined against X-ray and Neutron diffraction. • The alkali cations size has a dramatic effect on the crystal structure. • Smaller cations favouring a rhombohedral structure. • Oxygen vacancies to stabilise the rhombohedral structure in SrUO{sub 4}.« less

The Henry reaction of (1R)-(1,4:3,6-dianhydro-D-mannitol-2-yl)-1,4:3,6-dianhydro-D-fructose 5,5'-dinitrate. Different reactive features of nitromethane to nitroethane.

PubMed

Liu, Feng-Wu; Wang, Zhen-Ji; Song, Xiao-Ping; Zhang, Sai-Yang; Liu, Hong-Min

2009-12-14

Henry reactions of a novel higher sugar derivative, (1R)-(1,4:3,6-dianhydro-D-mannitol-2-yl)-1,4:3,6-dianhydro-D-fructose 5,5'-dinitrate (Alternate nomenclature: (1R)-(isomannid-2-yl)-1,4:3,6-dianhydro-D-fructose 5,5'-dinitrate), with nitromethane and nitroethane were studied. The kinetic and thermodynamic reactions with nitromethane under different conditions were carried out to afford (2S)- and (2R)-beta-nitroalcohols, respectively. But when using nitroethane the reaction gave a (2S)-beta-nitroalcohol with an inverted configuration at vicinal carbon C-1. Two stereogenic centers were generated, and one was altered in the reaction.

Optically active antifungal azoles. XII. Synthesis and antifungal activity of the water-soluble prodrugs of 1-[(1R,2R)-2-(2,4-difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-1-tetrazolyl)phenyl]-2-imidazolidinone.

PubMed

Ichikawa, T; Kitazaki, T; Matsushita, Y; Yamada, M; Hayashi, R; Yamaguchi, M; Kiyota, Y; Okonogi, K; Itoh, K

2001-09-01

1-[(1R,2R)-2-(2,4-Difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-1-tetrazolyl)phenyl]-2-imidazolidinone (1: TAK-456) was selected as a candidate for clinical trials, but since its water-solubility was insufficient for an injectable formulation, the quaternary triazolium salts 2 were designed as water-soluble prodrugs. Among the prodrugs prepared, 4-acetoxymethyl-1-[(2R,3R)-2-(2,4-difluorophenyl)-2-hydroxy-3-[2-oxo-3-[4-(1H-1-terazolyl)phenyl]-1-imidazolidinyl]butyl]-1H-1,2,4-triazolium chloride (2a: TAK-457) was selected as an injectable candidate for clinical trials based on the results of evaluations on solubility, stability, hemolytic effect and in vivo antifungal activities.

Utilizing a one-dimensional multispecies model to simulate the nutrient reduction and biomass structure in two types of H2-based membrane-aeration biofilm reactors (H2-MBfR): model development and parametric analysis.

PubMed

Wang, Zuowei; Xia, Siqing; Xu, Xiaoyin; Wang, Chenhui

2016-02-01

In this study, a one-dimensional multispecies model (ODMSM) was utilized to simulate NO3(-)-N and ClO4(-) reduction performances in two kinds of H2-based membrane-aeration biofilm reactors (H2-MBfR) within different operating conditions (e.g., NO3(-)-N/ClO4(-) loading rates, H2 partial pressure, etc.). Before the simulation process, we conducted the sensitivity analysis of some key parameters which would fluctuate in different environmental conditions, then we used the experimental data to calibrate the more sensitive parameters μ1 and μ2 (maximum specific growth rates of denitrification bacteria and perchlorate reduction bacteria) in two H2-MBfRs, and the diversity of the two key parameters' values in two types of reactors may be resulted from the different carbon source fed in the reactors. From the simulation results of six different operating conditions (four in H2-MBfR 1 and two in H2-MBfR 2), the applicability of the model was approved, and the variation of the removal tendency in different operating conditions could be well simulated. Besides, the rationality of operating parameters (H2 partial pressure, etc.) could be judged especially in condition of high nutrients' loading rates. To a certain degree, the model could provide theoretical guidance to determine the operating parameters on some specific conditions in practical application.

Synthesis, magnetic, spectral, and antimicrobial studies of Cu(II), Ni(II) Co(II), Fe(III), and UO 2(II) complexes of a new Schiff base hydrazone derived from 7-chloro-4-hydrazinoquinoline

NASA Astrophysics Data System (ADS)

El-Behery, Mostafa; El-Twigry, Haifaa

2007-01-01

A new hydrazone ligand, HL, was prepared by the reaction of 7-chloro-4-hydrazinoquinoline with o-hydroxybenzaldehyde. The ligand behaves as monoprotic bidentate. This was accounted for as the ligand contains a phenolic group and its hydrogen atom is reluctant to be replaced by a metal ion. The ligand reacted with Cu(II), Ni(II), Co(II), Fe(III), and UO 2(II) ions to yield mononuclear complexes. In the case of Fe(III) ion two complexes, mono- and binuclear complexes, were obtained in the absence and presence of LiOH, respectively. Also, mixed ligand complexes were obtained from the reaction of the metal cations Cu(II), Ni(II) and Fe(III) with the ligand (HL) and 8-hydroxyquinoline (8-OHqu) in the presence of LiOH, in the molar ratio 1:1:1:1. It is clear that 8-OHqu behaves as monoprotic bidentate ligand in such mixed ligand complexes. The ligand, HL, and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass, and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square-planar geometry, while Ni(II) mixed complex has also formed a tetrahedral configuration and UO 2(II) complex which formed a favorable pentagonal biprymidial geometry. Magnetic moment of the binuclear Fe(III) complex is quite low compared to calculated value for two iron ions complex and thus shows antiferromagnetic interactions between the two adjacent ferric ions. The HL and metal complexes were tested against one stain Gram positive bacteria ( Staphylococcus aureus), Gram negative bacteria ( Escherichia coli), and fungi ( Candida albicans). The tested compounds exhibited higher antibacterial acivities.

Proliferation resistance of small modular reactors fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polidoro, F.; Parozzi, F.; Fassnacht, F.

2013-07-01

In this paper the proliferation resistance of different types of Small Modular Reactors (SMRs) has been examined and classified with criteria available in the literature. In the first part of the study, the level of proliferation attractiveness of traditional low-enriched UO{sub 2} and MOX fuels to be used in SMRs based on pressurized water technology has been analyzed. On the basis of numerical simulations both cores show significant proliferation risks. Although the MOX core is less proliferation prone in comparison to the UO{sub 2} core, it still can be highly attractive for diversion or undeclared production of nuclear material. Inmore » the second part of the paper, calculations to assess the proliferation attractiveness of fuel in typical small sodium cooled fast reactor show that proliferation risks from spent fuel cannot be neglected. The core contains a highly attractive plutonium composition during the whole life cycle. Despite some aspects of the design like the sealed core that enables easy detection of unauthorized withdrawal of fissile material and enhances proliferation resistance, in case of open Non-Proliferation Treaty break-out, weapon-grade plutonium in sufficient quantities could be extracted from the reactor core.« less

Benchmark Evaluation of Fuel Effect and Material Worth Measurements for a Beryllium-Reflected Space Reactor Mockup

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Margaret A.; Bess, John D.

2015-02-01

The critical configuration of the small, compact critical assembly (SCCA) experiments performed at the Oak Ridge Critical Experiments Facility (ORCEF) in 1962-1965 have been evaluated as acceptable benchmark experiments for inclusion in the International Handbook of Evaluated Criticality Safety Benchmark Experiments. The initial intent of these experiments was to support the design of the Medium Power Reactor Experiment (MPRE) program, whose purpose was to study “power plants for the production of electrical power in space vehicles.” The third configuration in this series of experiments was a beryllium-reflected assembly of stainless-steel-clad, highly enriched uranium (HEU)-O 2 fuel mockup of a potassium-cooledmore » space power reactor. Reactivity measurements cadmium ratio spectral measurements and fission rate measurements were measured through the core and top reflector. Fuel effect worth measurements and neutron moderating and absorbing material worths were also measured in the assembly fuel region. The cadmium ratios, fission rate, and worth measurements were evaluated for inclusion in the International Handbook of Evaluated Criticality Safety Benchmark Experiments. The fuel tube effect and neutron moderating and absorbing material worth measurements are the focus of this paper. Additionally, a measurement of the worth of potassium filling the core region was performed but has not yet been evaluated Pellets of 93.15 wt.% enriched uranium dioxide (UO 2) were stacked in 30.48 cm tall stainless steel fuel tubes (0.3 cm tall end caps). Each fuel tube had 26 pellets with a total mass of 295.8 g UO 2 per tube. 253 tubes were arranged in 1.506-cm triangular lattice. An additional 7-tube cluster critical configuration was also measured but not used for any physics measurements. The core was surrounded on all side by a beryllium reflector. The fuel effect worths were measured by removing fuel tubes at various radius. An accident scenario was also simulated by

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

Health Physics State of the RA-1 Reactor, Period Between 1-1-62 and 10-8- 62. Report No. 87; ESTADO RADIOSANIT ARIO DEL REACTOR R.A. 1, PERIODO COMPRENDIDO ENTRE EL 1-1-62 Y EL 10-8-62. Informe No. 87

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaspar, R.; Moll, O.; Hermelo, C.

1963-01-01

The methods used to measure the irradiation levels and the radiation exposure of personnel of the RA-1 reactor are described. The criteria used to evaluate the risks from this exposure are reported. Typical graphs are shown of the radiation levels measured in the control room. (J.S.R.)

Preliminary study on new configuration with LEU fuel assemblies for the Dalat nuclear research reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Lam Pham; Vinh Vinh Le; Ton Nghiem Huynh

2008-07-15

The fuel conversion of the Dalat Nuclear Research Reactor (DNRR) is being realized. The DNRR is a pool type research reactor which was reconstructed from the 250 kW TRIGA- MARK II reactor. The reconstructed reactor attained its nominal power of 500 kW in February 1984. According to the results of design and safety analyses performed by the joint study between RERTR Program at Argonne National Laboratory (ANL) and Vietnam Atomic Energy Commission (VAEC) the mixed core of irradiated HEU and new LEU WWR-M2 fuel assemblies will be created soon. This paper presents the results of preliminary study on new configurationmore » with only LEU fuel assemblies for the DNRR. The codes MCNP, REBUS and VARI3D are used to calculate neutron flux performance in irradiation positions and kinetics parameters. The idea of change of Beryllium rod reloading enables to get working configuration assured shutdown margin, thermal-hydraulic safety and increase in thermal neutron flux in neutron trap at the center of DNRR active core. (author)« less

Experimental Criticality Benchmarks for SNAP 10A/2 Reactor Cores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krass, A.W.

2005-12-19

This report describes computational benchmark models for nuclear criticality derived from descriptions of the Systems for Nuclear Auxiliary Power (SNAP) Critical Assembly (SCA)-4B experimental criticality program conducted by Atomics International during the early 1960's. The selected experimental configurations consist of fueled SNAP 10A/2-type reactor cores subject to varied conditions of water immersion and reflection under experimental control to measure neutron multiplication. SNAP 10A/2-type reactor cores are compact volumes fueled and moderated with the hydride of highly enriched uranium-zirconium alloy. Specifications for the materials and geometry needed to describe a given experimental configuration for a model using MCNP5 are provided. Themore » material and geometry specifications are adequate to permit user development of input for alternative nuclear safety codes, such as KENO. A total of 73 distinct experimental configurations are described.« less

Space shuttle: Aerodynamic characteristics of various MDAC space shuttle ascent configurations with parallel burn pressure-fed and SRM boosters. Volume 1: Tanks T1 and T2 ascent configurations

NASA Technical Reports Server (NTRS)

Jarrett, T. W.

1972-01-01

Various space shuttle ascent configurations were tested in a trisonic wind tunnel to determine the aerodynamic characteristics. The ascent configuration consisted of a NASA/MSC 040 orbiter in combination with various HO centerline tank and booster geometries. The aerodynamic interference between components of the space shuttle and the effect on the orbiter aerodynamics was determined. The various aerodynamic configurations tested were: (1) centerline HO tanks T1 and T2, (2) centerline HO tank T3, and (3) centerline HO tank H4.

Thermophysical properties of liquid UO2, ZrO2 and corium by molecular dynamics and predictive models

NASA Astrophysics Data System (ADS)

Kim, Woong Kee; Shim, Ji Hoon; Kaviany, Massoud

2017-08-01

Predicting the fate of accident-melted nuclear fuel-cladding requires the understanding of the thermophysical properties which are lacking or have large scatter due to high-temperature experimental challenges. Using equilibrium classical molecular dynamics (MD), we predict the properties of melted UO2 and ZrO2 and compare them with the available experimental data and the predictive models. The existing interatomic potential models have been developed mainly for the polymorphic solid phases of these oxides, so they cannot be used to predict all the properties accurately. We compare and decipher the distinctions of those MD predictions using the specific property-related autocorrelation decays. The predicted properties are density, specific heat, heat of fusion, compressibility, viscosity, surface tension, and the molecular and electronic thermal conductivities. After the comparisons, we provide readily usable temperature-dependent correlations (including UO2-ZrO2 compounds, i.e. corium melt).

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

Loss-of-Flow and Loss-of-Pressure Simulations of the BR2 Research Reactor with HEU and LEU Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Licht, J.; Bergeron, A.; Dionne, B.

2016-01-01

Belgian Reactor 2 (BR2) is a research and test reactor located in Mol, Belgium and is primarily used for radioisotope production and materials testing. The Materials Management and Minimization (M3) Reactor Conversion Program of the National Nuclear Security Administration (NNSA) is supporting the conversion of the BR2 reactor from Highly Enriched Uranium (HEU) fuel to Low Enriched Uranium (LEU) fuel. The reactor core of BR2 is located inside a pressure vessel that contains 79 channels in a hyperboloid configuration. The core configuration is highly variable as each channel can contain a fuel assembly, a control or regulating rod, an experimentalmore » device, or a beryllium or aluminum plug. Because of this variability, a representative core configuration, based on current reactor use, has been defined for the fuel conversion analyses. The code RELAP5/Mod 3.3 was used to perform the transient thermal-hydraulic safety analyses of the BR2 reactor to support reactor conversion. The input model has been modernized relative to that historically used at BR2 taking into account the best modeling practices developed by Argonne National Laboratory (ANL) and BR2 engineers.« less

Electrochemical characterisation of CaCl2 deficient LiCl-KCl-CaCl2 eutectic melt and electro-deoxidation of solid UO2

NASA Astrophysics Data System (ADS)