Thermal conductivity of heterogeneous LWR MOX fuels

NASA Astrophysics Data System (ADS)

Staicu, D.; Barker, M.

2013-11-01

It is generally observed that the thermal conductivity of LWR MOX fuel is lower than that of pure UO2. For MOX, the degradation is usually only interpreted as an effect of the substitution of U atoms by Pu. This hypothesis is however in contradiction with the observations of Duriez and Philiponneau showing that the thermal conductivity of MOX is independent of the Pu content in the ranges 3-15 and 15-30 wt.% PuO2 respectively. Attributing this degradation to Pu only implies that stoichiometric heterogeneous MOX can be obtained, while we show that any heterogeneity in the plutonium distribution in the sample introduces a variation in the local stoichiometry which in turn has a strong impact on the thermal conductivity. A model quantifying this effect is obtained and a new set of experimental results for homogeneous and heterogeneous MOX fuels is presented and used to validate the proposed model. In irradiated fuels, this effect is predicted to disappear early during irradiation. The 3, 6 and 10 wt.% Pu samples have a similar thermal conductivity. Comparison of the results for this homogeneous microstructure with MIMAS (heterogeneous) fuel of the same composition showed no difference for the Pu contents of 3, 5.9, 6, 7.87 and 10 wt.%. A small increase of the thermal conductivity was obtained for 15 wt.% Pu. This increase is of about 6% when compared to the average of the values obtained for 3, 6 and 10 wt.% Pu. For comparison purposes, Duriez also measured the thermal conductivity of FBR MOX with 21.4 wt.% Pu with O/M = 1.982 and a density close to 95% TD and found a value in good agreement with the estimation obtained using the formula of Philipponneau [8] for FBR MOX, and significantly lower than his results corresponding to the range 3-15 wt.% Pu. This difference in thermal conductivity is of about 20%, i.e. higher than the measurement uncertainties.Thus, a significant difference was observed between FBR and PWR MOX fuels, but was not explained. This difference was observed for hypostoichiometric fuels, that correspond to the condition used for irradiation. However, if these two formulas are evaluated for O/M = 2.000, the difference between the predictions is negligible (Fig. 1). The difference becomes significant for non-stoichiometric fuels, as shown for O/M = 1.975 in Fig. 1. The microstructure of the FBR fuel with 21.4 wt.% Pu was not described in the paper of Duriez. Taking into account the rigorous experimental methodology used by Duriez (characterisation of the stoichiometry), a possible explanation is an interaction between the plutonium distribution and the stoichiometry. Another parameter having a strong impact on the conductivity is the porosity correction used to obtain the values for 95% TD. This correction is small in the work of Duriez as the samples density is very close to 95% TD. This was also the case for the samples selected by Philipponneau in order to obtain his recommendation. An effect due to differences in the pores shape can also be excluded, as the results are identical for stoichiometric fuels (Fig. 1). Usually the apparent stoichiometry is obtained by heat treatments and checked before and after the measurements, either by XRD or thermogravimetry. However, for non-perfectly homogeneous samples, the gradients in the plutonium distribution induce a non-uniform oxygen distribution, which is difficult to characterise experimentally. It has been proposed by Baron that the deviation from stoichiometry is the main cause for the differences observed between fresh UO2 and MOX [14,15], this effect is quantified in the next section. In the first model ("Model 1"), the effect of Pu is neglected over the entire relevant Pu compositions range (up to 24 wt.% PuO2), and a correlation obtained for non-stoichiometric homogeneous (U,Pu)O2 is used. In the second model ("Model 2", the effect of Pu is supposed to be present at all compositions, with the stoichiometry effect. The thermal conductivity is described by the correlations of Fink [16] for the UO2 matrix, Duriez at low PuO2 contents (coating phase) and of Philipponneau at high PuO2 contents (agglomerates). For the first model, applying a correlation for non-stoichiometric UO2 would be relevant, but such a correlation does not exist for physical reasons in the hypostoichiometric domain. A correlation for homogeneous (U,Pu)O2+x has to be obtained in order to predict the thermal conductivity of heterogeneous MOX fuel, supposing that the effect of Pu can be neglected, i.e. supposing that the thermal conductivities of homogeneous (U,Pu)O2 and UO2 are equal both for stoichiometric and non-stoichiometric fuels. Such a correlation has to be obtained considering reliable data for stoichiometric UO2 and stoichiometry dependence. Different correlations for non-stoichiometric fuels were reviewed [2,8,12,13,15,35,36]. The correlation of Martin [36], available for hyperstoichiometric UO2, was evaluated in the hypostoichiometric domain and the predictions were found to give a stoichiometry dependence very similar to a correlation already proposed [15]. Investigations by Molecular Dynamics [37] have confirmed the almost symmetric effect of the hypo- and hyper-stoichiometry in UO2. We therefore use the correlation of Martin, with however a correction, as for stoichiometric fuels it over predicts the conductivity of stoichiometric UO2 at high temperatures, when compared to the recommendation of Fink [16] (Fig. 4). Analysis has shown that this over-prediction was due to the high temperature term in the correlation of Martin, and that, if this term is removed, the predictions of Martin and Fink were identical for stoichiometric fuels in the temperature range 500-1500 K. The correlation proposed for homogeneous MOX is therefore given by the following equation. k=(0.035 The series and parallel bounds (Eq. (2)) were calculated using the thermal conductivity values given by Eq. (5) for the heterogeneous MOX constituents and the maximum difference between these two bounds is 2% over the considered temperature range. The predictions obtained with the equations of Maxwell-Eucken (Eq. (3)) and Bergman (Eq. (4)) are equal and are in the interval between the series and parallel bounds. This result shows that the use of a sophisticated analytical or numerical model to predict the thermal conductivity is not justified [38]. The model of Maxwell-Eucken [31] was therefore chosen to predict the equivalent thermal conductivity of the heterogeneous MOX.The equivalent thermal conductivity of the stoichiometric heterogeneous MOX with an average PuO2 content of 7.2 wt.% (constituted by a stoichiometric UO2 matrix containing 15 vol.% of (U0.76Pu0.24)O1.975 agglomerates and 55 vol.% of a coating phase of (U0.94Pu0.06)O1.995) was calculated. The results show that the apparent thermal conductivity of the heterogeneous MOX, calculated using homogeneous MOX data (Eq. (5)) with O/M = 2.000, 1.995 and 1.975 (labeled Model 1 in Fig. 4) is not significantly different from the values measured by Duriez. The latter values are also very similar to the thermal conductivity of homogeneous MOX with O/M = 1.995. This simple model shows that the stoichiometry effect is sufficient to explain the lower thermal conductivity of LWR MOX fuel as compared to UO2. The advantage of this simple model is its consistency, as the calculations for the heterogeneous MOX are based on a unique formula for non-stoichiometric homogeneous (U,Pu)O2.In the second model, the effect of the plutonium is taken into account for the coating phase and for the Pu-rich agglomerates. The thermal conductivity is described by the correlations of Fink [16] for UO2.000, of Duriez et al. [2] for (U0.94Pu0.06)O1.995 (coating phase with low PuO2 content) and of Philipponneau [8] for (U0.76Pu0.24)O1.975 (Pu-rich agglomerates with high PuO2 content). The results (labeled Model 2 in Fig. 5) show that the calculated thermal conductivity of the heterogeneous 'stoichiometric' MOX is lower than UO2 and also lower than for stoichiometric MOX as given by Duriez. Therefore taking into account both the heterogeneity in the oxygen distribution and the Pu content leads to an underprediction of the thermal conductivity of heterogeneous MOX. A possible cause for the lower thermal conductivity of unirradiated heterogeneous MOX is therefore the intrinsic fluctuations of the local stoichiometry and only to a lesser extent the perturbation of the heat transfer due to the substitution of the U by Pu atoms in the crystal lattice. This interpretation was already proposed by Baron [14,15]. This assumption is acceptable if the size of the heterogeneities is much smaller that the thickness of the sample. A theoretical criterion for the impact of these parameters, initially proposed by Kerrish [40], was checked experimentally by Lee and Taylor [41] and was found to be too restrictive. The conclusions resulting from the investigations of Lee are that for diffusivity ratios between 1 and 3.5 and volume fractions up to 30%, a ratio of 5 between the sample thickness and inclusions diameter is sufficient. Our heterogeneous samples fulfill this criterion, taking into account that the thermal diffusivity ratio is close to 1 in MOX, that the volume fraction of Pu rich agglomerates is under 30%, and that the agglomerates have a diameter of less than 200 μm compared to the sample (disc) thickness of 1 mm. The most severe requirement that one could use to define a medium behaving like a homogeneous material is that the heat transfer is not affected by the heterogeneities. This is the case for instance if we have a heterogeneous material where the two constituents have equal thermal diffusivity and no thermal resistance is present at the interfaces. This requirement is very close to be perfectly verified for the heterogeneous MOX, as UO2 and (U,Pu)O2 have very close values of the thermal diffusivity. An effect of the sample heterogeneity can also be excluded from the point of view of the location where the thermograms are recorded: the temperature transients on the rear face of the samples are measured with a pyrometer and the system is provided with a lens assembly which enables a 1 mm diameter spot of the sample surface to be focused onto the signal collecting fibre. The thermograms are therefore averaged over a 1 mm diameter surface, which is much larger than the size of the heterogeneities (Pu rich agglomerates with a size of less than 200 μm).The impact of sample thickness on the measured thermal diffusivity was experimentally investigated for the MIMAS MOX with 7.0 wt.% Pu. For this purpose, discs of 0.5, 1, 2, and 3 mm thickness were cut and the thermal diffusivity was measured. The same investigation was done for standard UO2, in order to verify the accuracy of the inverse technique used for the identification of the thermal diffusivity from the thermograms. The inverse technique [39] explicitly takes into account the sample thickness in the calculation of the heat losses. The results for UO2 (Fig. 6) show that the measured thermal diffusivity does not depend on sample thickness, and is in good agreement with the recommendation of Fink [16]. The results for the heterogeneous MOX (Fig. 7) also show no dependence on sample thickness.

Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s the different phases were studied by infrared transmission spectroscopy, but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparationmore » and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm-1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm-1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO22+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with but one in the hexahydrate.« less

A comment on the thermal conductivity of (U,Pu)O 2 and (U,Th)O 2 by molecular dynamics with adjustment for phonon-spin scattering

DOE PAGES

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

2016-07-15

In this study, a new approach for adjusting molecular dynamics results on UO 2 thermal conductivity to include phonon-spin scattering has been used to improve calculations on U x Pu 1–x O 2 and U xTh 1xO 2. We demonstrate that by including spin scattering a strong asymmetry as a function of uranium actinide fraction, x, is obtained. Greater degradation is shown for U xTh 1–xO 2 than U xPu 1-xO 2. Minimum thermal conductivities are predicted at U 0.97Pu 0.03O 2 and U 0.58Th 0.42O 2, although the degradation in U xPu 1–xO 2 is negligible relative to puremore » UO 2.« less

Failure of ESI Spectra to Represent Metal-Complex Solution Composition: A Study of Lanthanide-Carboxylate Complexes

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

McDonald, Luther W.; Campbell, James A.; Clark, Sue B.

2014-01-21

Electrospray ionization - mass spectrometry (ESI-MS) was used for the characterization of uranyl complexed to tributyl phosphate (TBP) and dibutyl phosphate (DBP). The stoichiometry of uranyl with TBP and DBP was determined, and the gas phase speciation was found to be dependent on the cone voltage applied to induce fragmentation on the gas phase complexes. To quantitatively compare the gas phase distribution of species to solution, apparent stability constants were calculated. With a cone voltage of 80V, the apparent stability constants for the complexes UO2(NO3)2•2TBP, UO2(NO3)2(H2O)•2TBP, and UO2(DBP)+ were determined. With a lower cone voltage applied, larger complexes were observedmore » and stability constants for the complexes UO2(NO3)2•3TBP and UO2(DBP)42- were determined.« less

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.

Development of UO2/PuO2 dispersed in uranium matrix CERMET fuel system for fast reactors

NASA Astrophysics Data System (ADS)

Sinha, V. P.; Hegde, P. V.; Prasad, G. J.; Pal, S.; Mishra, G. P.

2012-08-01

CERMET fuel with either PuO2 or enriched UO2 dispersed in uranium metal matrix has a strong potential of becoming a fuel for the liquid metal cooled fast breeder reactors (LMR's). In fact it may act as a bridge between the advantages and disadvantages associated with the two extremes of fuel systems (i.e. ceramic fuel and metallic fuel) for fast reactors. At Bhabha Atomic Research Centre (BARC), R & D efforts are on to develop this CERMET fuel by powder metallurgy route. This paper describes the development of flow sheet for preparation of UO2 dispersed in uranium metal matrix pellets for three different compositions i.e. U-20 wt%UO2, U-25 wt%UO2 and U-30 wt%UO2. It was found that the sintered pellets were having excellent integrity and their linear mass was higher than that of carbide fuel pellets used in Fast Breeder Test Reactor programme (FBTR) in India. The pellets were characterized by X-ray diffraction (XRD) technique for phase analysis and lattice parameter determination. The optical microstructures were developed and reported for all the three different U-UO2 compositions.

SEPARATION OF URANIUM AND PLUTONIUM OXIDES

DOEpatents

Benedict, G.E.; Lyon, W.L.

1961-12-01

ABS>A method of separating a mixture of UO/sub 2/ and PuO/sub 2/ is given which comprises immersing the mixture in a fused NaCl-KCl bath, chlorinating with chlorine or phosgene, and preferentially electrolytically or chemically reducing the UO/sub 2/Cl/sub 2/ so produced to UO/sub 2/ and filtering it out. (AEC)

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.

Recent advances in the study of the UO2-PuO2 phase diagram at high temperatures

NASA Astrophysics Data System (ADS)

Böhler, R.; Welland, M. J.; Prieur, D.; Cakir, P.; Vitova, T.; Pruessmann, T.; Pidchenko, I.; Hennig, C.; Guéneau, C.; Konings, R. J. M.; Manara, D.

2014-05-01

Recently, novel container-less laser heating experimental data have been published on the melting behaviour of pure PuO2 and PuO2-rich compositions in the uranium dioxide-plutonium dioxide system. Such data showed that previous data obtained by more traditional furnace heating techniques were affected by extensive interaction between the sample and its containment. It is therefore paramount to check whether data so far used by nuclear engineers for the uranium-rich side of the pseudo-binary dioxide system can be confirmed or not. In the present work, new data are presented both in the UO2-rich part of the phase diagram, most interesting for the uranium-plutonium dioxide based nuclear fuel safety, and in the PuO2 side. The new results confirm earlier furnace heating data in the uranium-dioxide rich part of the phase diagram, and more recent laser-heating data in the plutonium-dioxide side of the system. As a consequence, it is also confirmed that a minimum melting point must exist in the UO2-PuO2 system, at a composition between x(PuO2) = 0.4 and x(PuO2) = 0.7 and 2900 K ⩽ T ⩽ 3000 K. Taking into account that, especially at high temperature, oxygen chemistry has an effect on the reported phase boundary uncertainties, the current results should be projected in the ternary U-Pu-O system. This aspect has been extensively studied here by X-ray diffraction and X-ray absorption spectroscopy. The current results suggest that uncertainty bands related to oxygen behaviour in the equilibria between condensed phases and gas should not significantly affect the qualitative trend of the current solid-liquid phase boundaries.

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.

In situ high temperature X-Ray diffraction study of the phase equilibria in the UO2-PuO2-Pu2O3 system

NASA Astrophysics Data System (ADS)

Belin, Renaud C.; Strach, Michal; Truphémus, Thibaut; Guéneau, Christine; Richaud, Jean-Christophe; Rogez, Jacques

2015-10-01

The region of the U-Pu-O phase diagram delimited by the compounds UO2-PuO2-Pu2O3 is known to exhibit a miscibility gap at low temperature. Consequently, MOX fuels with a composition entering this region could decompose into two fluorite phases and thus exhibit chemical heterogeneities. The experimental data on this domain found in the literature are scarce and usually provided using DTA that is not suitable for the investigation of such decomposition phenomena. In the present work, new experimental data, i.e. crystallographic phases, lattice parameters, phase fractions and temperature of phase separation, were measured in the composition range 0.14 < Pu/(U + Pu) < 0.62 and 1.85 < O/(U + Pu) < 2 from 298 to 1750 K using a novel in situ high temperature X-ray diffraction apparatus. A very good agreement is found between the temperature of phase separation determined from our results and using the thermodynamic model of the U-Pu-O system based on the CALPHAD method. Also, the combined use of thermodynamic calculations and XRD results refinement proved helpful in the determination of the O/M ratio of the samples during cooling. The methodology used in the current work might be useful to investigate other oxides systems exhibiting a miscibility gap.

Development of Xe and Kr empirical potentials for CeO 2, ThO 2, UO 2 and PuO 2, combining DFT with high temperature MD

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

Cooper, M. W. D.; Kuganathan, N.; Burr, P. A.

In this study, the development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. 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 matchingmore » 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 were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO 2, ThO 2, UO 2 and PuO 2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO 2 as well as advanced MOX fuels.« less

Development of Xe and Kr empirical potentials for CeO 2, ThO 2, UO 2 and PuO 2, combining DFT with high temperature MD

DOE PAGES

Cooper, M. W. D.; Kuganathan, N.; Burr, P. A.; ...

2016-08-23

In this study, the development of embedded atom method (EAM) many-body potentials for actinide oxides and associated mixed oxide (MOX) systems has motivated the development of a complementary parameter set for gas-actinide and gas-oxygen interactions. 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 matchingmore » 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 were validated against DFT trapping energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO 2, ThO 2, UO 2 and PuO 2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO 2 as well as advanced MOX fuels.« 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.

Identification of NpO2+x in the binary Np-O system

NASA Astrophysics Data System (ADS)

Tayal, Akhil; Conradson, Steven D.; Baldinozzi, Gianguido; Namdeo, Sonu; Roberts, Kevin E.; Allen, Patrick G.; Shuh, David K.

2017-07-01

In contrast to UO2 and PuO2, there is no consensus on the existence of mixed valence NpO2+x, resulting in a gap between NpO2 and Np2O5 (the highest binary oxide of Np) in the Np-O phase diagram. We now show NpO2+x via Np LIII Extended X-ray Absorption Fine Structure (EXAFS) spectra of three samples of NpO2 that, analogous to U and Pu, exhibit multisite Np-O distributions with varying numbers of oxygen atoms at 1.87-1.91 Å. This is supported by the diffraction pattern of the sample with the largest amount of this oxo-type species that can be refined with both the simple fluorite structure and a trigonal one related to α-U4O9. The implied Np(V)-bridging oxo moieties as well as possible indications of OHbar found by detailed EXAFS analysis suggest that NpO2+x more closely resembles PuO2+x than UO2+x. An additional common characteristic suggested by the EXAFS and X-Ray Diffraction (XRD) is the phase separation into NpO2 and what would be previously unreported Np4O9(-δ), indicative of O clustering.

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

Carmack, Jon; Hayes, Steven; Walters, L. C.

This document explores startup fuel options for a proposed test/demonstration fast reactor. The fuel options considered are the metallic fuels U-Zr and U-Pu-Zr and the ceramic fuels UO 2 and UO 2-PuO 2 (MOX). Attributes of the candidate fuel choices considered were feedstock availability, fabrication feasibility, rough order of magnitude cost and schedule, and the existing irradiation performance database. The reactor-grade plutonium bearing fuels (U-Pu-Zr and MOX) were eliminated from consideration as the initial startup fuels because the availability and isotopics of domestic plutonium feedstock is uncertain. There are international sources of reactor grade plutonium feedstock but isotopics and availabilitymore » are also uncertain. Weapons grade plutonium is the only possible source of Pu feedstock in sufficient quantities needed to fuel a startup core. Currently, the available U.S. source of (excess) weapons-grade plutonium is designated for irradiation in commercial light water reactors (LWR) to a level that would preclude diversion. Weapons-grade plutonium also contains a significant concentration of gallium. Gallium presents a potential issue for both the fabrication of MOX fuel as well as possible performance issues for metallic fuel. Also, the construction of a fuel fabrication line for plutonium fuels, with or without a line to remove gallium, is expected to be considerably more expensive than for uranium fuels. In the case of U-Pu-Zr, a relatively small number of fuel pins have been irradiated to high burnup, and in no case has a full assembly been irradiated to high burnup without disassembly and re-constitution. For MOX fuel, the irradiation database from the Fast Flux Test Facility (FFTF) is extensive. If a significant source of either weapons-grade or reactor-grade Pu became available (i.e., from an international source), a startup core based on Pu could be reconsidered.« less

Vaporization chemistry of hypo-stoichiometric (U,Pu)O 2

NASA Astrophysics Data System (ADS)

Viswanathan, R.; Krishnaiah, M. V.

2001-04-01

Calculations were performed on hypo-stoichiometric uranium plutonium di-oxide to examine its vaporization behavior as a function of O/ M ( M= U+ Pu) ratio and plutonium content. The phase U (1- y) Pu yO z was treated as an ideal solid solution of (1- y)UO 2+ yPuO (2- x) such that x=(2- z)/ y. Oxygen potentials for different desired values of y, z, and temperature were used as the primary input to calculate the corresponding partial pressures of various O-, U-, and Pu-bearing gaseous species. Relevant thermodynamic data for the solid phases UO 2 and PuO (2- x) , and the gaseous species were taken from the literature. Total vapor pressure varies with O/M and goes through a minimum. This minimum does not indicate a congruently vaporizing composition. Vaporization behavior of this system can at best be quasi-congruent. Two quasi-congruently vaporizing compositions (QCVCs) exist, representing the equalities (O/M) vapor=(O/M) mixed-oxide and (U/Pu) vapor=(U/Pu) mixed-oxide, respectively. The (O/M) corresponding to QCVC1 is lower than that corresponding to QCVC2, but very close to the value where vapor pressure minimum occurs. The O/M values of both QCVCs increase with decrease in plutonium content. The vaporization chemistry of this system, on continuous vaporization under dynamic condition, is discussed.

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

Solvation of actinide salts in water using a polarizable continuum model.

PubMed

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

Uranyl extraction by N,N-dialkylamide ligands studied using static and dynamic DFT simulations.

PubMed

Sieffert, Nicolas; Wipff, Georges

2015-02-14

We report DFT static and dynamic studies on uranyl complexes [UO(2)(NO(3))x(H(2)O)(y)L(z)](2-x) involved in the uranyl extraction from water to an "oil" phase (hexane) by an amide ligand L (N,N-dimethylacetamide). Static DFT results "in solution" (continuum SMD models for water and hexane) predict that the stepwise formation of [UO(2)(NO(3))(2)L(2)] from the UO(2)(H(2)O)(5)(2+) species is energetically favourable, and allow us to compare cis/trans isomers of penta- and hexa-coordinated complexes and key intermediates in the two solvents. DFT-MD simulations of [UO(2)(NO(3))(2)L(2)], [UO(2)(NO(3))(2)(H(2)O)L(2)], and [UO(2)(NO(3))(H(2)O)L(2)](+) species in explicit solvent environments (water, hexane, or the water/hexane interface) represented at the MM or full-DFT level reveal a versatile solvent dependent binding mode of nitrates, also evidenced by metadynamics simulations. In water and at the interface, the latter exchange from bi- to monodentate, via in plane rotational motions in some cases. Remarkably, structures of complexes at the interface are more "water-like" than gas phase- or hexane-like. Thus, the order of U-O(NO(3))/U-O(L) bond distances observed in the gas phase (U-O(nit) < U-OL) is inverted at the interface and in water. Overall, the results are consistent with the experimental observation of uranyl extraction from nitric acid solutions by amide analogues (bearing "fatty" substituents), and allow us to propose possible extraction mechanisms, involving complexation of L "right at the interface". They also point to the importance of the solvent environment and the dynamics on the structure and stability of the complexes.

Chemical bonds and vibrational properties of ordered (U, Np, Pu) mixed oxides

NASA Astrophysics Data System (ADS)

Yang, Yu; Zhang, Ping

2013-01-01

We use density functional theory +U to investigate the chemical bonding characters and vibrational properties of the ordered (U, Np, Pu) mixed oxides (MOXs), UNpO4,NpPuO4, and UPuO4. It is found that the 5f electronic states of different actinide elements keep their localized characters in all three MOXs. The occupied 5f electronic states of different actinide elements do not overlap with each other and tend to distribute over the energy band gap of the other actinide element's 5f states. As a result, the three ordered MOXs all show smaller band gaps than those of the component dioxides, with values of 0.91, 1.47, and 0.19 eV for UNpO4,NpPuO4, and UPuO4, respectively. Through careful charge density analysis, we further show that the U-O and Pu-O bonds in MOXs show more ionic character than in UO2 and PuO2, while the Np-O bonds show more covalent character than in NpO2. The change in covalencies in the chemical bonds leads to vibrational frequencies of oxygen atoms that are different in MOXs.

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

Verkerk, B.

In 1959 a fuel development program was undertaken based on UO/sub 2/ in which it was intended to study all variables that could influence the quality of fabricated UO/sub 2/-pellets. Later this program was extended to a study of electrolytic UO/sub 2/ with the fabrication of swaged or vibratory compacted fuel elements in mind, and recently the study of the UO/sub 2/-PuO/sub 2/ system was incorporated in it. In order to obtain a better knowledge of the UO/sub 2/- powders that can be used for sintering purposes, an extensive study was made of various preparation methods. A small plutonium laboratorymore » containing equipment for the preparation of UO/sub 2/-- PuO/sub 2/ pellets containing 1 to 10% PuO/sub 2/ was set up and preliminary experiments were performed. Work on a small scale was done on pressing and sintering of UO/sub 2/ made along various routes. The reduction process was also studied. For the regeneration of scrap, especially for the case of enriched material, a 5-kg batch dissolution and precipitation plant was built. This installation is also used for various precipitation studies on a larger scale. Within the scope of tue fuel development program the study of canning materials is also of great importance. For the ship-propulsion reactor Zircaloy-2 was chosen as canning material. Various welding experiments were done in an argon-arc welding chamber and it was found that under well selected conditions very satisfactory end-cap welds could be obtained. 1n the corrosion program it became clear that proper conditioning is of utmost importance. Means of pre-operation treatment are being studied. In the HFR a low-temperature, low-pressure loop for the irradiation of capsules is in regular operation. The pressurized loop now under construction was designed for testing of fuel rods and clusters as planned for the ship-propulsion reactor, under conditions close to those of the actual reactor. The facilities for the post- irradiation measurements consist of two lead cells. (auth)« less

Analysis of key safety metrics of thorium utilization in LWRs

DOE PAGES

Ade, Brian J.; Bowman, Stephen M.; Worrall, Andrew; ...

2016-04-08

Here, thorium has great potential to stretch nuclear fuel reserves because of its natural abundance and because it is possible to breed the 232Th isotope into a fissile fuel ( 233U). Various scenarios exist for utilization of thorium in the nuclear fuel cycle, including use in different nuclear reactor types (e.g., light water, high-temperature gas-cooled, fast spectrum sodium, and molten salt reactors), along with use in advanced accelerator-driven systems and even in fission-fusion hybrid systems. The most likely near-term application of thorium in the United States is in currently operating light water reactors (LWRs). This use is primarily based onmore » concepts that mix thorium with uranium (UO 2 + ThO 2) or that add fertile thorium (ThO 2) fuel pins to typical LWR fuel assemblies. Utilization of mixed fuel assemblies (PuO 2 + ThO 2) is also possible. The addition of thorium to currently operating LWRs would result in a number of different phenomenological impacts to the nuclear fuel. Thorium and its irradiation products have different nuclear characteristics from those of uranium and its irradiation products. ThO 2, alone or mixed with UO 2 fuel, leads to different chemical and physical properties of the fuel. These key reactor safety–related issues have been studied at Oak Ridge National Laboratory and documented in “Safety and Regulatory Issues of the Thorium Fuel Cycle” (NUREG/CR-7176, U.S. Nuclear Regulatory Commission, 2014). Various reactor analyses were performed using the SCALE code system for comparison of key performance parameters of both ThO 2 + UO 2 and ThO 2 + PuO 2 against those of UO 2 and typical UO 2 + PuO 2 mixed oxide fuels, including reactivity coefficients and power sharing between surrounding UO 2 assemblies and the assembly of interest. The decay heat and radiological source terms for spent fuel after its discharge from the reactor are also presented. Based on this evaluation, potential impacts on safety requirements and identification of knowledge gaps that require additional analysis or research to develop a technical basis for the licensing of thorium fuel are identified.« less

Incorporation mechanisms of actinide elements into the structures of U 6+ phases formed during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Ewing, Rodney C.; Miller, Mark L.

1997-05-01

Uranyl oxide hydrate and uranyl silicate phases will form due to the corrosion and alteration of spent nuclear fuel under oxidizing conditions in silica-bearing solution. The actinide elements in the spent fuel may be incorporated into the structures of these secondary U6+ phases during the long-term corrosion of the UO 2 in spent fuel. The incorporation of actinide elements into the crystal structures of the alteration products may decrease actinide mobility. The crystal chemistry of the various oxidation states of the actinide elements of environmental concern is examined to identify possible incorporation mechanisms. The substitutions Pu 6+U 6+ and (Pu 5+, Np 5+)U 6+ should readily occur in many U 6+ structures, although structural modification may be required to satisfy local bond-valence requirements. Crystal-chemical characteristics of the U 6+ phases indicate that An 4+ (An: actinide)U 6+ substitution is likely to occur in the sheets of uranyl polyhedra that occur in the structures of the minerals schoepite, [(UO 2) 8O 2(OH) 12](H 2O) 12, ianthinite, [U 24+ (UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, becquerelite, Ca[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, compreignacite, K 2[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, α-uranophane, Ca[(UO 2)(SiO 3OH)] 2(H 2O) 5, and boltwoodite, K(H 2O)[(UO 2)(SiO 4)], all of which are likely to form due to the oxidation and alteration of the UO 2 in spent fuel. The incorporation of An 3+ into the sheets of the structures of α-uranophane and boltwoodite, as well as interlayer sites of various uranyl phases, may occur.

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates.

PubMed

Diwu, Juan; Wang, Shuao; Good, Justin J; DiStefano, Victoria H; Albrecht-Schmitt, Thomas E

2011-06-06

The heterobimetallic actinide compound UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O, UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O, and UO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U(0.9)Pu(0.1))O(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O, and the Pu(IV) phosphonate, Pu[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Np) and M[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·3H(2)O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Np, Pu) and An[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Np, Pu) formulas. © 2011 American Chemical Society

Space and Time Distribution of Pu Isotopes inside The First Experimental Fuel Pin Designed for PWR and Manufactured in Indonesia

NASA Astrophysics Data System (ADS)

Suwardi; Setiawan, J.; Susilo, J.

2017-01-01

The first short fuel pin containing natural UO2 pellet in Zry4 cladding has been prepared and planned to be tested in power ramp irradiation. An irradiation test should be designed to allow an experiment can be performed safely and giving maximum results of many performance aspects of design and manufacturing. Performance analysis to the fuel specimen shows that the specimen is not match to be used for power ramp testing. Enlargement by 0.20 mm of pellet diameter has been proposed. The present work is evaluation of modified design for important aspect of isotopic Pu distribution during irradiation test, because generated Pu isotopes in natural UO2 fuel, contribute more power relative to the contribution by enriched UO2 fuel. The axial profile of neutrons flux have been chosen from both experimental measurement and model calculation. The parameters of ramp power has been obtained from statistical experiment data. A simplified and typical base-load commercial PHWR profile of LHR history has been chosen, to determine the minimum irradiation time before ramp test can be performed. The data design and Mat pro XI materials properties models have been chosen. The axial profile of neutrons flux has been accommodated by 5 slices of discrete pin. The Pu distribution of slice-4 with highest power rate has been chosen to be evaluated. The radial discretion of pellet and cladding and numerical parameter have been used the default best practice of TU. The results shows that Pu 239 increased rapidly. The maximum burn up of slice 4 at upper the median slice, it reached nearly 90% of maximum value at about 6000 h with peak of 0.8%a Pu/HM at 22000 h, which is higher than initial U 235. Each 240, 241 and 240 Pu grows slower and ends up to 0.4, 0.2 and 0.18 % respectively. This results can be used for verification of other aspect of fuel behavior in the modeling results and also can be used as guide and comparison to the future post irradiation examination for Pu isotopes distribution.

Simulation of radiation driven fission gas diffusion in UO 2, ThO 2 and PuO 2

DOE PAGES

Cooper, Michael William D.; Stanek, Christopher Richard; Turnbull, James Anthony; ...

2016-12-01

Below 1000 K it is thought that fission gas diffusion in nuclear fuel during irradiation occurs through atomic mixing due to radiation damage. Here we present a molecular dynamics (MD) study of Xe, Kr, Th, U, Pu and O diffusion due to irradiation. It is concluded that the ballistic phase does not sufficiently account for the experimentally observed diffusion. Thermal spike simulations are used to confirm that electronic stopping remedies the discrepancy with experiment and the predicted diffusivities lie within the scatter of the experimental data. Here, our results predict that the diffusion coefficients are ordered such that D* 0more » > D* Kr > D* Xe > D* U. For all species >98.5% of diffusivity is accounted for by electronic stopping. Fission gas diffusivity was not predicted to vary significantly between ThO 2, UO 2 and PuO 2, indicating that this process would not change greatly for mixed oxide fuels.« less

Group Hexavalent Actinide Separations: A New Approach to Used Nuclear Fuel Recycling

DOE PAGES

Burns, Jonathan D.; Moyer, Bruce A.

2016-08-17

Hexavalent Np, Pu, and Am individually, and as a group, have all been cocrystallized with UO 2(NO 3) 2∙ 6H 2O, constituting the first demonstration of an An(VI) group cocrystalliza- tion. The hexavalent dioxo cations of Np, Pu, and Am cocrystallize with UO 2(NO 3) 2∙ 6H 2O in near proportion with a simple reduction in temperature, while the lower valence states, An(III) and An(IV), are only slightly removed from solution. A separation of An(VI) species from An(III) ions by crystallization has been demonstrated, with an observed separation factor of 14. Separation of An(VI) species from key fission products, 95Zr,more » 95Nb, 137Cs, and 144Ce, has also been demonstrated by crystallization, with separation factors ranging from 6.5 to 71 in the absence of Am(VI), while in the presence of Am(VI), the separation factors were reduced to 0.99 7.7. One interesting observation is that Am(VI) shows increased stability in the cocrystallized form, with no reduction observed after 13 days, as opposed to in solution, in which >50% is reduced after only 10 days. The ability to cocrystallize and stabilize hexavalent actinides from solution, especially Am(VI), introduces a new separations approach that can be applied to closing the nuclear fuel cycle.« less

Group Hexavalent Actinide Separations: A New Approach to Used Nuclear Fuel Recycling

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

Burns, Jonathan D.; Moyer, Bruce A.

Hexavalent Np, Pu, and Am individually, and as a group, have all been cocrystallized with UO 2(NO 3) 2∙ 6H 2O, constituting the first demonstration of an An(VI) group cocrystalliza- tion. The hexavalent dioxo cations of Np, Pu, and Am cocrystallize with UO 2(NO 3) 2∙ 6H 2O in near proportion with a simple reduction in temperature, while the lower valence states, An(III) and An(IV), are only slightly removed from solution. A separation of An(VI) species from An(III) ions by crystallization has been demonstrated, with an observed separation factor of 14. Separation of An(VI) species from key fission products, 95Zr,more » 95Nb, 137Cs, and 144Ce, has also been demonstrated by crystallization, with separation factors ranging from 6.5 to 71 in the absence of Am(VI), while in the presence of Am(VI), the separation factors were reduced to 0.99 7.7. One interesting observation is that Am(VI) shows increased stability in the cocrystallized form, with no reduction observed after 13 days, as opposed to in solution, in which >50% is reduced after only 10 days. The ability to cocrystallize and stabilize hexavalent actinides from solution, especially Am(VI), introduces a new separations approach that can be applied to closing the nuclear fuel cycle.« less

Activation volumes of oxygen self-diffusion in fluorite structured oxides

DOE PAGES

Christopoulos, S-R G.; Kordatos, A.; Cooper, Michael William D.; ...

2016-10-27

In this study, fluorite structured oxides are used in numerous applications and as such it is necessary to determine their materials properties over a range of conditions. In the present study we employ molecular dynamics calculations to calculate the elastic and expansivity data, which are then used in a thermodynamic model (the cBΩ model) to calculate the activation volumes of oxygen self-diffusion coefficient in ThO 2, UO 2 and PuO 2 fluorite structured oxides over a wide temperature range. We present relations to calculate the activation volumes of oxygen self-diffusion coefficient in ThO 2, UO 2 and PuO 2 formore » a wide range of temperature (300–1700 K) and pressure (–7.5 to 7.5 GPa).« less

Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

PubMed

Batuk, Olga N; Conradson, Steven D; Aleksandrova, Olga N; Boukhalfa, Hakim; Burakov, Boris E; Clark, David L; Czerwinski, Ken R; Felmy, Andrew R; Lezama-Pacheco, Juan S; Kalmykov, Stepan N; Moore, Dean A; Myasoedov, Boris F; Reed, Donald T; Reilly, Dallas D; Roback, Robert C; Vlasova, Irina E; Webb, Samuel M; Wilkerson, Marianne P

2015-06-02

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Optimization of burnable poison design for Pu incineration in fully fertile free PWR core

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

Fridman, E.; Shwageraus, E.; Galperin, A.

2006-07-01

The design challenges of the fertile-free based fuel (FFF) can be addressed by careful and elaborate use of burnable poisons (BP). Practical fully FFF core design for PWR reactor has been reported in the past [1]. However, the burnable poison option used in the design resulted in significant end of cycle reactivity penalty due to incomplete BP depletion. Consequently, excessive Pu loading were required to maintain the target fuel cycle length, which in turn decreased the Pu burning efficiency. A systematic evaluation of commercially available BP materials in all configurations currently used in PWRs is the main objective of thismore » work. The BP materials considered are Boron, Gd, Er, and Hf. The BP geometries were based on Wet Annular Burnable Absorber (WABA), Integral Fuel Burnable Absorber (IFBA), and Homogeneous poison/fuel mixtures. Several most promising combinations of BP designs were selected for the full core 3D simulation. All major core performance parameters for the analyzed cases are very close to those of a standard PWR with conventional UO{sub 2} fuel including possibility of reactivity control, power peaking factors, and cycle length. The MTC of all FFF cores was found at the full power conditions at all times and very close to that of the UO{sub 2} core. The Doppler coefficient of the FFF cores is also negative but somewhat lower in magnitude compared to UO{sub 2} core. The soluble boron worth of the FFF cores was calculated to be lower than that of the UO{sub 2} core by about a factor of two, which still allows the core reactivity control with acceptable soluble boron concentrations. The main conclusion of this work is that judicial application of burnable poisons for fertile free fuel has a potential to produce a core design with performance characteristics close to those of the reference PWR core with conventional UO{sub 2} fuel. (authors)« 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 of calcium vanadate minerals and related compounds

USGS Publications Warehouse

Marvin, Richard F.

1956-01-01

Synthesis of natural vanadates shows that most of them are stable in an acid environment. Phase studies of a portion of the system CaO-V2O5-H2O indicate that calcium vanadates are an indicator of environmental pH conditions. Some minerals, such as pascoute, indicate rapid evaporation of vanadite solutions; other minerals, such as hewettite, show that slow evaporation took place. Cursory examination of systems K2O-UO2-(NO3)2-V2O5 and CaO-UO2(NO3)2-V2O5, both in aqueous solution, has yielded information on the relationships among carnotite, tyuyamunite, and rauvite.

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.

Uranium (III)-Plutonium (III) co-precipitation in molten chloride

NASA Astrophysics Data System (ADS)

Vigier, Jean-François; Laplace, Annabelle; Renard, Catherine; Miguirditchian, Manuel; Abraham, Francis

2018-02-01

Co-management of the actinides in an integrated closed fuel cycle by a pyrochemical process is studied at the laboratory scale in France in the CEA-ATALANTE facility. In this context the co-precipitation of U(III) and Pu(III) by wet argon sparging in LiCl-CaCl2 (30-70 mol%) molten salt at 705 °C is studied. Pu(III) is prepared in situ in the molten salt by carbochlorination of PuO2 and U(III) is then introduced as UCl3 after chlorine purge by argon to avoid any oxidation of uranium up to U(VI) by Cl2. The oxide conversion yield through wet argon sparging is quantitative. However, the preferential oxidation of U(III) in comparison to Pu(III) is responsible for a successive conversion of the two actinides, giving a mixture of UO2 and PuO2 oxides. Surprisingly, the conversion of sole Pu(III) in the same conditions leads to a mixture of PuO2 and PuOCl, characteristic of a partial oxidation of Pu(III) to Pu(IV). This is in contrast with coconversion of U(III)-Pu(III) mixtures but in agreement with the conversion of Ce(III).

Chlorination of UO 2, PuO 2 and rare earth oxides using ZrCl 4 in LiCl-KCl eutectic melt

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2005-04-01

A new chlorination method using ZrCl 4 in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl 4 has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La 2O 3, CeO 2, Nd 2O 3 and Y 2O 3) and actinide oxides (UO 2 and PuO 2) were allowed to react with ZrCl 4 in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO 2. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl 4 chlorination method, free from corrosive gas, was very simple and useful.

Uranium bioprecipitation mediated by yeasts utilizing organic phosphorus substrates.

PubMed

Liang, Xinjin; Csetenyi, Laszlo; Gadd, Geoffrey Michael

2016-06-01

In this research, we have demonstrated the ability of several yeast species to mediate U(VI) biomineralization through uranium phosphate biomineral formation when utilizing an organic source of phosphorus (glycerol 2-phosphate disodium salt hydrate (C3H7Na2O6P·xH2O (G2P)) or phytic acid sodium salt hydrate (C6H18O24P6·xNa(+)·yH2O (PyA))) in the presence of soluble UO2(NO3)2. The formation of meta-ankoleite (K2(UO2)2(PO4)2·6(H2O)), chernikovite ((H3O)2(UO2)2(PO4)2·6(H2O)), bassetite (Fe(++)(UO2)2(PO4)2·8(H2O)), and uramphite ((NH4)(UO2)(PO4)·3(H2O)) on cell surfaces was confirmed by X-ray diffraction in yeasts grown in a defined liquid medium amended with uranium and an organic phosphorus source, as well as in yeasts pre-grown in organic phosphorus-containing media and then subsequently exposed to UO2(NO3)2. The resulting minerals depended on the yeast species as well as physico-chemical conditions. The results obtained in this study demonstrate that phosphatase-mediated uranium biomineralization can occur in yeasts supplied with an organic phosphate substrate as sole source of phosphorus. Further understanding of yeast interactions with uranium may be relevant to development of potential treatment methods for uranium waste and utilization of organic phosphate sources and for prediction of microbial impacts on the fate of uranium in the environment.

Environmental modeling of uranium interstitial compositions of non-stoichiometric oxides: experimental and theoretical analysis.

PubMed

Ivanova, Bojidarka

2016-10-01

Study of uranium interstitial compositions of non-stoichiometric oxides UO2+x (x ∈ 0.1-0.02) in gas and condense phases has been presented, using various soft-ionization mass spectrometric methods such as ESI-, APCI-, and MALDI-MS at a wide dynamic temperature gradient (∈ 25-300 °C). Linearly polarized vibrational spectroscopy has been utilized in order to assign unambiguously, the vibrational frequencies of uranium non-stoichiometric oxides. Experimental design has involved xUO2.66·yUO2.33, xUO2.66·yUO2.33/SiO2, xUO2.66·yUO2.33/SiO2 (NaOH) and SiO2/x'NaOH·y'UO2(NO3)2·6H2O, multicomponent systems (x = 1, y ∈ 0.1-1.0 and x' = 1, y' ∈ 0.1-0.6) as well as phase transitions UO2(NO3)2·6H2O → {U4O9(UO2.25)} → U3O7(UO2.33) → U3O8(UO2.66) → {UO3}, thus ensuring a maximal representativeness to real environmental conditions, where diverse chemical, geochemical and biochemical reactions, including complexation and sorption onto minerals have occurred. Experimental factors such as UV-irradiation, pH, temperature, concentration levels, solvent types and ion strength have been taken into consideration, too. As far as uranium speciation represents a challenging analytical task in terms of chemical identification diverse coordination species, mechanistic aspects relating incorporation of oxygen into UO 2+x form the shown full methods validation significantly impacts the field of environmental radioanalytical chemistry. UO2 is the most commonly used fuel in nuclear reactors around the globe; however, a large non-stoichiometric range ∈ UO1.65-UO2.25 has occurred due to radiolysis of water on UO2 surface yielding to H2O2, OH(·), and more. Each of those compositions has different oxygen diffusion. And in this respect enormous effort has been concentrated to study the potential impact of hazardous radionuclide on the environment, encompassing from the reprocessing to the disposal stages of the fuel waste, including the waste itself, the processes in the waste containers, the clay around the containers, and geological processes. In a broader sense, thereby, this study contributes to field of environmental analysis highlighting the great ability of various soft-ionization MS methods, particularly, MALDI-MS one, for direct assay of complex multicomponent heterogeneous mixtures at fmol-attomol concentration ranges, along with it the great instrumental features allowing, not only meaningful quantitative, but also structural information of the analytes, thus making the method indispensable for environmental speciation of radionuclides, generally.

METHOD FOR PREPARING URANIUM MONOCARBIDE-PLUTONIUM MONOCARBIDE SOLID SOLUTION

DOEpatents

Ogard, A.E.; Leary, J.A.; Maraman, W.J.

1963-03-19

A method is given for preparing solid solutions of uranium monocarbide- plutonium monocarbide. In this method, the powder form of uranium dioxide, plutonium dioxide, and graphite are mixed in a ratio determined by the equation: xUO/sub 2/ + yPuO/sub 2/ + (2+z)C yields UxPu/sub y/C/sub z/ +2CO, where x + y equ al 1.0 and z is greater than 0.9 but less than 1.0. The resulting mixture is compacted and heated in a vacuum at a temperature of 1850 deg C. (AEC)

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.

Thermal and X-ray diffraction analysis studies during the decomposition of ammonium uranyl nitrate.

PubMed

Kim, B H; Lee, Y B; Prelas, M A; Ghosh, T K

Two types of ammonium uranyl nitrate (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O and NH 4 UO 2 (NO 3 ) 3 , were thermally decomposed and reduced in a TG-DTA unit in nitrogen, air, and hydrogen atmospheres. Various intermediate phases produced by the thermal decomposition and reduction process were investigated by an X-ray diffraction analysis and a TG/DTA analysis. Both (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O and NH 4 UO 2 (NO 3 ) 3 decomposed to amorphous UO 3 regardless of the atmosphere used. The amorphous UO 3 from (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O was crystallized to γ-UO 3 regardless of the atmosphere used without a change in weight. The amorphous UO 3 obtained from decomposition of NH 4 UO 2 (NO 3 ) 3 was crystallized to α-UO 3 under a nitrogen and air atmosphere, and to β-UO 3 under a hydrogen atmosphere without a change in weight. Under each atmosphere, the reaction paths of (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O and NH 4 UO 2 (NO 3 ) 3 were as follows: under a nitrogen atmosphere: (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4 ·H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4  → NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → γ-UO 3  → U 3 O 8 , NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → α-UO 3  → U 3 O 8 ; under an air atmosphere: (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4 ·H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4  → NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → γ-UO 3  → U 3 O 8 , NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → α-UO 3  → U 3 O 8 ; and under a hydrogen atmosphere: (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4 ·H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4  → NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → γ-UO 3  → α-U 3 O 8  → UO 2 , NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → β-UO 3  → α-U 3 O 8  → UO 2 .

Oxygen diffusion model of the mixed (U,Pu)O2 ± x: Assessment and application

NASA Astrophysics Data System (ADS)

Moore, Emily; Guéneau, Christine; Crocombette, Jean-Paul

2017-03-01

The uranium-plutonium (U,Pu)O2 ± x mixed oxide (MOX) is used as a nuclear fuel in some light water reactors and considered for future reactor generations. To gain insight into fuel restructuring, which occurs during the fuel lifetime as well as possible accident scenarios understanding of the thermodynamic and kinetic behavior is crucial. A comprehensive evaluation of thermo-kinetic properties is incorporated in a computational CALPHAD type model. The present DICTRA based model describes oxygen diffusion across the whole range of plutonium, uranium and oxygen compositions and temperatures by incorporating vacancy and interstitial migration pathways for oxygen. The self and chemical diffusion coefficients are assessed for the binary UO2 ± x and PuO2 - x systems and the description is extended to the ternary mixed oxide (U,Pu)O2 ± x by extrapolation. A simulation to validate the applicability of this model is considered.

Recovery of UO{sub 2}/PuO{sub 2} in IFR electrorefining process

DOEpatents

Tomczuk, Z.; Miller, W.E.

1992-01-01

This invention is comprised of a process for converting PuO{sub 2} and U0{sub 2} present in an electrorefiner to the chlorides, by contacting the PuO{sub 2} and U0{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 U0{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 0{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 0{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}.

Modelling the thermal conductivity of (U xTh 1-x)O 2 and (U xPu 1-x)O 2

DOE PAGES

Cooper, M. W. D.; Middleburgh, S. C.; Grimes, R. W.

2015-07-15

The degradation of thermal conductivity due to the non-uniform cation lattice of (U xTh 1-x)O 2 and (U xPu 1-x)O 2 solid solutions has been investigated by molecular dynamics, using the non-equilibrium method, from 300 to 2000 K. Degradation of thermal conductivity is predicted in (U xTh 1-x)O 2 and (U xPu 1-x)O 2 as compositions deviate from the pure end members: UO 2, PuO 2 and ThO 2. The reduction in thermal conductivity is most apparent at low temperatures where phonon-defect scattering dominates over phonon-phonon interactions. The effect is greater for (U xTh 1-x)O 2 than U xPu 1-x)Omore » 2 due to the greater mismatch in cation size. Parameters for an analytical expressions have been developed that describe the predicted thermal conductivities over the full temperature and compositional ranges. Finally, these expressions may be used in higher level fuel performance codes.« less

Uranyl(VI) nitrate salts: modeling thermodynamic properties using the binding mean spherical approximation theory and determination of "fictive" binary data.

PubMed

Ruas, Alexandre; Bernard, Olivier; Caniffi, Barbara; Simonin, Jean-Pierre; Turq, Pierre; Blum, Lesser; Moisy, Philippe

2006-02-23

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O as a "simple" solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of "simple" solution, values for density and water activity for the binary system UO(2)(NO(3))(2)/H(2)O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O. This new set of binary data is "fictive" in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.

Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14-

NASA Astrophysics Data System (ADS)

Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

2003-08-01

Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

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 = 94.416(1) degrees, Z = 4.

Static electric dipole polarizabilities of An(5+/6+) and AnO2 (+/2+) (An = U, Np, and Pu) ions.

PubMed

Parmar, Payal; Peterson, Kirk A; Clark, Aurora E

2014-12-21

The parallel components of static electric dipole polarizabilities have been calculated for the lowest lying spin-orbit states of the penta- and hexavalent oxidation states of the actinides (An) U, Np, and Pu, in both their atomic and molecular diyl ion forms (An(5+/6+) and AnO2 (+/2+)) using the numerical finite-field technique within a four-component relativistic framework. The four-component Dirac-Hartree-Fock method formed the reference for MP2 and CCSD(T) calculations, while multireference Fock space coupled-cluster (FSCC), intermediate Hamiltonian Fock space coupled-cluster (IH-FSCC) and Kramers restricted configuration interaction (KRCI) methods were used to incorporate additional electron correlation. It is observed that electron correlation has significant (∼5 a.u.(3)) impact upon the parallel component of the polarizabilities of the diyls. To the best of our knowledge, these quantities have not been previously reported and they can serve as reference values in the determination of various electronic and response properties (for example intermolecular forces, optical properties, etc.) relevant to the nuclear fuel cycle and material science applications. The highest quality numbers for the parallel components (αzz) of the polarizability for the lowest Ω levels corresponding to the ground electronic states are (in a.u.(3)) 44.15 and 41.17 for UO2 (+) and UO2 (2+), respectively, 45.64 and 41.42 for NpO2 (+) and NpO2 (2+), respectively, and 47.15 for the PuO2 (+) ion.

DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

PubMed

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

Am phases in the matrix of a U–Pu–Zr alloy with Np, Am, and rare-earth elements

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

Janney, Dawn E.; Kennedy, J. Rory; Madden, James W.

2015-01-01

Phases and microstructures in the matrix of an as-cast U-Pu-Zr alloy with 3 wt% Am, 2% Np, and 8% rare-earth elements were characterized by scanning and transmission electron microscopy. The matrix consists primarily of two phases, both of which contain Am: ζ-(U, Np, Pu, Am) (~70 at% U, 5% Np, 14% Pu, 1% Am, and 10% Zr) and δ-(U, Np, Pu, Am)Zr 2 (~25% U, 2% Np, 10-15% Pu, 1-2% Am, and 55-60 at% Zr). These phases are similar to those in U-Pu-Zr alloys, although the Zr content in ζ-(U, Np, Pu, Am) is higher than that in ζ-(U, Pu)more » and the Zr content in δ-(U, Np, Pu, Am)Zr 2 is lower than that in δ-UZr 2. Nanocrystalline actinide oxides with structures similar to UO2 occurred in some areas, but may have formed by reactions with the atmosphere during sample handling. Planar features consisting of a central zone of ζ-(U, Np, Pu, Am) bracketed by zones of δ-(U, Np, Pu, Am)Zr 2 bound irregular polygons ranging in size from a few micrometers to a few tens of micrometers across. The rest of the matrix consists of elongated domains of ζ-(U, Np, Pu, Am) and δ-(U, Np, Pu, Am)Zr 2. Each of these domains is a few tens of nanometers across and a few hundred nanometers long. The domains display strong preferred orientations involving areas a few hundred nanometers to a few micrometers across.« less

Fabrication of high exposure nuclear fuel pellets

DOEpatents

Frederickson, James R.

1987-01-01

A method is disclosed for making a fuel pellet for a nuclear reactor. A mixture is prepared of PuO.sub.2 and UO.sub.2 powders, where the mixture contains at least about 30% PuO.sub.2, and where at least about 12% of the Pu is the Pu.sup.240 isotope. To this mixture is added about 0.3 to about 5% of a binder having a melting point of at least about 250.degree. F. The mixture is pressed to form a slug and the slug is granulated. Up to about 4.7% of a lubricant having a melting point of at least about 330.degree. F. is added to the granulated slug. Both the binder and the lubricant are selected from a group consisting of polyvinyl carboxylate, polyvinyl alcohol, naturally occurring high molecular weight cellulosic polymers, chemically modified high molecular weight cellulosic polymers, and mixtures thereof. The mixture is pressed to form a pellet and the pellet is sintered.

Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals

NASA Astrophysics Data System (ADS)

Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.

2015-12-01

Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and thorium (ThO, ThO2+) and nobelium (NoO, NoO2) oxides are studied.

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.

Raman spectroscopy characterization of actinide oxides (U 1-yPu y)O 2: Resistance to oxidation by the laser beam and examination of defects

NASA Astrophysics Data System (ADS)

Jégou, C.; Caraballo, R.; Peuget, S.; Roudil, D.; Desgranges, L.; Magnin, M.

2010-10-01

Structural changes in four (U 1-yPu y)O 2 materials with very different plutonium concentrations (0 ⩽ y ⩽ 1) and damage levels (up to 110 dpa) were studied by Raman spectroscopy. The novel experimental approach developed for this purpose consisted in using a laser beam as a heat source to assess the reactivity and structural changes of these materials according to the power supplied locally by the laser. The experiments were carried out in air and in water with or without hydrogen peroxide. As expected, the material response to oxidation in air depends on the plutonium content of the test oxide. At the highest power levels U 3O 8 generally forms with UO 2 whereas no significant change in the spectra indicating oxidation is observed for samples with high plutonium content ( 239PuO 2). Samples containing 25 wt.% plutonium exhibit intermediate behavior, typified mainly by a higher-intensity 632 cm -1 peak and the disappearance of the 1LO peak at 575 cm -1. This can be attributed to the presence of anion sublattice defects without any formation of higher oxides. The range of materials examined also allowed us to distinguish partly the chemical effects of alpha self-irradiation. The results obtained with water and hydrogen peroxide (a water radiolysis product) on a severely damaged 238PuO 2 specimen highlight a specific behavior, observed for the first time.

Phonon spectra and the one-phonon and two-phonon densities of states of UO2 and PuO2

NASA Astrophysics Data System (ADS)

Poplavnoi, A. S.; Fedorova, T. P.; Fedorov, I. A.

2017-04-01

The vibrational spectra of uranium dioxide UO2 and plutonium dioxide PuO2, as well as the one-phonon densities of states and thermal occupation number weighted two-phonon densities of states, have been calculated within the framework of the phenomenological rigid ion model. It has been shown that the acoustic and optical branches of the spectra are predominantly determined by vibrations of the metal and oxygen atoms, respectively, because the atomic masses of the metal and oxygen differ from each other by an order of magnitude. On this basis, the vibrational spectra can be represented in two Brillouin zones, i.e., in the Brillouin zone of the crystal and the Brillouin zone of the oxygen sublattice. In this case, the number of optical branches decreases by a factor of two. The two-phonon densities of states consist of two broad structured peaks. The temperature dependences of the upper peak exhibit a thermal broadening of the phonon lines L01 and L02 in the upper part of the optical branches. The lower peak is responsible for the thermal broadening of the lowest two optical (T02, T01) and acoustic (LA, TA) branches.

Chemical thermodynamic representations of and

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

Besmann, T.M.; Lindemer, T.B.

1984-01-01

All available oxygen potential-temperature-composition data for the calcium fluorite-structure phase were retrieved from the literature and utilized in the development of a binary solid solution representation of the phase. The data and phase relations are found to be best described by a solution of (Pu/sub 4/3/O/sub 2/) and (PuO/sub 2/) with a temperature dependent interaction energy. The fluorite-structure is assumed to be represented by a combination of the binaries and , and thus treated as a solution of (Pu/sub 4/3/O/sub 2/), (PuO/sub 2/), (UO/sub 2/), and either (U/sub 2/O/sub 4/./sub 5/) or (U/sub 3/O/sub 7/). The resulting equations wellmore » reproduce the large amount of oxygen potential-temperature-composition data for the mixed oxide system, all of which were also retrieved from the literature. These models are the first that appear to display the appropriate oxygen potential-temperature-composition and phase relation behavior over the entire range of existence for the phases. 39 refs., 10 figs., 3 tabs.« less

Development of spent fuel reprocessing process based on selective sulfurization: Study on the Pu, Np and Am sulfurization

NASA Astrophysics Data System (ADS)

Kirishima, Akira; Amano, Yuuki; Nihei, Toshifumi; Mitsugashira, Toshiaki; Sato, Nobuaki

2010-03-01

For the recovery of fissile materials from spent nuclear fuel, we have proposed a novel reprocessing process based on selective sulfurization of fission products (FPs). The key concept of this process is utilization of unique chemical property of carbon disulfide (CS2), i.e., it works as a reductant for U3O8 but works as a sulfurizing agent for minor actinides and lanthanides. Sulfurized FPs and minor actinides (MA) are highly soluble to dilute nitric acid while UO2 and PuO2 are hardly soluble, therefore, FPs and MA can be removed from Uranium and Plutonium matrix by selective dissolution. As a feasibility study of this new concept, the sulfurization behaviours of U, Pu, Np, Am and Eu are investigated in this paper by the thermodynamical calculation, phase analysis of chemical analogue elements and tracer experiments.

Supplemental Environmental Impact Statement, Guam and Commonwealth of the Northern Mariana Islands Military Relocation (2012 Roadmap Adjustments)

DTIC Science & Technology

2015-07-01

Improvements & Traffic Signal Activation RF C-32 UoG UoG Wind Turbine University Drive 2013 Complete A 70-foot (21.3 m) wind turbine RC C-33 UoG... turbine Talofofo 2013 Contract approved 15 MW solar / wind turbine farm to help power 2,200 homes P S-5 GovGuam GWA Santa Rita Springs Booster...Rehabilitation of Asan Springs P B X X B B B C-31 GovGuam Route 26/25 Intersection Improvements RF B B X X B B B C-32 UoG Wind Turbine P

Oxidizing dissolution mechanism of an irradiated MOX fuel in underwater aerated conditions at slightly acidic pH

NASA Astrophysics Data System (ADS)

Magnin, M.; Jégou, C.; Caraballo, R.; Broudic, V.; Tribet, M.; Peuget, S.; Talip, Z.

2015-07-01

The (U,Pu)O2 matrix behavior of an irradiated MIMAS-type (MIcronized MASter blend) MOX fuel, under radiolytic oxidation in aerated pure water at pH 5-5.5 was studied by combining chemical and radiochemical analyses of the alteration solution with Raman spectroscopy characterizations of the surface state. Two leaching experiments were performed on segments of irradiated fuel under different conditions: with or without an external γ irradiation field, over long periods (222 and 604 days, respectively). The gamma irradiation field was intended to be representative of the irradiation conditions for a fuel assembly in an underwater interim storage situation. The data acquired enabled an alteration mechanism to be established, characterized by uranium (UO22+) release mainly controlled by solubility of studtite over the long-term. The massive precipitation of this phase was observed for the two experiments based on high uranium oversaturation indexes of the solution and the kinetics involved depended on the irradiation conditions. External gamma irradiation accelerated the precipitation kinetics and the uranium concentrations (2.9 × 10-7 mol/l) were lower than for the non-irradiated reference experiment (1.4 × 10-5 mol/l), as the quantity of hydrogen peroxide was higher. Under slightly acidic pH conditions, the formation of an oxidized UO2+x phase was not observed on the surface and did not occur in the radiolysis dissolution mechanism of the fuel matrix. The Raman spectroscopy performed on the heterogeneous MOX fuel matrix surface, showed that the fluorite structure of the mainly UO2 phase surrounding the Pu-enriched aggregates had not been particularly impacted by any major structural change compared to the data obtained prior to leaching. For the plutonium, its behavior in solution involved a continuous release up to concentrations of approximately 3 × 10-6 mol L-1 with negligible colloid formation. This data appears to support a predominance of the +V oxidation state for plutonium in solution under highly oxidizing conditions. Furthermore, the Raman spectroscopy monitoring of the sample surface oxidation states did not point to any significant effect from the high Pu content of the aggregates (10-15%) and therefore did not indicate a better aggregate stability under radiolysis compared to the mainly UO2 matrix. This is because acidic pH conditions do not favor the development of oxidized layers on a fuel surface, with the exception of secondary phases.

Personal past experience with opioid consumption affects attitudes and knowledge related to pain management.

PubMed

Pud, Dorit

2004-12-01

The personal past experience with opioid consumption by hospital health care providers was examined for its influence on their attitudes toward and knowledge of pain management. Data were collected through a questionnaire that elicited demographic information, attitudes toward pain management, barriers to pain relief, and self-assessment of pain management knowledge. The sample ( N = 163) was divided into two groups according to past experience with opioids: 52% of participants had used opioids (UO) for pain relief in the past, and the rest had never done so (NO). UO participants noted that pain control treatment was not sufficient for pain relief, in contrast to NO participants ( p = .013). Pain management was considered a low priority relative to overall treatment by the UO group compared with the NO group ( p = .016). The former group also attributed major responsibility for inappropriate pain relief to the clinical staff (12% of the UO group vs. 1.4% of the NO group; p = .048) rather than to the patients (22.9% of the UO group vs. 32.9% of the NO group; p = .019). UO participants felt extremely competent in their ability to manage several aspects of pain therapy ( p < .05). These aspects included assessing cause of the pain (42.9% of the UO group vs. 29.3% of the NO group), selecting a starting dose for opioid therapy (26.9% of the UO group vs. 13.3% of the NO group), and using opioids intravenously (20.5% of the UO group vs. 8.3% of the NO group). Personal past experience regarding analgesic use is an important factor in evaluating attitudes toward pain and achieving optimal pain management outcomes.

The crystal structure of ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5: a possible phase for Pu 4+ incorporation during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Finch, Robert J.; Hawthorne, Frank C.; Miller, Mark L.; Ewing, Rodney C.

1997-10-01

Ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, is the only known uranyl oxide hydrate mineral that contains U 4+, and it has been proposed that ianthinite may be an important Pu 4+-bearing phase during the oxidative dissolution of spent nuclear fuel. The crystal structure of ianthinite, orthorhombic, a = 0.7178(2), b = 1.1473(2), c = 3.039(1) nm, V = 2.5027 nm 3Z = 4, space group P2 1cn, has been solved by direct methods and refined by least-squares methods to an R index of 9.7% and a wR index of 12.6% using 888 unique observed [| F| ≥ 5 σ | F|] reflections. The structure contains both U 4+. The U 6+ cations are present as roughly linear (U 6+O 2) 2+ uranyl ion (Ur) that are in turn coordinated by five O 2- and OH - located at the equatorial positions of pentagonal bipyramids. The U 4+ cations are coordinated by O 2-, OH - and H 2O in a distorted octahedral arrangement. The Ur φ5and U 4+| 6 (φ: O 2-, OH -, H 2O) polyhedra l sharing edges to for two symmetrically distinct sheets at z ≈ 0.0 and z ≈ 0.25 that are parallel to (001). The sheets have the β-U 3O 8 sheet anion-topology. There are five symmetrically distinct H 2O groips located at z ≈ 0.125 between the sheets of U φn polyhedra, and the sheets of U φn polyhedra are linked together only by hydrogen bonding to the intersheet H 2O groups. The crystal-chemical requirements of U 4+ and Pu 4+ are very similar, suggesting that extensive Pu 4+ ↔ U 4+ substitution may occur within the sheets of U φn polyhedra in trh structure of ianthinine.

Laboratory actinide partitioning - Whitlockite/liquid and influence of actinide concentration levels

NASA Technical Reports Server (NTRS)

Benjamin, T. M.; Jones, J. H.; Heuser, W. R.; Burnett, D. S.

1983-01-01

The partition coefficients between synthetic whitlockite (beta Ca-phosphate) and coexisting silicate melts are determined for the actinide elements Th, U and Pu. Experiments were performed at 1 bar pressure and 1250 C at oxygen fugacities from 10 to the -8.5 to 10 to the -0.7 bars, and partitioning was determined from trace element radiography combined with conventional electron microprobe analysis. Results show Pu to be more readily incorporated into crystalline phases than U or Th under reducing conditions, which is attributed to the observation that Pu exists primarily in the trivalent state, while U and Th are tetravalent. Corrected partition coefficients for whitlockite of 3.6, less than or equal to 0.6, 1.2, 0.5 and less than or equal to 0.002 are estimated for Pu(+3), Pu(+4), Th(+4), U(+4) and U(+6), respectively. Experiments performed at trace levels and percent levels of UO2 indicate that Si is involved in U substitution in whitlockite, and show a reduced partition coefficient at higher concentrations of U that can be explained by effects on melt structure or the fraction of tetravalent U.

Critical Safe Disposal of Spent Fuel: Behavior of Neutron Poisons

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

Kienzler, Bernhard; Gmal, Bernhard

2007-07-01

In contrast to Yucca Mountain, European repository concepts rely on deep underground conditions which guarantee permanently a reducing geochemical environment. As long as no water comes into contact with the disposed nuclear fuel, criticality is excluded by compliance with the disposal conditions (limitation of U/Pu in the canisters). Penetration of water into the canister may also be considered as a scenario. However, water in a disposal results in geochemical reactions proceeding over very long periods of time: (1) Presence of water allows the corrosion of the steel of the canister material forming hydrogen and iron corrosion products. (2) Hydrogen pressuresmore » affect the zircaloy cladding even at low temperatures. Failure of fuel cladding and spacers leads to changes in the geometrical configuration. (3) UO{sub 2} matrix corrosion results in geochemically controlled reformation of secondary phase. (4) Even if the dissolution rate of UO{sub 2} is low, elements accounting for burnup credit do not behave similar as uranium. Geochemical reactions are analyzed in detail and compositions are presented which have a high probability to be formed in the long-term needing to be analyzed with respect to K{sub eff}. (authors)« less

Topological analysis of void space in phosphate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4, and H 2

DOE PAGES

Cramer, Alisha J.; Cole, Jacqueline M.

2016-06-27

The entrapment of environmentally important materials to enable containment of polluting wastes from industry or energy production, storage of alternative fuels, or water sanitation, is of vital and immediate importance. Many of these materials are small molecules or ions that can be encapsulated via their adsorption into framework structures to create a host-guest complex. This is an ever-growing field of study and, as such, the search for more suitable porous materials for environmental applications is fundamental to progress. However, many industrial areas that require the use of adsorbents are fraught with practical challenges such as high temperatures, rapid gas expansion,more » radioactivity, or repetitive gas cycling, that the host material must withstand. Inorganic phosphates have a proven history of rigid structures, thermal stability, and are suspected to possess good resistance to radiation over geologic time scales. Furthermore, various experimental studies have established their ability to adsorb small molecules, such as water. In light of this, all known crystal structures of phosphate frameworks with meta- (P 3O 9) or ultra- (P 5O 14) stoichiometries are combined in a data-mining survey together with all theoretically possible structures of Ln aP bO c (where a, b, c are any integer, and Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, or Tm) that are statistically likely to form. Topological patterns within these framework structures are used to assess their suitability for hosting a variety of small guest molecules or ions that are important for environmental applications: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4 and H 2. A range of viable phosphate-based host-guest complexes are identified from this data-mining and pattern-based structural analysis. Moreover, distinct topological preferences for hosting such guests are found, and metaphosphate stoichiometries are generally preferred over ultraphosphate configurations.« less

Characterization of U/Pu Particles Originating From the Nuclear Weapon Accidents at Palomares, Spain, 1966 And Thule, Greenland, 1968

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

Lind, O.C.; Salbu, B.; Janssens, K.

2007-07-10

Following the USAF B-52 bomber accidents at Palomares, Spain in 1966 and at Thule, Greenland in 1968, radioactive particles containing uranium (U) and plutonium (Pu) were dispersed into the environment. To improve long-term environmental impact assessments for the contaminated ecosystems, particles from the two sites have been isolated and characterized with respect to properties influencing particle weathering rates. Low [239]Pu/[235]U (0.62-0.78) and [240]Pu/[239]Pu (0.055-0.061) atom ratios in individual particles from both sites obtained by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) show that the particles contain highly enriched U and weapon-grade Pu. Furthermore, results from electron microscopy with Energy Dispersive X-raymore » analysis (EDX) and synchrotron radiation (SR) based micrometer-scale X-ray fluorescence ({micro}-XRF) 2D mapping demonstrated that U and Pu coexist throughout the 1-50 {micro}m sized particles, while surface heterogeneities were observed in EDX line scans. SR-based micrometer-scale X-ray Absorption Near Edge Structure Spectroscopy ({micro}-XANES) showed that the particles consisted of an oxide mixture of U (predominately UO[2] with the presence ofU[3][8]) and Pu ((III)/(IV), (V)/(V) or (III), (IV) and (V)). Neither metallic U or Pu nor uranyl or Pu(VI) could be observed. Characteristics such as elemental distributions, morphology and oxidation states are remarkably similar for the Palomares and Thule particles, reflecting that they originate from similar source and release scenarios. Thus, these particle characteristics are more dependent on the original material from which the particles are derived (source) and the formation of particles (release scenario) than the environmental conditions to which the particles have been exposed since the late 1960s.« less

New measurement of the 242Pu(n,γ) cross section at n_TOF

NASA Astrophysics Data System (ADS)

Lerendegui-Marco, J.; Guerrero, C.; Cortés-Giraldo, M. A.; Quesada, J. M.; Mendoza, E.; Cano-Ott, D.; Eberhardt, K.; Junghans, A.

2016-03-01

The use of MOX fuel (mixed-oxide fuel made of UO2 and PuO2) in nuclear reactors allows substituting a large fraction of the enriched Uranium by Plutonium reprocessed from spent fuel. With the use of such new fuel composition rich in Pu, a better knowledge of the capture and fission cross sections of the Pu isotopes becomes very important. In particular, a new series of cross section evaluations have been recently carried out jointly by the European (JEFF) and United States (ENDF) nuclear data agencies. For the case of 242Pu, the two only neutron capture time-of-flight measurements available, from 1973 and 1976, are not consistent with each other, which calls for a new time-of flight capture cross section measurement. In order to contribute to a new evaluation, we have perfomed a neutron capture cross section measurement at the n_TOF-EAR1 facility at CERN using four C6D6 detectors, using a high purity target of 95 mg. The preliminary results assessing the quality and limitations (background, statistics and γ-flash effects) of this new experimental data are presented and discussed, taking into account that the aimed accuracy of the measurement ranges between 7% and 12% depending on the neutron energy region.

Comparisons of sodium void and Doppler reactivities in large oxide and carbide LMFBRs

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

Su, S F

Sodium void and Doppler reactivities in two full scale (3000 MWth) LMFBRs are analyzed; one is fueled with UO/sub 2/ - PuO/sub 2/ and the other is fueled with UC - PuC. These two reactors are analyzed for beginning of life as well as for beginning and end of equilibrium cycle conditions, and the variations of these two safety parameters with burnup are explained. A series of comperative analyses of these two and several hypothetical reactors are carried out to determine how differences in fuel type, sodium content, and heavy metal concentration between an oxide and a carbide reactor affectmore » their sodium void and Doppler reactivities. The effect of the presence of conrol poison on sodium void reactivity is also addressed.« less

A thermodynamic approach for advanced fuels of gas-cooled reactors

NASA Astrophysics Data System (ADS)

Guéneau, C.; Chatain, S.; Gossé, S.; Rado, C.; Rapaud, O.; Lechelle, J.; Dumas, J. C.; Chatillon, C.

2005-09-01

For both high temperature reactor (HTR) and gas cooled fast reactor (GFR) systems, the high operating temperature in normal and accidental conditions necessitates the assessment of the thermodynamic data and associated phase diagrams for the complex system constituted of the fuel kernel, the inert materials and the fission products. A classical CALPHAD approach, coupling experiments and thermodynamic calculations, is proposed. Some examples of studies are presented leading with the CO and CO 2 gas formation during the chemical interaction of [UO 2± x/C] in the HTR particle, and the chemical compatibility of the couples [UN/SiC], [(U, Pu)N/SiC], [(U, Pu)N/TiN] for the GFR system. A project of constitution of a thermodynamic database for advanced fuels of gas-cooled reactors is proposed.

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 were validated against DFT binding energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO 2, ThO 2, UO 2 and PuO 2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO 2 as well as advanced MOX fuels.« less

Rational Ligand Design for U(VI) and Pu(IV)

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

Szigethy, Geza

2009-08-12

Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interactionmore » of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO 2 2+). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these ligands exhibited increased uranyl affinity compared to bis-Me-3,2-HOPO ligands. This result is due in part to their increased denticity, but is primarily the result of the presence of the TAM moiety. In an effort to explore the relatively unexplored coordination chemistry of Pu(IV) with bidentate moieties, a series of Pu(IV) complexes were also crystallized using bidentate hydroxypyridinone and hydroxypyrone ligands. The geometries of these complexes are compared to that of the analogous Ce(IV) complexes. While in some cases these showed the expected structural similarities, some ligand systems led to significant coordination changes. A series of crystal structure analyses with Ce(IV) indicated that these differences are most likely the result of crystallization condition differences and solvent inclusion effects.« less

Prognostic implications of adding urine output to serum creatinine measurements for staging of acute kidney injury after major surgery: a cohort study.

PubMed

Quan, Samuel; Pannu, Neesh; Wilson, Todd; Ball, Chad; Tan, Zhi; Tonelli, Marcello; Hemmelgarn, Brenda R; Dixon, Elijah; James, Matthew T

2016-12-01

Current guidelines recommend staging acute kidney injury (AKI) according to the serum creatinine (SCr) or urine output (UO) criteria that achieve the highest stage. There is little information about the implications of adding UO to SCr measurements for staging AKI outside intensive care units and after cardiac surgery. We performed a cohort study of all adults without end-stage renal disease who underwent major noncardiac surgery between January 2005 and March 2011 in Calgary, AB, Canada. Participants required at least two SCr and UO measurements to be included. We examined the implications of adding UO to SCr to stage AKI based on Kidney Disease: Improving Global Outcomes criteria. Logistic and linear regression models were used to examine the associations between AKI stage and 30-day mortality or hospital length of stay (LOS), respectively. A total of 4229 (17%) surgical patients had sufficient SCr and UO measurements for inclusion in the cohort. The apparent incidence of postoperative AKI substantially increased with the addition of UO to SCr criteria (8.1% with SCr alone versus 64.0% with SCr and UO). Mortality for a given stage of AKI was lower when UO was added to SCr criteria (0.3, 3.2, 1.9 and 3.0% for no AKI and Stages 1, 2 and 3, respectively) versus with SCr alone (1.2, 4.2, 15.4 and 12.8%). However, among participants without AKI based on the SCr criterion, the odds of mortality and mean LOS both significantly increased with lower UO. Models that reclassified AKI stage based on UO in addition SCr criteria had the best discrimination for mortality and LOS. Adding UO to SCr criteria substantially increases the apparent incidence of AKI on hospital wards and significantly changes the prognostic implications of AKI identification and staging. These measures should not be considered equivalent criteria in AKI staging. © The Author 2016. Published by Oxford University Press on behalf of ERA-EDTA. All rights reserved.

Characterization of un-irradiated MIMAS MOX fuel by Raman spectroscopy and EPMA

NASA Astrophysics Data System (ADS)

Talip, Zeynep; Peuget, Sylvain; Magnin, Magali; Tribet, Magaly; Valot, Christophe; Vauchy, Romain; Jégou, Christophe

2018-02-01

In this study, Raman spectroscopy technique was implemented to characterize un-irradiated MIMAS (MIcronized - MASter blend) MOX fuel samples with average 7 wt.% Pu content and different damage levels, 13 years after fabrication, one year after thermal recovery and soon after annealing, respectively. The impacts of local Pu content, deviation from stoichiometry and self-radiation damage on Raman spectrum of the studied MIMAS MOX samples were assessed. MIMAS MOX fuel has three different phases Pu-rich agglomerate, coating phase and uranium matrix. In order to distinguish these phases, Raman results were associated with Pu content measurements performed by Electron Microprobe Analysis. Raman results show that T2g frequency significantly shifts from 445 to 453 cm-1 for Pu contents increasing from 0.2 to 25 wt.%. These data are satisfactorily consistent with the calculations obtained with Gruneisen parameters. It was concluded that the position of the T2g band is mainly controlled by Pu content and self-radiation damage. Deviation from stoichiometry does not have a significant influence on T2g band position. Self-radiation damage leads to a shift of T2g band towards lower frequency (∼1-2 cm-1 for the UO2 matrix of damaged sample). However, this shift is difficult to quantify for the coating phase and Pu agglomerates given the dispersion of high Pu concentrations. In addition, 525 cm-1 band, which was attributed to sub-stoichiometric structural defects, is presented for the first time for the self-radiation damaged MOX sample. Thanks to the different oxidation resistance of each phase, it was shown that laser induced oxidation could be alternatively used to identify the phases. It is demonstrated that micro-Raman spectroscopy is an efficient technique for the characterization of heterogeneous MOX samples, due to its low spatial resolution.

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.

Closed DTU fuel cycle with Np recycle and waste transmutation

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

Beller, D.E.; Sailor, W.C.; Venneri, F.

1999-09-01

A nuclear energy scenario for the 21st century that included a denatured thorium-uranium-oxide (DTU) fuel cycle and new light water reactors (LWRs) supported by accelerator-driven transmutation of waste (ATW) systems was previously described. This coupled system with the closed DTU fuel cycle provides several improvements beyond conventional LWR (CLWR) (once-through, UO{sub 2} fuel) nuclear technology: increased proliferation resistance, reduced waste, and efficient use of natural resources. However, like CLWR fuel cycles, the spent fuel in the first one-third core discharged after startup contains higher-quality Pu than the equilibrium fuel cycle. To eliminate this high-grade Pu, Np is separated and recycledmore » with Th and U--rather than with higher actinides [(HA) including Pu]. The presence of Np in the LWR feed greatly increases the production of {sup 238}Pu so that a few kilograms of Pu generated enough alpha-decay heat that the separated Pu is highly resistant to proliferation. This alternate process also simplifies the pyrochemical separation of fuel elements (Th and U) from HAs. To examine the advantages of this concept, the authors modeled a US deployment scenario for nuclear energy that includes DTU-LWRs plus ATW`s to burn the actinides produced by these LWRs and to close the back-end of the DTU fuel cycle.« less

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

Ultra-small plutonium oxide nanocrystals: an innovative material in plutonium science.

PubMed

Hudry, Damien; Apostolidis, Christos; Walter, Olaf; Janssen, Arne; Manara, Dario; Griveau, Jean-Christophe; Colineau, Eric; Vitova, Tonya; Prüssmann, Tim; Wang, Di; Kübel, Christian; Meyer, Daniel

2014-08-11

Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non-conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium-based nanomaterials. Here we show that ultra-small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2 ) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2 (NO3 )2 ]⋅3 H2 O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X-ray diffraction (PXRD), X-ray absorption fine structure (XAFS), X-ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous UO2 fuel irradiated up to a high burn-up: Investigation of the HBS and of fission product releases

NASA Astrophysics Data System (ADS)

Noirot, J.; Lamontagne, J.; Nakae, N.; Kitagawa, T.; Kosaka, Y.; Tverberg, T.

2013-11-01

A UO2 fuel with a heterogeneous distribution of 235U was irradiated up to a high burn-up in the Halden Boiling Water Reactor (HBWR). The last 100 days of irradiation were performed with an increased level of linear power. The effect of the heterogeneous fissile isotope distribution on the formation of the HBS was studied free of the possible influence of Pu which exists in heterogeneous MOX fuels. The HBS formed in 235U-rich agglomerates and its main characteristics were very similar to those of the HBS formed in Pu-rich agglomerates of heterogeneous MOX fuels. The maximum local contents of Nd and Xe before HBS formation were studied in this fuel. In addition to a Pu effect that promotes the HBS phenomenon, comparison with previous results for heterogeneous MOX fuels showed that the local fission product concentration was not the only parameter that has to be taken into consideration. It appears that the local actinide depletion by fission and/or the energy locally deposited through electronic interactions in the fission fragment recoils also have an effect on the HBS formation threshold. Moreover, a major release of fission gases from the peripheral 235U-rich agglomerates of HBS bubbles and a Cs radial movement are also evidenced in this heterogeneous UO2. Cs deposits on the peripheral grain boundaries, including the HBS grain boundaries, are considered to reveal the release paths. SUP>235U-rich agglomerates, SUP>235U-poor areas, an intermediate phase with intermediate 235U concentrations. Short fuel rods were fabricated with these pellets. The main characteristics of these fuel rods are shown in Table 1.These rods were irradiated to high burn-ups in the IFA-609/626 of the HBWR and then one was irradiated in the IFA-702 for 100 days. Fig. 2 shows the irradiation history of this fuel. The final average burn-up of the rod was 69 GWd/tU. Due to the flux differences along the rod, however, the average burn-up of the cross section examined was 63 GWd/tU. This fuel experienced high linear powers during the first year of irradiation, but at the end of the IFA-609/626 period, the average linear power of the rod was around 12 kW/m. In the IFA-702, the power was gradually increased over 7 days from 12 kW/m to 22.5 kW/m before it was decreased again to reach ˜19 kW/m at the end of the 100 days forming this part of the irradiation. A LEICA (DM RXA2) optical microscope. A shielded electronic microprobe (EPMA) SX-100R by CAMECA. A shielded scanning electron microscope (SEM): the Philips XL30. Image acquisitions were performed using the ADDA "SIS" system with the AnalySIS software for image analysis. A shielded secondary ion mass spectrometer (SIMS): the CAMECA IMS 6f was capable of analysing the same samples as the SEM and EPMA [16-22]. In the central part of the pellet for all three phases, Xe precipitated into bubbles with very little Xe remaining outside the bubbles. Some Xe-filled bubbles were detected under the surface in this area. They appear as bright spots. Around mid-radius on the periphery of the 235U-poor areas and in the intermediate phase, Xe was depleted on the periphery of the grains. This depletion was not associated with Xe-filled bubbles that would be detected under the polished surface. Moreover, no large intergranular open bubbles were visible. Therefore, this missing gas must have been released. In the 235U-rich agglomerates all over the section, Xe precipitated into bubbles with very little Xe remaining outside the bubbles. The Xe quantitative analyses through 235U-rich agglomerates on the pellet periphery (Fig. 9) confirmed the low quantity of Xe remaining outside the bubbles. This Xe content was around 0.1 wt%. Fig. 10 shows the Xe and Nd EPMA quantitative measurements along a radius of the cross section. In this figure and in Fig. 9, the weight percentage scales were set so that the two profiles would be almost identical without Xe release or precipitation. Along the Xe axis, the Nd profile can be considered as the local Xe production. Fig. 10 shows that the Xe measurement all through the central part is low except for a few points corresponding to unopened but close to the polished surface and detected by EPMA. These points correspond to the bright spots detected in the central part in Fig. 8. High concentrations were detected locally all over the radius on the Nd profile. They correspond to the 235U-rich agglomerates or their surroundings. Outside the central part, these high Nd concentrations correspond to low Xe concentrations, consistent with the maps in Fig. 8 and the detailed analyses across large 235U-rich agglomerates (Fig. 9).Fig. 11 shows a set of Xe (wt%) and (145Nd + 146Nd)/heavy metal radial profiles both acquired by SIMS. Three profiles are show for each set: one in the 235U-rich agglomerates, one in the 235U-poor areas and one in the intermediate phase. The three phases are not homogeneous themselves. This induces differences between (145Nd + 146Nd)/HM SIMS measurement points of a given phase. The (145Nd + 146Nd)/HM results are a reference for the Xe measurements, giving an estimation of the relative Xe local production. The (145Nd + 146Nd)/HM was high in the 235U-rich agglomerates, lower in the intermediate phase and even lower in the 235U-poor areas. Differences similar to those obtained herein between the phases would have been found in the Xe measurements if no release had occurred in any of those phases. The Xe (wt%) results show that this is not the case. The Xe measurements were quite similar in the intermediate phase and in the 235U-poor areas; they would have been higher in the intermediate phase if no release had occurred. The Xe measurements in the 235U-rich agglomerates were very low and lower than in the two other phases. For the 235U-rich agglomerates, there was a very big difference, across the entire radius, between the Xe measured and the Xe local production.In the SIMS Xe measurements, local depth profiles show peaks on a base line [19]. The base line corresponds to the solid solution Xe and to the nano-bubbles. The peaks correspond to Xe in larger bubbles opened by ion beam fuel sputtering. The SIMS total values correspond to the Xe outside these bubbles plus the Xe trapped in these bubbles.Fig. 12 shows the total Xe SIMS results (already shown in Fig. 11) together with the base line measurements for each measurement point and in separate graphs for each phase. The Xe EPMA quantitative measurements used as a background for these three graphs are the same as those in Fig. 10 and are the same for the three graphs, without any phase distinction. The SIMS Xe relative measurements were calibrated through a correspondence between the SIMS base line results and the EPMA measurements [20]. As expected, the SIMS base line profile was consistent with the EPMA all along the profile for each corresponding phase. For example, the SIMS base line in the 235U-rich agglomerates corresponds to the low EPMA measurement points of the Xe in this zone, i.e. the points of the EPMA profile in the 235U-rich agglomerates. By way of comparison between the Xe and the Nd measurements (the latter being rescaled to be representative of the creation level of Xe), Fig. 11 made it possible to identify two main parts on the Xe SIMS radius: The central part 0R to ˜0.5R: In the intermediate phase and the 235U-poor areas, the SIMS total was used to identify this part as a release area. The average fraction of gas measured in the bubbles (the ratio between the gas in the bubbles and the total measurement) was between 60% and 90%. The Xe content outside the bubbles was very low. In the 235U-rich agglomerates, the SIMS total represents only a small fraction of the produced Xe, which means that a large fraction of the Xe is released or not detected by SIMS due to the large size of some agglomerate bubbles compared with the volume of the crater analysed. sim;0.5R to ˜1R: The 235U-poor areas are not release areas. The fraction of gas in bubbles measured in these areas remained low, ˜5%. The intermediate phase is a release area with moderate release. The average fraction of gas measured in the bubbles was around 20%. In the 235U-rich agglomerates, the Xe SIMS total was very low. This part is a release area. Sharp transitions between initial microstructure and the HBS, often inside one grain. Increase in the resulting grain size with increasing distance from the pellet periphery. The grain sizes are in fact consistent with the MOX measurements [2]. Increase in the bubble size with the increasing distance from the pellet periphery, consistent with the MOX measurements. Smaller bubbles tend to be found in the peripheral part of the 235U-rich agglomerates rather than in their central part. Sharp transition, around 0.5R, between the peripheral area where the conventional form of HBS forms in the 235U-rich agglomerates and the central part where much larger bubbles form and where the grain size is also clearly larger. Xe concentration of 0.1 wt% outside the bubbles in the HBS areas is consistent with the [2] MOX measurements at equivalent local burn-ups. The heterogeneous MOX fuels examinations have firmly established that the HBS can extend outside the Pu-rich agglomerates due to the implantation of fission products around these agglomerates. Similarly, it has been shown that the small Pu-rich agglomerates can remain with the initial microstructure even if there is a similar actual local burn-up, a large rate of fission products being implanted outside the agglomerates themselves so that the local fission product concentration remains low.In this 235U heterogeneous UO2, the Xe and Nd concentration levels reached at the HBS formation limit ranged between 0.8 wt% and 1.1 wt% for Xe and between 0.63 wt% and 0.83 wt% for Nd. These ranges are similar to what was reported in [23] for the UO2 rim. These limits are, however, slightly higher than those found for Pu-rich agglomerates in heterogeneous MOX fuels in [2] or in [24]. Nonetheless, they are clearly lower than the concentrations reached without HBS in the special Pu-poor spots in [2]. In these spots, UO2 particles in heterogeneous MOX were really close or even surrounded by Pu-rich areas. As a result, their fission product content, due to recoil, was almost the same as that in the surrounding Pu-rich agglomerates themselves despite a very low actual local burn-up. In these special UO2 spots in MOX fuel, 1.4 wt% was reached for Xe and no HBS formed.If these high Xe concentrations without HBS in the special spots in [2] were made possible by the very low Pu local concentration only, very high Xe concentrations should have been common around the heterogeneous UO2 fuel 235U-rich agglomerates, since the Pu level was low everywhere in this fuel. This is not what was observed.Even if this effect due to a high fission product level reached without the formation of a HBS (as reported in [2] for heterogeneous MOX fuels in the special spots) is partially due to the very low local Pu level, it does not seem to be the only reason. It also seems to be partly due to the very low level of actual fissions occurring there. Between a rich agglomerate and such a highly implanted area there is: The same local fission product build-up and associated damage (due to cascades from the nuclei interactions during the last part of the fission fragment recoil). A large difference in the actinide isotope depletion to the extent that a difference in chemical composition exists between the two. A difference in the electronic excitation level at the beginning of the fission fragment recoil, higher in Pu agglomerates and in 235U-rich agglomerates than in the low fissile content areas, even surrounded by rich areas. The last two points may have an effect on the formation of a HBS though this paper cannot say which one is the most significant.The highest levels reached for Xe and Nd without HBS in the 235U heterogeneous fuel are very likely to correspond to places where the initial 235U content was particularly low but where fission recoil led to these high levels. The maximum concentrations of fission products reached before the formation of a HBS in the 235U heterogeneous fuel are lower than for the heterogeneous MOX special Pu-poor spots. This is most certainly due to the local 235U initial concentration in the 235U-poor areas which is nonetheless high when compared with the initial Pu concentrations in the Pu-poor areas in the MOX fuel. Consequently, there are more fission reactions there in the heterogeneous UO2 fuel than in the MOX fuel.This fission and/or fission spike effect has in fact little impact on the overall fuel behaviour, be it homogeneous or heterogeneous, but it has to be taken into account in the separate-effect experiments where unirradiated UO2 is submitted to ion irradiation to simulate the irradiation effects [9,25-30]. The depletion of the actinide isotopes cannot be simulated in these experiments. The IFA-702 re-irradiation, with the high power during the last period of the irradiation most certainly having played a role. The other major difference between this fuel was irradiated under BWR conditions, whereas those used in [2] were all PWR fuels. The images of the IFA-702 heterogeneous UO2 fuel on the periphery show that an internal zirconia layer was formed during the irradiation, which is a sign of gap closure under hot conditions, though a thin gap was still measured at room temperature. Therefore, the stress field in the pellet of this fuel must have been significantly different from that of the fuel used in [2]. The resulting release is all the more interesting since the release path is more or less revealed by the Cs deposits. This Cs is released from the hot central part of the pellet and is not only in the fuel-cladding gap and along the obvious radial cracks, but also in: All the grain boundaries around those radial cracks. The HBS 235U-rich agglomerates around those radial cracks. Like for Xe, the general trend for Cs was a release from the 235U peripheral agglomerates. The higher Cs measurement in the 235U-rich agglomerates close to the radial cracks results from both this release and the deposition of the Cs released from the hot central part.This singular release of Xe from the HBS bubbles of the 235U-rich agglomerates on the fuel periphery is all the more surprising that the Pu-rich agglomerates of the MIMAS MOX fuel irradiated under the same conditions [15] retained their fission gases in these areas. We found no definitive reason for that difference. the fission product implantation level has an effect. the local Pu content has also an effect. the actual local burn-up has an effect. This effect may be linked to fission through the local depletion of the fissile isotopes which changes the local chemical composition, as well as to the higher energy deposited there by electronic interactions at the beginning of the fission fragment recoils when compared with implanted areas with a low actual burn-up. Moreover, the major release of fission gases from the peripheral 235U-rich agglomerate HBS bubbles was evidenced in this heterogeneous UO2 fuel.The radial movement of Cs from the central part of the pellet towards its periphery was shown. This involved a deposition at the grain boundaries, including the HBS ones, around the radial cracks in the periphery. This showed the intergranular paths existing for the release of fission gases and Cs all through the fuel periphery. Grain Equivalent Circular Diameter (ECD) for which half of the surface is made of smaller grains and half of larger grains

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

Uranyl Coordination Polymers Incorporating η5-Cyclopentadienyliron-Functionalized η6-Phthalate Metalloligands: Syntheses, Structures and Photophysical Properties

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

Kerr, Andrew T.; Kumalah, Sayon A.; Holman, K. T.

2013-10-06

The reaction of two η5-cyclopentadienyliron(II)-functionalized terephthalate and phthalate metalloligands, namely [(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2)][PF6] and [(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2)][PF6]—hereafter [H2 CpFeTP][HCpFeTP][PF6] and [H2 CpFeP][HCpFeP][PF6], respectively—with [UO2(NO3)2]·6H2O under hydrothermal conditions yielded four new coordination polymers; (1) [(UO2)F(HCpFeTP)(PO4H2)]·2H2O, (2) [(UO2)2(CpFeTP)4]·5H2O, (3) [(UO2)2F3(H2O)(CpFeP)], and (4) [H2 CpFeP][UO2F3]. The use of metalloligands has proven to be a viable route towards the incorporation of a secondary metal center into uranyl bearing materials. Depending upon the protonation state, the iron sandwich metalloligands may vary from zwitterionic neutral or monoanionic coordinating species as observed in compounds 1–3, or a positively charged species that hydrogen bonds with anionic [UO2F3]- chains as observed in 4.more » Further, the hydrolysis of the charge balancing PF6 - anion increases the diversity of UO2 2+ coordinating species by contributing both F- and PO4 3- anions (1, 3, 4). The luminescent properties of 1–4 were also studied and revealed the absence of uranyl emission, suggestive of a possible energy transfer from the uranyl cation to the iron(II) metal center.« less

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.

Soft X-ray scanning transmission X-ray microscopy (STXM) of actinide particles.

PubMed

Nilsson, Hans J; Tyliszczak, Tolek; Wilson, Richard E; Werme, Lars; Shuh, David K

2005-09-01

A descriptive account is given of our most recent research on the actinide dioxides with the Advanced Light Source Molecular Environmental Science (ALS-MES) Beamline 11.0.2 soft X-ray scanning transmission X-ray microscope (STXM) at the Lawrence Berkeley National Laboratory (LBNL). The ALS-MES STXM permits near-edge X-ray absorption fine structure (NEXAFS) and imaging with 30-nm spatial resolution. The first STXM spectromicroscopy NEXAFS spectra at the actinide 4d5/2 edges of the imaged transuranic particles, NpO2 and PuO2, have been obtained. Radiation damage induced by the STXM was observed in the investigation of a mixed oxidation state particle (Np(V,VI)) and was minimized during collection of the actual spectra at the 4d5/2 edge of the Np(V,VI) solid. A plutonium elemental map was obtained from an irregular PuO2 particle with the dimensions of 650 x 650 nm. The Pu 4d5/2 NEXAFS spectra were collected at several different locations from the PuO2 particle and were identical. A representative oxygen K-edge spectrum from UO2 was collected and resembles the oxygen K-edge from the bulk material. The unique and current performance of the ALS-MES STXM at extremely low energies (ca. 100 eV) that may permit the successful measurement of the actinide 5d edge is documented. Finally, the potential of STXM as a tool for actinide investigations is briefly discussed.

PROCESS OF MAKING A NEUTRONIC REACTOR FUEL ELEMENT COMPOSITION

DOEpatents

Alter, H.W.; Davidson, J.K.; Miller, R.S.; Mewherter, J.L.

1959-01-13

A process is presented for making a ceramic-like material suitable for use as a nuclear fuel. The material consists of a solid solution of plutonium dioxide in uranium dioxide and is produced from a uranyl nitrate -plutonium nitrate solution containing uraniunm and plutonium in the desired ratio. The uranium and plutonium are first precipitated from the solution by addition of NH/ sub 4/OH and the dried precipitate is then calcined at 600 C in a hydrogen atmosphere to yield the desired solid solution of PuO/sub 2/ in UO/sub 2/.

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

USGS Publications Warehouse

Fox, P.M.; Davis, J.A.; Zachara, J.M.

2006-01-01

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO2 (CO3)32- and Ca2 UO2(CO3)30(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO3 solutions equilibrated with either ambient air (430 ppm CO2) or 2% CO2 in the presence of 0, 1.8, or 8.9 mM Ca2+. Under conditions where the Ca2UO2(CO3)30 (aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca2UO2(CO3)30(aq) accurately simulated the effect of Ca2+ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca2+ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers. ?? 2005 Elsevier Inc. All rights reserved.

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.

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

Kristo, Michael Joseph; Keegan, Elizabeth; Colella, Michael

Nuclear forensic analysis was conducted on two uranium samples confiscated during a police investigation in Victoria, Australia. The first sample, designated NSR-F-270409-1, was a depleted uranium powder of moderate purity (~1000 μg/g total elemental impurities). The chemical form of the uranium was a compound similar to K 2(UO 2) 3O 4·4H 2O. While aliquoting NSR-F-270409-1 for analysis, the body and head of a Tineid moth was discovered in the sample. The second sample, designated NSR-F-270409-2, was also a depleted uranium powder. It was of reasonably high purity (~380 μg/g total elemental impurities). The chemical form of the uranium was primarilymore » UO 3·2H 2O, with minor phases of U 3O 8 and UO 2. While aliquoting NSR-F-270409-2 for analysis, a metal staple of unknown origin was discovered in the sample. The presence of 236U and 232U in both samples indicates that the uranium feed stocks for these samples experienced a neutron flux at some point in their history. The reactor burn-up calculated from the isotopic composition of the uranium is consistent with that of spent fuel from natural uranium (NU) fueled Pu production. These nuclear forensic conclusions allow us to categorically exclude Australia as the origin of the material and greatly reduce the number of candidate sources.« less

Sequestration of radioactive iodine in silver-palladium phases in commercial spent nuclear fuel

NASA Astrophysics Data System (ADS)

Buck, Edgar C.; Mausolf, Edward J.; McNamara, Bruce K.; Soderquist, Chuck Z.; Schwantes, Jon M.

2016-12-01

Radioactive iodine is the Achilles' heel in the design for the safe geological disposal of spent uranium oxide (UO2) nuclear fuel. Furthermore, iodine's high volatility and aqueous solubility were mainly responsible for the high early doses released during the accident at Fukushima Daiichi in 2011. Studies Kienzler et al., however, have indicated that the instant release fraction (IRF) of radioiodine (131/129I) does not correlate directly with increasing fuel burn-up. In fact, there is a peak in the release of iodine at around 50-60 MW d/kgU, and with increasing burn-up, the IRF of 131/129I decreases. The reasons for this decrease have not fully been understood. We have performed microscopic analysis of chemically processed high burn-up UO2 fuel (80 MW d/kgU) and have found recalcitrant nano-particles containing, Pd, Ag, I, and Br, possibly consistent with a high pressure phase of silver iodide in the undissolved residue. It is likely that increased levels of Ag and Pd from 239Pu fission in high burnup fuels leads to the formation of these metal halides. The occurrence of these phases in UO2 nuclear fuels may reduce the impact of long-lived 129I on the repository performance assessment calculations.

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

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.

Variations of uranium concentrations in a multi-aquifer system under the impact of surface water-groundwater interaction

NASA Astrophysics Data System (ADS)

Wu, Ya; Li, Junxia; Wang, Yanxin; Xie, Xianjun

2018-04-01

Understanding uranium (U) mobility is vital to minimizing its concentrations in potential drinking water sources. In this study, we report spatial-seasonal variations in U speciation and concentrations in a multi-aquifer system under the impact of Sanggan River in Datong basin, northern China. Hydrochemical and H, O, Sr isotopic data, thermodynamic calculations, and geochemical modeling are used to investigate the mechanisms of surface water-groundwater mixing-induced mobilization and natural attenuation of U. In the study site, groundwater U concentrations are up to 30.2 μg/L, and exhibit strong spatial-seasonal variations that are related to pH and Eh values, as well as dissolved Ca2+, HCO3-, and Fe(III) concentrations. For the alkaline aquifers of this site (pH 7.02-8.44), U mobilization is due to the formation and desorption of Ca2UO2(CO3)30 and CaUO2(CO3)32- caused by groundwater Ca2+ elevation via mineral weathering and Na-Ca exchange, incorporated U(VI) release from calcite, and U(IV) oxidation by Fe(OH)3. U immobilization is linked to the adsorption of CaUO2(CO3)32- and UO2(CO3)34- shifted from Ca2UO2(CO3)30 because of HCO3- elevation and Ca2+ depletion, U(VI) co-precipitation with calcite, and U(VI) reduction by adsorbed Fe2+ and FeS. Those results are of great significance for the groundwater resource management of this and similar other surface water-groundwater interaction zones.

Time-resolved infrared reflectance studies of the dehydration-induced transformation of uranyl nitrate hexahydrate to the trihydrate form

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-09-08

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO 2(NO 3) 2(H 2O) 6] often called UNH), the trihydrate [UO 2(NO 3) 2(H 2O) 3 or UNT], and in very dry environments the dihydrate form [UO 2(NO 3) 2(H 2O) 2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples formore » transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N 2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO 2(NO 3) 2(H 2O) 6 has a distinct uranyl asymmetric stretch band at 949.0 cm –1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm –1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a structural and morphological change that has the lustrous lime green UO 2(NO 3) 2(H 2O) 6 crystals changing to the matte greenish yellow of the trihydrate solid. As a result, the phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate.« less

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

Sintering Uranium Dioxide of Domestic Production. Report No. 78; SINTERIZACION DE DIOXIDO DE URANIO DE PRODUCCION NACIONAL. Informe No. 78

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

Carrea, A.J.

1963-01-01

After a brief indication of the uranium- oxygen equilibrium and the methods for the preparation of UO/sub 2/, the sintering of UO/sub 2/ is considered. The effects of various sintering atmospheres on the properties of the product are discussed and tabulated. The method used for the processing of domestic ores for the preparation of UO/sub 2/ and the fabricition of the sintered UO/sub 2/are described. The properties of the product obtained are illustrated graphically. (J.S.R.)

Sequestration of radioactive iodine in silver-palladium phases in commercial spent nuclear fuel

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

Buck, Edgar C.; Mausolf, Edward J.; McNamara, Bruce K.

Radioactive iodine is the Achilles’ heel in the design for the safe geological disposal of spent UO2 nuclear fuel. Iodine’s high solubility and anticipated instant release during waste package compromise jeopardize performance assessment calculations. However, dissolution studies have indicated that the instant release fraction (IRF) of radioiodine (I) does not correlate with increasing fuel burn-up. In fact, there is a peak in the release iodine at around 50-60 Mwd/kgU and with increasing burn-up the instant release of iodine decreases. Detailed electron microscopy analysis of high burn-up fuel (~80 MWd/kgU) has revealed the presence of (Pd,Ag)(I,Br) nano-particles. As UO2 fuels aremore » irradiated, the Ag and Pd content increases, from 239Pu fission, enabling radioiodine to be retained. The occurrence of these phases in nuclear fuels may have significant implications for the long-term behavior of iodine.« less

Update of the α - n Yields for Reactor Fuel Materials for the Interest of Nuclear Safeguards

NASA Astrophysics Data System (ADS)

Simakov, S. P.; van den Berg, Q. Y.

2017-01-01

The neutron yields caused by spontaneous α-decay of actinides and subsequent (α,xn) reactions were re-evaluated for the reactor fuel materials UO2, UF6, PuO2 and PuF4. For this purpose, the most recent reference data for decay parameters, α-particle stopping powers and (α,xn) cross sections were collected, analysed and used in calculations. The input data and elaborated code were validated against available thick target neutron yields in pure and compound materials measured at accelerators or with radioactive sources. This paper provides the specific neutron yields and their uncertainties resultant from α-decay of actinides 241Am, 249Bk, 252Cf, 242,244Cm, 237Np, 238-242Pu, 232Th and 232-236,238U in oxide and fluoride compounds. The obtained results are an update of previous reference tables issued by the Los Alamos National Laboratory in 1991 which were used for the safeguarding of radioactive materials by passive non-destructive techniques. The comparison of the updated values with previous ones shows an agreement within one estimated uncertainty (≈ 10%) for oxides, and deviations of up to 50% for fluorides.

Integrated Structural/Control Design via Multiobjective Optimization

DTIC Science & Technology

1990-05-10

motivation is to yield a tractable 0 problem whose solution is readily synthesized and easily implemented. Likewise, the combinatorial approaches to...stations PsI, Ps2, Ps3, Ps4 on arms 3 and 4 and stations Ps5, Ps6, Ps7, Ps8 on arms I and 2. The sensor influence matrix H is 1 oT 0T 0 UoT (psi) T H= 0...t, Ps4 ), v (t,psS) ..... v (t,Ps8) ] T (4-30a) -V = Yp (4-30b) The locations Pul and Pu2 of the torque actuators and Psi, Ps2 .... Ps8 of the sensors

Nuclear forensic analysis of uranium oxide powders interdicted in Victoria, Australia

DOE PAGES

Kristo, Michael Joseph; Keegan, Elizabeth; Colella, Michael; ...

2015-04-13

Nuclear forensic analysis was conducted on two uranium samples confiscated during a police investigation in Victoria, Australia. The first sample, designated NSR-F-270409-1, was a depleted uranium powder of moderate purity (~1000 μg/g total elemental impurities). The chemical form of the uranium was a compound similar to K 2(UO 2) 3O 4·4H 2O. While aliquoting NSR-F-270409-1 for analysis, the body and head of a Tineid moth was discovered in the sample. The second sample, designated NSR-F-270409-2, was also a depleted uranium powder. It was of reasonably high purity (~380 μg/g total elemental impurities). The chemical form of the uranium was primarilymore » UO 3·2H 2O, with minor phases of U 3O 8 and UO 2. While aliquoting NSR-F-270409-2 for analysis, a metal staple of unknown origin was discovered in the sample. The presence of 236U and 232U in both samples indicates that the uranium feed stocks for these samples experienced a neutron flux at some point in their history. The reactor burn-up calculated from the isotopic composition of the uranium is consistent with that of spent fuel from natural uranium (NU) fueled Pu production. These nuclear forensic conclusions allow us to categorically exclude Australia as the origin of the material and greatly reduce the number of candidate sources.« less

Synthesis and structure of R{sub 2}[UO{sub 2}(NO{sub 3}){sub 2}(NCS){sub 2}] (R = Rb or Cs)

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

Serezhkin, V. N., E-mail: lserezh@samsu.ru; Peresypkina, E. V.; Grigor’eva, V. A.

2015-01-15

Crystals Rb{sub 2}[UO{sub 2}(NO{sub 3}){sub 2}(NCS){sub 2}] (I) and Cs{sub 2}[UO{sub 2}(NO{sub 3}){sub 2}(NCS){sub 2}] (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction. Crystals I are monoclinic, with the following parameters: a = 12.2118(5) Å, b = 10.2545(3) Å, c = 11.8754(4) Å, β = 110.287(1)°, sp. gr. C2/c, Z = 4, and R = 0.0523. Crystals II are orthorhombic, with a = 13.7309(3) Å, b = 10.5749(2) Å, c = 10.1891(2) Å, sp. gr. Pnma, Z = 4, and R = 0.0411. The basic structural units of crystals I and II are one-core complexes [UO{submore » 2}(NO{sub 3}){sub 2}(NCS){sub 2}]{sup 2−}, which belong to the crystallochemical group cis-AB{sub 2}{sup 01}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = NO{sub 3}{sup −}, M{sup 1} = NCS{sup −}), which are combined into a framework via electrostatic interactions with ions of alkaline metals R (R = Rb or Cs). The structural features of crystals I and II, which condition the formation of [UO{sub 2}(NO{sub 3}){sub 2}(NCS){sub 2}]{sup 2−} complexes with a cis rather than a trans position of isothiocyanate ions in the coordination sphere of uranyl ions, are discussed.« less

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.

Topological analysis of void spaces in tungstate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO 2, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4, and H 2

DOE PAGES

Cole, Jacqueline M.; Cramer, Alisha J.; Zeidler, Anita

2015-07-15

The identification of inorganic materials, which are able to encapsulate environmentally important small molecules or ions via host-guest interactions, is crucial for the design and development of next-generation energy sources and for storing environmental waste. Especially sought after are molecular sponges with the ability to incorporate CO 2, gas pollutants, or nuclear waste materials such as UO 2 and PuO 2 oxides or U, Pu, Sr 2+ or Cs + ions. Porous framework structures promise very attractive prospects for applications in environmental technologies, if they are able to incorporate CH 4 for biogas energy applications, or to store H 2,more » which is important for fuel cells e.g. in the automotive industry. All of these applications should benefit from the host being resistant to extreme conditions such as heat, nuclear radiation, rapid gas expansion, or wear and tear from heavy gas cycling. As inorganic tungstates are well known for their thermal stability, and their rigid open-framework networks, the potential of Na 2O-Al 2O 3-WO 3 and Na 2O-WO 3 phases for such applications was evaluated. To this end, all known experimentally-determined crystal structures with the stoichiometric formula M aM’ bW cO d (M = any element) are surveyed together with all corresponding theoretically calculated Na aAl bW cO d and Na xW yO z structures that are statistically likely to form. Network descriptors that categorize these host structures are used to reveal topological patterns in the hosts, including the nature of porous cages which are able to accommodate a certain type of guest; this leads to the classification of preferential structure types for a given environmental storage application. Crystal structures of two new tungstates NaAlW 2O 8 (1) and NaAlW 3O 11 (2) and one updated structure determination of Na 2W 2O 7 (3) are also presented from in-house X-ray diffraction studies, and their potential merits for environmental applications are assessed against those of this larger data-sourced survey. Altogether, results show that tungstate structures with three-nodal topologies are most frequently able to accommodate CH 4 or H 2, while CO 2 appears to be captured by a wide range of nodal structure types. The computationally generated host structures appear systematically smaller than the experimentally determined structures. For the structures of 1 and 2, potential applications in nuclear waste storage seem feasible.« less

The experience of stuttering among Ultra-Orthodox and Secular/Traditional Jews.

PubMed

Freud, Debora; Ezrati-Vinacour, Ruth; Katz-Bernstein, Nitza; Fostick, Leah

2017-12-01

This groundbreaking research compares the experience of stuttering among adult male People Who Stutter (PWS) from the ultra-Orthodox (UO) Jewish community in Israel to those from Secular/Traditional (ST) backgrounds. Participants were 32 UO and 31 ST PWS, aged 18-67 years. Self-report questionnaires utilized: Perceived Stuttering Severity (PSS); Overall Assessment of the Speaker's Experience of Stuttering (OASES-A); Students' Life Satisfaction Scale (SLSS); Situation Avoidance Behavior Checklist (SABC). Demographic, religious, and stuttering information was collected. Groups were compared on scales, and correlations between scales and the PSS. Subjective stuttering severity ratings were significantly higher among the UO. A significant group effect was found for the OASES-A quality of life subscale, but not other subscales. Significant positive correlations were found between: 1) PSS and OASES-A Total Impact; 2) PSS and 3 OASES subscales; and 3) PSS and SABC (indicating increased avoidance with increased stuttering severity rating). A significant negative correlation was found between the PSS and SLSS, indicating lower life satisfaction with higher rates of stuttering severity among the ST. Interestingly, when tested by group, significant correlations between the PSS and all other study measures were observed only among the ST. UO participants showed higher subjective stuttering severity ratings, yet less impact on quality of life, and no correlation between subjective stuttering and other measures of stuttering experience. These novel findings may result from the combined protective effect of religiosity and socio-cultural characteristics on UO PWS' well-being, despite heightened concern about social consequences of stuttering within UO society. Copyright © 2017 Elsevier Inc. All rights reserved.

The U(VI) speciation influenced by a novel Paenibacillus isolate from Mont Terri Opalinus clay.

PubMed

Lütke, Laura; Moll, Henry; Bachvarova, Velina; Selenska-Pobell, Sonja; Bernhard, Gert

2013-05-21

Bacterial cell walls have a high density of ionizable functional groups available for U(VI) binding, hence have a great potential to affect the speciation of this contaminant in the environment. The studied strain of the genus Paenibacillus is a novel isolate originating from the Mont Terri Opalinus clay formations (Switzerland) which are currently investigated as a potential host rock for future nuclear waste storage. U(VI) binding to the cell surface functional groups was studied by potentiometry combined with time-resolved laser-induced fluorescence spectroscopy (TRLFS). Four bacterial U(VI) surface complexes were identified: R-COO-UO2(+), R-O-PO3-UO2, R-O-PO3H-UO2(+), and (R-O-PO3)2-UO2(2-). The corresponding complex stability constants were calculated to be 5.33 ± 0.08, 8.89 ± 0.04, 12.92 ± 0.05, and 13.62 ± 0.08, respectively. Hence UO2(2+) displays a moderate to strong interaction with the bacterial surface functional groups. In the acidic pH range (pH 3) UO2(2+) binding onto the cell envelope is governed by coordination to hydrogen phosphoryl sites. Upon increasing the pH an increasing coordination of UO2(2+) to carboxylic and deprotonated phosphoryl sites was found. At a pH greater than 7 uranyl hydroxides dominate the speciation. Additionally the bacteria-mediated release of inorganic phosphate in dependence on [U(VI)] at different pH values was studied to assess the influence of phosphate release on U(VI) mobilization.

Translocation of uranium from water to foodstuff while cooking.

PubMed

Krishnapriya, K C; Baksi, Ananya; Chaudhari, Swathi; Gupta, Soujit Sen; Pradeep, T

2015-10-30

The present work report the unusual uranium uptake by foodstuff, especially those rich in carbohydrates like rice when they are cooked in water, contaminated with uranium. The major staple diet in South Asia, rice, was chosen to study its interaction with UO2(2+), the active uranium species in water, using inductively coupled plasma mass spectrometry. Highest uptake limit was checked by cooking rice at very high uranium concentration and it was found to be good scavenger of uranium. To gain insight into the mechanism of uptake, direct interaction of UO2(2+) with monosaccharides was also studied, using electrospray ionization mass spectrometry taking mannose as a model. The studies have been done with dissolved uranium salt, uranyl nitrate hexahydrate (UO2(NO3)2·6H2O), as well as the leachate of a stable oxide of uranium, UO2(s), both of which exist as UO2(2+) in water. Among the eight different rice varieties investigated, Karnataka Ponni showed the maximum uranium uptake whereas unpolished Basmati rice showed the minimum. Interaction with other foodstuffs (potato, carrot, peas, kidney beans and lentils) with and without NaCl affected the extent of chemical interaction but was not consistent with the carbohydrate content. Uranium interaction with D-mannose monitored through ESI-MS, under optimized instrumental parameters, identified the peaks corresponding to uranyl adduct with mannose monomer, dimer and trimer and the species were confirmed by MS/MS studies. The product ion mass spectra showed peaks illustrating water loss from the parent ion as the collision energy was increased, an evidence for the strong interaction of uranium with mannose. This study would constitute the essential background for understanding interaction of uranium with various foods. Extension of this work would involve identification of foodstuff as green heavy metal scavengers. Copyright © 2015. Published by Elsevier B.V.

Synthesis and structure of U(VI), Np(VI), and Pu(VI) propionates

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Grigor'ev, M. S.; Abdul'myanov, A. R.; Fedoseev, A. M.; Serezhkina, L. B.

2015-11-01

Crystals of [ AnO2(C2H5COO)2(H2O)2], where An = U (I), Np (II), or Pu (III), have been synthesized and studied by X-ray diffraction at 100 K. Compounds I-III are isostructural and crystallize in the monoclinic system, sp. gr. C2/ c, Z = 4, with the following unit-cell parameters: a = 7.4677(2), 7.4740(1), 7.512(2) Å, b = 14.2384(4), 14.1681(3), 14.182(4) Å, c = 10.5977(3), 10.5875(2), 10.607(3) Å, β = 92.384(1)°, 92.476(1)°, 92.668(17)°. Crystals I-III are composed of the mononuclear complexes [ AnO2(C2H5COO)2(H2O)2] as the main structural units belonging to the crystal-chemical group AB 01 2 M 1 2 ( A= AnO2+ 2, B 01 = C2H5COO-, M 1 = H2O). The crystal-chemical analysis of the structures of compounds of the composition UO2 L 2 · nH2O, where L is the carboxylate ion, is performed.

Neptunium incorporation into select uranyl phases and thermal analysis of select uranyl phases

NASA Astrophysics Data System (ADS)

Klingensmith, Amanda Leigh

Alteration of spent nuclear fuel in a geological repository under oxidizing conditions is likely to result in abundant uranyl compounds. The proposed repository at Yucca Mountain, Nevada is intended to store about 70,000 metric tons of spent nuclear fuel in the unsaturated zone of a welded tuff sequence. Following failure of canisters that encapsulate the waste, contents may be exposed both to air and water and undergo repetitive wetting and drying events. Incorporation of radionuclides into the uranyl alteration phases may significantly reduce their mobility, thereby impacting repository performance. Of particular interest is 237Np owing to its long half-life (2.14 x 106 years) and potential mobility in groundwater. Powders of the synthetic uranyl phase soddyite, (UO2) 2(SiO4)(H2O)2, a framework type structure, and uranophane, Ca[(UO2)(SiO3OH)]2(H 2O)5, kasolite, Pb[(UO2)(SiO4)]H 2O, Na compreignacite, Na2[(UO2)3O 2(OH)3]2(H2O)7, and becquerelite, Ca[(UO2)3O2(OH)3]2(H 2O)8, all of which are sheet type structures, were synthesized in the presence of Np5+ under varying temperature and pH conditions. Uranophane, kasolite, boltwoodite K[(UO2)(SiO3OH)](H 2O)1.5, and Na boltwoodite K,Na[(UO2)(SiO 3OH)](H2O)1.5 were synthesized in the presence of Np as well as P, Ca and/or Mg. Single crystals of Na metaschoepite, Na[(UO 2)4O2(OH)5]˙5H2O were synthesized in the presence of Np5+ and laser ablation verified that Np can be incorporated within the structure of a uranyl phase. Incorporation of Np5+ into soddyite increased steadily with synthesis temperature. Np incorporation into uranophane, becquerelite, and kasolite was not dependent on synthesis temperature. Np uptake in uranophane and kasolite was found to be dependent on synthesis pH, with an increase in Np uptake with higher pH. Uranophane, boltwoodite and Na boltwoodite showed an increase in Np incorporation in the presence of P. Boltwoodite showed an even higher Np uptake when Mg and P were both present in the synthesis. Thermal analysis was completed for the uranyl phases soddyite, becquerelite, Na compreignacite, uranophane, and kasolite. TGA curves for becquerelite, Na compreignacite and uranophane showed loss of interlayer water groups by 100°C. Soddyite and kasolite showed more gradual TGA curves and retention of water groups up to 400°C for soddyite and 550°C for kasolite, with agreement shown by high temperature powder XRD data.

Ring opening of azetidine cycle: First examples of 1-azetidinepropanamine molecules as a template in hybrid organic-inorganic compounds

NASA Astrophysics Data System (ADS)

Gurzhiy, Vladislav V.; Tyumentseva, Olga S.; Britvin, Sergey N.; Krivovichev, Sergey V.; Tananaev, Ivan G.

2018-01-01

Three novel uranyl selenate and sulfate oxysalts templated by protonated azetidine molecules, [AzH]+, and its ring-opened counterpart 1-azetidinepropanamine, [AzH(CH2)3NH3]2+, have been prepared and studied by X-ray structural analysis. Conformations of azetidinium cations were analysed by means of infrared vibrational assignments supported by the DFT calculations. Crystallization of [AzH]2 [(UO2)2(SeO4)3(H2O)] (I) from highly acidic solutions suggests that low pH does not necessarily result in the opening of azetidine ring. [AzH(CH2)3NH3][(UO2)2(SeO4)3(H2O)](H2O) (II) and [AzH(CH2)3NH3](H5O2)[(UO2)2(SO4)3(HSO4)] (III) are the first structurally characterized crystalline compounds bearing isolated ring-opened azetidine moiety.

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.

Durability test on irradiated rock-like oxide fuels

NASA Astrophysics Data System (ADS)

Kuramoto, K.; Nitani, N.; Yamashita, T.

2003-06-01

For a profitable use of Pu, Japan Atomic Energy Research Institute has been promoting researches for once-through type fuels. The strategy consists of stable rock-like oxide fuel fabrication in conventional fuel facilities followed by almost complete Pu burning in LWR and disposal of chemically stable spent fuel without further processing. Because leach rates of hazardous nuclides, such as TRU and β-emitters, that have long half-lives, are very important for the evaluation of geological safety, leaching tests in deionized water at 363 K were performed with reference to the MCC-1 method. Five irradiated fuel pellets, a single phase fuel of a yttria-stabilized zirconia (YSZ) containing UO 2 (U-YSZ), two fuels of U-YSZ particle dispersed in MgAl 2O 4 (SPI) or Al 2O 3 (COR) matrix, two homogeneous-blended fuels of U-YSZ and SPI or COR powders, were submitted to the tests. Stainless steel containers with Au coating and ethylene propylene diene monomer were used as leaching vessels and packing, respectively. The evaluated normalized leach rates of Zr, U and Pu were obviously lower than those of the other important elements and nuclides. Americium, Np and especially Y showed unexpectedly high evaluated normalized leach rates. The volatile elements, Cs and I, showed enhanced leaching within particle-dispersed type fuels because of crack formation around the particle.

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.

Transfer of aged Pu to cattle grazing on a contaminated environment

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

Gilbert, R.O.; Engel, D.W.; Smith, D.D.

1988-03-01

Estimates are obtained of the fraction of ingested or inhaled 239+240Pu transferred to blood and tissues of a reproducing herd of beef cattle, individuals of which grazed within fenced enclosures for up to 1064 d under natural conditions with no supplemental feeding at an arid site contaminated 16 y previously with Pu oxide. The estimated (geometric mean (GM)) fraction of Pu transferred from the gastrointestinal tract to blood serum was about 5 x 10(-6) (geometric standard error (GSE) = 1.4) with an approximate upper bound of about 2 x 10(-5). These results are in reasonable agreement with the value ofmore » 1 x 10(-5) recommended for human radiation protection purposes by the International Commission on Radiological Protection (ICRP) for insoluble Pu oxides that are free of very small particles. Also, results from a laboratory study by Stanley (St75), in which large doses of /sup 238/Pu were orally administered daily to dairy cattle for 19 consecutive days, suggest that aged 239+240Pu at this arid grazing site may not be more biologically available to blood serum than fresh 239+240Pu oxide. The estimated fractions of 239+240Pu transferred from blood serum to tissues of adult grazing cattle were: femur (3.2 X 10(-2), 1.8; GM, GSE), vertebra (1.4 X 10(-1), 1.6), liver (2.3 X 10(-1), 2.0), muscle (1.3 X 10(-1), 1.9), female gonads (7.9 X 10(-5), 1.5), and kidney (1.4 X 10(-3), 1.7). The blood-to-tissue fractional transfers for cattle initially exposed in utero were greater than those exposed only as adults by a factor of about 4 for femur (statistically significant) and of about 2 for other tissues (not significant). The estimated (GM) fraction of inhaled Pu initially deposited in the pulmonary lung was 0.34 (GSE = 1.3) for adults and 0.15 (GSE = 1.3) for cattle initially exposed in utero (a statistically significant difference).« less

Investigation of uranium binding forms in selected German mineral waters.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Bernhard, Gert; Worch, Eckhard

2013-12-01

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 μg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca2UO2(CO3)3 in all investigated waters, while other uranyl-carbonate complexes, viz, UO2CO3(aq) and UO2(CO3)2 (2-), only existed as minor species. The pH value, alkalinity (CO3 (2-)), and the main water inorganic constituents, specifically the Ca(2+) concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.

Effect of metallic iron on the oxidative dissolution of UO2 doped with a radioactive alpha emitter in synthetic Callovian-Oxfordian groundwater

NASA Astrophysics Data System (ADS)

Odorowski, Mélina; Jegou, Christophe; De Windt, Laurent; Broudic, Véronique; Jouan, Gauthier; Peuget, Sylvain; Martin, Christelle

2017-12-01

In the hypothesis of direct disposal of spent fuel in a geological nuclear waste repository, interactions between the fuel mainly composed of UO2 and its environment must be understood. The dissolution rate of the UO2 matrix, which depends on the redox conditions on the fuel surface, will have a major impact on the release of radionuclides into the environment. The reducing conditions expected for a geological disposal situation would appear to be favorable as regards the solubility and stability of the UO2 matrix, but may be disturbed on the surface of irradiated fuel. In particular, the local redox conditions will result from a competition between the radiolysis effects of water under alpha irradiation (simultaneously producing oxidizing species like H2O2, hydrogen peroxide, and reducing species like H2, hydrogen) and those of redox active species from the environment. In particular, Fe2+, a strongly reducing aqueous species coming from the corrosion of the iron canister or from the host rock, could influence the dissolution of the fuel matrix. The effect of iron on the oxidative dissolution of UO2 was thus investigated under the conditions of the French disposal site, a Callovian-Oxfordian clay formation chosen by the French National Radioactive Waste Management Agency (Andra), here tested under alpha irradiation. For this study, UO2 fuel pellets doped with a radioactive alpha emitter (238/239Pu) were leached in synthetic Callovian-Oxfordian groundwater (representative of the French waste disposal site groundwater) in the presence of a metallic iron foil to simulate the steel canister. The pellets had varying levels of alpha activity, in order to modulate the concentrations of species produced by water radiolysis on the surface and to simulate the activity of aged spent fuel after 50 and 10,000 years of alpha radioactivity decay. The experimental data showed that whatever the sample alpha radioactivity, the presence of iron inhibits the oxidizing dissolution of UO2 and leads to low uranium concentrations (between 4 × 10-10 and 4 × 10-9 M), through a reactional mechanism located in the very first microns of the UO2/water reactional interface. The mechanism involves consumption of oxidizing species, in particular of H2O2 by Fe2+ at the precise place where these species are produced, and is accompanied by the precipitation of an akaganeite-type Fe3+ hydroxide on the surface. The higher the radioactivity of the samples, the greater the precipitation induced. Modeling has been developed, coupling chemistry with transport and based on the main reactional mechanisms identified, which enables accurate reproduction of the mineralogy of the system under study, giving the nature of the phases under observation as well as the location of their precipitation. Obviously without excluding a potential contribution from the hydrogen produced by the anoxic corrosion of the iron foil, this study has shown that iron plays a major role in this oxidizing dissolution inhibition process for the system investigated (localized alpha radiolysis). This inhibitor effect associated with iron is therefore strongly dependent on the location of the redox front, which is found on the surface in the case of alpha irradiation UO2/water reactional interface.

Structure, equilibrium and ligand exchange dynamics in the binary and ternary dioxouranium(VI)-ethylenediamine-N,N'-diacetic acid-fluoride system: A potentiometric, NMR and X-ray crystallographic study.

PubMed

Palladino, Giuseppe; Szabó, Zoltán; Fischer, Andreas; Grenthe, Ingmar

2006-11-21

The structure, thermodynamics and kinetics of the binary and ternary uranium(VI)-ethylenediamine-N,N'-diacetate (in the following denoted EDDA) fluoride systems have been studied using potentiometry, 1H, 19F NMR spectroscopy and X-ray diffraction. The UO2(2+)-EDDA system could be studied up to -log[H3O+] = 3.4 where the formation of two binary complexes UO2(EDDA)(aq) and UO2(H3EDDA)3+ were identified, with equilibrium constants logbeta(UO2EDDA) = 11.63 +/- 0.02 and logbeta(UO2H3EDDA3+) = 1.77 +/- 0.04, respectively. In the ternary system the complexes UO2(EDDA)F-, UO2(EDDA)(OH)- and (UO2)2(mu-OH)2(HEDDA)2F2(aq) were identified; the latter through 19F NMR. 1H NMR spectra indicate that the EDDA ligand is chelate bonded in UO2(EDDA)(aq), UO2(EDDA)F- and UO2(EDDA)(OH)- while only one carboxylate group is coordinated in UO2(H3EDDA)3+. The rate and mechanism of the fluoride exchange between UO2(EDDA)F- and free fluoride was studied by 19F NMR spectroscopy. Three reactions contribute to the exchange; (i) site exchange between UO2(EDDA)F- and free fluoride without any net chemical exchange, (ii) replacement of the coordinated fluoride with OH- and (iii) the self dissociation of the coordinated fluoride forming UO2(EDDA)(aq); these reactions seem to follow associative mechanisms. (1)H NMR spectra show that the exchange between the free and chelate bonded EDDA is slow and consists of several steps, protonation/deprotonation and chelate ring opening/ring closure, the mechanism cannot be elucidated from the available data. The structure (UO2)2(EDDA)2(mu-H2EDDA) was determined by single crystal X-ray diffraction and contains two UO2(EDDA) units with tetracoordinated EDDA linked by H2EDDA in the "zwitterion" form, coordinated through a single carboxylate oxygen from each end to the two uranium atoms. The geometry of the complexes indicates that there is no geometric constraint for an associative ligand substitution mechanism.

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.

Progress on the chemical separation of fission fragments from 236Np produced by proton irradiation of natural uranium target

NASA Astrophysics Data System (ADS)

Larijani, C.; Jerome, S. M.; Lorusso, G.; Ivanov, P.; Russell, B.; Pearce, A. K.; Regan, P. H.

2017-11-01

The aim of the current work is to develop and validate a radiochemical separation scheme capable of separating both 236gNp and 236Pu from a uranium target of natural isotopic composition ( 1 g uranium) and 200 MBq of fission decay products. A target containing 1.2 g of UO2 was irradiated with a beam of 25 MeV protons with a typical beam current of 30 μA for 19 h in December 2013 at the University of Birmingham Cyclotron facility. Using literature values for the production cross-section for fusion of protons with uranium targets, we estimate that an upper limit of approximately 250 Bq of activity from the 236Np ground state was produced in this experiment. Using a radiochemical separation scheme, Np and Pu fractions were separated from the produced fission decay products, with analyses of the target-based final reaction products made using Inductively Couple Plasma Mass Spectrometry (ICP-MS) and high-resolution α particle and γ-ray spectrometry.

Assessment of empirical potential for MOX nuclear fuels and thermomechanical properties

NASA Astrophysics Data System (ADS)

Balboa, Hector; Van Brutzel, Laurent; Chartier, Alain; Le Bouar, Yann

2017-11-01

We assess five empirical interatomic potentials in the approximation of rigid ions and pair interactions for the (U1-y,Puy)O solid solution. The assessment compares available experimental data and Fink's recommendation with simulations on: the structural, thermodynamics, and mechanical properties over the full range of plutonium composition, from pure UO2 to pure PuO2 and for temperatures ranging from 300 K to the melting point. The best results are obtained by potentials referred as Cooper and Potashnikov potentials. The first one reproduces more accurately recommendations for the thermodynamics and mechanical properties exhibiting ductile-like behaviour during crack propagation, while the second one gives brittle behaviour at low temperature.

Stress Concentrations.

DTIC Science & Technology

1982-09-01

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Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation

DOE PAGES

Knope, Karah E.; Skanthakumar, S.; Soderholm, L.

2015-10-13

We report the room temperature synthesis and structural characterization of a μ2-hydroxobridged PuIV dimer obtained from an acidic, nitric acid solution. The discrete Pu 2(OH) 2(NO 3) 6(H 2O) 4 moiety crystallized with two distinct crystal structures, (1) [Pu 2(OH) 2(NO 3) 6(H 2O) 4] 2·11H 2O and (2) Pu 2(OH) 2(NO 3) 6(H 2O) 4·2H 2O, which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(10) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridgedmore » distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO 2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent-metal-ion condensation« less

Matrix isolation infrared spectra of O2 and N2 insertion reactions with atomic uranium

NASA Astrophysics Data System (ADS)

Hunt, Rodney D.; Toth, L. Mac; Yustein, Jason T.; Andrews, Lester

1993-10-01

Laser ablation of refractory metals can be an effective source of vapor for matrix isolation IR studies. This combination of techniques was used for the first time to study the mechanisms of U vapor reactions with atmospheric components. U atoms and O2 were codeposited with excess Ar at 12 K. The dominant codeposition products were UO2 and UO3. In contrast, the UO yield was always small because UO2 is formed by an insertion mechanism. This mechanism was verified in the 16O2/18O2 experiments which failed to produce 16OU18O. The effects of UV photolysis and matrix annealings were also examined. The U atoms and O2 reaction requires little or no activation energy since UO2 was formed from cold reagents. New charge-transfer species, (UO2+2)(O2-2) and (UO+2)(O-2), and a weak complex, UO3-O2, were primarily produced under conditions which favored further O2 reactions. Similar U atom and N2 experiments produced only linear NUN which is also produced by an insertion mechanism. This U reaction represents the first time that atom was observed breaking and inserting into the triple bond of N2. Photolysis dramatically increased the NUN yield by 3-fold. Matrix annealings produced weak UN2-N2 and UN2-2N2 complexes.

Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy

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

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.

Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO 2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d 3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree ofmore » the 5f localization in UO 2. The results support the covalent character of UO 2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.« less

Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy

DOE PAGES

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.; ...

2016-11-30

Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO 2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d 3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree ofmore » the 5f localization in UO 2. The results support the covalent character of UO 2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.« 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.

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1994-01-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO.sub.2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a .beta.-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

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

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE PAGES

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; ...

2017-10-24

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

Uncertainties for Swiss LWR spent nuclear fuels due to nuclear data

NASA Astrophysics Data System (ADS)

Rochman, Dimitri A.; Vasiliev, Alexander; Dokhane, Abdelhamid; Ferroukhi, Hakim

2018-05-01

This paper presents a study of the impact of the nuclear data (cross sections, neutron emission and spectra) on different quantities for spent nuclear fuels (SNF) from Swiss power plants: activities, decay heat, neutron and gamma sources and isotopic vectors. Realistic irradiation histories are considered using validated core follow-up models based on CASMO and SIMULATE. Two Pressurized and one Boiling Water Reactors (PWR and BWR) are considered over a large number of operated cycles. All the assemblies at the end of the cycles are studied, being reloaded or finally discharged, allowing spanning over a large range of exposure (from 4 to 60 MWd/kgU for ≃9200 assembly-cycles). Both UO2 and MOX fuels were used during the reactor cycles, with enrichments from 1.9 to 4.7% for the UO2 and 2.2 to 5.8% Pu for the MOX. The SNF characteristics presented in this paper are calculated with the SNF code. The calculated uncertainties, based on the ENDF/B-VII.1 library are obtained using a simple Monte Carlo sampling method. It is demonstrated that the impact of nuclear data is relatively important (e.g. up to 17% for the decay heat), showing the necessity to consider them for safety analysis of the SNF handling and disposal.

Evaluation of support materials for the immobilization of sulfate-reducing bacteria and methanogenic archaea.

PubMed

Silva, A J; Hirasawa, J S; Varesche, M B; Foresti, E; Zaiat, M

2006-04-01

This paper reports on the adhesion of sulfate-reducing bacteria (SRB) and methanogenic archaea on polyurethane foam (PU), vegetal carbon (VC), low-density polyethylene (PE) and alumina-based ceramics (CE). Anaerobic differential reactors fed with a sulfate-rich synthetic wastewater were used to evaluate the formation of a biofilm. The PU presented the highest specific biomass concentration throughout the experiment, achieving 872 mg TVS/g support, while 84 mg TVS/g support was the maximum value obtained for the other materials. FISH results showed that bacterial cells rather than archaeal cells were predominant on the biofilms. These cells, detected with EUB338 probe, accounted for 76.2% (+/-1.6%), 79.7% (+/-1.3%), 84.4% (+/-1.4%) and 60.2% (+/-1.0%) in PU, VC, PE and CE, respectively, of the 4'6-diamidino-2-phenylindole (DAPI)-stained cells. From these percentages, 44.8% (+/-2.1%), 55.4% (+/-1.2%), 32.7% (+/-1.4%) and 18.1% (+/-1.1%), respectively, represented the SRB group. Archaeal cells, detected with ARC915 probe, accounted for 33.1% (+/-1.6%), 25.4% (+/-1.3%), 22.6% (+/-1.1%) and 41.9% (+/-1.0%) in PU, VC, PE and CE, respectively, of the DAPI-stained cells. Sulfate reduction efficiencies of 39% and 45% and mean chemical oxygen demand (COD) removal efficiencies of 86% and 90% were achieved for PU and VC, respectively. The other two supports, PE and CE, provided mean COD removal efficiencies of 84% and 86%, respectively. However, no sulfate reduction was observed with these supports.

Oxidation kinetics for conversion of U 3O 8 to ε-UO 3 with NO 2

DOE PAGES

Johnson, J. A.; Rawn, C. J.; Spencer, B. B.; ...

2017-04-04

The oxidation kinetics of U 3O 8 powder to ε-UO 3 in an NO 2 environment was measured by in situ x-ray diffraction (XRD). Experiments were performed at temperatures of 195, 210, 235, and 250°C using a custom designed and fabricated sample isolation stage. Data were refined to quantify phase fractions using a newly proposed structure for the ε-UO 3 polymorph. The kinetics data were modeled using a shrinking core approach. A proposed two-step reaction process is presented based on the developed models.

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

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

NASA Astrophysics Data System (ADS)

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

2018-02-01

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

The use of MOX caramel fuel mixed with 241Am, 242mAm and 243Am as burnable absorber actinides for the MTR research reactors.

PubMed

Shaaban, Ismail; Albarhoum, Mohamad

2017-07-01

The MOX (UO 2 &PuO 2 ) caramel fuel mixed with 241 Am, 242m Am and 243 Am as burnable absorber actinides was proposed as a fuel of the MTR-22MW reactor. The MCNP4C code was used to simulate the MTR-22MW reactor and estimate the criticality and the neutronic parameters, and the power peaking factors before and after replacing its original fuel (U 3 O 8 -Al) by the MOX caramel fuel mixed with 241 Am, 242m Am and 243 Am actinides. The obtained results of the criticality, the neutronic parameters, and the power peaking factors for the MOX caramel fuel mixed with 241 Am, 242m Am and 243 Am actinides were compared with the same parameters of the U 3 O 8 -Al original fuel and a maximum difference is -6.18% was found. Additionally, by recycling 2.65% and 2.71% plutonium and 241 Am, 242m Am and 243 Am actinides in the MTR-22MW reactor, the level of 235 U enrichment is reduced from 4.48% to 3% and 2.8%, respectively. This also results in the reduction of the 235 U loading by 32.75% and 37.22% for the 2.65%, the 2.71% plutonium and 241 Am, 242m Am and 243 Am actinides, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Burnup calculations and chemical analysis of irradiated fuel samples studied in LWR-PROTEUS phase II

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

Grimm, P.; Guenther-Leopold, I.; Berger, H. D.

2006-07-01

The isotopic compositions of 5 UO{sub 2} samples irradiated in a Swiss PWR power plant, which were investigated in the LWR-PROTEUS Phase II programme, were calculated using the CASMO-4 and BOXER assembly codes. The burnups of the samples range from 50 to 90 MWd/kg. The results for a large number of actinide and fission product nuclides were compared to those of chemical analyses performed using a combination of chromatographic separation and mass spectrometry. A good agreement of calculated and measured concentrations is found for many of the nuclides investigated with both codes. The concentrations of the Pu isotopes are mostlymore » predicted within {+-}10%, the two codes giving quite different results, except for {sup 242}Pu. Relatively significant deviations are found for some isotopes of Cs and Sm, and large discrepancies are observed for Eu and Gd. The overall quality of the predictions by the two codes is comparable, and the deviations from the experimental data do not generally increase with burnup. (authors)« less

Dehydration of Uranyl Nitrate Hexahydrate to Uranyl Nitrate Trihydrate under Ambient Conditions as Observed via Dynamic Infrared Reflectance Spectroscopy

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-05-22

the hexahydrate [UO 2(NO 3) 2(H 2O) 6] (UNH) and the trihydrate [UO 2(NO 3) 2(H 2O) 3] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating them. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via knownmore » XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm -1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm -1. The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.« less

Significance of oliguria in critically ill patients with chronic liver disease.

PubMed

Amathieu, Roland; Al-Khafaji, Ali; Sileanu, Florentina E; Foldes, Emily; DeSensi, Rebecca; Hilmi, Ibtesam; Kellum, John A

2017-11-01

Clinical guidelines recommend using Kidney Disease Improving Global Outcomes (KDIGO) criteria for the diagnosis and classification of acute kidney injury (AKI) in patients with chronic liver disease (CLD). Concerns have been raised about the use of urine output (UO) criteria in CLD. We examined the significance of oliguria meeting the urine output criteria for AKI (AKI-UO) and examined its association with clinical outcomes in CLD patients. Using an 8-year clinical database from a large university medical center, 3458 patients with CLD were identified. AKI occurred in 2854 (82.5%) patients when they fulfilled any KDIGO criteria. When serum creatinine (SC) and UO criteria were used, 604 patients (17.5%) had no evidence of AKI and had the lowest hospital mortality rate (5%). Using AKI-UO criteria alone, 2103 patients (60.8%) were classified as stage 2-3 AKI. When only SC criteria were applied, 1281 (61%) of those patients with stage 2-3 AKI-UO were misclassified as either no AKI or AKI stage 1. Patients reclassified with AKI according to UO criteria (AKI-UO) had nearly a 3-fold increased rate of hospital mortality compared with patients without any AKI (14.6% versus 5%; P < 0.001) and more than a 50% increased mortality compared with stage 1 AKI-SC (14.6% versus 9%; P < 0.001). Patients with transient oliguria (AKI-UO stage 1) had increased mortality rates compared with patients without oliguria (14.9% versus 6.9%; P < 0.001). CLD patients have a high incidence of AKI. Compared with creatinine criteria alone, incorporating UO into the diagnostic criteria increased the measured incidence of AKI. Stage 2-3 AKI-UO has a high negative impact on hospital mortality. (Hepatology 2017;66:1592-1600). © 2017 by the American Association for the Study of Liver Diseases.

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.

Plutonium Isotopes (239-241Pu) Dissolved in Pacific Ocean Waters Detected by Accelerator Mass Spectrometry: No Effects of the Fukushima Accident Observed.

PubMed

Hain, Karin; Faestermann, Thomas; Fimiani, Leticia; Golser, Robin; Gómez-Guzmán, José Manuel; Korschinek, Gunther; Kortmann, Florian; Lierse von Gostomski, Christoph; Ludwig, Peter; Steier, Peter; Tazoe, Hirofumi; Yamada, Masatoshi

2017-02-21

The concentration of plutonium (Pu) and the isotopic ratios of 240 Pu to 239 Pu and 241 Pu to 239 Pu were determined by accelerator mass spectrometry (AMS) in Pacific Ocean water samples (20 L each) collected in late 2012. The isotopic Pu ratios are important indicators of different contamination sources and were used to identify a possible release of Pu into the ocean by the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. In particular, 241 Pu is a well-suited indicator for a recent entry of Pu because 241 Pu from fallout of nuclear weapon testings has already significantly decayed. A total of 10 ocean water samples were prepared at the Radiochemie München of the TUM and analyzed at the Vienna Environmental Research Laboratory (VERA). Several samples showed a slightly elevated 240 Pu/ 239 Pu ratio of up to 0.22 ± 0.02 compared to global fallout ( 240 Pu/ 239 Pu = 0.180 ± 0.007), whereas all measured 241 Pu-to- 239 Pu ratios were consistent with nuclear weapon fallout ( 241 Pu/ 239 Pu < 2.4 × 10 -3 ), which means that no impact from the Fukushima accident was detected. From the average 241 Pu-to- 239 Pu ratio of 8 -2 +3 ×10 -4 at a sampling station located at a distance of 39.6 km to FDNPP, the 1-σ upper limit for the FDNPP contribution to the 239 Pu inventory in the water column was estimated to be 0.2%. Pu, with the signature of weapon-grade Pu was found in a single sample collected around 770 km off the west coast of the United States.

Efficient uranium capture by polysulfide/layered double hydroxide composites.

PubMed

Ma, Shulan; Huang, Lu; Ma, Lijiao; Shim, Yurina; Islam, Saiful M; Wang, Pengli; Zhao, Li-Dong; Wang, Shichao; Sun, Genban; Yang, Xiaojing; Kanatzidis, Mercouri G

2015-03-18

There is a need to develop highly selective and efficient materials for capturing uranium (normally as UO2(2+)) from nuclear waste and from seawater. We demonstrate the promising adsorption performance of S(x)-LDH composites (LDH is Mg/Al layered double hydroxide, [S(x)](2-) is polysulfide with x = 2, 4) for uranyl ions from a variety of aqueous solutions including seawater. We report high removal capacities (q(m) = 330 mg/g), large K(d)(U) values (10(4)-10(6) mL/g at 1-300 ppm U concentration), and high % removals (>95% at 1-100 ppm, or ∼80% for ppb level seawater) for UO2(2+) species. The S(x)-LDHs are exceptionally efficient for selectively and rapidly capturing UO2(2+) both at high (ppm) and trace (ppb) quantities from the U-containing water including seawater. The maximum adsorption coeffcient value K(d)(U) of 3.4 × 10(6) mL/g (using a V/m ratio of 1000 mL/g) observed is among the highest reported for U adsorbents. In the presence of very high concentrations of competitive ions such as Ca(2+)/Na(+), S(x)-LDH exhibits superior selectivity for UO2(2+), over previously reported sorbents. Under low U concentrations, (S4)(2-) coordinates to UO2(2+) forming anionic complexes retaining in the LDH gallery. At high U concentrations, (S4)(2-) binds to UO2(2+) to generate neutral UO2S4 salts outside the gallery, with NO3(-) entering the interlayer to form NO3-LDH. In the presence of high Cl(-) concentration, Cl(-) preferentially replaces [S4](2-) and intercalates into LDH. Detailed comparison of U removal efficiency of S(x)-LDH with various known sorbents is reported. The excellent uranium adsorption ability along with the environmentally safe, low-cost constituents points to the high potential of S(x)-LDH materials for selective uranium capture.

From Layered Structures to Cubic Frameworks. Expanding the Structural Diversity of Uranyl Carboxyphosphonates via the Incorporation of Cobalt

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

Alsobrook, Andrea N.; Hauser, Brad G.; Hupp, Joseph T.

2011-02-08

Five heterobimetallic U(VI)/Co(II) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO 3, Co(CH 3CO 2) 2·4H 2O, and triethyl phosphonoacetate. These compounds, Co(H 2O) 4[(UO 2) 2(PO 3CH 2CO 2) 2(H 2O) 2] (CoUPAA-1), [Co(H 2O) 6][UO 2(PO 3CH 2CO 2)] 2·8H 2O (CoUPAA-2), Co(H 2O) 4[UO 2(PO 3CH 2CO 2)] 2·4H 2O (CoUPAA-3), Co(H 2O) 4[(UO 2) 62CH 2CO 2) 2O 2(OH) 3(H 2O) 3] 2·3H 2O (CoUPAA-4), and Co 2(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2·16H 2O (CoUPAA-5), range from two- to three-dimensional structures. CoUPAA-1 to CoUPAA-3 all possess uranyl carboxyphosphonate layersmore » that are separated by the Co(II) cation with varying degrees of hydration. CoUPAA-4 contains both UO 7 pentagonal bipyramids and UO 8 hexagonal bipyramids within the uranyl carboxyphosphonate plane. Unlike the first four low-symmetry compounds, CoUPAA-5 is a cubic, three-dimensional network with large cavities approximately 16 Å in diameter that are filled with cocrystallized water molecules. Differential gas absorption measurements performed on CoUPAA-5 displayed a surface area uptake for CO 2 of 40 m 2 g -1 at 273 K, and no uptake for N 2 at 77 K.« less

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.; ...

2017-11-14

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

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

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, W.E.; Tomczuk, Z.

1994-02-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO[sub 2] oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a [beta]-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

Self-irradiation damage to the local structure of plutonium and plutonium intermetallics

NASA Astrophysics Data System (ADS)

Booth, C. H.; Jiang, Yu; Medling, S. A.; Wang, D. L.; Costello, A. L.; Schwartz, D. S.; Mitchell, J. N.; Tobash, P. H.; Bauer, E. D.; McCall, S. K.; Wall, M. A.; Allen, P. G.

2013-03-01

The effect of self-irradiation damage on the local structure of δ-Pu, PuAl2, PuGa3, and other Pu intermetallics has been determined for samples stored at room temperature using the extended x-ray absorption fine-structure (EXAFS) technique. These measurements indicate that the intermetallic samples damage at a similar rate as indicated in previous studies of PuCoGa5. In contrast, δ-Pu data indicate a much slower damage accumulation rate. To explore the effect of storage temperature and possible room temperature annealing effects, we also collected EXAFS data on a δ-Pu sample that was held at less than 32 K for a two month period. This sample damaged much more quickly. In addition, the measurable damage was annealed out at above only 135 K. Data from samples of δ-Pu with different Ga concentrations and results on all samples collected from different absorption edges are also reported. These results are discussed in terms of the vibrational properties of the materials and the role of Ga in δ-Pu as a network former.

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere.

PubMed

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of 90Sr and Pu isotopes in contaminated groundwater samples by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Zoriy, Miroslav V.; Ostapczuk, Peter; Halicz, Ludwik; Hille, Ralf; Becker, J. Sabine

2005-04-01

A sensitive analytical method for determining the artificial radionuclides 90Sr, 239Pu and 240Pu at the ultratrace level in groundwater samples from the Semipalatinsk Test Site area in Kazakhstan by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) was developed. In order to avoid possible isobaric interferences at m/z 90 for 90Sr determination (e.g. 90Zr+, 40Ar50Cr+, 36Ar54Fe+, 58Ni16O2+, 180Hf2+, etc.), the measurements were performed at medium mass resolution under cold plasma conditions. Pu was separated from uranium by means of extraction chromatography using Eichrom TEVA resin with a recovery of 83%. The limits of detection for 90Sr, 239Pu and 240Pu in water samples were determined as 11, 0.12 and 0.1 fg ml-1, respectively. Concentrations of 90Sr and 239Pu in contaminated groundwater samples ranged from 18 to 32 and from 28 to 856 fg ml-1, respectively. The 240Pu/239Pu isotopic ratio in groundwater samples was measured as 0.17. This isotope ratio indicates that the most probable source of contamination of the investigated groundwater samples was the nuclear weapons tests at the Semipalatinsk Test Site conducted by the USSR in the 1960s.

Processing of uranium dioxide nuclear fuel pellets using spark plasma sintering

NASA Astrophysics Data System (ADS)

Ge, Lihao

Uranium dioxide (UO2), one of the most common nuclear fuels, has been applied in most of the nuclear plant these days for electricity generation. The main objective of this research is to introduce a novel method for UO 2 processing using spark plasma sintering technique (SPS). Firstly, an investigation into the influence of processing parameters on densification of UO2 powder during SPS is presented. A broad range of sintering temperatures, hold time and heating rates have been systematically varied to investigate their influence on the sintered pellet densification process. The results revealed that up to 96% theoretical density (TD) pellets can be obtained at a sintering temperature of 1050 °C for 30s hold time and a total run time of only 10 minutes. A systematic study is performed by varying the sintering temperature between 750°C to 1450°C and hold time between 0.5 min to 20 min to obtain UO2 pellets with a range of densities and grain sizes. The microstructure development in terms of grain size, density and porosity distribution is investigated. The Oxygen/Uranium (O/U) ratio of the resulting pellets is found to decrease after SPS. The mechanical and thermal properties of UO2 are evaluated. For comparable density and grain size, Vickers hardness and Young's modulus are in agreement with the literature value. The thermal conductivity of UO2 increases with the density but the grain size in the investigated range has no significant influence. Overall, the mechanical and thermal properties of UO2 are comparable with the one made using conventional sintering methods. Lastly, the influence of chromium dioxide (Cr2O3) and zirconium diboride (ZrB2) on the grain size of doped UO 2 fuel pellet is performed to investigate the feasibility of producing large-grain-size nuclear fuel using SPS. The benefits of using SPS over the conventional sintering of UO2 are summarized. The future work of designing macro-porous UO2 pellet and thorium dioxide (ThO 2) cored UO2 pellet is also proposed.

Optimized LWIR enhancement of nanosecond and femtosecond LIBS uranium emission

NASA Astrophysics Data System (ADS)

Akpovo, Codjo A.; Ford, Alan; Johnson, Lewis

2016-05-01

A carbon dioxide (CO2) transverse electrical breakdown in atmosphere (TEA), pulsed laser was used to enhance the laser-induced breakdown spectroscopy (LIBS) spectral signatures of uranium under nanosecond (ns) and femtosecond (fs) ablation. The peak areas of both ionic and neutral species increased by one order of magnitude for ns-ablation and two orders of magnitude for fs-ablation over LIBS when the CO2 TEA laser was used with samples of dried solutions of uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) on silicon wafers. Electron temperature and density measurements show that the spectral emission improvement from using the TEA laser comes from plasma reheating.

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.

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with Fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry.

PubMed

Pasilis, Sofie; Somogyi, Arpád; Herrmann, Kristin; Pemberton, Jeanne E

2006-02-01

Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of [(UO(2))(n)(A)(m)(CH(3)OH)(s)](+) or [(UO(2))(n)(O)(A)(m)(CH(3)OH)(s)](+) with n = 1-4, m = 1-7, s = 0 or 1, and A = OH, NO(3), CH(3)O or a combination of these, although the formation of NO(3)-containing species is preferred. In the negative ion mode, complexes of the form [(UO(2))(NO(3))(m)](-) (m = 1-3) are detected, although the formation of the oxo-containing ions [(UO(2))(O)(n)(NO(3))(m)](-) (n = 1-2, m = 1-2) and the hydroxy-containing ions [(UO(2))(OH)(n)(NO(3))(m)](-) (n = 1-2, m = 0-1) are also observed. The extent of coordinative unsaturation of both positive and negative ions can be determined by ligand association/exchange and H/D exchange experiments using D(2)O and CD(3)OD as neutral reaction partners in the gas-phase. Positive ions are of varying stability and reactivity and may fragment extensively upon collision with D(2)O, CD(3)OD and N(2) in sustained off-resonance irradiation/collision-induced dissociation (SORI-CID) experiments. Electron-transfer reactions, presumably occurring during electrospray ionization but also in SORI-CID, can result in reduction of U(VI) to U(V) and perhaps even U(IV).

Estimates of (239+240)Pu inventories in Gdańsk Bay and Gdańsk basin.

PubMed

Skwarzec, Bogdan; Strumińska, Dagmara I; Prucnal, Małgorzata

2003-01-01

This paper presents and discusses the results of (239+240)Pu determinations in different components of Gdańsk bay and Gdańsk basin ecosystem, as well as estimated sources and inventories of plutonium in these basins. The total plutonium (239+240)Pu activities deposited in Gdańsk bay and Gdańsk basin sediments are 1.18 TBq and 3.77 TBq, respectively. Two rivers, the Vistula and Neman rivers, and atmospheric fallout were distinguished as the main sources of plutonium in these basins. In seawater (with suspended matter included) there is about 2.33 GBq (239+240)Pu (0.2% of total activity) in Gdańsk bay and 9.92 GBq (239+240)Pu (0.3% of total activity) in Gdańsk basin. In both cases, 56% of (239+240)Pu is associated with suspended matter. Organisms contain 3.81 MBq in Gdańsk bay and 7.45 MBq (239+240)Pu in Gdańsk basin. From this value in Gdańsk bay 82.1% of plutonium is associated with zoobenthos, 13.6% with phytobenthos, 1.6% with phytoplankton, 1.5% with zooplankton and 1.2% with fish. In Gdańsk basin, 83.2% is associated with zoobenthos, 7.5% with phytobenthos, 3.6% with phytoplankton, 3.2% with zooplankton and 2.5% with fish.

Estimation of weekly 99Mo production by AHR 200 kW

NASA Astrophysics Data System (ADS)

Siregar, I. H.; Suharyana; Khakim, A.; Siregar, D.; Frida, A. R.

2016-11-01

The estimation of weekly 99Mo production by AHR 200 kW fueled with Low Enriched Uranium Uranyl Nitrate solution has been simulated by using MCNPX computer code. We have employed the AHR design of Babcock & Wilcox Medical Isotope Production System with 9Be Reflector and Stainless steel vessel. We found that when the concentration of uranium in the fresh fuel was 108 gr U/L of UO2(NO3)2 fuel solution, the multiplication factor was 1.0517. The 99Mo concentration reached saturated at tenth day operation. The AHR can produce approximately 1.96×103 6-day-Ci weekly.

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.

Aerosol Physics Considerations for Using Cerium Oxide CeO 2 as a Surrogate for Plutonium Oxide PuO 2 in Airborne Release Fraction Measurements for Storage Container Investigations

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

Moore, Murray E.; Tao, Yong

Cerium oxide (CeO2) dust is recommended as a surrogate for plutonium oxide (PuO2) in airborne release fraction experiments. The total range of applicable particle sizes for PuO2 extends from 0.0032 μm (the diameter of a single PuO2 molecule) to 10 μm (the defined upper boundary for respirable particles). For particulates with a physical particle diameter of 1.0 μm, the corresponding aerodynamic diameters for CeO2 and PuO2 are 2.7 μm and 3.4 μm, respectively. Cascade impactor air samplers are capable of measuring the size distributions of CeO2 or PuO2 particulates. In this document, the aerodynamic diameters for CeO2 and PuO2 weremore » calculated for seven different physical diameters (0.0032, 0.02, 0.11, 0.27, 1.0, 3.2, and 10 μm). For cascade impactor measurements, CeO2 and PuO2 particulates with the same physical diameter would be collected onto the same or adjacent collection substrates. The difference between the aerodynamic diameter of CeO2 and PuO2 particles (that have the same physical diameter) is 39% of the resolution of a twelve-stage MSP Inc. 125 cascade impactor, and 34% for an eight-stage Andersen impactor. An approach is given to calculate the committed effective dose (CED) coefficient for PuO2 aerosol particles, compared to a corresponding aerodynamic diameter of CeO2 particles. With this approach, use of CeO2 as a surrogate for PuO2 material would follow a direct conversion based on a molar equivalent. In addition to the analytical information developed for this document, several US national labs have published articles about the use of CeO2 as a PuO2 surrogate. Different physical and chemical aspects were considered by these investigators, including thermal properties, ceramic formulations, cold pressing, sintering, molecular reactions, and mass loss in high temperature gas flows. All of those US national lab studies recommended the use of CeO2 as a surrogate material for PuO2.« less

Extreme Performance Scalable Operating Systems Final Progress Report (July 1, 2008 - October 31, 2011)

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

Malony, Allen D; Shende, Sameer

This is the final progress report for the FastOS (Phase 2) (FastOS-2) project with Argonne National Laboratory and the University of Oregon (UO). The project started at UO on July 1, 2008 and ran until April 30, 2010, at which time a six-month no-cost extension began. The FastOS-2 work at UO delivered excellent results in all research work areas: * scalable parallel monitoring * kernel-level performance measurement * parallel I/0 system measurement * large-scale and hybrid application performance measurement * onlne scalable performance data reduction and analysis * binary instrumentation

Exploring the role of pain as an early predictor of category 2 pressure ulcers: a prospective cohort study.

PubMed

Smith, Isabelle L; Brown, Sarah; McGinnis, Elizabeth; Briggs, Michelle; Coleman, Susanne; Dealey, Carol; Muir, Delia; Nelson, E Andrea; Stevenson, Rebecca; Stubbs, Nikki; Wilson, Lyn; Brown, Julia M; Nixon, Jane

2017-01-20

To explore pressure area related pain as a predictor of category ≥2 pressure ulcer (PU) development. Multicentre prospective cohort study. UK hospital and community settings. Consenting acutely ill patients aged ≥18 years, defined as high risk (Braden bedfast/chairfast AND completely immobile/very limited mobility; pressure area related pain or; category 1 PU). Patients too unwell, unable to report pain, 2 or more category ≥2 PUs. Twice weekly for 30 days. Development and time to development of one or more category ≥2 PUs. Of 3819 screened, 1266 were eligible, 634 patients were recruited, 32 lost to follow-up, providing a 602 analysis population. 152 (25.2%) developed one or more category ≥2 PUs. 464 (77.1%) patients reported pressure area related pain on a healthy, altered or category 1 skin site of whom 130 (28.0%) developed a category ≥2 PU compared with 22 (15.9%) of those without pain. Full stepwise variable selection was used throughout the analyses. (1) Multivariable logistic regression model to assess 9 a priori factors: presence of category 1 PU (OR=3.25, 95% CI (2.17 to 4.86), p<0.0001), alterations to intact skin (OR=1.98, 95% CI (1.30 to 3.00), p=0.0014), pressure area related pain (OR=1.56, 95% CI (0.93 to 2.63), p=0.0931). (2) Multivariable logistic regression model to account for overdispersion: presence of category 1 PU (OR=3.20, 95% CI (2.11 to 4.85), p<0.0001), alterations to intact skin (OR=1.90, 95% CI (1.24 to 2.91), p=0.0032), pressure area related pain (OR=1.85, 95% CI (1.07 to 3.20), p=0.0271), pre-existing category 2 PU (OR=2.09, 95% CI (1.35 to 3.23), p=0.0009), presence of chronic wound (OR=1.66, 95% CI (1.06 to 2.62), p=0.0277), Braden activity (p=0.0476). (3) Accelerated failure time model: presence of category 1 PU (AF=2.32, 95% CI (1.73 to 3.12), p<0.0001), pressure area related pain (AF=2.28, 95% CI (1.59 to 3.27), p<0.0001). (4) 2-level random-intercept logistic regression model: skin status which comprised 2 levels (versus healthy skin); alterations to intact skin (OR=4.65, 95% CI (3.01 to 7.18), p<0.0001), presence of category 1 PU (OR=17.30, 95% CI (11.09 to 27.00), p<0.0001) and pressure area related pain (OR=2.25, 95% CI (1.53 to 3.29), p<0.0001). This is the first study to assess pain as a predictor of category ≥2 PU development. In all 4 models, pain emerged as a risk factor associated with an increased probability of category ≥2 PU development. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Application of the Baxter model for hard-spheres with surface adhesion to SANS data for the U(VI) - HNO{sub 3}, TBP-n-dodecane system.

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

Chiarizia, R.; Nash, K. L.; Jensen, M. P.

2003-11-11

Small-angle neutron scattering (SANS) data for the tri-n-butyl phosphate (TBP)-n-dodecane, HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2} solvent extraction system have been interpreted using the Baxter model for hard spheres with surface adhesion. The increase in the scattering intensity in the low Q range observed when increasing amounts of HNO{sub 3} or UO{sub 2}(NO{sub 3}){sub 2} are transferred into the organic phase has been interpreted as arising from interactions between solute particles. The SANS data have been reproduced using a 12--16 {angstrom} diameter of the hard sphere, d{sub hs}, and a 5.6k{sub B}T-7.1k{sub B}T stickiness parameter, {tau}{sup -1}. When in contact withmore » an aqueous phase, TBP in n-dodecane forms small reverse micelles containing three TBP molecules. Upon extraction of water, HNO{sub 3}, and UO{sub 2}(NO{sub 3}){sub 2}, the swollen micelles interact through attractive forces between their polar cores with a potential energy of about 2k{sub B}T and an effective Hamaker constant of about 4k{sub B}T. The intermicellar attraction, under suitable conditions, leads to third-phase formation. Upon phase splitting, most of the solutes in the original organic phase (water, TBP, HNO{sub 3}, and UO{sub 2}(NO{sub 3}){sub 2}) separate in a continuous phase containing interspersed layers of n-dodecane.« less

Review and statistical analysis of the use of ultrasonic velocity for estimating the porosity fraction in polycrystalline materials

NASA Technical Reports Server (NTRS)

Roth, D. J.; Swickard, S. M.; Stang, D. B.; Deguire, M. R.

1991-01-01

A review and statistical analysis of the ultrasonic velocity method for estimating the porosity fraction in polycrystalline materials is presented. Initially, a semiempirical model is developed showing the origin of the linear relationship between ultrasonic velocity and porosity fraction. Then, from a compilation of data produced by many researchers, scatter plots of velocity versus percent porosity data are shown for Al2O3, MgO, porcelain-based ceramics, PZT, SiC, Si3N4, steel, tungsten, UO2,(U0.30Pu0.70)C, and YBa2Cu3O(7-x). Linear regression analysis produces predicted slope, intercept, correlation coefficient, level of significance, and confidence interval statistics for the data. Velocity values predicted from regression analysis of fully-dense materials are in good agreement with those calculated from elastic properties.

Review and statistical analysis of the ultrasonic velocity method for estimating the porosity fraction in polycrystalline materials

NASA Technical Reports Server (NTRS)

Roth, D. J.; Swickard, S. M.; Stang, D. B.; Deguire, M. R.

1990-01-01

A review and statistical analysis of the ultrasonic velocity method for estimating the porosity fraction in polycrystalline materials is presented. Initially, a semi-empirical model is developed showing the origin of the linear relationship between ultrasonic velocity and porosity fraction. Then, from a compilation of data produced by many researchers, scatter plots of velocity versus percent porosity data are shown for Al2O3, MgO, porcelain-based ceramics, PZT, SiC, Si3N4, steel, tungsten, UO2,(U0.30Pu0.70)C, and YBa2Cu3O(7-x). Linear regression analysis produced predicted slope, intercept, correlation coefficient, level of significance, and confidence interval statistics for the data. Velocity values predicted from regression analysis for fully-dense materials are in good agreement with those calculated from elastic properties.

Criticality Safety Controls for 55-Gallon Drums with a Mass Limit of 200 grams Pu-239

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

Chou, P

The following 200-gram Pu drum criticality safety controls are applicable to RHWM drum storage operations: (1) Mass (Fissile/Pu) - each 55-gallon drum or its equivalent shall be limited to 200 gram Pu or Pu equivalent; (2) Moderation - Hydrogen materials with a hydrogen density greater than that (0.133 g H/cc) of polyethylene and paraffin are not allowed and hydrogen materials with a hydrogen density no greater than that of polyethylene and paraffin are allowed with unlimited amounts; (3) Interaction - a spacing of 30-inches (76 cm) is required between arrays and 200-gram Pu drums shall be placed in arrays formore » 200-gram Pu drums only (no mingling of 200-gram Pu drums with other drums not meeting the drum controls associated with the 200-gram limit); (4) Reflection - no beryllium and carbon/graphite (other than the 50-gram waiver amount) is allowed, (note that Nat-U exceeding the waiver amount is allowed when its U-235 content is included in the fissile mass limit of 200 grams); and (5) Geometry - drum geometry, only 55-gallon drum or its equivalent shall be used and array geometry, 55-gallon drums are allowed for 2-high stacking. Steel waste boxes may be stacked 3-high if constraint.« less

Influence of Background H2O on the Collision-Induced Dissociation Products Generated from [UO2NO3]+

NASA Astrophysics Data System (ADS)

Van Stipdonk, Michael J.; Iacovino, Anna; Tatosian, Irena

2018-04-01

Developing a comprehensive understanding of the reactivity of uranium-containing species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium for subsequent studies of intrinsic structure and reactivity. Recent experiments by our group have demonstrated that the relatively low levels of residual H2O in a 2-D, linear ion trap (LIT) make it possible to examine fragmentation pathways and reactions not observed in earlier studies conducted with 3-D ion traps (Van Stipdonk et al. J. Am. Soc. Mass Spectrom. 14, 1205-1214, 2003). In the present study, we revisited the dissociation of complexes composed of uranyl nitrate cation [UVIO2(NO3)]+ coordinated by alcohol ligands (methanol and ethanol) using the 2-D LIT. With relatively low levels of background H2O, collision-induced dissociation (CID) of [UVIO2(NO3)]+ primarily creates [UO2(O2)]+ by the ejection of NO. However, CID (using He as collision gas) of [UVIO2(NO3)]+ creates [UO2(H2O)]+ and UO2 + when the 2-D LIT is used with higher levels of background H2O. Based on the results presented here, we propose that product ion spectrum in the previous experiments was the result of a two-step process: initial formation of [UVIO2(O2)]+ followed by rapid exchange of O2 for H2O by ion-molecule reaction. Our experiments illustrate the impact of residual H2O in ion trap instruments on the product ions generated by CID and provide a more accurate description of the intrinsic dissociation pathway for [UVIO2(NO3)]+. [Figure not available: see fulltext.

The effect of ion irradiation on the dissolution of UO 2 and UO 2 -based simulant fuel

DOE PAGES

Popel, Aleksej J.; Wietsma, Thomas W.; Engelhard, Mark H.; ...

2017-11-21

Our aim is to study the separate effect of fission fragment damage on the dissolution of simulant UK advanced gas-cooled reactor nuclear fuel in water. Plain UO 2 and UO 2 samples, doped with inactive fission products to simulate 43 GWd/tU of burn-up, were fabricated. A set of these samples were then irradiated with 92 MeV 129Xe 23+ ions to a fluence of 4.8 × 10 15 ions/cm 2 to simulate the fission damage that occurs within nuclear fuels. The primary effect of the irradiation on the UO 2 samples, observed by scanning electron microscopy, was to induce a smootheningmore » of the surface features and formation of hollow blisters, which was attributed to multiple overlap of ion tracks. Dissolution experiments were conducted in single-pass flow-through (SPFT) mode under anoxic conditions (<0.1 O 2 ppm in Ar) to study the effect of the induced irradiation damage on the dissolution of the UO 2 matrix with data collection capturing six minute intervals for several hours. These time-resolved data showed that the irradiated samples showed a higher initial release of uranium than unirradiated samples, but that the uranium concentrations converged towards ~10 -9 mol/l after a few hours. And apart from the initial spike in uranium concentration, attributed to irradiation induced surficial micro-structural changes, no noticeable difference in uranium chemistry as measured by X-ray electron spectroscopy or ‘effective solubility’ was observed between the irradiated, doped and undoped samples in this work. Some secondary phase formation was observed on the surface of UO 2 samples after the dissolution experiment.« less

The effect of ion irradiation on the dissolution of UO 2 and UO 2 -based simulant fuel

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

Popel, Aleksej J.; Wietsma, Thomas W.; Engelhard, Mark H.

Our aim is to study the separate effect of fission fragment damage on the dissolution of simulant UK advanced gas-cooled reactor nuclear fuel in water. Plain UO 2 and UO 2 samples, doped with inactive fission products to simulate 43 GWd/tU of burn-up, were fabricated. A set of these samples were then irradiated with 92 MeV 129Xe 23+ ions to a fluence of 4.8 × 10 15 ions/cm 2 to simulate the fission damage that occurs within nuclear fuels. The primary effect of the irradiation on the UO 2 samples, observed by scanning electron microscopy, was to induce a smootheningmore » of the surface features and formation of hollow blisters, which was attributed to multiple overlap of ion tracks. Dissolution experiments were conducted in single-pass flow-through (SPFT) mode under anoxic conditions (<0.1 O 2 ppm in Ar) to study the effect of the induced irradiation damage on the dissolution of the UO 2 matrix with data collection capturing six minute intervals for several hours. These time-resolved data showed that the irradiated samples showed a higher initial release of uranium than unirradiated samples, but that the uranium concentrations converged towards ~10 -9 mol/l after a few hours. And apart from the initial spike in uranium concentration, attributed to irradiation induced surficial micro-structural changes, no noticeable difference in uranium chemistry as measured by X-ray electron spectroscopy or ‘effective solubility’ was observed between the irradiated, doped and undoped samples in this work. Some secondary phase formation was observed on the surface of UO 2 samples after the dissolution experiment.« less

Seaborg's plutonium? A case study in nuclear forensics

DOE PAGES

Norman, Eric B.; Thomas, Keenan J.; Telhami, Kristina E.

2015-10-01

Passive X-ray and gamma-ray analysis was performed on a curious sample from UC Berkeley's Hazardous Material Facility inventory, and the object was found to contain 239Pu. No other radioactive isotopes were observed. The mass of 239Pu contained in this object was determined to be 2.0 ± 0.3 μg. These observations are consistent with the identification of this object as containing the 2.77-μg PuO2 (2.44 μg 239Pu) sample produced in 1942 and described by Seaborg and his collaborators as the first sample of 239Pu that was large enough to be weighed.

Incipient class II mixed valency in a plutonium solid-state compound

NASA Astrophysics Data System (ADS)

Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L.; Hobart, David L.; Baumbach, Ryan E.; Cross, Justin N.; Stritzinger, Jared T.; Polinski, Matthew J.; Maron, Laurent; Albrecht-Schmitt, Thomas E.

2017-09-01

Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4]Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.

[The molecular composition and spectral properties of polysaccharide isolated from pu-erh tea and its material].

PubMed

Gong, Jia-shun; Hu, Xiao-jing; Peng, Chun-xiu; Zhou, Hong-jie

2010-07-01

Pu-erh tea, a kind of well-known tea from the ancient time, is originally produced in the Yunnan Lanchan River basin through a special solid state fermentation by fungi. It uses sun-dried green tea as its starting materials. To investigate the variation of composition and spectral properties of polysaccharide during solid state fermentation of pu-erh tea by using Saccharomyces cerevisiae as preponderant starter and using sun-dried green tea as materials in the present study. The results showed that the content of water soluble polysaccharide was increased, and the activity of hydrolase such as cellulase, pectinase and glucomylase were also enhanced. The content of neutral sugar increased with the ferment time increasing and the M(w) of raw polysaccharide showed significant difference during fermentation. The main polysaccharide TPS2 and TPS1 were isolated and purified from pu-erh tea and its materials by DEAE-52 and Sephadex G-150 column chromatography. TPS2 contains the higher content of uronic acid, but TPS1 contains the higher contents of neutral sugar and protein. Monosaccharide analysis by GC-MS revealed that TPS1 and TPS2 were composed of arabinose, galactose, glucose, rhamnose, xylose and mannose with molar ratios of 24.2 : 23.6 : 5.9 : 3.2 : 1.8 : 1.1 and 19.3 : 26.9 : 3.2 : 2.7 : 1.3 : 5.5, respectively. The average molecular weight of TPS1 and TPS2 was 1.68 x 10(4) and 1.21 x 10(4) Daltons, respectively. UV scanning spectrum showed that TPS1 and TPS2 had no characteristic absorption between 200 and 400 nm wavelength, it suggested that they contain trace protein. IR spectrum of TPS1 and TPS2 demonstrated that pyranoid rings were contained in them. As shown in the image of atomic force microscope, the molecular appearance of TPS1 and TPS2 resembled islands and apparently consisted of conglomerations. The height of conglomerations of TPS2 was about 40 nm and the length or width was 0.5-0.8 microm, while the height of conglomerations of TPS1 was about 4nm and the length or width was 0.2-0.4 microm. TPS2 shows sheet conglomerations with rough surface, but TPS1 shows squama conglomerations with smooth surface in the image of scanning electron micrograph. The experimental data suggested that the variation of composition and spectral properties of polysaccharide isolated from pu-erh tea and its materials owed to the action of microorganism and humid and thermal action for long time process.

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.

Renal pelvic and ureteral ultrasonographic characteristics of cats with chronic kidney disease in comparison with normal cats, and cats with pyelonephritis or ureteral obstruction.

PubMed

Quimby, Jessica M; Dowers, Kristy; Herndon, Andrea K; Randall, Elissa K

2017-08-01

Objectives The objective was to describe ultrasonographic characteristics of cats with stable chronic kidney disease (CKD) and determine if these were significantly different from cats with pyelonephritis (Pyelo) and ureteral obstruction (UO), to aid in clinical assessment during uremic crisis. Methods Sixty-six cats with stable CKD were prospectively enrolled, as well as normal control cats (n = 10), cats with a clinical diagnosis of Pyelo (n = 13) and cats with UO confirmed by surgical resolution (n = 11). Renal ultrasound was performed and routine still images and cine loops were obtained. Analysis included degree of pelvic dilation, and presence and degree of ureteral dilation. Measurements were compared between groups using non-parametric one-way ANOVA with Dunn's post-hoc analysis. Results In total, 66.6% of CKD cats had measurable renal pelvic dilation compared with 30.0% of normal cats, 84.6% of Pyelo cats and 100% of UO cats. There was no statistically significant difference in renal pelvic widths between CKD cats and normal cats, or CKD cats and Pyelo cats. On almost all measurement categories, UO cats had significantly greater renal pelvic widths compared with CKD cats and normal cats ( P <0.05) but not Pyelo cats. Six percent of stable CKD cats had measurable proximal ureteral dilation on one or both sides vs 46.2% of Pyelo cats and 81.8% of UO cats. There was no statistically significant difference in proximal ureteral width between normal and CKD cats, or between Pyelo and UO cats. There was a statistically significant difference in proximal ureteral width between CKD and Pyelo cats, CKD and UO cats, normal and UO cats, and normal and Pyelo cats. Conclusions and relevance No significant difference in renal pelvic widths between CKD cats and Pyelo cats was seen. These data suggest CKD cats should have a baseline ultrasonography performed so that abnormalities documented during a uremic crisis can be better interpreted.

Thienoquinolins exert diuresis by strongly inhibiting UT-A urea transporters

PubMed Central

Ren, Huiwen; Wang, Yanhua; Xing, Yongning; Ran, Jianhua; Liu, Ming; Lei, Tianluo; Zhou, Hong; Li, Runtao; Sands, Jeff M.

2014-01-01

Urea transporters (UT) play an important role in the urine concentration mechanism by mediating intrarenal urea recycling, suggesting that UT inhibitors could have therapeutic use as a novel class of diuretic. Recently, we found a thienoquinolin UT inhibitor, PU-14, that exhibited diuretic activity. The purpose of this study was to identify more potent UT inhibitors that strongly inhibit UT-A isoforms in the inner medullary collecting duct (IMCD). Efficient thienoquinolin UT inhibitors were identified by structure-activity relationship analysis. Urea transport inhibition activity was assayed in perfused rat terminal IMCDs. Diuretic activity of the compound was determined in rats and mice using metabolic cages. The results show that the compound PU-48 exhibited potent UT-A inhibition activity. The inhibition was 69.5% with an IC50 of 0.32 μM. PU-48 significantly inhibited urea transport in perfused rat terminal IMCDs. PU-48 caused significant diuresis in UT-B null mice, which indicates that UT-A is the target of PU-48. The diuresis caused by PU-48 did not change blood Na+, K+, or Cl− levels or nonurea solute excretion in rats and mice. No toxicity was detected in cells or animals treated with PU-48. The results indicate that thienoquinolin UT inhibitors induce a diuresis by inhibiting UT-A in the IMCD. This suggests that they may have the potential to be developed as a novel class of diuretics with fewer side effects than classical diuretics. PMID:25298523

Thienoquinolins exert diuresis by strongly inhibiting UT-A urea transporters.

PubMed

Ren, Huiwen; Wang, Yanhua; Xing, Yongning; Ran, Jianhua; Liu, Ming; Lei, Tianluo; Zhou, Hong; Li, Runtao; Sands, Jeff M; Yang, Baoxue

2014-12-15

Urea transporters (UT) play an important role in the urine concentration mechanism by mediating intrarenal urea recycling, suggesting that UT inhibitors could have therapeutic use as a novel class of diuretic. Recently, we found a thienoquinolin UT inhibitor, PU-14, that exhibited diuretic activity. The purpose of this study was to identify more potent UT inhibitors that strongly inhibit UT-A isoforms in the inner medullary collecting duct (IMCD). Efficient thienoquinolin UT inhibitors were identified by structure-activity relationship analysis. Urea transport inhibition activity was assayed in perfused rat terminal IMCDs. Diuretic activity of the compound was determined in rats and mice using metabolic cages. The results show that the compound PU-48 exhibited potent UT-A inhibition activity. The inhibition was 69.5% with an IC50 of 0.32 μM. PU-48 significantly inhibited urea transport in perfused rat terminal IMCDs. PU-48 caused significant diuresis in UT-B null mice, which indicates that UT-A is the target of PU-48. The diuresis caused by PU-48 did not change blood Na(+), K(+), or Cl(-) levels or nonurea solute excretion in rats and mice. No toxicity was detected in cells or animals treated with PU-48. The results indicate that thienoquinolin UT inhibitors induce a diuresis by inhibiting UT-A in the IMCD. This suggests that they may have the potential to be developed as a novel class of diuretics with fewer side effects than classical diuretics. Copyright © 2014 the American Physiological Society.

Investigation of low-level 242Pu contamination on nutrition disturbance and oxidative stress in Solanum tuberosum L.

PubMed

Gupta, Dharmendra K; Tawussi, Frank; Hölzer, Alex; Hamann, Linda; Walther, Clemens

2017-07-01

Plutonium associated with higher molecular weight molecules is presumed to be poorly mobile and hardly plant available. In our present study, we investigate the uptake and effects of Pu treatments on Solanum tuberosum plants in amended Hoagland medium at concentrations of [ 242 Pu] = 100 and 500 nm, respectively. We found a direct proof of oxidative stress in the plants caused by these rather low concentrations. For the confirmation of oxidative stress, we explored the production of nitric oxide (NO) and hydrogen peroxide (H 2 O 2 ) by epifluorescence microscopy. Oxidative stress markers like lipid peroxidation and superoxide radicals (O 2 •- ) are monitored through histochemical analysis. The biochemical parameters i.e. chlorophyll and carotenoids are measured as an indicator of cellular damage in the tested plants including the enzymatic parameters such as catalase and glutathione reductase. From our work, we conclude that Pu in low concentration has no significant effects on the uptake of many trace and macroelements. In contrast, the content of O 2 •- , malondialdehyde (MDA), and H 2 O 2 increases with increasing Pu concentration in the solution, while the opposite effects was found for NO, catalase, and glutathione reductase. These findings prove that even low concentration of Pu regulates ROS production and generate oxidative stress in S. tuberosum L.

Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

2008-02-15

A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

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

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 isolate A to UO(2) (2+) toxicity, and limited ability of isolate A to accumulate UO(2) (2+). (c) 2010 SETAC.

Investigating microstructural evolution during the electroreduction of UO2 to U in LiCl-KCl eutectic using focused ion beam tomography

NASA Astrophysics Data System (ADS)

Brown, L. D.; Abdulaziz, R.; Tjaden, B.; Inman, D.; Brett, D. J. L.; Shearing, P. R.

2016-11-01

Reprocessing of spent nuclear fuels using molten salt media is an attractive alternative to liquid-liquid extraction techniques. Pyroelectrochemical processing utilizes direct, selective, electrochemical reduction of uranium dioxide, followed by selective electroplating of a uranium metal. Thermodynamic prediction of the electrochemical reduction of UO2 to U in LiCl-KCl eutectic has shown to be a function of the oxide ion activity. The pO2- of the salt may be affected by the microstructure of the UO2 electrode. A uranium dioxide filled "micro-bucket" electrode has been partially electroreduced to uranium metal in molten lithium chloride-potassium chloride eutectic. This partial electroreduction resulted in two distinct microstructures: a dense UO2 and a porous U metal structure were characterised by energy dispersive X-ray spectroscopy. Focused ion beam tomography was performed on five regions of this electrode which revealed an overall porosity ranging from 17.36% at the outer edge to 3.91% towards the centre, commensurate with the expected extent of reaction in each location. The pore connectivity was also seen to reduce from 88.32% to 17.86% in the same regions and the tortuosity through the sample was modelled along the axis of propagation of the electroreduction, which was seen to increase from a value of 4.42 to a value of infinity (disconnected pores). These microstructural characteristics could impede the transport of O2- ions resulting in a change in the local pO2- which could result in the inability to perform the electroreduction.

Enhancement of fermentation process in Pu-erh tea by tea-leaf extract.

PubMed

Hou, C W; Jeng, K C; Chen, Y S

2010-01-01

Pu-erh tea is known as a fermented tea and longer storage enhances its flavor and taste. Recently, Aspergillus, Blastobotrys, and Streptomyces are found to play important roles in nutritional enhancement of Pu-erh tea by fermentation. Since water and temperature affect the microbial growth, we therefore explored the factors that might enhance the Pu-erh tea fermentation. The results showed that the addition of fresh tea-leaf extract (TLE) enhanced the withered tea fermentation (at 37 degrees C, 80 to 85% RH) as compared with the water only. Contents of statin, GABA, gallic acid, DPPH scavenging and polyphenol oxidase (PPO) activities were increased, whereas polyphenols and caffeine were decreased over 6 mo. TLE dose-dependently enhanced some of the qualities (that is, statin, PPO) of Pu-erh tea significantly as compared with the water only. The effect was related to the increase population of A. niger and A. carbonarius at 6 mo (from 7.6 +/- 1.2 x 10(1) and 3.2 +/- 1.3 x 10(1) to 3.1 +/- 1.2 x 10(6) and 2.4 +/- 1.1 x 10(5) colony forming units [CFU]/g, respectively). After drying process (90 degrees C, 30 min), the total microbial count from these samples returned to background level (3 +/- 0.5 x 10(2) CFU/g). None of ochratoxin and fumonisin, toxins from Aspergillus, was detected in the final products. The flavor and taste were also enhanced by treatment with TLE. The inoculation with S. cinereus Y11 with 2% TLE further enhanced these functional contents (about 2-fold increase of statin level) in the experimental Pu-erh tea. Therefore, this result may add a new process for Pu-erh tea manufacture.

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

Yamashita, T.; Fujino, T.; Masaki, N.

The structural parameters of ..cap alpha..- and ..beta..-CdUO/sub 4/ crystals are determined by x-ray powder diffraction technique. ..cap alpha..-CdUO/sub 4/ is rhombohedral and cell parameters are a = 6.233(3) A and ..cap alpha.. = 36.12(5)/sup 0/. ..beta..-CdUO/sub 4/ crystallizes in a C-centered orthorhombic cell with a = 7.023(4), b = 6.849(3), c = 3.514(2) A. The space groups are R3m for ..cap alpha..-CdUO/sub 4/ and Cmmm for ..beta..-CdUO/sub 4/. ..cap alpha..-CdUO/sub 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. ..beta..-CdUO/sub 4/: 2U in (000; 1/2more » 1/2 0), 2Cd in (1/2 0 1/2; 0 1/2 1/2), 40(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. ..beta..-CdUO/sub 4/ contains collinear uranyl UO/sub 2//sup 2 +/ groups with a U-O(1) distance of 1.91 A, located either along or parallel to the c axis whereas the U-O(1) bond length in ..cap alpha..-CdUO/sub 4/ is 1.98 A which is longer than the usual uranyl bond length.« less

High resolution photoelectron imaging of UO(-) and UO2(-) and the low-lying electronic states and vibrational frequencies of UO and UO2.

PubMed

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(-) and UO2(-). The spectra for UO2(-) 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 UO2 as 1.1688(6) eV. The symmetric stretching modes for the neutral and anionic ground states, and two neutral excited states for UO2 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 UO2 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.

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.

Enhancing BWR proliferation resistance fuel with minor actinides

NASA Astrophysics Data System (ADS)

Chang, Gray S.

2009-03-01

To reduce spent fuel for storage and enhance the proliferation resistance for the intermediate-term, there are two major approaches (a) increase the discharged spent fuel burnup in the advanced light water reactor- LWR (Gen-III Plus), which not only can reduce the spent fuel for storage, but also increase the 238Pu isotopes ratio to enhance the proliferation resistance, and (b) use of transuranic nuclides ( 237Np and 241Am) in the high burnup fuel, which can drastically increase the proliferation resistance isotope ratio of 238Pu/Pu. For future advanced nuclear systems, minor actinides (MA) are viewed more as a resource to be recycled, and transmuted to less hazardous and possibly more useful forms, rather than simply disposed of as a waste stream in an expensive repository facility. As a result, MAs play a much larger part in the design of advanced systems and fuel cycles, not only as additional sources of useful energy, but also as direct contributors to the reactivity control of the systems into which they are incorporated. In the study, a typical boiling water reactor (BWR) fuel unit lattice cell model with UO 2 fuel pins will be used to investigate the effectiveness of minor actinide reduction approach (MARA) for enhancing proliferation resistance and improving the fuel cycle performance in the intermediate-term goal for future nuclear energy systems. To account for the water coolant density variation from the bottom (0.76 g/cm 3) to the top (0.35 g/cm 3) of the core, the axial coolant channel and fuel pin were divided to 24 nodes. The MA transmutation characteristics at different elevations were compared and their impact on neutronics criticality discussed. The concept of MARA, which involves the use of transuranic nuclides ( 237Np and/or 241Am), significantly increases the 238Pu/Pu ratio for proliferation resistance, as well as serves as a burnable absorber to hold-down the initial excess reactivity. It is believed that MARA can play an important role in atoms for peace and the intermediate-term of nuclear energy reconnaissance.

A thermal conductivity model for U-­Si compounds

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

Zhang, Yongfeng; Andersson, Anders David Ragnar

U 3Si 2 is a candidate for accident tolerant nuclear fuel being developed as an alternative to UO 2 in commercial light water reactors (LWRs). One of its main benefits compared to UO 2 is higher thermal conductivity that increases with temperature. This increase is contrary to UO 2, for which the thermal conductivity decreases with temperature. The reason for the difference is the electronic origin of thermal conductivity in U 3Si 2, as compared to the phonon mechanism responsible for thermal transport in UO 2. The phonon thermal conductivity in UO 2 is unusually low for a fluorite oxidemore » due to the strong interaction with the spins in the paramagnetic phase. The thermal conductivity of U 3Si 2 as well as other U-­Si compounds has been measured experimentally [1-­4]. However, for fuel performance simulations it is also critical to model the degradation of the thermal conductivity due to damage and microstructure evolution caused by the reactor environment (irradiation and high temperature). For UO 2 this reduction is substantial and it has been the topic of extensive NEAMS research resulting in several publications [5, 6]. There are no data or models for the evolution of the U 3Si 2 thermal conductivity under irradiation. We know that the intrinsic thermal conductivities of UO 2 (semi-conductor) and U 3Si 2 (metal) are very different, and we do not necessarily expect the dependence on damage to be the same either, which could present another advantage for the silicide fuel. In this report we summarize the first step in developing a model for the thermal conductivity of U-­Si compounds with the goal of capturing the effect of damage in U 3Si 2. Next year, we will focus on lattice damage. We will also attempt to assess the impact of fission gas bubbles.« less

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

Reliability of laser Doppler, near-infrared spectroscopy and Doppler ultrasound for peripheral blood flow measurements during and after exercise in the heat.

PubMed

Choo, Hui C; Nosaka, Kazunori; Peiffer, Jeremiah J; Ihsan, Mohammed; Yeo, Chow C; Abbiss, Chris R

2017-09-01

This study examined the test-retest reliability of near-infrared spectroscopy (NIRS), laser Doppler flowmetry (LDF) and Doppler ultrasound to assess exercise-induced haemodynamics. Nine men completed two identical trials consisting of 25-min submaximal cycling at first ventilatory threshold followed by repeated 30-s bouts of high-intensity (90% of peak power) cycling in 32.8 ± 0.4°C and 32 ± 5% relative humidity (RH). NIRS (tissue oxygenation index [TOI] and total haemoglobin [tHb]) and LDF (perfusion units [PU]) signals were monitored continuously during exercise, and leg blood flow was assessed by Doppler ultrasound at baseline and after exercise. Cutaneous vascular conductance (CVC; PU/mean arterial pressure (MAP)) was expressed as the percentage change from baseline (%CVC BL ). Coefficients of variation (CVs) as indicators of absolute reliability were 18.7-28.4%, 20.2-33.1%, 42.5-59.8%, 7.8-12.4% and 22.2-30.3% for PU, CVC, %CVC BL , TOI and tHb, respectively. CVs for these variables improved as exercise continued beyond 10 min. CVs for baseline and post-exercise leg blood flow were 17.8% and 10.5%, respectively. CVs for PU, tHb (r 2  = 0.062) and TOI (r 2  = 0.002) were not correlated (P > 0.05). Most variables demonstrated CVs lower than the expected changes (35%) induced by training or heat stress; however, minimum of 10 min exercise is recommended for more reliable measurements.

Effects of Plutonium on Soil Microorganisms

PubMed Central

Wildung, Raymond E.; Garland, Thomas R.

1982-01-01

As a first phase in an investigation of the role of the soil microflora in Pu complex formation and solubilization in soil, the effects of Pu concentration, form, and specific activity on microbial types, colony-forming units, and CO2 evolution rate were determined in soils amended with C and N sources to optimize microbial activity. The effects of Pu differed with organism type and incubation time. After 30 days of incubation, aerobic sporeforming and anaerobic bacteria were significantly affected by soil Pu levels as low as 1 μg/g when Pu was added as the hydrolyzable 239Pu(NO3)4 (solubility, <0.1% in soil). Other classes of organisms, except the fungi, were significantly affected at soil Pu levels of 10 μg/g. Fungi were affected only at soil Pu levels of 180 μg/g. Soil CO2 evolution rate and total accumulated CO2 were affected by Pu only at the 180 μg/g level. Because of the possible role of resistant organisms in complex formation, the mechanisms of effects of Pu on the soil fungi were further evaluated. The effect of Pu on soil fungal colony-forming units was a function of Pu solubility in soil and Pu specific activity. When Pu was added in a soluble, complexed form [238Pu2(diethylenetriaminepentaacetate)3], effects occurred at Pu levels of 1 μg/g and persisted for at least 95 days. Toxicity was due primarily to radiation effects rather than to chemical effects, suggesting that, at least in the case of the fungi, formation of Pu complexes would result primarily from ligands associated with normal (in contrast to chemically-induced) biochemical pathways. PMID:16345947

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

Membrane optode for uranium(VI) ions preconcentration and quantification based on a synergistic combination of 4-(2-thiazolylazo)-resorcinol with 8-hydroxyquinaldine

NASA Astrophysics Data System (ADS)

Kalyan, Y.; Pandey, A. K.; Naidu, G. R. K.; Reddy, A. V. R.

2009-12-01

A membrane optode was developed utilizing the 8-hydroxyquinaldine (HQ) facilitated preconcentration of UO 22+ ions and subsequent colored complex formation of UO 22+ with 4-(2-thiazolylazo)-resorcinol (TAR) in optode matrix. The composition of the membrane optode was optimized by scanning several extractants immobilized in different plasticized polymer matrices. It was observed that the chelating agent HQ along with an indicator TAR immobilized in the tri-(2-ethylhexyl)phosphate (TEHP) plasticized cellulose triacetate matrix (CTA) was best suited as an optode for the UO 22+ ions in aqueous samples. On sorption of UO 22+ in the optode matrix, TAR changes color of the optode from yellow to magenta having a maximum absorbance ( λmax) at 546 nm. The uptake of UO 22+ ions in the optode was found to be pH dependent and was maximum (>90%) at pH above 3. The acetate buffer (0.1 mol L -1 sodium acetate + 0.1 mol L -1 acetic acid) was found to be necessary for the stable response. The optimum equilibration time for the optode (2 cm × 1 cm) was found to be 30 min in 10 mL aqueous sample containing acetate buffer (pH 4.75). The equilibration time was found to increase with increase in aqueous sample volume. The optode response was found to be linear in the UO 22+ ions concentration range of 0.01-0.11 μmol L -1 in tap water as well as aqueous solutions containing 0.1 mol L -1 NaCl or NaNO 3. The tolerance to the presence of several cations and anions in the determination of UO 22+ ion was studied. It was observed that the optode in the presence of buffer can tolerate presence of large amounts of interfering cations (Ce 4+, V 4+, Eu 3+, Al 3+, Fe 3+, Ni 2+, Cd 2+, Co 2+, Pb 2+, Hg 2+, Cu 2+ and Th 4+ ions) without hindering the sorption of UO 22+ ions in the optode matrix. The present work indicated that 50 ppb UO 22+ ions in 100 mL sample can easily be quantified using this optode. The optode was found to be fully reversible, can readily be regenerated by equilibrating it with 0.1 mol L -1 HNO 3 and reusable up to three cycles. The applicability of the developed optode in real samples was studied by determining uranium in the ground water samples spiked with a known quantity of UO 22+ ions.

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.)

Oxygen chemical diffusion in hypo-stoichiometric MOX

NASA Astrophysics Data System (ADS)

Kato, Masato; Morimoto, Kyoichi; Tamura, Tetsuya; Sunaoshi, Takeo; Konashi, Kenji; Aono, Shigenori; Kashimura, Motoaki

2009-06-01

Kinetics of the oxygen-to-metal ratio change in (U 0.8Pu 0.2)O 2-x and (U 0.7Pu 0.3)O 2-x was evaluated in the temperature range of 1523-1623 K using a thermo-gravimetric technique. The oxygen chemical diffusion coefficients were decided as a function of temperature from the kinetics of the reduction process under a hypo-stoichiometric composition. The diffusion coefficient of (U 0.7Pu 0.3)O 2-x was smaller than that of (U 0.8Pu 0.2)O 2-x. No strong dependence was observed for the diffusion coefficient on the O/M variation of samples.

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.

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(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-) indicates that the entering/leaving water molecules are located outside the plane formed by the spectator ligands.

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.

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.

Oxygen potentials of mixed oxide fuels for fast reactors

NASA Astrophysics Data System (ADS)

Kato, M.; Tamura, T.; Konashi, K.

2009-03-01

Oxygen potentials of homogenous (Pu0.2U0.8)O2-x and (Am0.02Pu0.30Np0.02U0.66)O2-x which have been developed as fuels for fast breeder reactors were measured at temperatures of 1473-1623 K by a gas equilibrium method using an (Ar, H2, H2O) gas mixture. The measured oxygen potentials of (Pu0.2U0.8)O2-x were about 25 kJ mol-1 lower than those of (Pu0.3U0.7)O2-x measured previously and were consistent with the values calculated by Besmann and Lindemer's model. The measured oxygen potentials of (Am0.02Pu0.30Np0.02U0.66)O2-x were slightly higher than those of MOX without minor actinides. No fuel-cladding chemical interaction is affected significantly by adding their minor actinides.

Results of Uranium Dioxide-Tungsten Irradiation Test and Post-Test Examination

NASA Technical Reports Server (NTRS)

Collins, J. F.; Debogdan, C. E.; Diianni, D. C.

1973-01-01

A uranium dioxide (UO2) fueled capsule was fabricated and irradiated in the NASA Plum Brook Reactor Facility. The capsule consisted of two bulk UO2 specimens clad with chemically vapor deposited tungsten (CVD W) 0.762 and 0.1016 cm (0.030-and 0.040-in.) thick, respectively. The second specimen with 0.1016-cm (0.040-in.) thick cladding was irradiated at temperature for 2607 hours, corresponding to an average burnup of 1.516 x 10 to the 20th power fissions/cu cm. Postirradiation examination showed distortion in the bottom end cap, failure of the weld joint, and fracture of the central vent tube. Diametral growth was 1.3 percent. No evidence of gross interaction between CVD tungsten or arc-cast tungsten cladding and the UO2 fuel was observed. Some of the fission gases passed from the fuel cavity to the gas surrounding the fuel specimen via the vent tube and possibly the end-cap weld failure. Whether the UO2 loss rates through the vent tube were within acceptable limits could not be determined in view of the end-cap weld failure.

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

Valderrama, Billy; He, Lingfeng; Henderson, Hunter B.

Fission products, such as krypton (Kr), are known to be insoluble within UO 2, segregating towards grain boundaries, eventually leading to a lowering of the thermal conductivity and fuel swelling. Recent computational studies have identified that differences in grain boundary structure have a significant effect on the segregation behavior of fission products. However, experimental work supporting these simulations is lacking. Atom probe tomography was used to measure the Kr distribution across grain boundaries in UO 2. Polycrystalline depleted-UO 2 samples was irradiated with 0.7 and 1.8 MeV Kr-ions and annealed to 1000ºC, 1300ºC, and 1600°C for 1 hour to producemore » a Kr-bubble dominated microstructure. The results of this work indicate a strong dependence of Kr concentration as a function of grain boundary structure. Temperature also influences grain boundary chemistry with greater Kr concentration evident at higher temperatures, resulting in a reduced Kr concentration in the bulk. While Kr migration is active at elevated temperatures, no changes in grain size or texture were observed in the irradiated UO 2 samples.« less

Intensive Monitoring of Urine Output Is Associated With Increased Detection of Acute Kidney Injury and Improved Outcomes.

PubMed

Jin, Kui; Murugan, Raghavan; Sileanu, Florentina E; Foldes, Emily; Priyanka, Priyanka; Clermont, Gilles; Kellum, John A

2017-11-01

Urine output (UO) is a vital sign for critically ill patients, but standards for monitoring and reporting vary widely between ICUs. Careful monitoring of UO could lead to earlier recognition of acute kidney injury (AKI) and better fluid management. We sought to determine if the intensity of UO monitoring is associated with outcomes in patients with and those without AKI. This was a retrospective cohort study including 15,724 adults admitted to ICUs from 2000 to 2008. Intensive UO monitoring was defined as hourly recordings and no gaps > 3 hours for the first 48 hours after ICU admission. Intensive monitoring for UO was conducted in 4,049 patients (26%), and we found significantly higher rates of AKI (OR, 1.22; P < .001) in these patients. After adjustment for age and severity of illness, intensive UO monitoring was associated with improved survival but only among patients experiencing AKI. With or without AKI, patients with intensive monitoring also had less cumulative fluid volume (2.98 L vs 3.78 L; P < .001) and less fluid overload (2.49% vs 5.68%; P < .001) over the first 72 hours of ICU stay. In this large ICU population, intensive monitoring of UO was associated with improved detection of AKI and reduced 30-day mortality in patients experiencing AKI, as well as less fluid overload for all patients. Our results should help inform clinical decisions and ICU policy about frequency of monitoring of UO, especially for patients at high risk of AKI or fluid overload, or both. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Structure of complexes of uranyl succinate with carbamide and dimethylurea

NASA Astrophysics Data System (ADS)

Serezhkina, L. B.; Grigor'ev, M. S.; Seliverstova, N. V.; Serezhkin, V. N.

2017-09-01

Three new succinate-containing complexes of uranyl with carbamide ( Urea) and N,N'-dimethylurea ( s-Dmur) are synthesized and studied by IR spectroscopy and X-ray diffraction. Structures of the same type, [UO2( Urea)4(H2O)][(UO2)2(C4H4O4)3] · 3H2O and [UO2( Urea)4(H2O)][(UO2)2(C4H4O4)3] · 2 Urea contain two sorts of uranium-containing complex groups, namely, mononuclear [UO2( Urea)4(H2O)]2+ cations and two-dimensional [(UO2)2(C4H4O4)3]2- anions described by crystal-chemical formulas AM 5 1 and A 2 Q 3 02, respectively ( A = UO2 2+, M 1 = Urea or H2O, Q 02 = C4H4O4 2-), and differ only in the nature of noncoordinated molecules—water and carbamide. The main structural groups of the [(UO2)2(C4H4O4)2( s-Dmur)3] crystals are [(UO2)2(C4H4O4)2( s-Dmur)3] chains belonging to the A 2 Q 2 02 M 3 1 ( A = UO2 2+, Q 02 = C4H4O4 2-, M 1 = s-Dmur) crystal-chemical group. Specific features of intermolecular interactions in the crystal structures are revealed using the Voronoi-Dirichlet method of molecular polyhedra.

Safety and Regulatory Issues of the Thorium Fuel Cycle

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

Ade, Brian; Worrall, Andrew; Powers, Jeffrey

2014-02-01

Thorium has been widely considered an alternative to uranium fuel because of its relatively large natural abundance and its ability to breed fissile fuel (233U) from natural thorium (232Th). Possible scenarios for using thorium in the nuclear fuel cycle include use in different nuclear reactor types (light water, high temperature gas cooled, fast spectrum sodium, molten salt, etc.), advanced accelerator-driven systems, or even fission-fusion hybrid systems. The most likely near-term application of thorium in the United States is in currently operating light water reactors (LWRs). This use is primarily based on concepts that mix thorium with uranium (UO2 + ThO2),more » add fertile thorium (ThO2) fuel pins to LWR fuel assemblies, or use mixed plutonium and thorium (PuO2 + ThO2) fuel assemblies. The addition of thorium to currently operating LWRs would result in a number of different phenomenological impacts on the nuclear fuel. Thorium and its irradiation products have nuclear characteristics that are different from those of uranium. In addition, ThO2, alone or mixed with UO2 fuel, leads to different chemical and physical properties of the fuel. These aspects are key to reactor safety-related issues. The primary objectives of this report are to summarize historical, current, and proposed uses of thorium in nuclear reactors; provide some important properties of thorium fuel; perform qualitative and quantitative evaluations of both in-reactor and out-of-reactor safety issues and requirements specific to a thorium-based fuel cycle for current LWR reactor designs; and identify key knowledge gaps and technical issues that need to be addressed for the licensing of thorium LWR fuel in the United States.« 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.

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.

Method of immobilizing weapons plutonium to provide a durable, disposable waste product

DOEpatents

Ewing, Rodney C.; Lutze, Werner; Weber, William J.

1996-01-01

A method of atomic scale fixation and immobilization of plutonium to provide a durable waste product. Plutonium is provided in the form of either PuO.sub.2 or Pu(NO.sub.3).sub.4 and is mixed with and SiO.sub.2. The resulting mixture is cold pressed and then heated under pressure to form (Zr,Pu)SiO.sub.4 as the waste product.

Uranyl coordination in ionic liquids: the competition between ionic liquid anions, uranyl counterions, and Cl- anions investigated by extended X-ray absorption fine structure and UV-visible spectroscopies and molecular dynamics simulations.

PubMed

Gaillard, C; Chaumont, A; Billard, I; Hennig, C; Ouadi, A; Wipff, G

2007-06-11

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X-=nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C4mimA, A-=PF6-, Tf2N-, BF4- and C4mim=1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and X- anions. Furthermore, the comparison of UO2Cl(4)2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmClp2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

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

Comparisons of plutonium, thorium, and cerium tellurite sulfates.

PubMed

Lin, Jian; Cross, Justin N; Diwu, Juan; Meredith, Nathan A; Albrecht-Schmitt, Thomas E

2013-04-15

The hydrothermal reaction of PuCl3 or CeCl3 with TeO2 in the presence of sulfuric acid under the comparable conditions results in the crystallization of Pu(TeO3)(SO4) or Ce2(Te2O5)(SO4)2, respectively. Pu(TeO3)(SO4) and its isotypic compound Th(TeO3)(SO4) are characterized by a neutral layer structure with no interlamellar charge-balancing ions. However, Ce2(Te2O5)(SO4)2 possesses a completely different dense three-dimensional framework. Bond valence calculation and UV-vis-NIR spectra indicate that the Ce compound is trivalent whereas the Pu and Th compounds are tetravalent leading to the formation of significantly different compounds. Pu(TeO3)(SO4), Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2 represent the first plutonium/thorium/cerium tellurite sulfate compounds. Our study strongly suggests that the chemistries of Pu and Ce are not the same, and this is another example of the failure of Ce as a surrogate.

Neutronics Benchmarks for the Utilization of Mixed-Oxide Fuel: Joint U.S./ Russian Progress Report for Fiscal Year 1997, Volume 4, Part 8 - Neutron Poison Plates in Assemblies Containing Homogeneous Mixtures of Polystyrene-Moderated Plutonium and Uranium Oxides

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

Yavuz, M.

1999-05-01

In the 1970s at the Battelle Pacific Northwest Laboratory (PNL), a series of critical experiments using a remotely operated Split-Table Machine was performed with homogeneous mixtures of (Pu-U)O{sub 2}-polystyrene fuels in the form of square compacts having different heights. The experiments determined the critical geometric configurations of MOX fuel assemblies with and without neutron poison plates. With respect to PuO{sub 2} content and moderation [H/(Pu+U)atomic] ratio (MR), two different homogeneous (Pu-U) O{sub 2}-polystyrene mixtures were considered: Mixture (1) 14.62 wt% PuO{sub 2} with 30.6 MR, and Mixture (2) 30.3 wt% PuO{sub 2} with 2.8 MR. In all mixtures, the uraniummore » was depleted to about O.151 wt% U{sup 235}. Assemblies contained copper, copper-cadmium or aluminum neutron poison plates having thicknesses up to {approximately}2.5 cm. This evaluation contains 22 experiments for Mixture 1, and 10 for Mixture 2 compacts. For Mixture 1, there are 10 configurations with copper plates, 6 with aluminum, and 5 with copper-cadmium. One experiment contained no poison plate. For Mixture 2 compacts, there are 3 configurations with copper, 3 with aluminum, and 3 with copper-cadmium poison plates. One experiment contained no poison plate.« less

Model for the Formation and Evolution of Sand Ridges on the Continental Shelf

DTIC Science & Technology

1992-10-01

difficulties of conducting laboratory experiments involving liquid/sediment media (such as leveling the sediment bed after each trial, extracting gas...reflected component, the 54 55 bottom velocities to lowest order are Uob = uo+ 32’.uoxr = E’= 1 Cja(X, y)e(•k’x-W’t) + c.c. (3.3) Vob = VO + 02 2 h(3 Vb2 To

Carbothermic reduction of uranium oxides into solvent metallic baths

NASA Astrophysics Data System (ADS)

Guisard Restivo, Thomaz A.; Capocchi, José D. T.

2004-09-01

The carbothermic reduction of UO 2 and U 3O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3O 8 charges, respectively. One example for another system containing Al 2O 3 is also shown.

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.

Compressive properties of commercially available polyurethane foams as mechanical models for osteoporotic human cancellous bone

PubMed Central

Patel, Purvi SD; Shepherd, Duncan ET; Hukins, David WL

2008-01-01

Background Polyurethane (PU) foam is widely used as a model for cancellous bone. The higher density foams are used as standard biomechanical test materials, but none of the low density PU foams are universally accepted as models for osteoporotic (OP) bone. The aim of this study was to determine whether low density PU foam might be suitable for mimicking human OP cancellous bone. Methods Quasi-static compression tests were performed on PU foam cylinders of different lengths (3.9 and 7.7 mm) and of different densities (0.09, 0.16 and 0.32 g.cm-3), to determine the Young's modulus, yield strength and energy absorbed to yield. Results Young's modulus values were 0.08–0.93 MPa for the 0.09 g.cm-3 foam and from 15.1–151.4 MPa for the 0.16 and 0.32 g.cm-3 foam. Yield strength values were 0.01–0.07 MPa for the 0.09 g.cm-3 foam and from 0.9–4.5 MPa for the 0.16 and 0.32 g.cm-3 foam. The energy absorbed to yield was found to be negligible for all foam cylinders. Conclusion Based on these results, it is concluded that 0.16 g.cm-3 PU foam may prove to be suitable as an OP cancellous bone model when fracture stress, but not energy dissipation, is of concern. PMID:18844988

²³⁹Pu and ²⁴⁰Pu inventories and ²⁴⁰Pu/²³⁹Pu atom ratios in the equatorial Pacific Ocean water column.

PubMed

Yamada, Masatoshi; Zheng, Jian

2012-07-15

The (239+240)Pu concentrations and (240)Pu/(239)Pu atom ratios were determined by alpha spectrometry and inductively coupled plasma mass spectrometry for seawater samples from two stations, one at the equator and the other in the equatorial South Pacific. To better understand the fate of Pu isotopes, this study dealt with the contribution of the close-in fallout Pu from the Pacific Proving Grounds (PPG) in water columns of the Pacific Ocean. The (239)Pu, (240)Pu and (239+240)Pu inventories over the depth interval 0-3000 m at the equator station were 10.4, 8.9 and 19.3 Bq m(-2), respectively. Further, no noticeable difference was observed in (239)Pu, (240)Pu and (239+240)Pu inventories over the depth interval 0-3000 m between the two stations. The total (239+240)Pu inventories were significantly higher than the expected cumulative deposition density of global fallout. Water column (239+240)Pu inventories measured in this study were lower than those reported for comparable stations in the Geochemical Ocean Sections Study, indicating that these inventories have been decreasing at average rates of 0.89 ± 0.07 and 0.16 ± 0.07 Bq m(-2)yr(-1) at the equator and equatorial South Pacific stations, respectively, from 1973 to 1990. The obtained (240)Pu/(239)Pu atom ratios were higher than the mean global fallout ratio of 0.18. These high atom ratios proved the existence of close-in tropospheric fallout Pu from the PPG in the Marshall Islands. The (239+240)Pu inventories originating from the close-in fallout in the entire water column were estimated to be 11.1 Bq m(-2) at the equator station and 7.1 Bq m(-2) at the equatorial South Pacific Ocean station, and the relative percentages of close-in fallout Pu were 40% at the former and 34% at the latter. A significant amount of close-in fallout Pu originating from the PPG has been transported to deep layers below the 1000 m depth in the equatorial Pacific Ocean. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

URANIUM DIOXIDE OXIDATION WITH FORMING INTERMEDIATE PHASES (in German)

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

Scheibe, H.; Ermischer, W.

1964-02-01

An experimental study was made of the UO/sub 2/ to U/sub 3/O/sub 8/ oxidation process. At low temperatures, depending on the activity of the powder, the oxidation of UO/sub 2/ yield a U/sub 3/O/sub 7/ shell around the UO/sub 2/ grain (160 to 220 deg C). Further oxidation is determined by the diffusion of oxygen through this shell and yields U/sub 5/O/sub 12/ (280 to 290 deg C). Their follows U/sub 5/O/sub (375 to 400 deg C) and finally U/sub 3/O/sub 8/ as more oxigen is absorbed. No further increase of the oxygen content occurs up to 800 deg C.more » The exothermal effects established through differential thermal analysis may be due to lattice transformation. (OTS)« less

Structure and cation ordering in La 2UO 6, Ce 2UO 6, LaUO 4, and CeUO 4 by first principles calculations

DOE PAGES

Casillas-Trujillo, Luis; Xu, H.; McMurray, Jake W.; ...

2016-07-06

In the present work, we have used density functional theory (DFT) and DFT+U to investigate the crystal structure and phase stability of four model compounds in the Ln 2O 3-UO 2-UO 3 ternary oxide system: La2UO 6, Ce 2UO 6, LaUO 4, CeUO 4, due to the highly-correlated nature of the f-electrons in uranium. We have considered both hypothetical ordered compounds and compounds in which the cations randomly occupy atomic sites in a fluorite-like lattice. We determined that ordered compounds are stable and are energetically favored compared to disordered configurations, though the ordering tendencies are weak. To model and analyzemore » the structures of these complex oxides, we have used supercells based on a layered atomic model. In the layer model, the supercell is composed of alternating planes of anions and cations. We have considered two different ordering motifs for the cations, namely single species (isoatomic) cation layers versus mixed species cation layers. Energy differences between various ordered cationic arrangements were found to be small. This may have implications regarding radiation stability, since cationic arrangements should be able to change under irradiation with little cost in energy.« less

Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation.

PubMed

Xiao, Cheng-Liang; Wang, Cong-Zhi; Mei, Lei; Zhang, Xin-Rui; Wall, Nathalie; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

2015-08-28

The tetradentate N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard-soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu-L species ([EuL2(NO3)](2+)) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu-L species ([EuL(NO3)2](+)) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)](+)) is the only detected species for the uranyl complexes. The [ThL2(NO3)2](2+) species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)](3+)) and a new 1 : 1 species ([ThL(NO3)3](+)) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal-ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M-L complexes in acetonitrile are found to be in good agreement with the ESI-MS results.

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/.

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

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

Katsenovich, Yelena P.; Cardona, Claudia; Lapierre, Robert

2016-10-01

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH3 to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. Themore » objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al3+ (2.8 or 5 mM), HCO3- (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO2(CO3)2-2 and UO2(CO3)3-4) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO2(OH)3- and UO2(OH)4-2) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO2CO3], cejkaite [Na4(UO2)(CO3)3] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO2)(SiO4)·1.5H2O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.« less

Design and synthesis of target-responsive hydrogel for portable visual quantitative detection of uranium with a microfluidic distance-based readout device.

PubMed

Huang, Yishun; Fang, Luting; Zhu, Zhi; Ma, Yanli; Zhou, Leiji; Chen, Xi; Xu, Dunming; Yang, Chaoyong

2016-11-15

Due to uranium's increasing exploitation in nuclear energy and its toxicity to human health, it is of great significance to detect uranium contamination. In particular, development of a rapid, sensitive and portable method is important for personal health care for those who frequently come into contact with uranium ore mining or who investigate leaks at nuclear power plants. The most stable form of uranium in water is uranyl ion (UO2(2+)). In this work, a UO2(2+) responsive smart hydrogel was designed and synthesized for rapid, portable, sensitive detection of UO2(2+). A UO2(2+) dependent DNAzyme complex composed of substrate strand and enzyme strand was utilized to crosslink DNA-grafted polyacrylamide chains to form a DNA hydrogel. Colorimetric analysis was achieved by encapsulating gold nanoparticles (AuNPs) in the DNAzyme-crosslinked hydrogel to indicate the concentration of UO2(2+). Without UO2(2+), the enzyme strand is not active. The presence of UO2(2+) in the sample activates the enzyme strand and triggers the cleavage of the substrate strand from the enzyme strand, thereby decreasing the density of crosslinkers and destabilizing the hydrogel, which then releases the encapsulated AuNPs. As low as 100nM UO2(2+) was visually detected by the naked eye. The target-responsive hydrogel was also demonstrated to be applicable in natural water spiked with UO2(2+). Furthermore, to avoid the visual errors caused by naked eye observation, a previously developed volumetric bar-chart chip (V-Chip) was used to quantitatively detect UO2(2+) concentrations in water by encapsulating Au-Pt nanoparticles in the hydrogel. The UO2(2+) concentrations were visually quantified from the travelling distance of ink-bar on the V-Chip. The method can be used for portable and quantitative detection of uranium in field applications without skilled operators and sophisticated instruments. Copyright © 2016 Elsevier B.V. All rights reserved.

Statistical properties of Pu 243 , and Pu 242 ( n , γ ) cross section calculation

DOE PAGES

Laplace, T. A.; Zeiser, F.; Guttormsen, M.; ...

2016-01-29

The level density and γ-ray strength function (γSF) of 243Pu have been measured in the quasicontinuum using the Oslo method. Excited states in 243Pu were populated using the 242Pu(d,p) reaction. The level density closely follows the constant-temperature level density formula for excitation energies above the pairing gap. The γSF displays a double-humped resonance at low energy as also seen in previous investigations of actinide isotopes. The structure is interpreted as the scissors resonance and has a centroid of ω SR = 2.42(5) MeV and a total strength of B SR = 10.1(15) μ 2 N, which is in excellent agreementmore » with sum-rule estimates. Lastly, the measured level density and γSF were used to calculate the 242Pu(n,γ) cross section in a neutron energy range for which there were previously no measured data.« less

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

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.

Design Study of Modular Nuclear Power Plant with Small Long Life Gas Cooled Fast Reactors Utilizing MOX Fuel

NASA Astrophysics Data System (ADS)

Ilham, Muhammad; Su'ud, Zaki

2017-01-01

Growing energy needed due to increasing of the world’s population encourages development of technology and science of nuclear power plant in its safety and security. In this research, it will be explained about design study of modular fast reactor with helium gas cooling (GCFR) small long life reactor, which can be operated over 20 years. It had been conducted about neutronic design GCFR with Mixed Oxide (UO2-PuO2) fuel in range of 100-200 MWth NPPs of power and 50-60% of fuel fraction variation with cylindrical pin cell and cylindrical balance of reactor core geometry. Calculation method used SRAC-CITATION code. The obtained results are the effective multiplication factor and density value of core reactor power (with geometry optimalization) to obtain optimum design core reactor power, whereas the obtained of optimum core reactor power is 200 MWth with 55% of fuel fraction and 9-13% of percentages.

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.

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

PubMed

Liu, Xiao-yu; Wang, Lu-hua; Zheng, Zhong; Kang, Ming-liang; Li, Chun; Liu, Chun-li

2013-01-15

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Ageing of a phosphate ceramic used to immobilize chloride contaminated actinide waste

NASA Astrophysics Data System (ADS)

Metcalfe, B. L.; Donald, I. W.; Fong, S. K.; Gerrard, L. A.; Strachan, D. M.; Scheele, R. D.

2009-03-01

A process for the immobilization of intermediate level waste containing a significant quantity of chloride using Ca3(PO4)2 as the host material has been developed. Waste ions are incorporated into two phosphate-based phases, chlorapatite [Ca5(PO4)3Cl] and spodiosite [Ca2(PO4)Cl]. Non-active trials performed using Sm as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process, in which actinide-doped materials were used, were performed at PNNL which confirmed the wasteform resistant to aqueous leaching. Initial leach trials conducted on 239Pu/241Am loaded ceramic at 313 K/28 days gave normalized mass losses of 1.2 × 10-5 g m-2 and 2.7 × 10-3 g m-2 for Pu and Cl, respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced with 238Pu. No changes to the crystalline structure of the waste were detected in the XRD spectra after the samples had experienced an α radiation fluence of 4 × 1018 g-1. Leach trials showed that there was an increase in the P and Ca release rates but no change in the Pu release rate.

Selective Se-for-S substitution in Cs-bearing uranyl compounds

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Tyumentseva, Olga S.; Krivovichev, Sergey V.

Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]more » (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the pure sulfate and selenate compounds. The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded 4-connected site. - Highlights: • Single crystals of novel mixed sulfate-selenate uranyl oxysalts were prepared by evaporation method. • Topological analysis and information-based complexity calculations were used for structure description. • The selective Se-for-S substitution was observed. • Evolution of phase formation in the aqueous Cs{sup +}–UO{sub 2}{sup 2+}–SO{sub 4}{sup 2–}–SeO{sub 4}{sup 2–} system was analyzed.« less

Are Surrogate Assumptions and Use of Diuretics Associated with Diagnosis and Staging of Acute Kidney Injury after Cardiac Surgery?

PubMed Central

Hussein, Hayder K.; Prabhu, Mahesh; Kanagasundaram, N. Suren

2012-01-01

Summary Background and objectives This study measured the association between the Acute Kidney Injury Network (AKIN) diagnostic and staging criteria and surrogates for baseline serum creatinine (SCr) and body weight, compared urine output (UO) with SCr criteria, and assessed the relationships between use of diuretics and calibration between criteria and prediction of outcomes. Design, setting, participants, & measurements This was a retrospective cohort study using prospective measurements of SCr, hourly UO, body weight, and drug administration records from 5701 patients admitted, after cardiac surgery, to a cardiac intensive care unit between 1995 and 2006. Results More patients (n=2424, 42.5%) met SCr diagnostic criteria with calculated SCr assuming a baseline estimated GFR of 75 ml/min per 1.73 m2 than with known baseline SCr (n=1043, 18.3%). Fewer patients (n=484, 8.5%) met UO diagnostic criteria with assumed body weight (70 kg) than with known weight (n=624, 10.9%). Agreement between SCr and UO criteria was fair (κ=0.28; 95% confidence interval 0.25–0.31). UO diagnostic criteria were specific (0.95; 0.94–0.95) but insensitive (0.36; 0.33–0.39) compared with SCr. Intravenous diuretics were associated with higher probability of falling below the UO diagnostic threshold compared with SCr, higher 30-day mortality (relative risk, 2.27; 1.08–4.76), and the need for renal support (4.35; 1.82–10.4) compared with no diuretics. Conclusions Common surrogates for baseline estimated GFR and body weight were associated with misclassification of AKIN stage. UO criteria were insensitive compared with SCr. Intravenous diuretic use further reduced agreement and confounded association between AKIN stage and 30-day mortality or need for renal support. PMID:22246280

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.

Molecular cloning, characterization, and expression analysis of a heat shock protein (HSP) 70 gene from Paphia undulata.

PubMed

Wu, Xiangwei; Tan, Jing; Cai, Mingyi; Liu, Xiande

2014-06-15

In this study, a full-length HSP70 cDNA from Paphia undulata was cloned using reverse transcriptase polymerase chain reaction (RT-PCR) coupled with rapid amplification of cDNA ends (RACE). The full-length cDNA is 2,351 bp, consisting of a 5'-untranslated region (UTR) of 83 bp, a 3'-UTR of 315 bp, and an open reading frame (ORF) of 1,953 bp. This cDNA encodes 650 amino acids with an estimated molecular weight of 71.3 kDa and an isoelectric point of 5.51. Based on the amino acid sequence analysis and phylogenetic analysis, this HSP70 gene was identified as a member of the cytoplasmic HSP70 family, being the constitutive expression, and it was designated as PuHSC70. The distribution of PuHSC70 mRNA in the mantle, digestive gland, adductor muscle, gonad, gill, heart, and hemocytes suggested that PuHSC70 is ubiquitously expressed. The mRNA levels of PuHSC70 under high temperature and high salinity stresses were analyzed by real-time PCR. Under high temperature stress of 32°C, PuHSC70 mRNA in the mantle, digestive gland, gill, and heart was significantly up-regulated at 1h and 2h, and it was then progressively down-regulated. In the adductor muscle, the level of PuHSC70 mRNA gradually increased throughout the study period; the mRNA levels in the gonad and hemocytes increased significantly at 4h and 8h (P<0.05) and then decreased at 8h and 14 h, respectively, however they increased again afterwards, reaching the highest levels at 50h. Under high salinity (32 ‰) stress, the mRNA levels of PuHSC70 in the mantle and gonad were increased significantly only at 24h and 48 h (P<0.05), and at the rest of the study period they were slightly elevated. Compared with the pretreatment level, the levels of expression in the digestive gland and gill were unchanged or reduced throughout the study period. The levels of PuHSC70 mRNA in the adductor muscle, hemocytes, and heart were significantly increased, reaching a maximum at 24h, and then they gradually decreased; moreover, in the heart, the mRNA expression recovered to the pretreatment level at 50h; while in the adductor muscle and hemocytes, the expression level remained higher than that of the control. The cloning and expression analyses of PuHSC70 provide theoretical basis to further study the mechanism of physiological response to thermal and high salinity stresses. Copyright © 2014 Elsevier B.V. All rights reserved.

Measurement of the 242Pu neutron capture cross section

NASA Astrophysics Data System (ADS)

Buckner, M. Q.; Wu, C. Y.; Henderson, R. A.; Bucher, B.; Bredeweg, T. A.; Baramsai, B.; Couture, A.; Jandel, M.; Mosby, S.; O'Donnell, J. M.; Ullmann, J. L.; Chyzh, A.; Dance Collaboration

2015-10-01

Precision (n,f) and (n, γ) cross sections are important for the network calculations of the radiochemical diagnostic chain for the U.S. DOE's Stockpile Stewardship Program. 242Pu(n, γ) cross section is relevant to the network calculations of Pu and Am. Additionally, new reactor concepts have catalyzed considerable interest in the measurement of improved cross sections for neutron-induced reactions on key actinides. To date, little or no experimental data has been reported on 242Pu(n, γ) for incident neutron energy below 50 keV. A new measurement of the 242Pu(n, γ) reaction was performed with the DANCE together with an improved PPAC for fission-fragment detection at LANSCE during FY14. The relative scale of the 242Pu(n, γ) cross section spans four orders of magnitude for incident neutron energies from thermal to ~ 30 keV. The absolute scale of the 242Pu(n, γ) cross section is set according to the measured 239Pu(n,f) resonance at 7.8 eV; the target was spiked with 239Pu for this measurement. The absolute 242Pu(n, γ) neutron capture cross section is ~ 30% higher than the cross section reported in ENDF for the 2.7 eV resonance. Latest results to be reported. Funded by U.S. DOE Contract No. DE-AC52-07NA27344 (LLNL) and DE-AC52-06NA25396 (LANL). U.S. DOE/NNSA Office of Defense Nuclear Nonproliferation Research and Development. Isotopes (ORNL).

Concentrations of selected radionuclides and their spatial distribution in marine sediments from the northwestern Gulf, Kuwait.

PubMed

Uddin, Saif; Behbehani, Montaha

2018-02-01

This study focuses on creating a baseline for 40 K, 210 Pb, 137 Cs, 90 Sr, 226 Ra, 228 Ra, 238 U, 235 U, 234 U, 239+240 Pu and 238 Pu in marine sediments in the northwestern Gulf. The respective measured concentration ranges were 386-489, 32.3-48.8, 1.5-2.9, 4.53-5.42, 18.3-23.1, 18.8-23.0, 22.3-30.5, 0.99-1.33, 25.6-34.8, 0.30-0.93, and 0.0008-0.00018Bqkg -1 . The levels of these radionuclides are generally comparable to values reported for other marine waters in the northern hemisphere. The 137 Cs activity in the Gulf sediments offshore Kuwait is an order of magnitude lower compared to sediments from northeastern Iran. Other than that finding, no hot spots were observed in sediments adjacent to power and desalination plants, oil and gas industrial activities or wastewater treatment facilities. These data will serve as a baseline to gauge possible future inputs of radionuclides in the northern Gulf. The calculated average ratio of 235 U/ 238 U activity in the area is in agreement with the reported figure of the natural uranium ratio, suggesting the absence of depleted uranium (DU) at all the stations. The low concentration of 239+240 Pu suggests that there is no significant source of plutonium except that from atmospheric fallout from weapon testing and possible dry deposition via long-range dust transport. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Human data demonstrating extra long retention of plutonium in the lung

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

Bihl, D.E.; Carbaugh, E.H.; Sula, M.J.

1991-01-01

Case histories are presented of 10 humans with inhalation depositions of Pu in which the Pu is retained in the lung or pulmonary lymph system for extremely long periods. The retention half-times range from 5000 to at least 20,000 d for most (in some cases all) of the initial deposition. In no case was a clearance half-time in the hundreds of days observed. The form of Pu involved in these cases is believed to be calcined Pu oxide. 9 refs., 1 fig., 2 tabs.

U(VI) uranyl cation-cation interactions in framework germanates.

PubMed

Morrison, Jessica M; Moore-Shay, Laura J; Burns, Peter C

2011-03-21

The isomorphous compounds NH(4)[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (1), K[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (2), Li(3)O[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (3), and Ba[(UO(6))(2)(UO(2))(9)(GeO(4))(2)] (4) were synthesized by hydrothermal reaction at 220 °C. The structures were determined using single crystal X-ray diffraction and refined to R(1) = 0.0349 (1), 0.0232 (2), 0.0236 (3), 0.0267 (4). Each are trigonal, P(3)1c. 1: a = 10.2525(5), c = 17.3972(13), V = 1583.69(16) Å(3), Z = 2; 2: a = 10.226(4), c = 17.150(9), V = 1553.1(12) Å(3), Z = 2; 3: a = 10.2668(5), c = 17.0558(11), V = 1556.94(15) Å(3), Z = 2; 4: a = 10.2012(5), c = 17.1570(12), V = 1546.23(15) Å(3), Z = 2. There are three symmetrically independent U sites in each structure, two of which correspond to typical (UO(2))(2+) uranyl ions and the other of which is octahedrally coordinated by six O atoms. One of the uranyl ions donates a cation-cation interaction, and accepts a different cation-cation interaction. The linkages between the U-centered polyhedra result in a relatively dense three-dimensional framework. Ge and low-valence sites are located within cavities in the framework of U-polyhedra. Chemical, thermal, and spectroscopic characterizations are provided.

Influence of radiation quality on mouse chromosome 2 deletions in radiation-induced acute myeloid leukaemia.

PubMed

Brown, Natalie; Finnon, Rosemary; Manning, Grainne; Bouffler, Simon; Badie, Christophe

2015-11-01

Leukaemia is the prevailing neoplastic disorder of the hematopoietic system. Epidemiological analyses of the survivors of the Japanese atomic bombings show that exposure to ionising radiation (IR) can cause leukaemia. Although a clear association between radiation exposure and leukaemia development is acknowledged, the underlying mechanisms remain incompletely understood. A hemizygous deletion on mouse chromosome 2 (del2) is a common feature in several mouse strains susceptible to radiation-induced acute myeloid leukaemia (rAML). The deletion is an early event detectable 24h after exposure in bone marrow cells. Ultimately, 15-25% of exposed animals develop AML with 80-90% of cases carrying del2. Molecular mapping of leukaemic cell genomes identified a minimal deleted region (MDR) on chromosome 2 (chr2) in which a tumour suppressor gene, Sfpi1 is located, encoding the transcription factor PU.1, essential in haematopoiesis. The remaining copy of Sfpi1 has a point mutation in the coding sequence for the DNA-binding domain of the protein in 70% of rAML, which alters a single CpG sequence in the codon for arginine residue R235. In order to identify chr2 deletions and Sfpi.1/PU.1 loss, we performed array comparative genomic hybridization (aCGH) on a unique panel of 79rAMLs. Using a custom made CGH array specifically designed for mouse chr2, we analysed at unprecedentedly high resolution (1.4M array- 148bp resolution) the size of the MDR in low LET and high-LET induced rAMLs (32 X-ray- and 47 neutron-induced). Sequencing of Sfpi1/PU.1DNA binding domain identified the presence of R235 point mutations, showing no influence of radiation quality on R235 type or frequency. We identified for the first time rAML cases with complex del2 in a subset of neutron-induced AMLs. This study allowed us to re-define the MDR to a much smaller 5.5Mb region (still including Sfpi1/PU.1), identical regardless of radiation quality. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Analysis of actinides in an ombrotrophic peat core - evidence of post-depositional migration of fallout radionuclides

NASA Astrophysics Data System (ADS)

Quinto, Francesca; Hrnecek, Erich; Krachler, Michael; Shotyk, William; Steier, Peter; Winkler, Stephan R.

2013-04-01

Plutonium (239Pu, 240Pu, 241Pu, 242Pu) and uranium (236U, 238U) isotopes were analyzed in an ombrotrophic peat core from the Black Forest, Germany, representing the last 80 years of atmospheric deposition. The reliable determination of these isotopes at ultra-trace levels was possible using ultra-clean laboratory procedures and accelerator mass spectrometry. The 240Pu/239Pu isotopic ratios are constant along the core with a mean value of 0.19 ±0.02 (N = 32). This result is consistent with the acknowledged average 240Pu/239Pu isotopic ratio from global fallout in the Northern Hemisphere. The global fallout origin of Pu is confirmed by the corresponding 241Pu/239Pu (0.0012 ±0.0005) and 242Pu/239Pu (0.004 ± 0.001) isotopic ratios. The identification of the Pu isotopic composition characteristic for global fallout in peat layers pre-dating the period of atmospheric atom bomb testing (AD 1956 - AD 1980) is a clear evidence of the migration of Pu downwards the peat profile. The maximum of global fallout derived 236U is detected in correspondence to the age/depth layer of maximum stratospheric fallout (AD 1963). This finding demonstrates that the 236U bomb peak can be successfully used as an independent chronological marker complementing the 210Pb dating of peat cores. The profiles of the global fallout derived 236U and 239Pu are compared with those of 137Cs and 241Am. As typical of ombrothrophic peat, the temporal fallout pattern of 137Cs is poorly retained. Similarly like for Pu, post-depositional migration of 241Am in peat layers preceding the era of atmospheric nuclear tests is observed.

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.

$sup 18$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.

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.

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.

Irradiation effects and micro-structural changes in large grain uranium dioxide fuel investigated by micro-beam X-ray diffraction

NASA Astrophysics Data System (ADS)

Mieszczynski, C.; Kuri, G.; Degueldre, C.; Martin, M.; Bertsch, J.; Borca, C. N.; Grolimund, D.; Delafoy, Ch.; Simoni, E.

2014-01-01

Microstructural changes in a set of commercial grade UO2 fuel samples have been investigated using synchrotron based micro-focused X-ray fluorescence (μ-XRF) and X-ray diffraction (μ-XRD) techniques. The results are associated with conventional UO2 materials and relatively larger grain chromia-doped UO2 fuels, irradiated in a commercial light water reactor plant (average burn-up: 40 MW d kg-1). The lattice parameters of UO2 in fresh and irradiated specimens have been measured and compared with theoretical predictions. In the pristine state, the doped fuel has a somewhat smaller lattice parameter than the standard UO2 as a result of chromia doping. Increase in micro-strain and lattice parameter in irradiated materials is highlighted. All irradiated samples behave in a similar manner with UO2 lattice expansion occurring upon irradiation, where any Cr induced effect seems insignificant and accumulated lattice defects prevail. Elastic strain energy densities in the irradiated fuels are also evaluated based on the UO2 crystal lattice strain and non-uniform strain. The μ-XRD patterns further allow the evaluation of the crystalline domain size and sub-grain formation at different locations of the irradiated UO2 pellets.

Both lavender fleur oil and unscented oil aromatherapy reduce preoperative anxiety in breast surgery patients: a randomized trial.

PubMed

Franco, Lola; Blanck, Thomas J J; Dugan, Kimberly; Kline, Richard; Shanmugam, Geetha; Galotti, Angela; von Bergen Granell, Annelise; Wajda, Michael

2016-09-01

The objective of this study was to determine whether lavender fleur oil (LFO) aromatherapy would reduce anxiety when administered to women before undergoing breast surgery. This was a single-site, randomized study comparing the effect of LFO to unscented oil (UO). The study was conducted in the preoperative holding area of the ambulatory surgery department of NYU Langone Medical Center. Ninety three women, 18 years and older, scheduled for breast surgery. Women meeting inclusion/exclusion criteria were randomized to either LFO or UO aromatherapy and were blind to their assigned treatment. Subjects completed a Speilberger State Anxiety Inventory for Adults (STAI) before and after aromatherapy. Vital signs were recorded before and after aromatherapy. STAI-State questions were divided into positive and negative emotions for analysis. Before aromatherapy, there was no significant difference between groups by individual questions or overall average answer of either positive or negative questions. The use of both LFO and UO increased the positive STAI score totals, with the LFO group having a slightly, but statistically significant, greater increase. Both resulted in a statistically significant decrease in the negative score totals after treatment. There were no differences in vital signs between groups for either treatment. Following the conclusion of the trial LFO was analyzed and found to contain a very low content of the 2 major Lavandula angustifolia constituents. Both LFO and UO aromatherapy treatments lowered anxiety before surgery despite no significant changes in vital signs. LFO treatment generated a slight but statistically significant increase in positive feelings compared with UO treatment. It is probable that the beneficial effect observed was due to both aromatherapy with LFO and a placebo effect related to the added attention given to the patients. Copyright © 2016 Elsevier Inc. All rights reserved.

Dissolution process for ZrO.sub.2 -UO.sub.2 -CaO fuels

DOEpatents

Paige, Bernice E.

1976-06-22

The present invention provides an improved dissolution process for ZrO.sub.2 -UO.sub.2 -CaO-type pressurized water reactor fuels. The zirconium cladding is dissolved with hydrofluoric acid, immersing the ZrO.sub.2 -UO.sub.2 -CaO fuel wafers in the resulting zirconium-dissolver-product in the dissolver vessel, and nitric acid is added to the dissolver vessel to facilitate dissolution of the uranium from the ZrO.sub.2 -UO.sub.2 -CaO fuel wafers.

Ageing of a phosphate ceramic used to immobilize chloride-contaminated actinide waste

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

Metcalfe, Brian; Donald, Ian W.; Fong, Shirley K.

2009-03-31

At AWE, we have developed a process for the immobilization of ILW waste containing a significant quantity of chloride with Ca 3(PO 4) 2 as the host material. Waste ions are incorporated into two phosphate-based phases, chlorapatite [Ca 5(PO 4) 3Cl] and spodiosite [Ca 2(PO 4)Cl]. Non-active trials performed at AWE with Sm as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process, in which actinide-doped materials were used, wer performed at PNNL where the waste form was found to be resistant to aqueous leaching. Initial leach trials conducted on 239Pu / 241Ammore » loaded ceramic at 40°C/28 days gave normalized mass losses of 1.2 x 10 -5 g.m -2 and 2.7 x 10 -3 g.m -2 for Pu and Cl respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced with 238Pu. No changes to the crystalline structure of the waste were detected in the XRD patterns after the samples had experienced an α radiation dose of 4 x 10 18 g -1. Leach trials showed that there was an increase in the P and Ca release rates but no change in the Pu release rate.« less

Ageing of a phosphate ceramic used to immobilize chloride contaminated actinide waste

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

Metcalfe, Brian L.; Donald, Ian W.; Fong, Shirley K.

2009-03-31

AWE has developed a process for the immobilization of ILW waste containing a significant quantity of chloride using Ca3(PO4)2 as the host material. Waste ions are incorporated into two phosphate based phases, chlorapatite, Ca5(PO4)3Cl, and spodiosite, Ca2(PO4)Cl. Non-active trials performed at AWE using samarium as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process using actinide-doped material were performed at PNNL which confirmed the immobilized wasteform resistant to aqueous leaching. Initial leach trials conducted on 239Pu /241Am loaded ceramic at 40°C/28 days gave normalized mass losses of 1.2 x 10-5 g.m-2 and 2.7more » x 10-3 g.m-2 for Pu and Cl respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced by 238Pu. No changes to the crystalline structure of the waste were detected using XRD after the samples had experienced a radiation dose of 4 x 1018 α.g-1. Leach trials showed that there had been an increase in the P and Ca release rates but no change in the Pu release rate.« less

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

Neutron Radiation Characteristics of Plutonium Dioxide Fuel

NASA Technical Reports Server (NTRS)

Taherzadeh, M.

1972-01-01

The major sources of neutrons from plutonium dioxide nuclear fuel are considered in detail. These sources include spontaneous fission of several of the Pu isotopes, reactions with low Z impurities in the fuel, and reactions with O-18. For spontaneous fission neutrons a value of (1.95 plus or minus 0.07) X 1,000 n/s/q PuO2 is obtained. The neutron yield from (alpha, neutron) reactions with oxygen is calculated by integrating the reaction rate equation over all alpha particle energies and all center-of-mass angles. The results indicate a neutron emission rate of (1.42 plus or minus 0.32) X 10,000 n/s/q PuO2. The neutron yield from (alpha, neutron) reactions with low Z impurities in the fuel is presented in tabular form for one part per million of each impurity. The total neutron flux emitted from a particular fuel geometry is estimated by adding the neutron yield due to the induced fission to the other neutron sources.

Periodic trends in hexanuclear actinide clusters.

PubMed

Diwu, Juan; Wang, Shuao; Albrecht-Schmitt, Thomas E

2012-04-02

Four new Th(IV), U(IV), and Np(IV) hexanuclear clusters with 1,2-phenylenediphosphonate as the bridging ligand have been prepared by self-assembly at room temperature. The structures of Th(6)Tl(3)[C(6)H(4)(PO(3))(PO(3)H)](6)(NO(3))(7)(H(2)O)(6)·(NO(3))(2)·4H(2)O (Th6-3), (NH(4))(8.11)Np(12)Rb(3.89)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·15H(2)O (Np6-1), (NH(4))(4)U(12)Cs(8)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·18H(2)O (U6-1), and (NH(4))(4)U(12)Cs(2)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(18)·40H(2)O (U6-2) are described and compared with other clusters of containing An(IV) or Ce(IV). All of the clusters share the common formula M(6)(H(2)O)(m)[C(6)H(3)(PO(3))(PO(3)H)](6)(NO(3))(n)((6-n)) (M = Ce, Th, U, Np, Pu). The metal centers are normally nine-coordinate, with five oxygen atoms from the ligand and an additional four either occupied by NO(3)(-) or H(2)O. It was found that the Ce, U, and Pu clusters favor both C(3i) and C(i) point groups, while Th only yields in C(i), and Np only C(3i). In the C(3i) clusters, there are two NO(3)(-) anions bonded to the metal centers. In the C(i) clusters, the number of NO(3)(-) anions varies from 0 to 2. The change in the ionic radius of the actinide ions tunes the cavity size of the clusters. The thorium clusters were found to accept larger ions including Cs(+) and Tl(+), whereas with uranium and later elements, only NH(4)(+) and/or Rb(+) reside in the center of the clusters.

Thermal diffusivity and conductivity of thorium- uranium mixed oxides

NASA Astrophysics Data System (ADS)

Saoudi, M.; Staicu, D.; Mouris, J.; Bergeron, A.; Hamilton, H.; Naji, M.; Freis, D.; Cologna, M.

2018-03-01

Thorium-uranium oxide pellets with high densities were prepared at the Canadian Nuclear Laboratories (CNL) by co-milling, pressing, and sintering at 2023 K, with UO2 mass contents of 0, 1.5, 3, 8, 13, 30, 60 and 100%. At the Joint Research Centre, Karlsruhe (JRC-Karlsruhe), thorium-uranium oxide pellets were prepared using the spark plasma sintering (SPS) technique with 79 and 93 wt. % UO2. The thermal diffusivity of (Th1-xUx)O2 (0 ≤ x ≤ 1) was measured at CNL and at JRC-Karlsruhe using the laser flash technique. ThO2 and (Th,U)O2 with 1.5, 3, 8 and 13 wt. % UO2 were found to be semi-transparent to the infrared wavelength of the laser and were coated with graphite for the thermal diffusivity measurements. This semi-transparency decreased with the addition of UO2 and was lost at about 30 wt. % of UO2 in ThO2. The thermal conductivity was deduced using the measured density and literature data for the specific heat capacity. The thermal conductivity for ThO2 is significantly higher than for UO2. The thermal conductivity of (Th,U)O2 decreases rapidly with increasing UO2 content, and for UO2 contents of 60% and higher, the conductivity of the thorium-uranium oxide fuel is close to UO2. As the mass difference between the Th and U atoms is small, the thermal conductivity decrease is attributed to the phonon scattering enhanced by lattice strain due to the introduction of uranium in ThO2 lattice. The new results were compared to the data available in the literature and were evaluated using the classical phonon transport model for oxide systems.

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

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

Thangavelu, Sonia G.; Cahill, Christopher L.

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

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

Thangavelu, Sonia G.; Cahill, Christopher L.

2016-01-06

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

AFS-2 FLOWSHEET MODIFICATIONS TO ADDRESS THE INGROWTH OF PU(VI) DURING METAL DISSOLUTION

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

Crapse, K.; Rudisill, T.; O'Rourke, P.

2014-07-02

In support of the Alternate Feed Stock Two (AFS-2) PuO{sub 2} production campaign, Savannah River National Laboratory (SRNL) conducted a series of experiments concluding that dissolving Pu metal at 95°C using a 6–10 M HNO{sub 3} solution containing 0.05–0.2 M KF and 0–2 g/L B could reduce the oxidation of Pu(IV) to Pu(VI) as compared to dissolving Pu metal under the same conditions but at or near the boiling temperature. This flowsheet was demonstrated by conducting Pu metal dissolutions at 95°C to ensure that PuO{sub 2} solids were not formed during the dissolution. These dissolution parameters can be used formore » dissolving both Aqueous Polishing (AP) and MOX Process (MP) specification materials. Preceding the studies reported herein, two batches of Pu metal were dissolved in the H-Canyon 6.1D dissolver to prepare feed solution for the AFS-2 PuO{sub 2} production campaign. While in storage, UV-visible spectra obtained from an at-line spectrophotometer indicated the presence of Pu(VI). Analysis of the solutions also showed the presence of Fe, Ni, and Cr. Oxidation of Pu(IV) produced during metal dissolution to Pu(VI) is a concern for anion exchange purification. Anion exchange requires Pu in the +4 oxidation state for formation of the anionic plutonium(IV) hexanitrato complex which absorbs onto the resin. The presence of Pu(VI) in the anion feed solution would require a valence adjustment step to prevent losses. In addition, the presence of Cr(VI) would result in absorption of chromate ion onto the resin and could limit the purification of Pu from Cr which may challenge the purity specification of the final PuO{sub 2} product. Initial experiments were performed to quantify the rate of oxidation of Pu(IV) to Pu(VI) (presumed to be facilitated by Cr(VI)) as functions of the HNO{sub 3} concentration and temperature in simulated dissolution solutions containing Cr, Fe, and Ni. In these simulated Pu dissolutions studies, lowering the temperature from near boiling to 95 °C reduced the oxidation rate of Pu(IV) to Pu(VI). For 8.1 M HNO{sub 3} simulated dissolution solutions, at near boiling conditions >35% Pu(VI) was present in 50 h while at 95 °C <10% Pu(VI) was present at 50 h. At near boiling temperatures, eliminating the presence of Cr and varying the HNO{sub 3} concentration in the range of 7–8.5 M had little effect on the rate of conversion of Pu(IV) to Pu(VI). HNO{sub 3} oxidation of Pu(IV) to Pu(VI) in a pure solution has been reported previously. Based on simulated dissolution experiments, this study concluded that dissolving Pu metal at 95°C using a 6 to 10 M HNO{sub 3} solution 0.05–0.2 M KF and 0–2 g/L B could reduce the rate of oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. To demonstrate this flowsheet, two small-scale experiments were performed dissolving Pu metal up to 6.75 g/L. No Pu-containing residues were observed in the solutions after cooling. Using Pu metal dissolution rates measured during the experiments and a correlation developed by Holcomb, the time required to completely dissolve a batch of Pu metal in an H-Canyon dissolver using this flowsheet was estimated to require nearly 5 days (120 h). This value is reasonably consistent with an estimate based on the Batch 2 and 3 dissolution times in the 6.1D dissolver and Pu metal dissolution rates measured in this study and by Rudisill et al. Data from the present and previous studies show that the Pu metal dissolution rate decreases by a factor of approximately two when the temperature decreased from boiling (112 to 116°C) to 95°C. Therefore, the time required to dissolve a batch of Pu metal in an H-Canyon dissolver at 95°C would likely double (from 36 to 54 h) and require 72 to 108 h depending on the surface area of the Pu metal. Based on the experimental studies, a Pu metal dissolution flowsheet utilizing 6–10 M HNO{sub 3} containing 0.05–0.2 M KF (with 0–2 g/L B) at 95°C is recommended to reduce the oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. The time required to completely dissolve a batch of Pu metal will increase, however, by approximately a factor of two as compared to initial dissolutions at near boiling (assuming the KF concentration is maintained at nominally 0.1 M). By lowering the temperature to 95°C under otherwise the same operating parameters as previous dissolutions, the Pu(VI) concentration should not exceed 15% after a 120 h heating cycle. Increasing the HNO{sub 3} concentration and lowering Pu concentration are expected to further limit the amount of Pu(VI) formed.« less

10 CFR Appendix J to Part 110 - Illustrative List of Uranium Conversion Plant Equipment and Plutonium Conversion Plant Equipment...

Code of Federal Regulations, 2013 CFR

2013-01-01

... cracked ammonia gas or hydrogen. (4) Especially Designed or Prepared Systems for the conversion of UO2 to UF4. Conversion of UO2 to UF4 can be performed by reacting UO2 with hydrogen fluoride gas (HF) at 300... hydrolyzed to UO2 using hydrogen and steam. In the second, UF6 is hydrolyzed by solution in water, ammonia is...

10 CFR Appendix J to Part 110 - Illustrative List of Uranium Conversion Plant Equipment and Plutonium Conversion Plant Equipment...

Code of Federal Regulations, 2012 CFR

2012-01-01

... cracked ammonia gas or hydrogen. (4) Especially Designed or Prepared Systems for the conversion of UO2 to UF4. Conversion of UO2 to UF4 can be performed by reacting UO2 with hydrogen fluoride gas (HF) at 300... UO2 using hydrogen and steam. In the second, UF6 is hydrolyzed by solution in water, ammonia is added...

10 CFR Appendix J to Part 110 - Illustrative List of Uranium Conversion Plant Equipment and Plutonium Conversion Plant Equipment...

Code of Federal Regulations, 2014 CFR

2014-01-01

... cracked ammonia gas or hydrogen. (4) Especially Designed or Prepared Systems for the conversion of UO2 to UF4. Conversion of UO2 to UF4 can be performed by reacting UO2 with hydrogen fluoride gas (HF) at 300... hydrolyzed to UO2 using hydrogen and steam. In the second, UF6 is hydrolyzed by solution in water, ammonia is...

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

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 mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

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

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh’s and Poisson’s ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Debye temperatures of 294 and 271 K are predicted formore » polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.« less

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

2015-09-11

The mechanical properties and stability of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, and metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO 2)(O 2)(H 2O) 2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO 2)(O 2)(H 2O) 2·2H 2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh's and Poisson's ratios and the Cauchy pressure, both phases are considered ductile and shearmore » modulus is the parameter limiting their mechanical stability. Furthermore, debye temperatures of 294 and 271 K are predicted for polycrystalline (UO 2)(O 2)(H 2O) 2·2H 2O and (UO 2)(O 2)(H 2O) 2, suggesting a lower micro-hardness of metastudtite.« less

Reduced live-birth rates after IVF/ICSI in women with previous unilateral oophorectomy: results of a multicentre cohort study.

PubMed

Lind, Tekla; Holte, Jan; Olofsson, Jan I; Hadziosmanovic, Nermin; Gudmundsson, Johannes; Nedstrand, Elizabeth; Lood, Mikael; Berglund, Lars; Rodriguez-Wallberg, Kenny

2018-02-01

Is there a reduced live-birth rate (LBR) after IVF/ICSI treatment in women with a previous unilateral oophorectomy (UO)? A significantly reduced LBR after IVF/ICSI was found in women with previous UO when compared with women with intact ovaries in this large multicentre cohort, both crudely and after adjustment for age, BMI, fertility centre and calendar period and regardless of whether the analysis was based on transfer of embryos in the fresh cycle only or on cumulative results including transfers using frozen-thawed embryos. Similar pregnancy rates after IVF/ICSI have been previously reported in case-control studies and small cohort studies of women with previous UO versus women without ovarian surgery. In all previous studies multiple embryos were transferred. No study has previously evaluated LBR in a large cohort of women with a history of UO. This research was a multicentre cohort study, including five reproductive medicine centres in Sweden: Carl von Linné Clinic (A), Karolinska University Hospital (B), Uppsala University Hospital (C), Linköping University Hospital (D) and Örebro University Hospital (E). The women underwent IVF/ICSI between January 1999 and November 2015. Single embryo transfer (SET) was performed in approximately 70% of all treatments, without any significant difference between UO exposed women versus controls (68% versus 71%), respectively (P = 0.32), and a maximum of two embryos were transferred in the remaining cases. The dataset included all consecutive treatments and fresh and frozen-thawed cycles. The exposed cohort included 154 women with UO who underwent 301 IVF/ICSI cycles and the unexposed control cohort consisted of 22 693 women who underwent 41 545 IVF/ICSI cycles. Overall, at the five centres (A-E), the exposed cohort underwent 151, 34, 35, 41 and 40 treatments, respectively, and they were compared with controls of the same centre (18 484, 8371, 5575, 4670 and 4445, respectively). The primary outcome was LBR, which was analysed per started cycle, per ovum pick-up (OPU) and per embryo transfer (ET). Secondary outcomes included the numbers of oocytes retrieved and supernumerary embryos obtained, the Ovarian Sensitivity Index (OSI), embryo quality scores and cumulative pregnancy rates. We used a Generalized Estimating Equation (GEE) model for statistical analysis in order to account for repeated treatments. The exposed (UO) and control women's groups were comparable with regard to age and performance of IVF or ICSI. Significant differences in LBR, both crude and age-adjusted, were observed between the UO and control groups: LBR per started cycle (18.6% versus 25.4%, P = 0.007 and P = 0.014, respectively), LBR/OPU (20.3% versus 27.1%, P = 0.012 and P = 0.015, respectively) and LBR/ET (23.0% versus 29.7%, P = 0.022 and P = 0.025, respectively). The differences in LBR remained significant after inclusion of both fresh and frozen-thawed transfers (both crude and age-adjusted data): LBR/OPU (26.1% versus 34.4%, P = 0.005 and P = 0.006, respectively) and LBR/ET (28.3% versus 37.1%, P = 0.006 and P = 0.006, respectively). The crude cancellation rate was significantly higher among women with a history of UO than in controls (18.9% versus 14.5%, P = 0.034 and age-adjusted, P = 0.178). In a multivariate GEE model, the cumulative odds ratios for LBR (fresh and frozen-thawed)/OPU (OR 0.70, 95% CI 0.52-0.94, P = 0.016) and LBR (fresh and frozen-thawed)/ET (OR 0.68, 95% CI 0.51-0.92, P = 0.012) were approximately 30% lower in the group of women with UO when adjusted for age, BMI, reproductive centre, calendar period and number of embryos transferred when appropriate. The OSI was significantly lower in women with a history of UO than in controls (3.6 versus 6.0) and the difference was significant for both crude and age-adjusted data (P = <0.001 for both). Significantly fewer oocytes were retrieved in treatments of women with UO than in controls (7.2 versus 9.9, P = <0.001, respectively). Due to the nature of the topic, this is a retrospective analysis, with all its inherent limitations. Furthermore, the cause for UO was not possible to obtain in all cases. A diagnosis of endometriosis was also more common in the UO group, i.e. a selection bias in terms of poorer patient characteristics in the UO group cannot be completely ruled out. However, adjustment for all known confounders did not affect the general results. To date, this is the largest cohort investigated and the first study indicating an association of achieving reduced live birth after IVF/ICSI in women with previous UO. These findings are novel and contradict the earlier notion that IVF/ICSI treatment is not affected, or is only marginally affected by previous UO. None. Not applicable. © The Author 2017. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com

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.

Improvement of the cloud point extraction of uranyl ions by the addition of ionic liquids.

PubMed

Gao, Song; Sun, Taoxiang; Chen, Qingde; Shen, Xinghai

2013-12-15

The cloud point extraction (CPE) of uranyl ions by different kinds of extractants in Triton X-114 (TX-114) micellar solution was investigated upon the addition of ionic liquids (ILs) with various anions, i.e., bromide (Br(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)) and bis[(trifluoromethyl)sulfonyl]imide (NTf2(-)). A significant increase of the extraction efficiency was found on the addition of NTf2(-) based ILs when using neutral extractant tri-octylphosphine oxide (TOPO), and the extraction efficiency kept high at both nearly neutral and high acidity. However, the CPE with acidic extractants, e.g., bis(2-ethylhexyl) phosphoric acid (HDEHP) and 8-hydroxyquinoline (8-HQ) which are only effective at nearly neutral condition, was not improved by ILs. The results of zeta potential and (19)F NMR measurements indicated that the anion NTf2(-) penetrated into the TX-114 micelles and was enriched in the surfactant-rich phase during the CPE process. Meanwhile, NTf2(-) may act as a counterion in the CPE of UO2(2+) by TOPO. Furthermore, the addition of IL increased the separation factor of UO2(2+) and La(3+), which implied that in the micelle TOPO, NTf2(-) and NO3(-) established a soft template for UO2(2+). Therefore, the combination of CPE and IL provided a supramolecular recognition to concentrate UO2(2+) efficiently and selectively. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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

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.

Six uranyl-organic frameworks with naphthalene-dicarboxylic acid and bipyridyl-based spacers: syntheses, structures, and properties.

PubMed

Xu, Wei; Ren, Ya-Nan; Xie, Miao; Zhou, Lin-Xia; Zheng, Yue-Qing

2018-03-28

A new series of uranium coordination polymers have been hydrothermally synthesized by using 1,4-naphthalene dicarboxylic acid (H 2 NDC), namely, (H 3 O) 2 [(UO 2 ) 2 (NDC) 3 ]·H 2 O (1), (H 2 -bpp)[(UO 2 ) 2 (NDC) 3 ]·EtOH·5H 2 O (2), (H 2 -bpe) 2/2 [(UO 2 ) 2 (NDC) 3 ]·EtOH (3), (H 2 -bpp)[(UO 2 ) 2 (NDC) 3 ]·5H 2 O (4), (H 2 -bpp)[(UO 2 )(HNDC)(NDC)] 2 ·2H 2 O (5), and (H 2 -bpy)[(UO 2 )(NDC) 2 ] (6) [bpp = 1,3-di(4-pyridyl) propane, bpe = 4,4'-vinylenedipyridine, bpy = 4,4'-bipyridine]. Single-crystal X-ray diffraction demonstrates that complex 1 represents the uranyl-organic polycatenated framework derived from a simple two-dimensional honeycomb grid network structure via a H 2 NDC linker. Complexes 2-4 contain the dinuclear motifs of the two UO 7 pentagonal and one UO 8 hexagonal bipyramids which are linked by NDC 2- anions creating a (UO 2 ) 4 (NDC) 2 unit, and further extend to a 2D layer through NDC 2- anions. Complex 5 displays a 1D zigzag double chain structure, in which the carboxylate groups of the NDC 2- anions adopt a chelate mode and further extends to a 2D framework via hydrogen bonds. The 1D structure of complex 6 is similar to the zigzag chain of complex 5. In addition, powder X-ray diffraction, elemental analysis, IR, thermal stability and luminescence properties of all complexes have also been investigated in this paper. The photocatalytic properties of the six complexes for the degradation of tetracycline hydrochloride (TC) under UV irradiation have been examined. Moreover, density functional theory (DFT) calculations were carried out to explore the electronic structural and bonding properties of the uranyl complexes 1-6.

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

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.

[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

Molten uranium dioxide structure and dynamics

DOE PAGES

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

2014-11-21

Uranium dioxide (UO 2) is the major nuclear fuel component of fission power reactors. A key concern during severe accidents is the melting and leakage of radioactive UO 2 as it corrodes through its zirconium cladding and steel containment. Yet, the very high temperatures (>3140 kelvin) and chemical reactivity of molten UO 2 have prevented structural studies. In this work, we combine laser heating, sample levitation, and synchrotron x-rays to obtain pair distribution function measurements of hot solid and molten UO 2. The hot solid shows a substantial increase in oxygen disorder around the lambda transition (2670 K) but negligiblemore » U-O coordination change. On melting, the average U-O coordination drops from 8 to 6.7 ± 0.5. Molecular dynamics models refined to this structure predict higher U-U mobility than 8-coordinated melts.« less

Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

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

Peyton, Brent M.; Timothy, Ginn R.; Sani, Rajesh K.

2013-08-14

Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO 2. We have shown that SRB reduce U(VI) to nanometer-sized UO 2 particles (1-5 nm) which are both intra- and extracellular, with UO 2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO 2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phasemore » when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO 2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO 2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO 2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO 2 reoxidation with ferrihydrite. The highest rate of UO 2 reoxidation occurred when the chelator promoted UO 2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO 2 dissolution did not occur, UO 2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO 2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO 2 reoxidation as Fe(III) oxidizes HS– preferentially over UO 2. The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO 2) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO 2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.« 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

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

NASA Astrophysics Data System (ADS)

Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

2011-08-01

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

Electronic spectrum of the UO and UO(+) molecules.

PubMed

Tyagi, Rajni; Zhang, Zhiyong; Pitzer, Russell M

2014-12-18

Electronic theory calculations are applied to the study of the UO molecule and the UO(+) ion. Relativistic effective core potentials are used along with the accompanying valence spin-orbit operators. Polarized double-ς and triple-ς basis sets are used. Molecular orbitals are obtained from state-averaged multiconfiguration self-consistent field calculations and then used in multireference spin-orbit configuration interaction calculations with a number of millions of terms. The ground state of UO has open shells of 5f(3)7s(1), angular momentum Ω = 4, and a spin-orbit-induced avoided crossing near the equilibrium internuclear distance. Many UO excited states are studied with rotational constants, intensities, and experimental comparisons. The ground state of UO(+) is of 5f(3) nature with Ω = 9/2. Many UO(+) excited states are also studied. The open-shell nature of both UO and UO(+) leads to many low-lying excited states.

Dosage effects of histamine-2 receptor antagonist on the primary prophylaxis of non-steroidal anti-inflammatory drug (NSAID)-associated peptic ulcers: a retrospective cohort study.

PubMed

He, Ying; Chan, Esther W; Man, Kenneth K C; Lau, Wallis C Y; Leung, Wai K; Ho, Lai M; Wong, Ian C K

2014-09-01

A histamine-2 receptor antagonist (H2RA) is one of the common gastroprotective co-therapies used with non-steroidal anti-inflammatory drugs (NSAIDs) for the prevention or treatment of peptic ulcers (PUs). To date, no study has directly compared the prophylactic effectiveness between high-dose and low-dose H2RA. Our objective was to compare the effectiveness of high-dose versus low-dose H2RAs in the primary prophylaxis of PUs among short-term NSAID users. A retrospective cohort study was conducted using the Clinical Data Analysis and Reporting System (CDARS) in Hong Kong. Patients aged 18 years or above who received a single prescription of oral NSAID with oral H2RA were identified within the study period (1 January 2009-31 December 2012). Patients with a history of or risk factors for PU in the corresponding 2 years prior to the index date (of the first NSAID prescription) were excluded. Log binomial regression analysis was used to calculate the relative risk of PU among NSAID users with high-dose H2RA versus low-dose H2RA exposure. Among the NSAID cohort (n = 102,042), 77,509 (76 %) were on low-dose H2RA and 24,533 (24 %) were on high-dose H2RA. Of the total 69 PU cases identified during the drug exposure period, 64 (0.08 %) received low-dose-H2RA and five (0.02 %) received high-dose H2RA. The overall absolute risk of PUs for NSAID users whilst on H2RA was approximately 1 per 1,479 patients. The adjusted relative risk for NSAID users receiving high-dose H2RA versus low-dose H2RA was 0.32 (95 % confidence interval [CI] 0.13-0.79). Patients aged ≥65 years, receiving a longer duration of treatment, or with concomitant use of antiplatelet agents were found to be at higher risk of PU. High-dose H2RA showed greater effectiveness than low-dose H2RA in the primary prophylaxis of NSAID-associated PUs in short-term new users.

Determination of ultra-low level plutonium isotopes (239Pu, 240Pu) in environmental samples with high uranium.

PubMed

Xing, Shan; Zhang, Weichao; Qiao, Jixin; Hou, Xiaolin

2018-09-01

In order to measure trace plutonium and its isotopes ratio ( 240 Pu/ 239 Pu) in environmental samples with a high uranium, an analytical method was developed using radiochemical separation for separation of plutonium from matrix and interfering elements including most of uranium and ICP-MS for measurement of plutonium isotopes. A novel measurement method was established for extensively removing the isobaric interference from uranium ( 238 U 1 H and 238 UH 2 + ) and tailing of 238 U, but significantly improving the measurement sensitivity of plutonium isotopes by employing NH 3 /He as collision/reaction cell gases and MS/MS system in the triple quadrupole ICP-MS instrument. The results show that removal efficiency of uranium interference was improved by more than 15 times, and the sensitivity of plutonium isotopes was increased by a factor of more than 3 compared to the conventional ICP-MS. The mechanism on the effective suppress of 238 U interference for 239 Pu measurement using NH 3 -He reaction gases was explored to be the formation of UNH + and UNH 2 + in the reactions of UH + and U + with NH 3 , while no reaction between NH 3 and Pu + . The detection limits of this method were estimated to be 0.55 fg mL -1 for 239 Pu, 0.09 fg mL -1 for 240 Pu. The analytical precision and accuracy of the method for Pu isotopes concentration and 240 Pu/ 239 Pu atomic ratio were evaluated by analysis of sediment reference materials (IAEA-385 and IAEA-412) with different levels of plutonium and uranium. The developed method were successfully applied to determine 239 Pu and 240 Pu concentrations and 240 Pu/ 239 Pu atomic ratios in soil samples collected in coastal areas of eastern China. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

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.

TOF-SIMS for Rapid Nuclear Forensics Evaluation of Uranium Oxide Particles

DTIC Science & Technology

2011-03-01

Fraction U-238 nU U metal CRM 112-A NBL Metal Assay and Isotopic .000052458 .0072017 --- .9927458 nUO2 UO2 --- NBL Commercial material...0 .992745 dU U metal CRM 115 NBL Uranium Assay .0000076 .0020291 .0000322 .9979311 dUO2 UO2 --- IBI Labs Commercial material --- .002- .0035...U500* U3O8 CRM U500 NBL Isotopic .005181 .49696 .000755 .49711 U900* U3O8 CRM U900 NBL Isotopic .007777 .90196 .003327 .08693 *Sample

Chemical resolution of Pu+ from U+ and Am+ using a band-pass reaction cell inductively coupled plasma mass spectrometer.

PubMed

Tanner, Scott D; Li, Chunsheng; Vais, Vladimir; Baranov, Vladimir I; Bandura, Dmitry R

2004-06-01

Determination of the concentration and distribution of the Pu and Am isotopes is hindered by the isobaric overlaps between the elements themselves and U, generally requiring time-consuming chemical separation of the elements. A method is described in which chemical resolution of the elemental ions is obtained through ion-molecule reactions in a reaction cell of an ICPMS instrument. The reactions of "natural" U(+), (242)Pu(+), and (243)Am(+) with ethylene, carbon dioxide, and nitric oxide are reported. Since the net sensitivities to the isotopes of an element are similar, chemical resolution is inferred when one isobaric element reacts rapidly with a given gas and the isobar (or in this instance surrogate isotope) is unreactive or slowly reactive. Chemical resolution of the m/z 238 isotopes of U and Pu can be obtained using ethylene as a reaction gas, but little improvement in the resolution of the m/z 239 isobars is obtained. However, high efficiency of reaction of U(+) and UH(+) with CO(2), and nonreaction of Pu(+), allows the sub-ppt determination of (239)Pu, (240)Pu, and (242)Pu (single ppt for (238)Pu) in the presence of 7 orders of magnitude excess U matrix without prior chemical separation. Similarly, oxidation of Pu(+) by NO, and nonreaction of Am(+), permit chemical resolution of the isobars of Pu and Am over 2-3 orders of magnitude relative concentration. The method provides the potential for analysis of the actinides with reduced sample matrix separation.

Investigation of Plutonium and Uranium Precipitation Behavior with Gadolinium as a Neutron Poison

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

Visser, A.E.

2003-10-17

The caustic precipitation of plutonium (Pu)-containing solutions has been investigated to determine whether the presence of 3:1 uranium (U):Pu in solutions stored in the H-Canyon Facility at the U.S. Department of Energy's (DOE) Savannah River Site (SRS) would adversely impact the use of gadolinium nitrate (Gd(NO3)3) as a neutron poison. In the past, this disposition strategy has been successfully used to discard solutions containing approximately 100 kg of Pu to the SRS high level waste (HLW) system. In the current experiments, gadolinium (as Gd(NO3)3) was added to samples of a 3:1 U:Pu solution, a surrogate 3 g/L U solution, andmore » a surrogate 3 g/L U with 1 g/L Pu solution. A series of experiments was then performed to observe and characterize the precipitate at selected pH values. Solids formed at pH 4.5 and were found to contain at least 50 percent of the U and 94 percent of the Pu, but only 6 percent of the Gd. As the pH of the solution increased (e.g., pH greater than 14 with 1.2 or 3.6 M sodium hydroxide (NaOH) excess), the precipitate contained greater than 99 percent of the Pu, U, and Gd. After the pH greater than 14 systems were undisturbed for one week, no significant changes were found in the composition of the solid or supernate for each sample. The solids were characterized by X-ray diffraction (XRD) which found sodium diuranate (Na2U2O7) and gadolinium hydroxide (Gd(OH)3) at pH 14. Thermal gravimetric analysis (TGA) indicated sufficient water molecules were present in the solids to thermalize the neutrons, a requirement for the use of Gd as a neutron poison. Scanning electron microscopy (SEM) was also performed and the accompanying back-scattering electron analysis (BSE) found Pu, U, and Gd compounds in all pH greater than 14 precipitate samples. The rheological properties of the slurries at pH greater than 14 were also investigated by performing precipitate settling rate studies and measuring the viscosity and density of the materials. Based on the results of these experiments, poisoning the Pu-U solutions with Gd and subsequent neutralization is a viable process for discarding the Pu to the SRS HLW system.« less

Lung, liver and bone cancer mortality after plutonium exposure in beagle dogs and nuclear workers.

PubMed

Wilson, Dulaney A; Mohr, Lawrence C; Frey, G Donald; Lackland, Daniel; Hoel, David G

2010-01-01

The Mayak Production Association (MPA) worker registry has shown evidence of plutonium-induced health effects. Workers were potentially exposed to plutonium nitrate [(239)Pu(NO(3))(4)] and plutonium dioxide ((239)PuO(2)). Studies of plutonium-induced health effects in animal models can complement human studies by providing more specific data than is possible in human observational studies. Lung, liver, and bone cancer mortality rate ratios in the MPA worker cohort were compared to those seen in beagle dogs, and models of the excess relative risk of lung, liver, and bone cancer mortality from the MPA worker cohort were applied to data from life-span studies of beagle dogs. The lung cancer mortality rate ratios in beagle dogs are similar to those seen in the MPA worker cohort. At cumulative doses less than 3 Gy, the liver cancer mortality rate ratios in the MPA worker cohort are statistically similar to those in beagle dogs. Bone cancer mortality only occurred in MPA workers with doses over 10 Gy. In dogs given (239)Pu, the adjusted excess relative risk of lung cancer mortality per Gy was 1.32 (95% CI 0.56-3.22). The liver cancer mortality adjusted excess relative risk per Gy was 55.3 (95% CI 23.0-133.1). The adjusted excess relative risk of bone cancer mortality per Gy(2) was 1,482 (95% CI 566.0-5686). Models of lung cancer mortality based on MPA worker data with additional covariates adequately described the beagle dog data, while the liver and bone cancer models were less successful.

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

PubMed

Thuéry, Pierre; Harrowfield, Jack

2016-03-07

Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to those in helicates, and the counterions are embedded in intralayer cavities. Emission spectra measured in the solid state show in most cases various degrees of quenching, with intense and well-resolved uranyl emission being observed only for complexes 2 and 11.

Effects of Beryllium and Compaction Pressure on the Thermal Diffusivity of Uranium Dioxide Fuel Pellets

NASA Astrophysics Data System (ADS)

Camarano, D. M.; Mansur, F. A.; Santos, A. M. M.; Ferraz, W. B.; Ferreira, R. A. N.

2017-09-01

In nuclear reactors, the performance of uranium dioxide (UO2) fuel is strongly dependent on the thermal conductivity, which directly affects the fuel pellet temperature, the fission gas release and the fuel rod mechanical behavior during reactor operation. The use of additives to improve UO2 fuel performance has been investigated, and beryllium oxide (BeO) appears as a suitable additive because of its high thermal conductivity and excellent chemical compatibility with UO2. In this paper, UO2-BeO pellets were manufactured by mechanical mixing, pressing and sintering processes varying the BeO contents and compaction pressures. Pellets with BeO contents of 2 wt%, 3 wt%, 5 wt% and 7 wt% BeO were pressed at 400 MPa, 500 MPa and 600 MPa. The laser flash method was applied to determine the thermal diffusivity, and the results showed that the thermal diffusivity tends to increase with BeO content. Comparing thermal diffusivity results of UO2 with UO2-BeO pellets, it was observed that there was an increase in thermal diffusivity of at least 18 % for the UO2-2 wt% BeO pellet pressed at 400 MPa. The maximum relative expanded uncertainty (coverage factor k = 2) of the thermal diffusivity measurements was estimated to be 9 %.

First evaluation of automated specimen inoculation for wound swab samples by use of the Previ Isola system compared to manual inoculation in a routine laboratory: finding a cost-effective and accurate approach.

PubMed

Mischnik, Alexander; Mieth, Markus; Busch, Cornelius J; Hofer, Stefan; Zimmermann, Stefan

2012-08-01

Automation of plate streaking is ongoing in clinical microbiological laboratories, but evaluation for routine use is mostly open. In the present study, the recovery of microorganisms from the Previ Isola system plated polyurethane (PU) swab samples is compared to manually plated control viscose swab samples from wounds according to the CLSI procedure M40-A (quality control of microbiological transport systems). One hundred twelve paired samples (224 swabs) were analyzed. In 80/112 samples (71%), concordant culture results were obtained with the two methods. In 32/112 samples (29%), CFU recovery of microorganisms from the two methods was discordant. In 24 (75%) of the 32 paired samples with a discordant result, Previ Isola plated PU swabs were superior. In 8 (25%) of the 32 paired samples with a discordant result, control viscose swabs were superior. The quality of colony growth on culture media for further investigations was superior with Previ Isola inoculated plates compared to manual plating techniques. Gram stain results were concordant between the two methods in 62/112 samples (55%). In 50/112 samples (45%), the results of Gram staining were discordant between the two methods. In 34 (68%) of the 50 paired samples with discordant results, Gram staining of PU swabs was superior to that of control viscose swabs. In 16 (32%) of the 50 paired samples, Gram staining of control viscose swabs was superior to that of PU swabs. We report the first clinical evaluation of Previ Isola automated specimen inoculation for wound swab samples. This study suggests that use of an automated specimen inoculation system has good results with regard to CFU recovery, quality of Gram staining, and accuracy of diagnosis.

First Evaluation of Automated Specimen Inoculation for Wound Swab Samples by Use of the Previ Isola System Compared to Manual Inoculation in a Routine Laboratory: Finding a Cost-Effective and Accurate Approach

PubMed Central

Mieth, Markus; Busch, Cornelius J.; Hofer, Stefan; Zimmermann, Stefan

2012-01-01

Automation of plate streaking is ongoing in clinical microbiological laboratories, but evaluation for routine use is mostly open. In the present study, the recovery of microorganisms from the Previ Isola system plated polyurethane (PU) swab samples is compared to manually plated control viscose swab samples from wounds according to the CLSI procedure M40-A (quality control of microbiological transport systems). One hundred twelve paired samples (224 swabs) were analyzed. In 80/112 samples (71%), concordant culture results were obtained with the two methods. In 32/112 samples (29%), CFU recovery of microorganisms from the two methods was discordant. In 24 (75%) of the 32 paired samples with a discordant result, Previ Isola plated PU swabs were superior. In 8 (25%) of the 32 paired samples with a discordant result, control viscose swabs were superior. The quality of colony growth on culture media for further investigations was superior with Previ Isola inoculated plates compared to manual plating techniques. Gram stain results were concordant between the two methods in 62/112 samples (55%). In 50/112 samples (45%), the results of Gram staining were discordant between the two methods. In 34 (68%) of the 50 paired samples with discordant results, Gram staining of PU swabs was superior to that of control viscose swabs. In 16 (32%) of the 50 paired samples, Gram staining of control viscose swabs was superior to that of PU swabs. We report the first clinical evaluation of Previ Isola automated specimen inoculation for wound swab samples. This study suggests that use of an automated specimen inoculation system has good results with regard to CFU recovery, quality of Gram staining, and accuracy of diagnosis. PMID:22692745

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.

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

How to Adapt Chemical Risk Assessment for Unconventional Hydrocarbon Extraction Related to the Water System.

PubMed

Faber, Ann-Hélène; Annevelink, Mark; Gilissen, Herman Kasper; Schot, Paul; van Rijswick, Marleen; de Voogt, Pim; van Wezel, Annemarie

2017-12-27

We identify uncertainties and knowledge gaps of chemical risk assessment related to unconventional drillings and propose adaptations. We discuss how chemical risk assessment in the context of unconventional oil and gas (UO&G) activities differs from conventional chemical risk assessment and the implications for existing legislation. A UO&G suspect list of 1,386 chemicals that might be expected in the UO&G water samples was prepared which can be used for LC-HRMS suspect screening. We actualize information on reported concentrations in UO&G-related water. Most information relates to shale gas operations, followed by coal-bed methane, while only little is available for tight gas and conventional gas. The limited research on conventional oil and gas recovery hampers comparison whether risks related to unconventional activities are in fact higher than those related to conventional activities. No study analyzed the whole cycle from fracturing fluid, flowback and produced water, and surface water and groundwater. Generally target screening has been used, probably missing contaminants of concern. Almost half of the organic compounds analyzed in surface water and groundwater exceed TTC values, so further risk assessment is needed, and risks cannot be waived. No specific exposure scenarios toward groundwater aquifers exist for UO&G-related activities. Human errors in various stages of the life cycle of UO&G production play an important role in the exposure. Neither at the international level nor at the US federal and the EU levels, specific regulations for UO&G-related activities are in place to protect environmental and human health. UO&G activities are mostly regulated through general environmental, spatial planning, and mining legislation.

Implementation of a spark plasma sintering facility in a hermetic glovebox for compaction of toxic, radiotoxic, and air sensitive materials

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

Tyrpekl, V., E-mail: vaclav.tyrpekl@ec.europa.eu, E-mail: vaclav.tyrpekl@gmail.com; Berkmann, C.; Holzhäuser, M.

Spark plasma sintering (SPS) is a rapidly developing method for densification of powders into compacts. It belongs to the so-called “field assisted sintering techniques” that enable rapid sintering at much lower temperatures than the classical approaches of pressureless sintering of green pellets or hot isostatic pressing. In this paper, we report the successful integration of a SPS device into a hermetic glovebox for the handling of highly radioactive material containing radioisotopes of U, Th, Pu, Np, and Am. The glovebox implantation has been facilitated by the replacement of the hydraulic system to apply pressure with a compact electromechanical unit. Themore » facility has been successfully tested using UO{sub 2} powder. Pellets with 97% of the theoretical density were obtained at 1000 °C for 5 min, significantly lower than the ∼1600 °C for 5-10 h used in conventional pellet sintering.« less

Attenuation and Transport Mechanisms of Depleted Uranium in Groundwater at Lawrence Livermore National Laboratory Site 300

NASA Astrophysics Data System (ADS)

Danny, K. R.; Taffet, M. J.; Brusseau, M. L. L.; Chorover, J.

2015-12-01

Lawrence Livermore National Laboratory (LLNL) Site 300 was established in 1955 to support weapons research and development. Depleted uranium was used as a proxy for fissile uranium-235 (235U) in open-air explosives tests conducted at Building 812. As a result, oxidized depleted uranium was deposited on the ground, eventually migrating to the underlying sandstone aquifer. Uranium (U) groundwater concentrations exceed the California and Federal Maximum Contaminant Level of 20 pCi L-1 (30 ug L-1). However, the groundwater plume appears to attenuate within 60 m of the source, beyond which no depleted U is detected. This study will determine the relative contribution of physical (e.g. dilution), chemical (e.g. surface adsorption, mineral precipitation), and biological (e.g. biotransformation) processes that contribute to the apparent attenuation of U, which exists as uranyl (UO22+) complexes, at the site. Methods of investigation include evaluating 15 yr of hydrogeologic and chemical data, creating a site conceptual model, and applying equilibrium (e.g. aqueous species complexation, mineral saturation indices) and reactive transport models using Geochemist's WorkbenchTM. Reactive transport results are constrained by direct field observations, including U major ion, and dissolved O2 concentrations, pH, and others, under varying chemical and hydraulic conditions. Aqueous speciation calculations indicate that U primarily exists as anionic CaUO2(CO3)32- or neutral Ca2UO2(CO3)30 species. Additionally, nucleation and growth of Ca/Mg uranyl carbonate solids are predicted to affect attenuation. Initial reactive transport results suggest surface adsorption (e.g. ion exchange, surface complexation) to layer silicate clays is limited under the aqueous geochemical conditions of the site. Current and future work includes XRD analysis of aquifer solids to constrain iron and aluminum (oxy)hydroxides, and coupling advective-dispersive transport with the chemical and physical processes. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-ABS-675707.

Structure-Activity Relationships for Some Diamine, Triamine and Schiff Base Derivatives and Their Copper(II) Complexes.

PubMed

Bolos, C A; Nikolov, G S; Ekateriniadou, L; Kortsaris, A; Kyriakidis, D A

1998-01-01

Ethylenediamine (en), putrescine (pu), diethylenetriamine (dien), dipropylenetriamine (dpta), spermidine (spmd) and their Cu(II) compounds as well as the Schiff bases with 2-furaldehyde (dienOO), 2- thiophenecarboxaldehyde (dienSS) and pyrrole-2-carboxaldehyde (dienNN) of dien and that of dpta with 2- thiophenecarboxaldehyde (dptaSS), were prepared and characterised. They were tested against Bacillus substilis, Bacillus cereus, Staphylococcus aureus, Escherichia coli, Proteus vulgaris and Xanthomonas campestris as antibacterial reagents, the highest activity being exhibited by Cu(dptaSS)(NO(3))(2) complex, which acts as antibiotic. In the antiproliferative tests (vs. T(47)D,L(929) and BHK(21/c13) cell lines) the best results were obtained with Cu(dptaSS)(2+) and Cu(dienSS)(2+). Electronic structure calculations gave for dptaSS and dienSS the higher negative charges on the N atoms. The counter-ions (Br(-), NO(3) (-) and SO(4) (2-)) play an important role by modulating the reagent's selectivity versus the bacteria [Gram(+) or Gram(-)], but they have no effect on the antiproliferative activity.

Closure of the Mott gap and formation of a superthermal metal in the Fröhlich-type nonequilibrium polaron Bose-Einstein condensate in U O 2 + x

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

Conradson, Steven D.; Andersson, David A.; Boland, Kevin S.

Mixed valence O-doped UO 2+x and photoexcited UO 2 containing transitory U 3+ and U 5+ host a coherent polaronic quantum phase (CPQP) that exhibits the characteristics of a Fröhlich-type, nonequilibrium, phonon-coupled Bose-Einstein condensate whose stability and coherence are amplified by collective, anharmonic motions of atoms and charges. Complementary to the available, detailed, real space information from scattering and EXAFS, an outstanding question is the electronic structure. Mapping the Mott gap in UO 2, U 4O 9, and U 3O 7 with O XAS and NIXS and UM5 RIXS shows that O doping raises the peak of the U5f statesmore » of the valence band by ~0.4 eV relative to a calculated value of 0.25 eV. However, it lowers the edge of the conduction band by 1.5 eV vs the calculated 0.6 eV, a difference much larger than the experimental error. This 1.9 eV reduction in the gap width constitutes most of the 2–2.2 eV gap measured by optical absorption. In addition, the XAS spectra show a tail that will intersect the occupied U5f states and give a continuous density-of-states that increases rapidly above its constricted intersection. Femtosecond-resolved photoemission measurements of UO 2, coincident with the excitation pulse with 4.7 eV excitation, show the unoccupied U5f states of UO 2 and no hot electrons. 3.1 eV excitation, however, complements the O-doping results by giving a continuous population of electrons for several eV above the Fermi level. The CPQP in photoexcited UO 2 therefore fulfills the criteria for a nonequilibrium condensate. The electron distributions resulting from both excitations persist for 5–10 ps, indicating that they are the final state that therefore forms without passing through the initial continuous distribution of nonthermal electrons observed for other materials. Three exceptional findings are: (1) the direct formation of both of these long lived (>3–10 ps) excited states without the short lived nonthermal intermediate; (2) the superthermal metallic state is as or more stable than typical photoinduced metallic phases; and (3) the absence of hot electrons accompanying the insulating UO 2 excited state. This heterogeneous, nonequilibrium, Fröhlich BEC stabilized by a Fano-Feshbach resonance therefore continues to exhibit unique properties.« 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.

Carcinogenesis From Inhaled (PuO2)-Pu-239 in Beagles: Evidence for Radiation Homeostasis at Low Doses?

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

Fisher, Darrell R.; Weller, Richard E.

From the early 1970s to the late 1980s, Pacific Northwest National Laboratory conducted life-span studies in beagle dogs on the biological effects of inhaled plutonium (239PuO2, 238PuO2, and 239Pu[NO3]4) to help predict risks associated with accidental intakes in workers. Years later, the purpose of the present follow-up study is to reassess the dose-response relationship for lung cancer induction in the 239PuO2 dogs compared to controls, with particular focus on the dose-response at low lung doses. A 239PuO2 aerosol (2.3 μm AMAD, 1.9 μm GSD) was administered to six groups of 20 young (18-month old) beagle dogs (10 males and 10more » females) by inhalation at six different activity levels, as previously described in Laboratory reports. Control dogs were sham-exposed. In dose level 1, initial pulmonary lung depositions were 130 ± 48 Bq (3.5 ± 1.3 nCi), corresponding to 1 Bq g-1 lung tissue (0.029 ± 0.001 nCi g-1. Groups 2 through 6 received initial lung depositions (mean values) of 760, 2724, 10345, 37900, and 200000 Bq (22, 79, 300, 1100, and 5800 nCi) 239PuO2, respectively. For each dog, the absorbed dose to lungs was calculated from the initial lung burden and the final lung burden at time of death and lung mass, assuming a single, long-term retention function. Insoluble plutonium oxide exhibited long retention times in the lungs. Increased dose-dependent mortality due to lung cancer (bronchiolar-alveolar carcinoma, adenocarcinoma, epidermoid carcinoma) and radiation pneumonitis (highest exposures group) was observed in dogs exposed to 239PuO2. Calculated lung doses ranged from a few cGy in early-sacrificed dogs to 7764 cGy in dogs that experienced early deaths from radiation pneumonitis. Data were regrouped by lifetime lung dose and plotted as a function of lung tumor incidence. Lung tumor incidence in controls and zero-dose exposed dogs was 18% (5/28). However, no lung tumors were observed in 16 dogs with the lowest lung doses (8 to 22 cGy, mean 14.4 ± 7.6 cGy), and only one lung tumor was observed in 10 dogs with lung doses ranging from 27 to 48 cGy (mean 37.5 ± 10.9 cGy). By least-squares analysis, a quadratic function represented the overall dose-response (n = 137, r = 0.96) with no dose threshold. Reducing this function to three linear dose-response components, risk coefficients were calculated for each. The incidence of lung tumors at zero dose was significantly greater than the incidence at low dose (at the p ≤ 0.053 confidence level), suggesting a protective effect (radiation homeostasis) of alpha-particle radiation from 239PuO2. If a threshold for lung cancer incidence exists, it will be observed in the range 15 to 40 cGy.« less

Silver nanoparticle decorated reduced graphene oxide (rGO) nanosheet: a platform for SERS based low-level detection of uranyl ion.

PubMed

Dutta, Soumen; Ray, Chaiti; Sarkar, Sougata; Pradhan, Mukul; Negishi, Yuichi; Pal, Tarasankar

2013-09-11

Herein, a simple wet-chemical pathway has been demonstrated for the synthesis of silver nanoparticle conjugated reduced graphene oxide nanosheets where dimethylformamide (DMF) is judiciously employed as an efficient reducing agent. Altogether, DMF reduces both silver nitrate (AgNO3) and graphene oxide (GO) in the reaction mixture. Additionally, the presence of polyvinylpyrolidone (PVP) assists the nanophasic growth and homogeneous distribution of the plasmonic nanoparticle Ag(0). Reduction of graphene oxide and the presence of aggregated Ag NPs on reduced graphene oxide (rGO) nanosheets are confirmed from various spectroscopic techniques. Finally, the composite material has been exploited as an intriguing platform for surface enhanced Raman scattering (SERS) based selective detection of uranyl (UO2(2+)) ion. The limit of detection has been achieved to be as low as 10 nM. Here the normal Raman spectral (NRS) band of uranyl acetate (UAc) at 838 cm(-1) shifts to 714 and 730 cm(-1) as SERS bands for pH 5.0 and 12.0, respectively. This distinguished Raman shift of the symmetric stretching mode for UO2(2+) ion is indicative of pronounced charge transfer (CT) effect. This CT effect even supports the higher sensitivity of the protocol toward UO2(2+) over other tested oxo-ions. It is anticipated that rGO nanosheets furnish a convenient compartment to favor the interaction between Ag NPs and UO2(2+) ion through proximity induced adsorption even at low concentration.

UO₂²⁺ uptake by proteins: understanding the binding features of the super uranyl binding protein and design of a protein with higher affinity.

PubMed

Odoh, Samuel O; Bondarevsky, Gary D; Karpus, Jason; Cui, Qiang; He, Chuan; Spezia, Riccardo; Gagliardi, Laura

2014-12-17

The capture of uranyl, UO2(2+), by a recently engineered protein (Zhou et al. Nat. Chem. 2014, 6, 236) with high selectivity and femtomolar sensitivity has been examined by a combination of density functional theory, molecular dynamics, and free-energy simulations. It was found that UO2(2+) is coordinated to five carboxylate oxygen atoms from four amino acid residues of the super uranyl binding protein (SUP). A network of hydrogen bonds between the amino acid residues coordinated to UO2(2+) and residues in its second coordination sphere also affects the protein's uranyl binding affinity. Free-energy simulations show how UO2(2+) capture is governed by the nature of the amino acid residues in the binding site, the integrity and strength of the second-sphere hydrogen bond network, and the number of water molecules in the first coordination sphere. Alteration of any of these three factors through mutations generally results in a reduction of the binding free energy of UO2(2+) to the aqueous protein as well as of the difference between the binding free energies of UO2(2+) and other ions (Ca(2+), Cu(2+), Mg(2+), and Zn(2+)), a proxy for the protein's selectivity over these ions. The results of our free-energy simulations confirmed the previously reported experimental results and allowed us to discover a mutant of SUP, specifically the GLU64ASP mutant, that not only binds UO2(2+) more strongly than SUP but that is also more selective for UO2(2+) over other ions. The predictions from the computations were confirmed experimentally.

Transient Ureteral Obstruction Prevents against Kidney Ischemia/Reperfusion Injury via Hypoxia-Inducible Factor (HIF)-2α Activation

PubMed Central

Chen, Xiao-Song; Zhang, Ming; Xu, Long-Mei; Zhang, Jian-Jun; Xia, Qiang

2012-01-01

Although the protective effect of transient ureteral obstruction (UO) prior to ischemia on subsequent renal ischemia/reperfusion (I/R) injury has been documented, the underlying molecular mechanism remains to be understood. We showed in the current study that 24 h of UO led to renal tubular hypoxia in the ipsilateral kidney in mice, with the accumulation of hypoxia-inducible factor (HIF)-2α, which lasted for a week after the release of UO. To address the functions of HIF-2α in UO-mediated protection of renal IRI, we utilized the Mx-Cre/loxP recombination system to knock out target genes. Inactivation of HIF-2α, but not HIF-1α blunted the renal protective effects of UO, as demonstrated by much higher serum creatinine level and severer histological damage. UO failed to prevent postischemic neutrophil infiltration and apoptosis induction in HIF-2α knockout mice, which also diminished the postobstructive up-regulation of the protective molecule, heat shock protein (HSP)-27. The renal protective effects of UO were associated with the improvement of the postischemic recovery of intra-renal microvascular blood flow, which was also dependent on the activation of HIF-2α. Our results demonstrated that UO protected the kidney via activation of HIF-2α, which reduced tubular damages via preservation of adequate renal microvascular perfusion after ischemia. Thus, preconditional HIF-2α activation might serve as a novel therapeutic strategy for the treatment of ischemic acute renal failure. PMID:22295069

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Kovrugin, Vadim M.; Tyumentseva, Olga S.

2015-09-15

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){submore » 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • The method of orientation matrices was applied to distinguish geometrical isomers. • The flexibility of structural complexes specifies the undulation of layered structural units.« less

Pu-239 and Pu-240 inventories and Pu-240/ Pu-239 atom ratios in the water column off Sanriku, Japan.

NASA Astrophysics Data System (ADS)

Yamada, Masatoshi; Zheng, Jian; Aono, Tatsuo

2013-04-01

A magnitude 9.0 earthquake and subsequent tsunami occurred in the Pacific Ocean off northern Honshu, Japan, on 11 March 2011 which caused severe damage to the Fukushima Dai-ichi Nuclear Power Plant. This accident has resulted in a substantial release of radioactive materials to the atmosphere and ocean, and has caused extensive contamination of the environment. However, no information is available on the amounts of radionuclides such as Pu isotopes released into the ocean at this time. Investigating the background baseline concentration and atom ratio of Pu isotopes in seawater is important for assessment of the possible contamination in the marine environment. Pu-239 (half-life: 24,100 years), Pu-240 (half-life: 6,560 years) and Pu-241 (half-life: 14.325 years) mainly have been released into the environment as the result of atmospheric nuclear weapons testing. The atom ratio of Pu-240/Pu-239 is a powerful fingerprint to identify the sources of Pu in the ocean. The Pu-239 and Pu-240 inventories and Pu-240/Pu-239 atom ratios in seawater samples collected in the western North Pacific off Sanriku before the accident at Fukushima Dai-ichi Nuclear Power Plant will provide useful background baseline data for understanding the process controlling Pu transport and for distinguishing additional Pu sources. Seawater samples were collected with acoustically triggered quadruple PVC sampling bottles during the KH-98-3 cruise of the R/V Hakuho-Maru. The Pu-240/Pu-239 atom ratios were measured with a double-focusing SF-ICP-MS, which was equipped with a guard electrode to eliminate secondary discharge in the plasma and to enhance overall sensitivity. The Pu-239 and Pu-240 concentrations were 2.07 and 1.67 mBq/m3 in the surface water, respectively, and increased with depth; a subsurface maximum was identified at 750 m depth, and the concentrations decreased with depth, then increased at the bottom layer. The total Pu-239+240 inventory in the entire water column (depth interval 0-bottom) was 69.8 Bq/m2. This was significantly higher than the expected cumulative deposition density of atmospheric global fallout. The Pu-240/Pu-239 atom ratios were 0.22 in the surface water and increased gradually with depth reaching 0.26 at the 5000 m depth. The obtained Pu-240/Pu-239 atom ratios were higher than the mean global fallout ratio of 0.18. These high atom ratios proved the existence of close-in tropospheric fallout Pu from the Pacific Proving Grounds in the Marshall Islands.

A Fock space coupled cluster study on the electronic structure of the UO(2), UO(2) (+), U(4+), and U(5+) species.

PubMed

Infante, Ivan; Eliav, Ephraim; Vilkas, Marius J; Ishikawa, Yasuyuki; Kaldor, Uzi; Visscher, Lucas

2007-09-28

The ground and excited states of the UO(2) molecule have been studied using a Dirac-Coulomb intermediate Hamiltonian Fock-space coupled cluster approach (DC-IHFSCC). This method is unique in describing dynamic and nondynamic correlation energies at relatively low computational cost. Spin-orbit coupling effects have been fully included by utilizing the four-component Dirac-Coulomb Hamiltonian from the outset. Complementary calculations on the ionized systems UO(2) (+) and UO(2) (2+) as well as on the ions U(4+) and U(5+) were performed to assess the accuracy of this method. The latter calculations improve upon previously published theoretical work. Our calculations confirm the assignment of the ground state of the UO(2) molecule as a (3)Phi(2u) state that arises from the 5f(1)7s(1) configuration. The first state from the 5f(2) configuration is found above 10,000 cm(-1), whereas the first state from the 5f(1)6d(1) configuration is found at 5,047 cm(-1).

Structure-Activity Relationships for Some Diamine, Triamine and Schiff Base Derivatives and Their Copper(II) Complexes

PubMed Central

Bolos, C. A.; Nikolov, G. St.; Ekateriniadou, L.; Kortsaris, A.; Kyriakidis, D. A.

1998-01-01

Ethylenediamine (en), putrescine (pu), diethylenetriamine (dien), dipropylenetriamine (dpta), spermidine (spmd) and their CuII compounds as well as the Schiff bases with 2-furaldehyde (dienOO), 2- thiophenecarboxaldehyde (dienSS) and pyrrole-2-carboxaldehyde (dienNN) of dien and that of dpta with 2- thiophenecarboxaldehyde (dptaSS), were prepared and characterised. They were tested against Bacillus substilis, Bacillus cereus, Staphylococcus aureus, Escherichia coli, Proteus vulgaris and Xanthomonas campestris as antibacterial reagents, the highest activity being exhibited by Cu(dptaSS)(NO3)2 complex, which acts as antibiotic. In the antiproliferative tests (vs. T47D,L929 and BHK21/c13 cell lines) the best results were obtained with Cu(dptaSS)2+ and Cu(dienSS)2+. Electronic structure calculations gave for dptaSS and dienSS the higher negative charges on the N atoms. The counter-ions (Br-, NO3- and SO42-) play an important role by modulating the reagent's selectivity versus the bacteria [Gram(+) or Gram(-)], but they have no effect on the antiproliferative activity. PMID:18475868

Release of plutonium isotopes into the environment from the Fukushima Daiichi Nuclear Power Plant accident: what is known and what needs to be known.

PubMed

Zheng, Jian; Tagami, Keiko; Uchida, Shigeo

2013-09-03

The Fukushima Daiichi Nuclear Power Plant (FDNPP) accident has caused serious contamination in the environment. The release of Pu isotopes renewed considerable public concern because they present a large risk for internal radiation exposure. In this Critical Review, we summarize and analyze published studies related to the release of Pu from the FDNPP accident based on environmental sample analyses and the ORIGEN model simulations. Our analysis emphasizes the environmental distribution of released Pu isotopes, information on Pu isotopic composition for source identification of Pu releases in the FDNPP-damaged reactors or spent fuel pools, and estimation of the amounts of Pu isotopes released from the FDNPP accident. Our analysis indicates that a trace amount of Pu isotopes (∼2 × 10(-5)% of core inventory) was released into the environment from the damaged reactors but not from the spent fuel pools located in the reactor buildings. Regarding the possible Pu contamination in the marine environment, limited studies suggest that no extra Pu input from the FDNPP accident could be detected in the western North Pacific 30 km off the Fukushima coast. Finally, we identified knowledge gaps remained on the release of Pu into the environment and recommended issues for future studies.

A Method for Continuous (239)Pu Determinations in Arctic and Antarctic Ice Cores.

PubMed

Arienzo, M M; McConnell, J R; Chellman, N; Criscitiello, A S; Curran, M; Fritzsche, D; Kipfstuhl, S; Mulvaney, R; Nolan, M; Opel, T; Sigl, M; Steffensen, J P

2016-07-05

Atmospheric nuclear weapons testing (NWT) resulted in the injection of plutonium (Pu) into the atmosphere and subsequent global deposition. We present a new method for continuous semiquantitative measurement of (239)Pu in ice cores, which was used to develop annual records of fallout from NWT in ten ice cores from Greenland and Antarctica. The (239)Pu was measured directly using an inductively coupled plasma-sector field mass spectrometer, thereby reducing analysis time and increasing depth-resolution with respect to previous methods. To validate this method, we compared our one year averaged results to published (239)Pu records and other records of NWT. The (239)Pu profiles from the Arctic ice cores reflected global trends in NWT and were in agreement with discrete Pu profiles from lower latitude ice cores. The (239)Pu measurements in the Antarctic ice cores tracked low latitude NWT, consistent with previously published discrete records from Antarctica. Advantages of the continuous (239)Pu measurement method are (1) reduced sample preparation and analysis time; (2) no requirement for additional ice samples for NWT fallout determinations; (3) measurements are exactly coregistered with all other chemical, elemental, isotopic, and gas measurements from the continuous analytical system; and (4) the long half-life means the (239)Pu record is stable through time.

Colloids from the aqueous corrosion of uranium nuclear fuel

NASA Astrophysics Data System (ADS)

Kaminski, M. D.; Dimitrijevic, N. M.; Mertz, C. J.; Goldberg, M. M.

2005-12-01

Colloids may enhance the subsurface transport of radionuclides and potentially compromise the long-term safe operation of the proposed radioactive waste repository at Yucca Mountain. Little data is available on colloid formation for the many different waste forms expected to be buried in the repository. This work expands the sparse database on colloids formed during the corrosion of metallic uranium nuclear fuel. We characterized spherical UO 2 and nickel-rich montmorilonite smectite-clay colloids formed during the corrosion of uranium metal fuel under bathtub conditions at 90 °C. Iron and chromium oxides and calcium carbonate colloids were present but were a minor population. The estimated upper concentration of the UO 2 and clays was 4 × 10 11 and 7 × 10 11-3 × 10 12 particles/L, respectively. However, oxygen eventually oxidized the UO 2 colloids, forming long filaments of weeksite K 2(UO 2) 2Si 6O 15 · 4H 2O that settled from solution, reducing the UO 2 colloid population and leaving predominantly clay colloids. The smectite colloids were not affected by oxygen. Plutonium was not directly observed within the UO 2 colloids but partitioned completely to the colloid size fraction. The plutonium concentration in the colloidal fraction was slightly higher than the value used in the viability assessment model, and does not change in concentration with exposure to oxygen. This paper provides conclusive evidence for single-phase radioactive colloids composed of UO 2. However, its impact on repository safety is probably small since oxygen and silica availability will oxidize and effectively precipitate the UO 2 colloids from concentrated solutions.

Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides

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

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.

2016-03-23

A systematic X-ray absorption study at actinide N 6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO 2, PuO 2, and UO 3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L 2,3 (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurementsmore » demonstrated an enhanced sensitivity of the N 6,7 spectral shape to changes in the compound crystal structure. Finally, for nonstoichiometric NpO 2-x, the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO 2 which is in agreement with the tentative Np-O phase diagram.« less

Uptake and translocation of plutonium in two plant species using hydroponics.

PubMed

Lee, J H; Hossner, L R; Attrep, M; Kung, K S

2002-01-01

This study presents determinations of the uptake and translocation of Pu in Indian mustard (Brassica juncea) and sunflower (Helianthus annuus) from Pu contaminated solution media. The initial activity levels of Pu were 18.50 and 37.00 Bq ml(-1), for Pu-nitrate [239Pu(NO3)4] and for Pu-citrate [239Pu(C6H5O7)+] in nutrient solution. Plutonium-diethylenetriaminepentaacetic acid (DTPA: [239Pu-C14H23O10N3] solution was prepared by adding 0, 5, 10, and 50 microg of DTPA ml(-1) with 239Pu(NO3)4 in nutrient solution. Concentration ratios (CR, Pu concentration in dry plant material/Pu concentration in nutrient solution) and transport indices (Tl, Pu content in the shoot/Pu content in the whole plant) were calculated to evaluate Pu uptake and translocation. All experiments were conducted in hydroponic solution in an environmental growth chamber. Plutonium concentration in the plant tissue was increased with increased Pu contamination. Plant tissue Pu concentration for Pu-nitrate and Pu-citrate application was not correlated and may be dependent on plant species. For plants receiving Pu-DTPA, the Pu concentration was increased in the shoots but decreased in the roots resulting in a negative correlation between the Pu concentrations in the plant shoots and roots. The Pu concentration in shoots of Indian mustard was increased for application rates up to 10 microg DTPA ml(-1) and up to 5 microg DTPA ml(-1) for sunflower. Similar trends were observed for the CR of plants compared to the Pu concentration in the shoots and roots, whereas the Tl was increased with increasing DTPA concentration. Plutonium in shoots of Indian mustard was up to 10 times higher than that in shoots of sunflower. The Pu concentration in the apparent free space (AFS) of plant root tissue of sunflower was more affected by concentration of DTPA than that of Indian mustard.

Inclusions and Substructures in Uranium of Nuclear Purity. Report No. 51; INCLUSIONES Y SUBESTRUCTURAS EN URANIO DE PUREZA NUCLEAR. INFORME NO. 51

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

Biloni, H.; Lindenvald, N.; Sabato, J.A.

1961-01-01

The inclusions in uranium of nuclear purity (UC, UH/sub 3/, UO/sub 2/, UO, UN, and the complexes which include the intersolubility of U with C and N or with C, N, and O) were . analyzed metallographically, and the results reported by other authors were discussed critically. The existence of the fine precipitate reticular substructure, sensitive to thermal treatments, which generally appears in uraniunn was analyzed. Its origins were discussed in accordance with bibliographic data. Complementary data for its comprehension are given from the metallographic analysis of U--Al and U-- Fe alloys with low Al and Fe concentrations. (tr-auth)

Synthesis and sintering of UN-UO2 fuel composites

NASA Astrophysics Data System (ADS)

Jaques, Brian J.; Watkins, Jennifer; Croteau, Joseph R.; Alanko, Gordon A.; Tyburska-Püschel, Beata; Meyer, Mitch; Xu, Peng; Lahoda, Edward J.; Butt, Darryl P.

2015-11-01

The design and development of an economical, accident tolerant fuel (ATF) for use in the current light water reactor (LWR) fleet is highly desirable for the future of nuclear power. Uranium mononitride has been identified as an alternative fuel with higher uranium density and thermal conductivity when compared to the benchmark, UO2, which could also provide significant economic benefits. However, UN by itself reacts with water at reactor operating temperatures. In order to reduce its reactivity, the addition of UO2 to UN has been suggested. In order to avoid carbon impurities, UN was synthesized from elemental uranium using a hydride-dehydride-nitride thermal synthesis route prior to mixing with up to 10 wt% UO2 in a planetary ball mill. UN and UN - UO2 composite pellets were sintered in Ar - (0-1 at%) N2 to study the effects of nitrogen concentration on the evolved phases and microstructure. UN and UN-UO2 composite pellets were also sintered in Ar - 100 ppm N2 to assess the effects of temperature (1700-2000 °C) on the final grain morphology and phase concentration.

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)

Study on the leaching behavior of actinides from nuclear fuel debris

NASA Astrophysics Data System (ADS)

Kirishima, Akira; Hirano, Masahiko; Akiyama, Daisuke; Sasaki, Takayuki; Sato, Nobuaki

2018-04-01

For the prediction of the leaching behavior of actinides contained in the nuclear fuel debris generated by the Fukushima Daiichi nuclear power plant accident in Japan, simulated fuel debris consisting of a UO2-ZrO2 solid solution doped with 137Cs, 237Np, 236Pu, and 241Am tracers was synthesized and investigated. The synthesis of the debris was carried out by heat treatment at 1200 °C at different oxygen partial pressures, and the samples were subsequently used for leaching tests with Milli-Q water and seawater. The results of the leaching tests indicate that the leaching of actinides depends on the redox conditions under which the debris was generated; for example, debris generated under oxidative conditions releases more actinide nuclides to water than that generated under reductive conditions. Furthermore, we found that, as Zr(IV) increasingly substituted U(IV) in the fluorite crystal structure of the debris, the actinide leaching from the debris decreased. In addition, we found that seawater leached more actinides from the debris than pure water, which seems to be caused by the complexation of actinides by carbonate ions in seawater.

Transfer of aged 239+240Pu, 238Pu, 241Am, and 137Cs to cattle grazing a contaminated arid environment.

PubMed

Gilbert, R O; Engel, D W; Anspaugh, L R

1989-09-01

In this paper, estimates are obtained of the fraction of ingested 239+240Pu, 238Pu, 241Am and 137Cs transferred to blood, muscle, liver, kidney, femur, vertebra, and gonads of a reproducing herd of 17 beef cattle, individuals of which grazed within fenced enclosures for up to 1064 days under natural conditions with no supplemental feeding at an arid site contaminated 16 years previously with transuranic radionuclides. The estimated geometric mean (GM) GI-to-blood fractional transfer of 238Pu (0.0001) was about 20 times larger than the estimated transfer of 239+240Pu (0.000005), while the estimated transfer of 241Am (0.00001) was about 2 times larger than that of 239+240Pu. These GM GI-to-blood transfers were smaller than the GI-to-blood transfer value of 0.001 recommended by the International Commission on Radiological Protection (ICRP) for humans exposed via food chains or occupationally from unknown mixtures or compounds of plutonium and americium. Statistical tests indicated significantly (p less than 0.05) larger GI-to-tissue transfers of (1) 238Pu as compared to 239+240Pu for all tissues examined, (2) of 238Pu as compared to 241Am for muscle, liver, femur, and vertebra, and (3) of 241Am as compared to 239+240Pu for blood serum, femur, and kidney. The estimated GM fractional transfers of 137Cs from GI to muscle and liver were 0.03 (n = 8) and 0.001 (n = 3), respectively, assuming a 50-day biological half-time of 137Cs in cattle tissue.

Severe anemia in cats with urethral obstruction: 17 cases (2002-2011).

PubMed

Beer, Kari Santoro; Drobatz, Kenneth J

2016-05-01

To characterize clinical parameters of cats with severe anemia due to suspected urinary bladder hemorrhage associated with urethral obstruction. Retrospective case-control study. University teaching hospital. Seventeen cats with urethral obstruction and severe anemia (group "UO-A") that required transfusion were identified via medical record database search. Thirty cats with urethral obstruction and mild or no anemia (group "UO") were included as controls. None. The median PCV of all cases at presentation was 28% (range, 9%-47%). Seven cats had PCV ≤20% at presentation, and all transfused cats had PCV ≤20% at the time of transfusion. Three cats did not receive a transfusion despite PCV ≤18%. Cats in the UO-A group had a significantly longer duration of clinical signs (P = 0.001), and were more likely to have a history of previous urethral obstruction (P = 0.011), have a heart murmur (P = 0.002), have a gallop rhythm (P = 0.005), and have lower blood pressure (P = 0.007) compared to those in the UO group. Additionally, UO-A cats had significantly lower pH, more negative base excess, higher BUN, and higher creatinine compared to UO cats. Duration of urinary catheterization was significantly (P = 0.016) longer in UO-A cats. All UO cats survived to discharge, whereas 4/17 (23.5%) UO-A cats were euthanized (P = 0.013). A history of previous urethral obstruction and longer duration of clinical signs may be important risk factors for severe anemia in UO cats. Additionally, UO-A cats appeared to be more severely affected, as evidenced by lower blood pressure, more severe metabolic acidosis, higher BUN and creatinine, and worse outcome. © Veterinary Emergency and Critical Care Society 2016.

Rigid Polyurethane Nanocomposites Prepared by Direct Incorporation: Effects of Nanoclay, Carbon Nanotubes and Mixing Speed on Physical and Morphological Properties

NASA Astrophysics Data System (ADS)

Ramadhoni, Benni; Ujianto, Onny; Nadapdap, Maxwell

2018-03-01

Rigid polyurethane (PU) nanocomposites were fabricated via solution mixing of PU, nanoclay and multiwalled carbon nanotubes (MWCNT) according to full factorial DoE. The nanoclay and MWCNT concentration as well as mixing speed were varied. The effects of controlled variables on reduced compressive strength, fire retardancy, hardness and morphological properties were analized. In general, the results showed that incorporation of nanofillers into PU matrix successfully elevated nanocomposites performance. The properties changed from -12% to 45% for reduced compressive strength, 9% to 30% for reduced fire retardancy and -32% to 101% for reduced hardness. The results suggested that the improvements were affected by nanoclay dispersion that acted as nucleating agent which resulted in smaller close cells of PU structures.

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

Design of a Uranium Dioxide Spheroidization System

NASA Technical Reports Server (NTRS)

Cavender, Daniel P.; Mireles, Omar R.; Frendi, Abdelkader

2013-01-01

The plasma spheroidization system (PSS) is the first process in the development of tungsten-uranium dioxide (W-UO2) fuel cermets. The PSS process improves particle spherocity and surface morphology for coating by chemical vapor deposition (CVD) process. Angular fully dense particles melt in an argon-hydrogen plasma jet at between 32-36 kW, and become spherical due to surface tension. Surrogate CeO2 powder was used in place of UO2 for system and process parameter development. Particles range in size from 100 - 50 microns in diameter. Student s t-test and hypothesis testing of two proportions statistical methods were applied to characterize and compare the spherocity of pre and post process powders. Particle spherocity was determined by irregularity parameter. Processed powders show great than 800% increase in the number of spherical particles over the stock powder with the mean spherocity only mildly improved. It is recommended that powders be processed two-three times in order to reach the desired spherocity, and that process parameters be optimized for a more narrow particles size range. Keywords: spherocity, spheroidization, plasma, uranium-dioxide, cermet, nuclear, propulsion

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.

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

Electronic, structural, and thermodynamic properties of mixed actinide dioxides (U, Pu, Am) O2 from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Ma, Li; Ray, Asok K.

2010-03-01

As a continuation of our studies of pure actinide metals using hybrid density functional theory,footnotetextR. Atta-Fynn and A. K. Ray, Europhysics Letters, 85, 27008-p1- p6 (2009); Chemical Physics Letters, 482, 223-227 (2009). we present here a systematic study of the electronic and geometric structure properties of mixed actinide dioxides, U0.5Pu0.5O2, U0.5Am0.5O2, Pu0.5Am0.5 O2 and U0.8Pu0.2O2. The fraction of exact Hartree-Fock exchange used was 40%. To investigate the effect of spin-orbit coupling on the ground state electronic and geometric structure properties, computations have been carried out at two theoretical levels, one at the scalar-relativistic level with no spin-orbit coupling and one at the fully relativistic level with spin-orbit coupling. Thermodynamic properties have been calculated by a coupling of first-principles calculation and lattice dynamics.

Equilibrium, kinetic, and reactive transport models for plutonium

NASA Astrophysics Data System (ADS)

Schwantes, Jon Michael

Equilibrium, kinetic, and reactive transport models for plutonium (Pu) have been developed to help meet environmental concerns posed by past war-related and present and future peacetime nuclear technologies. A thorough review of the literature identified several hurdles that needed to be overcome in order to develop capable predictive tools for Pu. These hurdles include: (1) missing or ill-defined chemical equilibrium and kinetic constants for environmentally important Pu species; (2) no adequate conceptual model describing the formation of Pu oxy/hydroxide colloids and solids; and (3) an inability of two-phase reactive transport models to adequately simulate Pu behavior in the presence of colloids. A computer program called INVRS K was developed that integrates the geochemical modeling software of PHREEQC with a nonlinear regression routine. This program provides a tool for estimating equilibrium and kinetic constants from experimental data. INVRS K was used to regress on binding constants for Pu sorbing onto various mineral and humic surfaces. These constants enhance the thermodynamic database for Pu and improve the capability of current predictive tools. Time and temperature studies of the Pu intrinsic colloid were also conducted and results of these studies were presented here. Formation constants for the fresh and aged Pu intrinsic colloid were regressed upon using INVRS K. From these results, it was possible to develop a cohesive diagenetic model that describes the formation of Pu oxy/hydroxide colloids and solids. This model provides for the first time a means of deciphering historically unexplained observations with respect to the Pu intrinsic colloid, as well as a basis for simulating the behavior within systems containing these solids. Discussion of the development and application of reactive transport models is also presented and includes: (1) the general application of a 1-D in flow, three-phase (i.e., dissolved, solid, and colloidal), reactive transport model; (2) a simulation of the effects of dissolution of PuO2 solid and radiolysis on the behavior of Pu diffusing out of a confined pore space; and (3) application of a steady-state three phase reactive transport model to groundwater at the Nevada Test Site.

Experimental investigation of 150-KG-scale corium melt jet quenching in water

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

Magallon, D.; Hohmann, H.

This paper compares and discusses the results of two large scale FARO quenching tests known as L-11 and L-14, which involved, respectively, 151 kg of W% 76.7 UO{sub 2} + 19.2 ZrO{sub 2} + 4.1 Zr and 125 kg of W% 80 UO{sub 2} + 20 ZrO{sub 2} melts poured into 600-kg, 2-m-depth water at saturation at 5.0 MPa. The results are further compared with those of two previous tests performed using a pure oxidic melt, respectively 18 and 44 kg of W% 80 UO{sub 2} + 20 ZrO{sub 2} melt quenched in 1-m-depth water at saturation at 5.0 MPa.more » In all the tests, significant breakup and quenching took place during the melt fall through the water. No steam explosion occurred. In the tests performed with a pure oxide UO{sub 2}-ZrO{sub 2} melt, part of the corium (from 1/6 to 1/3) did not breakup and reached the bottom plate still molten whatever the water depth was. Test L-11 data suggest that full oxidation and complete breakup of the melt occurred during the melt fall through the water. A proportion of 64% of the total energy content of the melt was released to the water during this phase ({approximately}1.5 s), against 44% for L-14. The maximum temperature increase of the bottom plate was 330 K (L-14). The mean particle size of the debris ranged between 2.5 and 4.8mm.« less

Ruthenium Nanoparticles Mediated Electrocatalytic Reduction of UO22+ Ions for Its Rapid and Sensitive Detection in Natural Waters.

PubMed

Gupta, Ruma; Sundararajan, Mahesh; Gamare, Jayashree S

2017-08-01

Reduction of UO 2 2+ ions to U 4+ ions is difficult due to involvement of two axially bonded oxygen atoms, and often requires a catalyst to lower the activation barrier. The noble metal nanoparticles (NPs) exhibit high electrocatalytic activity, and could be employed for the sensitive and rapid quantifications of U0 2 2+ ions in the aqueous matrix. Therefore, the Pd, Ru, and Rh NPs decorated glassy carbon electrode were examined for their efficacy toward electrocatalytic reduction of UO 2 2+ ions and observed that Ru NPs mediate efficiently the electro-reduction of UO 2 2+ ions. The mechanism of the electroreduction of UO 2 2+ by the RuNPs/GC was studied using density functional theory calculations which pointed different approach of 5f metal ions electroreduction unlike 4p metal ions such as As(III). RuNP decorated on the glassy carbon would be hydrated, which in turn assist to adsorb the uranyl sulfates through hydrogen bonding thus facilitated electro-reduction. Differential pulse voltammetric (DPV) technique, was used for rapid and sensitive quantification of UO 2 2+ ions. The RuNPs/GC based DPV technique could be used to determine the concentration of uranyl in a few minutes with a detection limit of 1.95 ppb. The RuNPs/GC based DPV was evaluated for its analytical performance using seawater as well lake water and groundwater spiked with known amounts of UO 2 2+ .

An evaluation of UO2-CNT composites made by SPS as an accident tolerant nuclear fuel pellet and the feasibility of SPS as an economical fabrication process for the nuclear fuel cycle

NASA Astrophysics Data System (ADS)

Cartas, Andrew R.

The innovative and advanced purpose of this study is to understand and establish proper sintering procedures for Spark Plasma Sintering process in order to fabricate high density, high thermal conductivity UO2 -CNT pellets. Mixing quality and chemical reactions have been investigated by field emission scanning electron microscopy (FESEM), wavelength dispersive spectroscopy (WDS), and X-ray diffraction (XRD). The effect of various types of CNTs on the mixing and sintering quality of UO2-CNT pellets with SPS processing have been examined. The Archimedes Immersion Method, laser flash method, and FE-SEM will be used to investigate the density, thermal conductivity, grain size, pinning effects, and CNT dispersion of fabricated UO2-CNT pellets. Pre-fabricated CNT's were added to UO 2 powder and dispersed via sonication and/or ball milling and then made into composite nuclear pellets. An investigation of the economic impact of SPS on the nuclear fuel cycle for producing pure and composite UO2 fuels was conducted.

Uranyl carboxyphosphonates that incorporate Cd(II)

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

Alsobrook, Andrea N.; Alekseev, Evgeny V.; Depmeier, Wulf

2011-05-15

The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered watermore » molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. > Heterobimetallic compounds.« less

Can 239 + 240Pu replace 137Cs as an erosion tracer in agricultural landscapes contaminated with Chernobyl fallout?

PubMed

Schimmack, W; Auerswald, K; Bunzl, K

2001-01-01

Erosion studies often use 137Cs from the global fallout (main period: 1953-1964) as a tracer in the soil. In many European countries, where 137Cs was deposited in considerable amounts also by the Chernobyl fallout in 1986, the global fallout fraction (GF-Cs) has to be separated from the Chernobyl fraction by means of the isotope 134Cs. In a few years, this will no longer be possible due to the short half-life of 134Cs (2 yr). Because GF-Cs in the soil can then no longer be determined, the potential of using 239 + 240Pu as a tracer is evaluated. This radionuclide originates in most European countries essentially only from the global fallout. The activities and spatial distributions of Pu and GF-Cs were compared in the soil of a steep field (inclination about 20%, area ca. 3 ha, main soil type Dystric Eutrochrept), sampled at 48 nodes of a 25 x 25 m2 grid. The reference values were determined at 12 points adjacent to the field. Their validity was assured by an inventory study of radiocaesium in a 70 ha area surrounding the field sampling 275 nodes of a 50 x 50 m2 grid. In the field studied, the activity concentrations of GF-Cs and Pu in the Ap horizon were not correlated (Spearman correlation coefficient R = 0.20, p > 0.05), and the activity balance of Pu differed from that of GF-Cs. Whereas no net loss of GF-Cs from the field was observed as compared to the reference site, Pu was more mobile with an average loss of ca. 11% per unit area. In addition, the spatial pattern of GF-Cs and Pu in the field differed significantly. The reason may be that due to their different associations with soil constituents, Pu and Cs represent different fractions of the soil, exhibiting different properties with respect to erosion/deposition processes. This indicates that both radionuclides or one of them may not be appropriate to quantity past erosion. When tracer losses are used to calibrate or verify erosion prediction models, systematic deviations may not only stem from model shortcomings but also from tracer technique.

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

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.

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.

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 smaller than found in the bulk structure of UO2 (0.385 nm). This indicates contraction within the nanoparticles due to tensile surface stress. Microbially formed UO2 is highly reactive, thus will be oxidized quickly as redox conditions change. Our findings support a growing number of studies that indicate that biominerals formed as the result of enzyme-mediated redox reactions are nanoparticulate. Preliminary results suggest that these particles will be readily transported through sandy aquifers, especially when conditions prevent high degrees of flocculation. Thus, despite its low (but size-dependent) solubility, UO2 nanoparticle transport may exert a fundamental control on mobility of U in contaminated environments.

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.

Extended study on oxidation behaviors of UN0.68 and UN1.66 by XPS

NASA Astrophysics Data System (ADS)

Luo, Lizhu; Hu, Yin; Pan, Qifa; Long, Zhong; Lu, Lei; Liu, Kezhao; Wang, Xiaolin

2018-04-01

The surface oxidation behaviors of UN0.68 and UN1.66 thin films are investigated by X-ray photoelectron spectroscopy (XPS), and the traditional U4f/N1s, O1s, valence band spectra as well as the unconventional U4d and U5d spectra are collected for the understanding of their oxidation behavior in-depth. Similar asymmetrical peak shape of the U4f spectra to uranium is observed for both uranium nitrides, despite of a slight shift to higher energy side for UN1.66 clean surface. However, significant difference among the corresponding spectra of UN0.68 and UN1.66 during oxidation reveals the distinctive properties of each own. The coexistence of UO2-x, UO2 and UO2-x.Ny on UN0.68 surface results in the peculiar features of U4f spectra as well as the others within the XPS energy scale, where peaks of the oxidized species firstly shift to higher energy side compared to the clean surface, and then return closely towards those of stoichiometric UO2. For UN1.66, the generation of U-N-O ternary compounds on the surface is identified with the symmetrical U4f peaks at 379.9eV and 390.8 eV, which locate intermediate between UO2 and UN1.66, and gradually expanding to higher energy side during the progressive oxidation. Furthermore, the formation of N-O species on UN1.66 surface is also detected as an oxidation product. The metallic character of UN1.66 is identified by the intense signal at Fermi level, which is greatly suppressed by the increasing oxygen exposure and implies the weakening metallic properties of the as-generated U-N-O compounds. Higher uranium oxides, such as UO3 and U4O9, are deduced to be the final oxidation products, and a multistage mechanism for UN1.66 following the exposure to oxygen is discussed.

Oxide particle size distribution from shearing irradiated and unirradiated LWR fuels in Zircaloy and stainless steel cladding: significance for risk assessment

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

Davis, W. Jr.; West, G.A.; Stacy, R.G.

1979-03-22

Sieve fractionation was performed with oxide particles dislodged during shearing of unirradiated or irradiated fuel bundles or single rods of UO/sub 2/ or 96 to 97% ThO/sub 2/--3 to 4% UO/sub 2/. Analyses of these data by nonlinear least-squares techniques demonstrated that the particle size distribution is lognormal. Variables involved in the numerical analyses include lognormal median size, lognormal standard deviation, and shear cut length. Sieve-fractionation data are presented for unirradiated bundles of stainless-steel-clad or Zircaloy-2-clad UO/sub 2/ or ThO/sub 2/--UO/sub 2/ sheared into lengths from 0.5 to 2.0 in. Data are also presented for irradiated single rods (sheared intomore » lengths of 0.25 to 2.0 in.) of Zircaloy-2-clad UO/sub 2/ from BWRs and of Zircaloy-4-clad UO/sub 2/ from PWRs. Median particle sizes of UO/sub 2/ from shearing irradiated stainless-steel-clad fuel ranged from 103 to 182 ..mu..m; particle sizes of ThO/sub 2/--UO/sub 2/, under these same conditions, ranged from 137 to 202 ..mu..m. Similarly, median particle sizes of UO/sub 2/ from shearing unirradiated Zircaloy-2-clad fuel ranged from 230 to 957 ..mu..m. Irradiation levels of fuels from reactors ranged from 9,000 to 28,000 MWd/MTU. In general, particle sizes from shearing these irradiated fuels are larger than those from the unirradiated fuels; however, unirradiated fuel from vendors was not available for performing comparative shearing experiments. In addition, variations in particle size parameters pertaining to samples of a single vendor varied as much as those between different vendors. The fraction of fuel dislodged from the cladding is nearly proportional to the reciprocal of the shear cut length, until the cut length attains some minimum value below which all fuel is dislodged. Particles of fuel are generally elongated with a long-to-short axis ratio usually less than 3. Using parameters of the lognormal distribution estimates can be made of fractions of dislodged fuel having dimensions less than specified values.« less

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

Perrhenate complexation by uranyl in traditional solvents and in ionic liquids: a joint molecular dynamics/spectroscopic study.

PubMed

Chaumont, Alain; Klimchuk, Olga; Gaillard, Clotilde; Billard, Isabelle; Ouadi, Ali; Hennig, Christoph; Wipff, Georges

2012-03-15

The complexation of perrhenate (ReO(4)(-)) anions by the uranyl (UO(2)(2+)) cation has been investigated by joint molecular dynamics simulations and spectroscopic (UV-vis, TRLFS, and EXAFS) studies in aqueous solution, acetonitrile, and three ionic liquids (ILs), namely, [Bmi][Tf(2)N], [Me(3)BuN][Tf(2)N], and [Bu(3)MeN][Tf(2)N] that are based on the same Tf(2)N(-) anion (bis(trifluoromethylsulfonyl)imide) and either Bmi(+) (1-butyl,3-methylimidazolium), Me(3)BuN(+), or Bu(3)MeN(+) cations. They show that ReO(4)(-) behaves as a weak ligand in aqueous solution and as a strong ligand in acetonitrile and in the ILs. According to MD simulations in aqueous solution, the UO(2)(ReO(4))(2) complex quickly dissociates to form UO(2)(H(2)O)(5)(2+), while in acetonitrile, a stable UO(2)(ReO(4))(5)(3-) species forms from dissociated ions. In the ILs, the UO(2)(ReO(4))(n)(2-n) complexes (n = 1 to 5) remained stable along the dynamics, and to assess their relative stabilities, we computed the free energy profiles for stepwise ReO(4)(-) complexation to uranyl. In the two studied ILs, complexation is favored, leading to the UO(2)(ReO(4))(5)(3-) species in [Bmi][Tf(2)N] and to UO(2)(ReO(4))(4)(2-) in [Bu(3)MeN][Tf(2)N]. Furthermore, in both acetonitrile and [Bmi][Tf(2)N] solutions, MD and PMF simulations support the formation of dimeric uranyl complexes [UO(2)(ReO(4))(4)](2)(4-) with two bridging ReO(4)(-) ligands. The simulation results are qualitatively consistent with spectroscopic observations in the different solvents, without firmly concluding, however, on the precise composition and structure of the complexes in the solutions. © 2012 American Chemical Society

Initial results from safety testing of US AGR-2 irradiation test fuel

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

Morris, Robert Noel; Hunn, John D.; Baldwin, Charles A.

Two cylindrical compacts containing tristructural isotropic (TRISO)-coated particles with kernels that contained a mixture of uranium carbide and uranium oxide (UCO) and two compacts with UO 2-kernel TRISO particles have undergone 1600°C safety testing. These compacts were irradiated in the US Advanced Gas Reactor Fuel Development and Qualification Program's second irradiation test (AGR-2). The time-dependent releases of several radioisotopes ( 110mAg, 134Cs, 137Cs, 154Eu, 155Eu, 90Sr, and 85Kr) were monitored while heating the fuel specimens to 1600°C in flowing helium for 300 h. The UCO compacts behaved similarly to previously reported 1600°C-safety-tested UCO compacts from the AGR-1 irradiation. No failedmore » TRISO or failed SiC were detected (based on krypton and cesium release), and cesium release through intact SiC was very low. Release behavior of silver, europium, and strontium appeared to be dominated by inventory originally released through intact coating layers during irradiation but retained in the compact matrix until it was released during safety testing. Both UO 2 compacts exhibited cesium release from multiple particles whose SiC failed during the safety test. Europium and strontium release from these two UO 2 compacts appeared to be dominated by release from the particles with failed SiC. Silver release was characteristically like the release from the UCO compacts in that an initial release of the majority of silver trapped in the matrix occurred during ramping to 1600°C. However, additional silver release was observed later in the safety testing due to the UO 2 TRISO with failed SiC. Failure of the SiC layer in the UO 2 fuel appears to have been dominated by CO corrosion, as opposed to the palladium degradation observed in AGR-1 UCO fuel.« less

Initial results from safety testing of US AGR-2 irradiation test fuel

DOE PAGES

Morris, Robert Noel; Hunn, John D.; Baldwin, Charles A.; ...

2017-08-18

Two cylindrical compacts containing tristructural isotropic (TRISO)-coated particles with kernels that contained a mixture of uranium carbide and uranium oxide (UCO) and two compacts with UO 2-kernel TRISO particles have undergone 1600°C safety testing. These compacts were irradiated in the US Advanced Gas Reactor Fuel Development and Qualification Program's second irradiation test (AGR-2). The time-dependent releases of several radioisotopes ( 110mAg, 134Cs, 137Cs, 154Eu, 155Eu, 90Sr, and 85Kr) were monitored while heating the fuel specimens to 1600°C in flowing helium for 300 h. The UCO compacts behaved similarly to previously reported 1600°C-safety-tested UCO compacts from the AGR-1 irradiation. No failedmore » TRISO or failed SiC were detected (based on krypton and cesium release), and cesium release through intact SiC was very low. Release behavior of silver, europium, and strontium appeared to be dominated by inventory originally released through intact coating layers during irradiation but retained in the compact matrix until it was released during safety testing. Both UO 2 compacts exhibited cesium release from multiple particles whose SiC failed during the safety test. Europium and strontium release from these two UO 2 compacts appeared to be dominated by release from the particles with failed SiC. Silver release was characteristically like the release from the UCO compacts in that an initial release of the majority of silver trapped in the matrix occurred during ramping to 1600°C. However, additional silver release was observed later in the safety testing due to the UO 2 TRISO with failed SiC. Failure of the SiC layer in the UO 2 fuel appears to have been dominated by CO corrosion, as opposed to the palladium degradation observed in AGR-1 UCO fuel.« less

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

Synthesis and sintering of UN-UO 2 fuel composites

DOE PAGES

Jaques, Brian J.; Watkins, Jennifer; Croteau, Joseph R.; ...

2015-06-17

In this study, the design and development of an economical, accident tolerant fuel (ATF) for use in the current light water reactor (LWR) fleet is highly desirable for the future of nuclear power. Uranium mononitride has been identified as an alternative fuel with higher uranium density and thermal conductivity when compared to the benchmark, UO 2, which could also provide significant economic benefits. However, UN by itself reacts with water at reactor operating temperatures. In order to reduce its reactivity, the addition of UO 2 to UN has been suggested. In order to avoid carbon impurities, UN was synthesized frommore » elemental uranium using a hydride-dehydride-nitride thermal synthesis route prior to mixing with up to 10 wt% UO 2 in a planetary ball mill. UN and UN – UO 2 composite pellets were sintered in Ar – (0–1 at%) N 2 to study the effects of nitrogen concentration on the evolved phases and microstructure. UN and UN-UO 2 composite pellets were also sintered in Ar – 100 ppm N 2 to assess the effects of temperature (1700–2000 °C) on the final grain morphology and phase concentration.« less

Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

DOE PAGES

Berg, John M.; Gaunt, Andrew J.; May, Iain; ...

2015-04-22

A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW 9O 34] 9-, [AsW 9O 34] 9-, [SiW 9O 34] 10- and [GeW 9O 34] 10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO 2} 2+, {NpO 2} +, {NpO 2} 2+ & {PuO 2} 2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na +, K + or NH 4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinylmore » cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH 4) 13 [Na(NpO 2) 2(A-α- PW 9O 34) 2]·12H 2O. The anion in this complex, [Na(NpO 2) 2(PW 9O 34) 2] 13-, contains one Na + cation and two {NpO 2} 2+ cations held between two [PW 9O 34] 9- anions – with an additional partial occupancy NH 4 + or {NpO 2} 2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH 4Cl in the parent solution, it was previously shown that [(NH 4) 2(U VIO 2) 2(A-PW 9O 34) 2] 12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO 2} 2+/[PW 9O 34] 9- and {UO 2} 2+/[PW 9O 34] 9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

NASA Astrophysics Data System (ADS)

Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; Chave, Tony; Dumas, Thomas; Hennig, Christoph; Wiss, Thierry; Dieste Blanco, Oliver; Shuh, David K.; Tyliszcak, Tolek; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I.

2017-03-01

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell.

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

PubMed Central

Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; Chave, Tony; Dumas, Thomas; Hennig, Christoph; Wiss, Thierry; Dieste Blanco, Oliver; Shuh, David K.; Tyliszcak, Tolek; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I.

2017-01-01

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell. PMID:28256635

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

DOE PAGES

Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; ...

2017-03-03

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO 2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO 2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV)more » colloid. A comparative study of nanostructured PuO 2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO 2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO 2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO 2 cores and hydrolyzed Pu(IV) moieties at the surface shell.« less

Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

DOE PAGES

Weck, Philippe F.; Kim, Eunja

2016-07-11

The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, into metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO 2)(O 2)(H 2O) 2·2H 2O → (UO 2)(O 2)(H 2O) 2 + 2H 2O reaction is ΔS 0 = +80 J·mol –1·K –1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similarmore » to bulk H 2O(l), the bulk modulus of (UO 2)(O 2)(H 2O) 2·2H 2O increases with temperature, contrasting with (UO 2)(O 2)(H 2O) 2 which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H 2O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.« less

Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

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

Weck, Philippe F.; Kim, Eunja

The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, into metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO 2)(O 2)(H 2O) 2·2H 2O → (UO 2)(O 2)(H 2O) 2 + 2H 2O reaction is ΔS 0 = +80 J·mol –1·K –1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similarmore » to bulk H 2O(l), the bulk modulus of (UO 2)(O 2)(H 2O) 2·2H 2O increases with temperature, contrasting with (UO 2)(O 2)(H 2O) 2 which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H 2O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.« less

Complexation of uranium(VI) with glutarimidoxioxime: thermodynamic and computational studies.

PubMed

Endrizzi, Francesco; Melchior, Andrea; Tolazzi, Marilena; Rao, Linfeng

2015-08-21

The complex formation between a cyclic ligand glutarimidoxioxime (denoted as HL(III) in this paper) and UO2(2+) is studied by potentiometry and microcalorimetry. Glutarimidoxioxime (HL(III)), together with glutarimidedioxime (H2L(I)) and glutardiamidoxime (H2L(II)), belongs to a family of amidoxime derivatives with prospective applications as binding agents for the recovery of uranium from seawater. An optimized procedure of synthesis that leads to the preparation of glutarimidoxioxime in the absence of other amidoxime byproducts is described in this paper. Speciation models based on the thermodynamic results from this study indicate that, compared with H2L(I) and H2L(II), HL(III) forms a much weaker complex with UO2(2+), UO2(L(III))(+), and cannot effectively compete with the hydrolysis equilibria of UO2(2+) under neutral or alkaline conditions. DFT computations, taking into account the solvation by including discrete hydration water molecules and bulk solvent effects, were performed to evaluate the structures and energies of the possible isomers of UO2(L(III))(+). Differing from the tridentate or η(2)-coordination modes previously found in the U(vi) complexes with amidoxime-related ligands, a bidentate mode, involving the oxygen of the oxime group and the nitrogen of the imino group, is found to be the most probable mode in UO2(L(III))(+). The bidentate coordination mode seems to be stabilized by the formation of a hydrogen bond between the carbonyl group of HL(III) and a water molecule in the hydration sphere of UO2(2+).

Evaluations of Energy Spectra of Neutrons Emitted Promptly in Neutron-induced Fission of 235 U and 239 Pu

DOE PAGES

Neudecker, Denise; Talou, Patrick; Kawano, Toshihiko; ...

2018-02-01

The energy spectra of neutrons emitted promptly in the neutron-induced fission reactions of 235U and 239Pu were re-evaluated for ENDF/B-VIII.0. The evaluations presented here are based on a careful modeling of all relevant physics processes, an extensive analysis of experimental data and a detailed quantification of pertinent uncertainties. Energy spectra of neutrons emitted in up to fourth chance fission are considered and both compound and pre-equilibrium processes are included. Also, important nuclear model parameters, such as the average total kinetic energy of the fission fragments and the multiple chance fission probabilities, and their uncertainties are estimated based on experimental knowledge,more » model information and evaluated data. In addition to experimental information already available for ENDF/B-VII.1, these new evaluations make use of recently published experimental data either of high precision or spanning a broad incident energy range, information on legacy measurements explaining discrepancies and recently measured data of the average total kinetic energy as a function of incident neutron energy. The resulting evaluated data and covariances agree well with the experimental database used for the evaluation. However, the evaluated spectra are softer than the 235U and 239Pu ENDF/B-VII.1, JENDL-4.0 and JEFF-3.2 evaluations for incident neutron energies E inc ≤ 1.5 MeV and E inc ≤ 5 MeV, respectively. For E inc > 5 MeV, the evaluated spectra show structures due to the improved modeling which are not present in ENDF/B-VII.1 and JEFF-3.2 but can be observed in JENDL-4.0 evaluations. Part of these new evaluations were adopted for ENDF/B-VIII.0, while the ENDF/B-VII.1 239Pu PFNS was retained for E inc ≤ 5 MeV awaiting more conclusive experimental evidence.« less

Evaluations of Energy Spectra of Neutrons Emitted Promptly in Neutron-induced Fission of 235U and 239Pu

NASA Astrophysics Data System (ADS)

Neudecker, D.; Talou, P.; Kawano, T.; Kahler, A. C.; White, M. C.; Taddeucci, T. N.; Haight, R. C.; Kiedrowski, B.; O'Donnell, J. M.; Gomez, J. A.; Kelly, K. J.; Devlin, M.; Rising, M. E.

2018-02-01

The energy spectra of neutrons emitted promptly in the neutron-induced fission reactions of 235U and 239Pu were re-evaluated for ENDF/B-VIII.0. These evaluations are based on a careful modeling of all relevant physics processes, an extensive analysis of experimental data and a detailed quantification of pertinent uncertainties. Energy spectra of neutrons emitted in up to fourth chance fission are considered and both compound and pre-equilibrium processes are included. Also, important nuclear model parameters, such as the average total kinetic energy of the fission fragments and the multiple chance fission probabilities, and their uncertainties are estimated based on experimental knowledge, model information and evaluated data. In addition to experimental information already available for ENDF/B-VII.1, these new evaluations make use of recently published experimental data either of high precision or spanning a broad incident energy range, information on legacy measurements explaining discrepancies and recently measured data of the average total kinetic energy as a function of incident neutron energy. The resulting evaluated data and covariances agree well with the experimental database used for the evaluation. However, the evaluated spectra are softer than the 235U and 239Pu ENDF/B-VII.1, JENDL-4.0 and JEFF-3.2 evaluations for incident neutron energies Einc ≤ 1.5 MeV and Einc ≤ 5 MeV, respectively. For Einc > 5 MeV, the evaluated spectra show structures due to the improved modeling which are not present in ENDF/B-VII.1 and JEFF-3.2 but can be observed in JENDL-4.0 evaluations. Part of these new evaluations were adopted for ENDF/B-VIII.0, while the ENDF/B-VII.1 239Pu PFNS was retained for Einc ≤ 5 MeV awaiting more conclusive experimental evidence.

Evaluations of Energy Spectra of Neutrons Emitted Promptly in Neutron-induced Fission of 235 U and 239 Pu

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

Neudecker, Denise; Talou, Patrick; Kawano, Toshihiko

The energy spectra of neutrons emitted promptly in the neutron-induced fission reactions of 235U and 239Pu were re-evaluated for ENDF/B-VIII.0. The evaluations presented here are based on a careful modeling of all relevant physics processes, an extensive analysis of experimental data and a detailed quantification of pertinent uncertainties. Energy spectra of neutrons emitted in up to fourth chance fission are considered and both compound and pre-equilibrium processes are included. Also, important nuclear model parameters, such as the average total kinetic energy of the fission fragments and the multiple chance fission probabilities, and their uncertainties are estimated based on experimental knowledge,more » model information and evaluated data. In addition to experimental information already available for ENDF/B-VII.1, these new evaluations make use of recently published experimental data either of high precision or spanning a broad incident energy range, information on legacy measurements explaining discrepancies and recently measured data of the average total kinetic energy as a function of incident neutron energy. The resulting evaluated data and covariances agree well with the experimental database used for the evaluation. However, the evaluated spectra are softer than the 235U and 239Pu ENDF/B-VII.1, JENDL-4.0 and JEFF-3.2 evaluations for incident neutron energies E inc ≤ 1.5 MeV and E inc ≤ 5 MeV, respectively. For E inc > 5 MeV, the evaluated spectra show structures due to the improved modeling which are not present in ENDF/B-VII.1 and JEFF-3.2 but can be observed in JENDL-4.0 evaluations. Part of these new evaluations were adopted for ENDF/B-VIII.0, while the ENDF/B-VII.1 239Pu PFNS was retained for E inc ≤ 5 MeV awaiting more conclusive experimental evidence.« less

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.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

Elastic moduli of δ-Pu 239 reveal aging in real time

DOE PAGES

Maiorov, Boris; Betts, Jonathan B.; Söderlind, Per; ...

2017-03-28

We study the time evolution (aging) of the elastic moduli of an eight-year-old polycrystalline δ- Pu 2.0 at % Ga alloy (δ-Pu:Ga ) from 295K to nearly 500K in real time using Resonant Ultrasound Spectroscopy (RUS). After 8 years of aging at 295K, the bulk and shear moduli increase at a normalized rate of 0.2%/year and 0.6%/year respectively. As the temperature is raised, two time dependences are observed, an exponential one of about a week, followed by a linear one (constant rate). The linear rate is thermally activated with an activation energy of 0.33+0.06 eV. Above 420K a qualitative changemore » in the time evolution is observed; the bulk modulus decreases with time while the shear modulus continues to stiffen. No change is observed as the α-β transition temperature is crossed as would be expected if a decomposition of δ-Pu:Ga to α-Pu and Pu 3Ga occurred over the temperature range studied. Our results indicate that the main mechanism of aging is creation of defects that are partially annealed starting at T = 420 K.« less

Elastic moduli of δ-Pu 239 reveal aging in real time

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

Maiorov, Boris; Betts, Jonathan B.; Söderlind, Per

We study the time evolution (aging) of the elastic moduli of an eight-year-old polycrystalline δ- Pu 2.0 at % Ga alloy (δ-Pu:Ga ) from 295K to nearly 500K in real time using Resonant Ultrasound Spectroscopy (RUS). After 8 years of aging at 295K, the bulk and shear moduli increase at a normalized rate of 0.2%/year and 0.6%/year respectively. As the temperature is raised, two time dependences are observed, an exponential one of about a week, followed by a linear one (constant rate). The linear rate is thermally activated with an activation energy of 0.33+0.06 eV. Above 420K a qualitative changemore » in the time evolution is observed; the bulk modulus decreases with time while the shear modulus continues to stiffen. No change is observed as the α-β transition temperature is crossed as would be expected if a decomposition of δ-Pu:Ga to α-Pu and Pu 3Ga occurred over the temperature range studied. Our results indicate that the main mechanism of aging is creation of defects that are partially annealed starting at T = 420 K.« less

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.

Composite thermochemistry of gas phase U(VI)-containing molecules

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

Bross, David H.; Peterson, Kirk A., E-mail: kipeters@wsu.edu

Reaction energies have been calculated for a series of reactions involving UF{sub 6}, UO{sub 3}, UO{sub 2}(OH){sub 2}, and UO{sub 2}F{sub 2} using coupled cluster singles and doubles with perturbative triples, CCSD(T), with a series of correlation consistent basis sets, including newly developed pseudopotential (PP)- and all-electron (AE) Douglas-Kroll-Hess-based sets for the U atom. The energies were calculated using a Feller-Peterson-Dixon composite approach in which CCSD(T) complete basis set (CBS) limits were combined with a series of additive contributions for spin-orbit coupling, outer-core correlation, and quantum electrodynamics effects. The calculated reaction enthalpies (both PP and AE) were combined with themore » accurately known heat of formation of UF{sub 6} to determine the enthalpies of formation of UO{sub 3}, UO{sub 2}(OH){sub 2}, and UO{sub 2}F{sub 2}. The contribution to the reaction enthalpies due to correlation of the 5s5p5d electrons of U was observed to be very slowly convergent with basis set and at the CBS limit their impact on the final enthalpies was on the order of 1 kcal/mol or less. For these closed shell molecules, spin-orbit effects contributed about 1 kcal/mol to the final enthalpies. Interestingly, the PP and AE approaches yielded quite different spin-orbit contributions (similar magnitude but opposite in sign), but the total scalar plus spin-orbit results from the two approaches agreed to within ∼1 kcal/mol of each other. The final composite heat of formation for UO{sub 2}F{sub 2} was in excellent agreement with experiment, while the two results obtained for UO{sub 3} were just outside the ±2.4 kcal/mol error bars of the currently recommended experimental value. An improved enthalpy of formation (298 K) for UO{sub 2}(OH){sub 2} is predicted from this work to be −288.7 ± 3 kcal/mol, compared to the currently accepted experimental value of −292.7 ± 6 kcal/mol.« less

Humic acids facilitated microbial reduction of polymeric Pu(IV) under anaerobic conditions.

PubMed

Xie, Jinchuan; Liang, Wei; Lin, Jianfeng; Zhou, Xiaohua; Li, Mei

2018-01-01

Flavins and humic substances have been extensively studied with emphasis on their ability to transfer extracellular electrons to insoluble metal oxides. Nevertheless, whether the low-solubility Pu(IV) polymers are microbially reduced to aqueous Pu(III) remains uncertain. Experiments were conducted under anaerobic and slightly alkaline conditions to study the difference between humic acids and flavins to transport extracellular electrons to Pu(IV) polymers. Our study demonstrates that Shewanella putrefaciens was unable to directly reduce polymeric Pu(IV) with a notably low reduction rate (3.4×10 -12 mol/L Pu(III) aq within 144h). The relatively high redox potential of flavins reveals the thermodynamically unfavorable reduction: E h (PuO 2 (am)/Pu 3+ )

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

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

Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru; Grigor’ev, M. S.

2016-05-15

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 3}] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes.more » Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.« less

Free energies and mechanisms of water exchange around Uranyl from first principles molecular dynamics

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

Atta-Fynn, Raymond; Bylaska, Eric J.; De Jong, Wibe A.

2012-02-01

From density functional theory (DFT) based ab initio (Car-Parrinello) metadynamics, we compute the activation energies and mechanisms of water exchange between the first and second hydration shells of aqueous Uranyl (UO{sub 2}{sup 2+}) using the primary hydration number of U as the reaction coordinate. The free energy and activation barrier of the water dissociation reaction [UO{sub 2}(OH{sub 2}){sub 5}]{sup 2+}(aq) {yields} [UO{sub 2}(OH{sub 2})4]{sup 2+}(aq) + H{sub 2}O are 0.7 kcal and 4.7 kcal/mol respectively. The free energy is in good agreement with previous theoretical (-2.7 to +1.2 kcal/mol) and experimental (0.5 to 2.2 kcal/mol) data. The associative reaction [UO{submore » 2}(OH{sub 2}){sub 5}]{sup 2+}(aq) + H{sub 2}O {yields} [UO{sub 2}(OH{sub 2})6]{sup 2+}(aq) is short-lived with a free energy and activation barrier of +7.9 kcal/mol and +8.9 kca/mol respectively; it is therefore classified as associative-interchange. On the basis of the free energy differences and activation barriers, we predict that the dominant exchange mechanism between [UO{sub 2}(OH{sub 2}){sub 5}]{sup 2+}(aq) and bulk water is dissociative.« less

Urine output on ICU entry is associated with hospital mortality in unselected critically ill patients.

PubMed

Zhang, Zhongheng; Xu, Xiao; Ni, Hongying; Deng, Hongsheng

2014-02-01

Urine output (UO) is routinely measured in the intensive care unit (ICU) but its prognostic value remains debated. The study aimed to investigate the association between day 1 UO and hospital mortality. Clinical data were abstracted from the Multiparameter Intelligent Monitoring in Intensive Care II (version 2.6) database. UO was recorded for the first 24 h after ICU entry, and was classified into three categories: UO >0.5, 0.3-0.5 and ≤0.3 ml/kg per hour. The primary endpoint was the hospital mortality. Four models were built to adjust for the hazards ratio of mortality. A total of 21,207 unselected ICU patients including 2,401 non-survivors and 18,806 survivors were included (mortality rate 11.3 %). Mortality rate increased progressively across UO categories: >0.5 (7.67 %), 0.3-0.5 (11.27 %) and ≤0.3 ml/kg/h (18.29 %), and this relationship remained statistically significant after rigorous control of confounding factors with the Cox proportional hazards regression model. With UO >0.5 as the referent group, the hazards ratios for UO 0.3-0.5 and UO ≤0.3 were 1.41 (95 % CI 1.29-1.54) and 1.52 (95 % CI 1.38-1.67), respectively. UO obtained on ICU entry is an independent predictor of mortality irrespective of diuretic use. It would be interesting to examine whether strategies to increase UO would improve clinical outcome.

Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-11-01

Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

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.

Crystal Chemistry of the Potassium and Rubidium Uranyl Borate Families Derived from Boric Acid Fluxes

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

Wang, Shuao; Alekseev, Evgeny V.; Stritzinger, Jared T.

2010-07-19

The reaction of uranyl nitrate with a large excess of molten boric acid in the presence of potassium or rubidium nitrate results in the formation of three new potassium uranyl borates, K{sub 2}[(UO{sub 2}){sub 2}B{sub 12}O{sub 19}(OH){sub 4}]·0.3H{sub 2}O (KUBO-1), K[(UO{sub 2}){sub 2}B{sub 10}O{sub 15}(OH){sub 5}] (KUBO-2), and K[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (KUBO-3) and two new rubidium uranyl borates Rb{sub 2}[(UO{sub 2}){sub 2}B{sub 13}O{sub 20}(OH){sub 5}] (RbUBO-1) and Rb[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (RbUBO-2). The latter is isotypic with KUBO-3. These compounds share a common structural motif consisting of a linear uranyl, UO{sub 2}{sup 2+},more » cation surrounded by BO{sub 3} triangles and BO{sub 4} tetrahedra to create an UO{sub 8} hexagonal bipyramidal environment around uranium. The borate anions bridge between uranyl units to create sheets. Additional BO{sub 3} triangles extend from the polyborate layers and are directed approximately perpendicular to the sheets. All of these compounds adopt layered structures. With the exception of KUBO-1, the structures are all centrosymmetric. All of these compounds fluoresce when irradiated with long-wavelength UV light. The fluorescence spectrum yields well-defined vibronically coupled charge-transfer features.« less

A study on recovery of uranium in the anode basket residues delivered from the pyrochemical process of used nuclear fuel

NASA Astrophysics Data System (ADS)

Eun, H. C.; Kim, T. J.; Jang, J. H.; Kim, G. Y.; Park, S. B.; Yoon, D. S.; Kim, S. H.; Paek, S. W.; Lee, S. J.

2018-04-01

In this study, the chlorination of uranium oxide (UO2) using ammonium chloride and zirconium as chemical agents was conducted to recover the uranium in the anode basket residues from the pyrochemical process of used nuclear fuel. The chlorination of UO2 was predicted using thermodynamic equilibrium calculations. The experimental conditions for the chlorination were determined using a chlorination test with cerium oxide (CeO2). In the chlorination test, it was confirmed that UO2 was chlorinated into UCl3 at 320 °C, some UO2 remained without changes in the chemical form, and ZrO2, Zr2O, and ZrCl2 were generated as byproducts.

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.

LOW-TEMPERATURE MAGNETIC PROPERTIES OF SOME URANIUM OXIDES

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

Leask, M.J.M.; Roberts, L.E.J.; Walter, A.J.

1963-10-01

The magnetic susceptibilities of UO/sub 2/, UO/sub 2.1/, U/sub 4/O/sub 9/ , U/s ub 3/O/sub 7/, and U/sub 3/O/sub 8/ at temperatures between 1.5 and 44 deg K were determined using an a-c inductance method. The susceptibility Of U/sub 3/ O/sub 8/ rises to a sharp maximum at 4.2 deg K, with smaller effects at 8 and at 25.3 deg K. The susceptibility of UO/sub 2/ reaches a maximum at 29 deg K and remains constant between 25 and 2 deg K. A maximum in the susceptibility- temperature plot for U/sub 4/O/sub 9/ at 6.4 deg K occurs also-in themore » plots for UO/sub 2.1/ an d U/sub 3/O/sub 7/ and appears to be primarily due to the inclusion of interstitial oxygen ions in the UO/sub 2/ lattice, independent of the precise nature of subsequent ordering effects. (auth)« less

A DFT+U study of Pu immobilization in Gd2Zr2O7

NASA Astrophysics Data System (ADS)

Zhao, F. A.; Xiao, H. Y.; Jiang, M.; Liu, Z. J.; Zu, X. T.

2015-12-01

The solubility of Pu in Gd2Zr2O7 has been investigated by the density functional theory plus Hubbard U correction. It is found that the formation of PuGdZr2O7, Gd2PuZrO7 and Gd2Pu1.5Zr0.5O7 are exothermic, whereas Pu0.5Gd1.5Zr2O7, Pu1.5Gd0.5Zr2O7 and Gd2Pu0.5Zr1.5O7 are energetically less stable than their respective separated states. The calculations show that both the Gd and Zr lattice sites can be substituted by the Pu, which is consistent with the immobilization behavior of uranium in Gd2Zr2O7 observed experimentally. The site preference of Pu in Gd2Zr2O7 is found to be dependent on the chemical environment, i.e., Pu prefers to substitute for Gd-site under Gd-rich and O2-rich conditions and for Zr-site under Zr-rich and O2-rich conditions.

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).

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.

CAPABILITY TO RECOVER PLUTONIUM-238 IN H-CANYON/HB-LINE

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

Fuller, Kenneth S. Jr.; Smith, Robert H. Jr.; Goergen, Charles R.

2013-01-09

Plutonium-238 is used in Radioisotope Thermoelectric Generators (RTGs) to generate electrical power and in Radioisotope Heater Units (RHUs) to produce heat for electronics and environmental control for deep space missions. The domestic supply of Pu-238 consists of scrap material from previous mission production or material purchased from Russia. Currently, the United States has no significant production scale operational capability to produce and separate new Pu-238 from irradiated neptunium-237 targets. The Department of Energy - Nuclear Energy is currently evaluating and developing plans to reconstitute the United States capability to produce Pu-238 from irradiated Np-237 targets. The Savannah River Site hadmore » previously produced and/or processed all the Pu-238 utilized in Radioisotope Thermoelectric Generators (RTGs) for deep space missions up to and including the majority of the plutonium for the Cassini Mission. The previous full production cycle capabilities included: Np-237 target fabrication, target irradiation, target dissolution and Np-237 and Pu-238 separation and purification, conversion of Np-237 and Pu-238 to oxide, scrap recovery, and Pu-238 encapsulation. The capability and equipment still exist and could be revitalized or put back into service to recover and purify Pu-238/Np-237 or broken General Purpose Heat Source (GPHS) pellets utilizing existing process equipment in HB-Line Scrap Recovery, and H-anyon Frame Waste Recovery processes. The conversion of Np-237 and Pu-238 to oxide can be performed in the existing HB-Line Phase-2 and Phase-3 Processes. Dissolution of irradiated Np-237 target material, and separation and purification of Np-237 and Pu-238 product streams would be possible at production rates of ~ 2 kg/month of Pu-238 if the existing H-Canyon Frames Process spare equipment were re-installed. Previously, the primary H-Canyon Frames equipment was removed to be replaced: however, the replacement project was stopped. The spare equipment is stored and still available for installation. Out of specification Pu-238 scrap material can be purified and recovered by utilizing the HB-Line Phase-1 Scrap Recovery Line and the Phase-3 Pu-238 Oxide Conversion Line along with H-Canyon Frame Waste Recovery process. In addition, it also covers and describes utilizing the Phase-2 Np-237 Oxide Conversion Line, in conjunction with the H-Canyon Frames Process to restore the H-Canyon capability to process and recover Np-237 and Pu-238 from irradiated Np-237 targets and address potential synergies with other programs like recovery of Pu-244 and heavy isotopes of curium from other target material.« less

A comparative, descriptive study of systemic factors and survival in elderly patients with sacral pressure ulcers.

PubMed

Jaul, Efraim; Menczel, Jacob

2015-03-01

Sacral pressure ulcers (PUs) are a serious complication in frail elderly patients. Thin tissue in the sacral area, low body mass index, and anatomical location contribute to the development of sacral PUs. A comparative, descriptive study was conducted to identify patient systemic factors associated with sacral PUs and to compare survival time in patients with and without PU. All consecutive patients with PUs (n = 77) and without sacral PUs (n = 53) admitted to the skilled nursing department of a geriatric hospital in Jerusalem, Israel between July 1, 2008 and December 31, 2011 were eligible to participate. Charts of previously admitted patients were abstracted and patients were prospectively followed until discharge, death, or the end of the study. Patient demographics, comorbidities, nutritional status, physical and cognitive function (measured using the Reisberg's Functional Assessment Staging Tool [FAST], Stages of Dementia of Alzheimer Scale, and the Glasgow Coma Scale), PU status, number of courses of antibiotic treatment during admission, length of hospitalization, and mortality were compared between patients admitted with and without a sacral PU using descriptive and univariate statistics. Logistic regression models were used to estimate the odds ratio (OR) and 95% confidence intervals (CI) for sacral PU versus without PU by study covariate. The association between sacral PU and survival time was assessed using Kaplan-Meier models. Patients with a sacral PU were significantly older (average age 81.60 ±10.78 versus 77.06±11.19 years old, P = 0.02) and had a higher prevalence of dementia (70% versus 30%, P = 0.007), Parkinson's disease (92.3% versus 7.7%, P = 0.03), and anemia (67.7% versus 32.3%, P = 0.06) than patients admitted without a PU. Patients with a sacral PU also had a lower body mass index (23.1 versus 25.4, P = 0.04), and lower hemoglobin (10.54 versus 11.11, P = 0.03), albumin (26.2 versus 29.7, P = 0.002), and total protein levels (61.3 versus 65.7, P = 0.04). In addition, antibiotic treatment was significantly higher in the patients with PU (50.6% versus 28.3%, P = 0.01). Patients with a sacral PU also had significantly lower physical and cognitive functioning scores and their median survival time was 70 days compared to 401 days in the non-PU group (P <0.001). These findings are generally consistent with the literature regarding risk factors for PU development and confirm the need for preventive measures. In addition, clinicians need to address the overall goal of patient care and patient quality of life when considering PU management interventions in this patient population.

Evaluation of phases in Pu-C-O and (U, Pu)-C-O systems by X-ray diffractometry and chemical analysis

NASA Astrophysics Data System (ADS)

Jain, G. C.; Ganguly, C.

1993-12-01

Preparation and characterisation of the carbides of uranium, plutonium and mixed uranium and plutonium form a part of advanced fuel development programs for fast breeder reactors. In the present study, the compositions of the phases of Pu-C-O and (U.Pu)-C-O systems have been determined by chemical analysis and lattice parameter measurement. The carbide samples have been prepared by vacuum carbothermic synthesis of tabletted oxide-graphite powder mixture. Dependence of stoichiometry of Pu 2C 3 phase on the oxygen content of Pu(C,O) phase in Pu(C,O) + Pu 2C 3 phase mixture has been evaluated. Stoichiometry and oxygen solubility of (U 0.3Pu 0.7)(C,O) phase in multiple phase mixture have been determined. Segregation of plutonium in (U,Pu) 2C 3 phase of (U,Pu)(C,O) + (U,Pu) 2C 3 phase mixture and its dependence on the oxygen content of (U,Pu)(C,O) phase have also been determined from the measurement of the lattice parameter of (U,Pu) 2C 3 phase.

Magnetic beads-based DNAzyme recognition and AuNPs-based enzymatic catalysis amplification for visual detection of trace uranyl ion in aqueous environment.

PubMed

Zhang, Hongyan; Lin, Ling; Zeng, Xiaoxue; Ruan, Yajuan; Wu, Yongning; Lin, Minggui; He, Ye; Fu, FengFu

2016-04-15

We herein developed a novel biosensor for the visual detection of trace uranyl ion (UO2(2+)) in aqueous environment with high sensitivity and specificity by using DNAzyme-functionalized magnetic beads (MBs) for UO2(2+) recognition and gold nano-particles (AuNPs)-based enzymatic catalysis oxidation of TMB (3,3',5,5'-tetramethylbenzidine sulfate) for signal generation. The utilization of MBs facilitates the magnetic separation and collection of sensing system from complex sample solution, which leads to more convenient experimental operation and more strong resistibility of the biosensor to the matrix of sample, and the utilization of AuNPs-based enzymatic catalysis amplification greatly improved the sensitivity of the biosensor. Compared with the previous DNAzyme-based UO2(2+) sensors, the proposed biosensor has outstanding advantages such as relative high sensitivity and specificity, operation convenience, low cost and more strong resistibility to the matrix of sample. It can be used to detect as low as 0.02 ppb (74 pM) of UO2(2+) in aqueous environment by only naked-eye observation and 1.89 ppt (7.0 pM) of UO2(2+) by UV-visible spectrophotometer with a recovery of 93-99% and a RSD ≤ 5.0% (n=6) within 3h. Especially, the visual detection limit of 0.02 ppb (74 pM) is much lower than the maximum allowable level of UO2(2+) (130 nM) in the drinking water defined by the U.S. Environmental Protection Agency (EPA), indicating that our method meets the requirement of rapid and on-site detection of UO2(2+) in the aqueous environment by only naked-eye observation. Copyright © 2015 Elsevier B.V. All rights reserved.

Structure, phase transitions, and isotope effects in [(CH3)4N]2PuCl6

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

Wilson, Richard E.

2015-11-02

The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) Å. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature,more » giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.« less

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

NASA Astrophysics Data System (ADS)

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

2016-02-01

The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between the interior of the UO2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO2 oxidation rate constants determined here relative to prior studies. Our results suggest that the natural presence or addition of Ca and PO4 in groundwater could slow the rates of UIV oxidation, but that the rates are still fast enough to cause complete oxidation of UIV within days under fully oxygenated conditions.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous U IV–phosphate

DOE PAGES

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

2015-11-17

The mobility of uranium in subsurface environments depends strongly on its redox state, with U IV phases being significantly less soluble than U VI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of U VI reduction in natural systems, a nanoparticulate UO 2 phase and an amorphous U IV–Ca–PO 4 analog to ningyoite (CaU IV(PO 4) 2·1–2H 2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for U IVO 2 and U IV–phosphate in solutions equilibrated with atmospheric O 2 and CO 2 at pH 7.0more » (k obs,UO2 = 0.17 ± 0.075 h -1 vs. k obs,U IV PO4 = 0.30 ± 0.25 h -1). Addition of up to 400 μM Ca and PO 4 decreased the oxidation rate constant by an order of magnitude for both UO 2 and U IV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO 4, the product of UO 2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO 4 and low carbonate concentration), resulting in low concentrations of dissolved U VI (<2.5 × 10 -7 M). Oxidation of U IV–phosphate produced a Na-autunite phase (Na 2(UO 2)PO 4·xH 2O), resulting in similarly low dissolved U concentrations (<7.3 × 10 -8 M). When Ca and PO 4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO 2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO 4 layer on the UO 2 surface and suggest a passivation layer mechanism for the decreased rate of UO 2 oxidation in the presence of Ca and PO 4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO 2 solids, suggesting that oxidized U is distributed between the interior of the UO 2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO 2 oxidation rate constants determined here relative to prior studies. In conclusion, our results suggest that the natural presence or addition of Ca and PO 4 in groundwater could slow the rates of U IV oxidation, but that the rates are still fast enough to cause complete oxidation of U IV within days under fully oxygenated conditions.« less

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

PubMed

Kowal-Fouchard, A; Drot, R; Simoni, E; Ehrhardt, J J

2004-03-01

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Electronic and thermodynamic properties of α-Pu2O3

NASA Astrophysics Data System (ADS)

Lu, Yong; Yang, Yu; Zheng, Fawei; Zhang, Ping

2014-08-01

Based on density functional theory+U calculations and the quasi-annealing simulation method, we obtain the ground electronic state for α-Pu2O3 and present its phonon dispersion curves as well as various thermodynamic properties, which have seldom been theoretically studied because of the huge unit cell. We find that the Pu-O chemical bonding is weaker in α-Pu2O3 than in fluorite PuO2, and subsequently a frequency gap appears between oxygen and plutonium vibration density of states. Based on the calculated Helmholtz free energies at different temperatures, we further study the reaction energies for Pu oxidation, PuO2 reduction, and transformation between PuO2 and α-Pu2O3. Our reaction energy results are in agreements with available experiment. And it is revealed that high temperature and insufficient oxygen environment are in favor of the formation of α-Pu2O3.

Oxidation and reduction behaviors of a prototypic MgO-PuO2-x inert matrix fuel

NASA Astrophysics Data System (ADS)

Miwa, Shuhei; Osaka, Masahiko

2017-04-01

Oxidation and reduction behaviors of prototypic MgO-based inert matrix fuels (IMFs) containing PuO2-x were experimentally investigated by means of thermogravimetry. The oxidation and reduction kinetics of the MgO-PuO2-x specimen were determined. The oxidation and reduction rates of the MgO-PuO2-x were found to be low compared with those of PuO2-x. It is note that the changes in O/Pu ratios of MgO-PuO2-x from stoichiometry were smaller than those of PuO2-x at high oxygen partial pressure.

A cross-sectional study on self-management of pressure ulcer prevention in paraplegic patients.

PubMed

de Laat, H E W; de Munter, A C; van der Burg, M J; Ulrich, D J O; Kloeters, O

2017-02-01

Little is known about health activation and self-management behavior in preventing pressure ulcers (PU) in paraplegic patients. Therefore this study aimed to describe the extent of health activation and self-management behavior in paraplegics to prevent PU's and associations between this behavior and patient characteristics. Furthermore, we aimed to find differences in health activation in paraplegics who never had a PU compared to paraplegics with a previous history of PU's or a new-onset PU's. A cross-sectional survey on health activation and self-management behavior was conducted among adult paraplegics recruited from two rehabilitation centers in the Netherlands. The Patient Activation Measure (PAM-score) was used to measure the extent of health activation. Patient statements on their level of self management behavior to prevent PU were evaluated. The mean PAM-score (0-100) was 54 (±8.1; n = 162) indicating a low level of health activation. Two indicators turned out to be statistically significant associated with health activation: level of education (OR = 2.2, p = 0.017) and degree of paraplegia (OR = 2.8, p = 0.036). Evaluation of health activation levels amongst paraplegics with or without a PU- history showed no significant difference. Analysis of patients statements demonstrated a large discrepancy between intended and actual behavior to prevent pressure ulcers. Level of education and level of paraplegia are significantly associated with health activation. A positive PU-history is not associated with future responsible behavior nor for compliant behavior in terms of health management. Copyright © 2016 Tissue Viability Society. Published by Elsevier Ltd. All rights reserved.

No Fukushima Dai-ichi derived plutonium signal in marine sediments collected 1.5-57km from the reactors.

PubMed

Wendel, C C S; Lind, O C; Fifield, L K; Tims, S G; Salbu, B; Oughton, D H

2017-11-01

Based on AMS analysis, it is shown that no Pu signals from the Fukushima accident could be discerned in marine sediments collected 1.5-57km away from the Fukushima Da-ichi power plant (FDNPP), which were clearly influenced by accident-derived radiocesium. The 240 Pu/ 239 Pu atom ratios (0.21-0.28) were significantly higher than terrestrial global fallout (0.182 ± 0.005), but still in agreement with pre-FDNPP accident baseline data for Pu in near coastal seawaters influenced by global fallout and long-range transport of Pu from the Pacific Proving Grounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

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 theoretical). Scanning electron microscopy (SEM) of the mixed powders and the sintered samples along with energy dispersive x-ray analysis was obtained. The SEM of the powders clearly show the fine W powder adhered to the larger HfO2 particles and a uniform distribution of HfO2 particles in a tungsten matrix upon densification. Vicker's Microhardness testing was also performed on all samples using 0.5, 1.0 and 2.0 kg loads. Five indents were made at each load level. All indents were placed in the tungsten matrix to assist as a proxy in measuring densification. The highest hardness value was obtained for the 1700C specimens. The hardness average for these samples was 312.14 MPa. This powder processing method has been applied to W/UO2 powders with the SEM of the powders appearing similar to the W/HfO2 powder images.

Plutonium activities and 240Pu/ 239Pu atom ratios in sediment cores from the east China sea and Okinawa Trough: Sources and inventories

NASA Astrophysics Data System (ADS)

Wang, Zhong-liang; Yamada, Masatoshi

2005-05-01

Plutonium concentrations and 240Pu/ 239Pu atom ratios in the East China Sea and Okinawa Trough sediment cores were determined by isotope dilution inductively coupled plasma mass spectrometry after separation using ion-exchange chromatography. The results showed that 240Pu/ 239Pu atom ratios in the East China Sea and Okinawa Trough sediments, ranging from 0.21 to 0.33, were much higher than the reported value of global fallout (0.18). The highest 240Pu/ 239Pu ratios (0.32-0.33) were observed in the deepest Okinawa Trough sediment samples. These ratios suggested the US nuclear weapons tests in the early 1950s at the Pacific Proving Grounds in the Marshall Islands were a major source of plutonium in the East China Sea and Okinawa Trough sediments, in addition to the global fallout source. It was proposed that close-in fallout plutonium was delivered from the Pacific Proving Grounds test sites via early direct tropospheric fallout and transportation by the North Pacific Equatorial Circulation system and Kuroshio Current into the Okinawa Trough and East China Sea. The total 239 + 240 Pu inventories in the cores were about 150-200% of that expected from direct global fallout; about 46-67% of the total inventories were delivered from the Pacific Proving Grounds. Much higher 239 + 240 Pu inventories were observed in the East China Sea sediments than in sediments of the Okinawa Trough, because in the open oceans, part of the 239 + 240 Pu was still retained in the water column, and continued Pu scavenging was higher over the margin than the trough. According to the vertical distributions of 239 + 240 Pu activities and 240Pu/ 239Pu atom ratios in these cores, it was concluded that sediment mixing was the dominant process in controlling profiles of plutonium in this area. Faster mixing in the coastal samples has homogenized the entire 240Pu/ 239Pu ratio record today; slightly slower mixing and less scavenging in the Okinawa Trough have left the surface sediment ratios closer to the modern North Pacific water end member and higher ratios (0.30-0.34) at the bottom of the cores.

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 test contained six independently controlled and monitored capsules. Each U.S. capsule contained 12 compacts of either UCO or UO2 AGR coated fuel. No fuel particles failed during the AGR-2 irradiation. Final burnup values on a per compact basis ranged from 7.26 to 13.15% FIMA (fissions per initial heavy-metal atom) for UCO fuel, and 9.01 to 10.69% FIMA for UO 2 fuel, while fast fluence values ranged from 1.94 to 3.47 x 10 25 n/m 2 (E >0.18 MeV) for UCO fuel, and from 3.05 to 3.53 x 10 25 n/m 2 (E >0.18 MeV) for UO 2 fuel. Time-average volume-average (TAVA) temperatures on a capsule basis at the end of irradiation ranged from 987°C in Capsule 6 to 1296°C in Capsule 2 for UCO, and from 996 to 1062°C in UO 2-fueled Capsule 3. By the end of the irradiation, all of the installed thermocouples (TCs) had failed. Fission product release-to-birth (R/B) ratios were quite low. In the UCO capsules, R/B values during the first three cycles were below 10 -6 with the exception of the hotter Capsule 2, in which the R/Bs reached 2 x 10 -6. In the UO 2 capsule (Capsule 3), the R/B values during the first three cycles were below 10 -7. R/B values for all following cycles are not reliable due to gas flow and cross talk issues.« less

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.

Insight into the Am-O Phase Equilibria: A Thermodynamic Study Coupling High-Temperature XRD and CALPHAD Modeling.

PubMed

Epifano, Enrica; Guéneau, Christine; Belin, Renaud C; Vauchy, Romain; Lebreton, Florent; Richaud, Jean-Christophe; Joly, Alexis; Valot, Christophe; Martin, Philippe M

2017-07-03

In the frame of minor actinide transmutation, americium can be diluted in UO 2 and (U, Pu)O 2 fuels burned in fast neutron reactors. The first mandatory step to foresee the influence of Am on the in-reactor behavior of transmutation targets or fuel is to have fundamental knowledge of the Am-O binary system and, in particular, of the AmO 2-x phase. In this study, we coupled HT-XRD (high-temperature X-ray diffraction) experiments with CALPHAD thermodynamic modeling to provide new insights into the structural properties and phase equilibria in the AmO 2-x -AmO 1.61+x -Am 2 O 3 domain. Because of this approach, we were able for the first time to assess the relationships between temperature, lattice parameter, and hypostoichiometry for fcc AmO 2-x . We showed the presence of a hyperstoichiometric existence domain for the bcc AmO 1.61+x phase and the absence of a miscibility gap in the fcc AmO 2-x phase, contrary to previous representations of the phase diagram. Finally, with the new experimental data, a new CALPHAD thermodynamic model of the Am-O system was developed, and an improved version of the phase diagram is presented.

Electrospray ionization of uranyl-citrate complexes

NASA Astrophysics Data System (ADS)

Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

2007-09-01

Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures and charge state distributions.

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+).

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.

Amoeba behavior of UO/sub 2/ coated particle fuel

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

Wagner-Loeffler, M.

1977-09-01

The data extracted from numerous irradiation tests were used to derive amoeba endurance parameters for UO/sub 2/. The data do not yet allow an unambiguous definition of the controlling mechanism, which may be due to either gaseous or solid-state diffusion processes. Adequate data on the amoeba effect are available for design of a steam-raising high-temperature gas-cooled reactor using UO/sub 2/ fuel.

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

Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

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

Liezers, Martin; Lehn, Scott A; Olsen, Khris B

2009-10-01

Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO 3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by themore » applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.« less

Measurements Conducted on an Unknown Object Labeled Pu-239

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

Hoteling, Nathan

Measurements were carried out on 12 November 2013 to determine whether Pu-239 was present on an object discovered in a plastic bag with label “Pu-­239 6 uCi.” Following initial survey measurements to verify that the object was not leaking or contaminated, spectra were collected with a High Purity Germanium (HPGe) detector with object positioned in two different configurations. Analysis of the spectra did not yield any direct evidence of Pu-­239. From the measured spectra, minimum detectable activity (MDA) was determined to be approximately 2 uCi for the gamma-­ray measurements. Although there was no direct evidence of Pu-239, a peak atmore » 60 keV characteristic of Am-­241 decay was observed. Since it is very likely that Am-­241 would be present in aged plutonium samples, this was interpreted as indirect evidence for the presence of plutonium on the object. Analysis of this peak led to an estimated Pu-­239 activity of 0.02–0.04 uCi, or <1x10 -6 grams.« less

U-PuO2, U-PuC, U-PuN cermet fuel for fast reactor

NASA Astrophysics Data System (ADS)

Mishra, Sudhir; Kaity, Santu; Banerjee, Joydipta; Nandi, Chiranjeet; Dey, G. K.; Khan, K. B.

2018-02-01

Cermet fuel combines beneficial properties of both ceramic and metal and attracts global interest for research as a candidate fuel for nuclear reactors. In the present study, U matrix PuC/PuN/PuO2 cermet for fast reactor have been fabricated on laboratory scale by the powder metallurgy route. Characterization of the fuel has been carried out using Dilatometer, Differential Thermal analysis (DTA), X-ray diffractometer and Optical microscope. X ray diffraction study of the fuel reveals presence of different phases. The PuN dispersed cermet was observed to have high solidus temperature as compared to PuC and PuO2 dispersed cermet. Swelling was observed in U matrix PuO2 cermet which also showed higher thermal expansion. Among the three cermets studied, U matrix PuC cermet showed maximum thermal conductivity.

A prospective randomized comparison of unsedated ultrathin versus standard esophagogastroduodenoscopy in routine outpatient gastroenterology practice: does it work better through the nose?

PubMed

Birkner, B; Fritz, N; Schatke, W; Hasford, J

2003-08-01

In an outpatient gastroenterological practice setting, highly effective diagnostic procedures and patient satisfaction play an important role. Ultrathin endoscopy in unsedated patients has been shown to be more cost-effective and time-efficient in comparison with standard endoscopy. A prospective randomized study was carried out in unsedated patients to compare performance, feasibility, safety, and patient tolerance between ultrathin transnasal (UT), ultrathin oral (UO), and standard (SO) esophagogastroduodenoscopy (EGD). A total of 200 of 600 eligible patients consented to participate in the study, and were randomly assigned to undergo UT, UO, or SO. Patients reported their tolerance of the procedure (anxiety, pain, gagging, and overall satisfaction; Likert scale 1-10), and the endoscopists reported the effectiveness of the procedure (handling, picture quality, and overall performance; Likert scale 1-10). Statistics were calculated using the Kruskal-Wallis test. After randomization, 65, 67, and 68 patients were allocated to the UT, UO, and SO groups, respectively. Failure to achieve complete EGD by the intended route occurred in 14 patients (22 %) in the UT group. Compared to the SO group, patients in the UT and UO groups rated anxiety before the procedure as being more intense - median score (10 % quantile estimate; 90 % quantile estimate): UT, 2.0 (1.0; 4.0); UO, 2.0 (1.0; 4.0); SO, 0.0 (0.0; 2.0); p < 0.0001), whereas SO patients experienced a higher level of anxiety during the procedure ( P < 0.0001). Pain during insertion of the endoscope was the least intense in the UO group: UT, 2.0 (1.0; 5.0); UO, 1.0 (1.0; 3.0); SO, 2.0 (1.0; 4.0); P < 0.001). Gagging during insertion was more pronounced in the UO group: UT, 2.0 (1.0; 4.0); UO, 3.0 (1.0; 7.0); SO, 2.0 (1.0; 5.0); P < 0.01). The patients' score for the overall assessment was better in the SO group ( P < 0.0001). The endoscopists' overall assessment for ultrathin EGD was poorer than for standard EGD: UT, 3.0 (2.0; 5.0); UO, 3.0 (2.0; 5.0); SO, 2.0 (1.0; 3.0); P < 0.0001). Ultrathin endoscopy through both the transnasal and oral routes has limited use in routine outpatient practice. Techniques for reducing pain and gagging may improve patient tolerance. Further technical improvements are needed to allow routine implementation.

Structural evolution of the double perovskites Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) upon reduction: Magnetic behavior of the uranium cations

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

Pinacca, R.M., E-mail: rmp@unsl.edu.ar; Viola, M.C.; Pedregosa, J.C.

2011-11-15

Highlights: {yields} Evolution of the double perovskites Sr{sub 2}B'UO{sub 6} upon reduction were studied by XRPD. {yields} Orthorhombic (Pnma) disordered perovskites SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} were obtained at 900 {sup o}C. {yields} U{sup 5+/4+} and Zn{sup 2+} cations are distributed at random over the octahedral positions. {yields} AFM ordering for the perovskite with B' = Zn appears below 30 K. -- Abstract: We describe the preparation of five perovskite oxides obtained upon reduction of Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) with H{sub 2}/N{sub 2} (5%/95%) at 900 {sup o}C during 8 h, and their structural characterizationmore » by X-ray powder diffraction (XRPD). During the reduction process there is a partial segregation of the elemental metal when B' = Co, Ni, Fe, and the corresponding B'O oxide when B' = Mn, Zn. Whereas the parent, oxygen stoichiometric double perovskites Sr{sub 2}B'UO{sub 6} are long-range ordered concerning B' and U cations. The crystal structures of the reduced phases, SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} with 0.37 < x < 0.27, correspond to simple, disordered perovskites; they are orthorhombic, space group Pnma (No. 62), with a full cationic disorder at the B site. Magnetic measurements performed on the phase with B' = Zn, indicate uncompensated antiferromagnetic ordering of the U{sup 5+}/U{sup 4+} sublattice below 30 K.« less

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

Jaques, Brian J.; Watkins, Jennifer; Croteau, Joseph R.

In this study, the design and development of an economical, accident tolerant fuel (ATF) for use in the current light water reactor (LWR) fleet is highly desirable for the future of nuclear power. Uranium mononitride has been identified as an alternative fuel with higher uranium density and thermal conductivity when compared to the benchmark, UO 2, which could also provide significant economic benefits. However, UN by itself reacts with water at reactor operating temperatures. In order to reduce its reactivity, the addition of UO 2 to UN has been suggested. In order to avoid carbon impurities, UN was synthesized frommore » elemental uranium using a hydride-dehydride-nitride thermal synthesis route prior to mixing with up to 10 wt% UO 2 in a planetary ball mill. UN and UN – UO 2 composite pellets were sintered in Ar – (0–1 at%) N 2 to study the effects of nitrogen concentration on the evolved phases and microstructure. UN and UN-UO 2 composite pellets were also sintered in Ar – 100 ppm N 2 to assess the effects of temperature (1700–2000 °C) on the final grain morphology and phase concentration.« less

Structural properties of lanthanide and actinide compounds within the plane wave pseudopotential approach

PubMed

Pickard; Winkler; Chen; Payne; Lee; Lin; White; Milman; Vanderbilt

2000-12-11

We show that plane wave ultrasoft pseudopotential methods readily extend to the calculation of the structural properties of lanthanide and actinide containing compounds. This is demonstrated through a series of calculations performed on UO, UO2, UO3, U3O8, UC2, alpha-CeC2, CeB6, CeSe, CeO2, NdB6, TmOI, LaBi, LaTiO3, YbO, and elemental Lu.

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

A Uranyl Peroxide Dimer in the Gas Phase

DOE PAGES

Dau, Phuong D.; Dau, Phuong V.; Rao, Linfeng; ...

2017-03-14

For this study, the gas-phase uranyl peroxide dimer, [(UO 2) 2(O2)(L) 2] 2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO 2 2+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO 2) 2(O)(L) 2] 2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO 2) 2(OH) 2(L) 2] 2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide ofmore » particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO 2) 2(O 2)(L) 2] 2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO 2) 2(O 2)] 2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.« less

Diffusion of radiogenic helium in natural uranium oxides

NASA Astrophysics Data System (ADS)

Roudil, Danièle; Bonhoure, Jessica; Pik, Raphaël; Cuney, Michel; Jégou, Christophe; Gauthier-Lafaye, F.

2008-08-01

The issue of nuclear waste management - and especially spent fuel disposal - demands further research on the long-term behavior of helium and its impact on physical changes in UO 2 and (U,Pu)O 2 matrices subjected to self-irradiation. Helium produced by radioactive decay of the actinides concentrates in the grains or is trapped at the grain boundaries. Various scenarios can be considered, and can have a significant effect on the radionuclide source terms that will be accessible to water after the canisters have been breached. Helium production and matrix damage is generally simulated by external irradiation or with actinide-doped materials. A natural uranium oxide sample was studied to acquire data on the behavior of radiogenic helium and its diffusion under self-irradiation in spent fuel. The sample from the Pen Ar Ran deposit in the Vendée region of France dated at 320 ± 9 million of years was selected for its simple geological history, making it a suitable natural analog of spent fuel under repository conditions during the initial period in a closed system not subject to mass transfer with the surrounding environment. Helium outgassing measured by mass spectrometry to determine the He diffusion coefficients through the ore shows that: (i) a maximum of 5% (2.1% on average) of the helium produced during the last 320 Ma in this natural analog was conserved, (ii) about 33% of the residual helium is occluded in the matrix and vacancy defects (about 10 -5 mol g -1) and 67% in bubbles that were analyzed by HRTEM. A similar distribution has been observed in spent fuel and in (U 0.9,Pu 0.1)O 2. The results obtained for the natural Pen Ar Ran sample can be applied by analogy to spent fuel, especially in terms of the apparent solubility limit and the formation, characteristics and behavior of the helium bubbles.

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.

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.

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.

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.

Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

PubMed Central

Conroy, David J.R.; Millner, Paul A.; Stewart, Douglas I.; Pollmann, Katrin

2010-01-01

The fabrication of novel uranyl (UO22+) binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+. PMID:22399904

Developing uranium dicarbide-graphite porous materials for the SPES project

NASA Astrophysics Data System (ADS)

Biasetto, L.; Zanonato, P.; Carturan, S.; Di Bernardo, P.; Colombo, P.; Andrighetto, A.; Prete, G.

2010-09-01

Uranium carbide dispersed in graphite was produced under vacuum by means of carbothermic reduction of different uranium oxides (UO 2, U 3O 8 and UO 3), using graphite as the source of carbon. The thermal process was monitored by mass spectrometry and the gas evolution confirmed the reduction of the U 3O 8 and UO 3 oxides to UO 2 before the carbothermic reaction, that started to occur at T > 1000 °C. XRD analysis confirmed the formation of α-UC 2 and of a minor amount of UC. The morphology of the produced uranium carbide was not affected by the oxides employed as the source of uranium.

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

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

Mixed-Ligand Uranyl Polyrotaxanes Incorporating a Sulfate/Oxalate Coligand: Achieving Structural Diversity via pH-Dependent Competitive Effect.

PubMed

Xie, Zhen-Ni; Mei, Lei; Hu, Kong-Qiu; Xia, Liang-Shu; Chai, Zhi-Fang; Shi, Wei-Qun

2017-03-20

A mixed-ligand system provides an alternative route to tune the structures and properties of metal-organic compounds by introducing functional organic or inorganic coligands. In this work, five new uranyl-based polyrotaxane compounds incorporating a sulfate or oxalate coligand have been hydrothermally synthesized via a mixed-ligand method. Based on C6BPCA@CB6 (C6BPCA = 1,1'-(hexane-1,6-diyl)bis(4-(carbonyl)pyridin-1-ium), CB6 = cucurbit[6]uril) ligand, UPS1 (UO 2 (L) 0.5 (SO 4 )(H 2 O)·2H 2 O, L = C6BPCA@CB6) is formed by the alteration of initial aqueous solution pH to a higher acidity. The resulting 2D uranyl polyrotaxane sheet structure of UPS1 is based on uranyl-sulfate ribbons connected by the C6BPCA@CB6 pseudorotaxane linkers. By using oxalate ligand instead of sulfate, four oxalate-containing uranyl polyrotaxane compounds, UPO1-UPO4, have been acquired by tuning reaction pH and ligand concentration: UPO1 (UO 2 (L) 0.5 (C 2 O 4 ) 0.5 (NO 3 )·3H 2 O) in one-dimensional chain was obtained at a low pH value range (1.47-1.89) and UPO2 (UO 2 (L)(C 2 O 4 )(H 2 O)·7H 2 O)obtained at a higher pH value range (4.31-7.21). By lowering the amount of oxalate, another two uranyl polyrotaxane network UPO3 ((UO 2 ) 2 (L) 0.5 (C 2 O 4 ) 2 (H 2 O)) and UPO4 ((UO 2 ) 2 O(OH)(L) 0.5 (C 2 O 4 ) 0.5 (H 2 O)) could be acquired at a low pH value of 1.98 and a higher pH value over 6, respectively. The UPO1-UPO4 compounds, which display structural diversity via pH-dependent competitive effect of oxalate, represent the first series of mixed-ligand uranyl polyrotaxanes with organic ligand as the coligand. Moreover, the self-assembly process and its internal mechanism concerning pH-dependent competitive effect and other related factors such as concentration of the reagents and coordination behaviors of the coligands were discussed in detail.

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.

On the multi-reference nature of plutonium oxides: PuO22+, PuO2, PuO3 and PuO2(OH)2.

PubMed

Boguslawski, Katharina; Réal, Florent; Tecmer, Paweł; Duperrouzel, Corinne; Gomes, André Severo Pereira; Legeza, Örs; Ayers, Paul W; Vallet, Valérie

2017-02-08

Actinide-containing complexes present formidable challenges for electronic structure methods due to the large number of degenerate or quasi-degenerate electronic states arising from partially occupied 5f and 6d shells. Conventional multi-reference methods can treat active spaces that are often at the upper limit of what is required for a proper treatment of species with complex electronic structures, leaving no room for verifying their suitability. In this work we address the issue of properly defining the active spaces in such calculations, and introduce a protocol to determine optimal active spaces based on the use of the Density Matrix Renormalization Group algorithm and concepts of quantum information theory. We apply the protocol to elucidate the electronic structure and bonding mechanism of volatile plutonium oxides (PuO 3 and PuO 2 (OH) 2 ), species associated with nuclear safety issues for which little is known about the electronic structure and energetics. We show how, within a scalar relativistic framework, orbital-pair correlations can be used to guide the definition of optimal active spaces which provide an accurate description of static/non-dynamic electron correlation, as well as to analyse the chemical bonding beyond a simple orbital model. From this bonding analysis we are able to show that the addition of oxo- or hydroxo-groups to the plutonium dioxide species considerably changes the π-bonding mechanism with respect to the bare triatomics, resulting in bent structures with a considerable multi-reference character.

Capability to Recover Plutonium-238 in H-Canyon/HB-Line - 13248

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

Fuller, Kenneth S. Jr.; Smith, Robert H. Jr.; Goergen, Charles R.

2013-07-01

Plutonium-238 is used in Radioisotope Thermoelectric Generators (RTGs) to generate electrical power and in Radioisotope Heater Units (RHUs) to produce heat for electronics and environmental control for deep space missions. The domestic supply of Pu-238 consists of scrap material from previous mission production or material purchased from Russia. Currently, the United States has no significant production scale operational capability to produce and separate new Pu-238 from irradiated neptunium-237 targets. The Department of Energy - Nuclear Energy is currently evaluating and developing plans to reconstitute the United States capability to produce Pu-238 from irradiated Np-237 targets. The Savannah River Site hadmore » previously produced and/or processed all the Pu-238 utilized in Radioisotope Thermoelectric Generators (RTGs) for deep space missions up to and including the majority of the plutonium for the Cassini Mission. The previous full production cycle capabilities included: Np- 237 target fabrication, target irradiation, target dissolution and Np-237 and Pu-238 separation and purification, conversion of Np-237 and Pu-238 to oxide, scrap recovery, and Pu-238 encapsulation. The capability and equipment still exist and could be revitalized or put back into service to recover and purify Pu-238/Np-237 or broken General Purpose Heat Source (GPHS) pellets utilizing existing process equipment in HB-Line Scrap Recovery, and H-Canyon Frame Waste Recovery processes. The conversion of Np-237 and Pu-238 to oxide can be performed in the existing HB-Line Phase-2 and Phase- 3 Processes. Dissolution of irradiated Np-237 target material, and separation and purification of Np-237 and Pu-238 product streams would be possible at production rates of ∼2 kg/month of Pu-238 if the existing H-Canyon Frames Process spare equipment were re-installed. Previously, the primary H-Canyon Frames equipment was removed to be replaced: however, the replacement project was stopped. The spare equipment is stored and still available for installation. Out of specification Pu-238 scrap material can be purified and recovered by utilizing the HB-Line Phase- 1 Scrap Recovery Line and the Phase-3 Pu-238 Oxide Conversion Line along with H-Canyon Frame Waste Recovery process. In addition, it also covers and describes utilizing the Phase-2 Np-237 Oxide Conversion Line, in conjunction with the H-Canyon Frames Process to restore the H-Canyon capability to process and recover Np-237 and Pu-238 from irradiated Np-237 targets and address potential synergies with other programs like recovery of Pu-244 and heavy isotopes of curium from other target material. (authors)« less

Biokinetics of nuclear fuel compounds and biological effects of nonuniform radiation.

PubMed Central

Lang, S; Servomaa, K; Kosma, V M; Rytömaa, T

1995-01-01

Environmental releases of insoluble nuclear fuel compounds may occur at nuclear power plants during normal operation, after nuclear power plant accidents, and as a consequence of nuclear weapons testing. For example, the Chernobyl fallout contained extensive amounts of pulverized nuclear fuel composed of uranium and its nonvolatile fission products. The effects of these highly radioactive particles, also called hot particles, on humans are not well known due to lack of reliable data on the extent of the exposure. However, the biokinetics and biological effects of nuclear fuel compounds have been investigated in a number of experimental studies using various cellular systems and laboratory animals. In this article, we review the biokinetic properties and effects of insoluble nuclear fuel compounds, with special reference to UO2, PuO2, and nonvolatile, long-lived beta-emitters Zr, Nb, Ru, and Ce. First, the data on hot particles, including sources, dosimetry, and human exposure are discussed. Second, the biokinetics of insoluble nuclear fuel compounds in the gastrointestinal tract and respiratory tract are reviewed. Finally, short- and long-term biological effects of nonuniform alpha- and beta-irradiation on the gastrointestinal tract, lungs, and skin are discussed. Images p920-a Figure 1. PMID:8529589

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

In situ speciation of uranium in treated acid mine drainage using the diffusion gradients in thin films technique (DGT).

PubMed

Pedrobom, Jorge Henrique; Eismann, Carlos Eduardo; Menegário, Amauri A; Galhardi, Juliana Aparecida; Luko, Karen Silva; Dourado, Thiago de Araujo; Kiang, Chang Hung

2017-02-01

The exchange membranes P81 and DE81 and Chelex-100 resin were used to perform in situ speciation of uranium in treated acid mine drainage at the Osamu Utsumi mining site, Poços de Caldas city, Southeast Brazil. To investigate possible chemical modifications in the samples during analysis, the three ligands were deployed in situ and in a laboratory (in lab). The results obtained in situ were also compared to a speciation performed using Visual MINTEQ software. Chelex-100 retained total labile U for a period of up to 48 h. The labile U fraction determined by Chelex 100 ranged from 107 ± 6% to 147 ± 44% in situ and from 115 ± 22% to 191 ± 5% in lab. DE81 retained anionic U species up to 8 h, with labile fractions ranging from 37 ± 2% to 76 ± 3% in situ and 34 ± 12% to 180 ± 17% in lab. P81 exhibited a lower efficiency in retaining U species, with concentrations ranging from 6± 2% to 19± 2% in situ and 3± 2% to 18± 2% in lab. The speciation obtained from MINTEQ suggests that the major U species were UO 2 OH + , UO 2 (OH) 3- , UO 2 (OH) 2(aq) , Ca 2 UO 2 (CO 3 ) 3(aq) , CaUO 2 (CO 3 ) 3 2- , UO 2 (CO 3 ) 2 2- , and UO 2 (CO 3 ) 3 4- . This result is in accordance with the results obtained in situ. Differences concerning speciation and the total and soluble U concentrations were observed between the deployments performed in situ and in the laboratory, indicating that U speciation must be performed in situ. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical Dissolution of Simulant FCA Cladding and Plates

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

Daniel, G.; Pierce, R.; O'Rourke, P.

The Savannah River Site (SRS) has received some fast critical assembly (FCA) fuel from the Japan Atomic Energy Agency (JAEA) for disposition. Among the JAEA FCA fuel are approximately 7090 rectangular Stainless Steel clad fuel elements. Each element has an internal Pu-10.6Al alloy metal wafer. The thickness of each element is either 1/16 inch or 1/32 inch. The dimensions of each element ranges from 2 inches x 1 inch to 2 inches x 4 inches. This report discusses the potential chemical dissolution of the FCA clad material or stainless steel. This technology uses nitric acid-potassium fluoride (HNO 3-KF) flowsheets ofmore » H-Canyon to dissolve the FCA elements from a rack of materials. Historically, dissolution flowsheets have aimed to maximize Pu dissolution rates while minimizing stainless steel dissolution (corrosion) rates. Because the FCA cladding is made of stainless steel, this work sought to accelerate stainless steel dissolution.« less

Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

NASA Astrophysics Data System (ADS)

Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

2015-11-01

In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

Synthesis and crystal structure analysis of uranyl triple acetates

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

Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com; Department of Chemistry, Samara National Research University, 443086 Samara; Serezhkina, Larisa B.

2016-12-15

Single crystals of triple acetates NaR[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O (R=Mg, Co, Ni, Zn), well-known for their use as reagents for sodium determination, were grown from aqueous solutions and their structural and spectroscopic properties were studied. Crystal structures of the mentioned phases are based upon (Na[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}){sup 2–} clusters and [R(H{sub 2}O){sub 6}]{sup 2+} aqua-complexes. The cooling of a single crystal of NaMg[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O from 300 to 100 K leads to a phase transition from trigonal to monoclinic crystal system. Intermolecular interactions between the structural units and their mutual packing were studiedmore » and compared from the point of view of the stereoatomic model of crystal structures based on Voronoi-Dirichlet tessellation. Using this method we compared the crystal structures of the triple acetates with Na[UO{sub 2}(CH{sub 3}COO){sub 3}] and [R(H{sub 2}O){sub 6}][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} and proposed reasons of triple acetates stability. Infrared and Raman spectra were collected and their bands were assigned. - Graphical abstract: Single crystals of uranium based triple acetates, analytical reagents for sodium determination, were synthesized and structurally, spectroscopically and topologically characterized. The structures were compared with the structures of compounds from preceding families [M(H{sub 2}O){sub 6})][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} (M = Mg, Co, Ni, Zn) and Na[UO{sub 2}(CH{sub 3}COO){sub 3}]. Analysis was performed with the method of molecular Voronoi-Dirichlet polyhedra to reveal a large contribution of the hydrogen bonds into intermolecular interactions which can be a reason of low solubility of studied complexes.« less

A two-arm cluster randomized control trial to determine the effectiveness of a pressure ulcer prevention bundle for critically ill patients.

PubMed

Tayyib, Nahla; Coyer, Fiona; Lewis, Peter A

2015-05-01

This study tested the effectiveness of a pressure ulcer (PU) prevention bundle in reducing the incidence of PUs in critically ill patients in two Saudi intensive care units (ICUs). A two-arm cluster randomized experimental control trial. Participants in the intervention group received the PU prevention bundle, while the control group received standard skin care as per the local ICU policies. Data collected included demographic variables (age, diagnosis, comorbidities, admission trajectory, length of stay) and clinical variables (Braden Scale score, severity of organ function score, mechanical ventilation, PU presence, and staging). All patients were followed every two days from admission through to discharge, death, or up to a maximum of 28 days. Data were analyzed with descriptive correlation statistics, Kaplan-Meier survival analysis, and Poisson regression. The total number of participants recruited was 140: 70 control participants (with a total of 728 days of observation) and 70 intervention participants (784 days of observation). PU cumulative incidence was significantly lower in the intervention group (7.14%) compared to the control group (32.86%). Poisson regression revealed the likelihood of PU development was 70% lower in the intervention group. The intervention group had significantly less Stage I (p = .002) and Stage II PU development (p = .026). Significant improvements were observed in PU-related outcomes with the implementation of the PU prevention bundle in the ICU; PU incidence, severity, and total number of PUs per patient were reduced. Utilizing a bundle approach and standardized nursing language through skin assessment and translation of the knowledge to practice has the potential to impact positively on the quality of care and patient outcome. © 2015 Sigma Theta Tau International.

Enhanced thermal conductivity oxide nuclear fuels by co-sintering with BeO: II. Fuel performance and neutronics

NASA Astrophysics Data System (ADS)

McCoy, Kevin; Mays, Claude

2008-04-01

The fuel rod performance and neutronics of enhanced thermal conductivity oxide (ECO) nuclear fuel with BeO have been compared to those of standard UO 2 fuel. The standards of comparison were that the ECO fuel should have the same infinite neutron-multiplication factor kinf at end of life and provide the same energy extraction per fuel assembly over its lifetime. The BeO displaces some uranium, so equivalence with standard UO 2 fuel was obtained by increasing the burnup and slightly increasing the enrichment. The COPERNIC fuel rod performance code was adapted to account for the effect of BeO on thermal properties. The materials considered were standard UO 2, UO 2 with 4.0 vol.% BeO, and UO 2 with 9.6 vol.% BeO. The smaller amount of BeO was assumed to provide increases in thermal conductivity of 0, 5, or 10%, whereas the larger amount was assumed to provide an increase of 50%. A significant improvement in performance was seen, as evidenced by reduced temperatures, internal rod pressures, and fission gas release, even with modest (5-10%) increases in thermal conductivity. The benefits increased monotonically with increasing thermal conductivity. Improvements in LOCA initialization performance were also seen. A neutronic calculation considered a transition from standard UO 2 fuel to ECO fuel. The calculation indicated that only a small increase in enrichment is required to maintain the kinf at end of life. The smallness of the change was attributed to the neutron-multiplication reaction of Be with fast neutrons and the moderating effect of BeO. Adoption of ECO fuel was predicted to provide a net reduction in uranium cost. Requirements for industrial hygiene were found to be comparable to those for processing of UO 2.

Carbon monoxide formation in UO2 kerneled HTR fuel particles containing oxygen getters

NASA Astrophysics Data System (ADS)

Proksch, E.; Strigl, A.; Nabielek, H.

1986-01-01

Mass spectrometric measurements of CO in irradiated UO2 fuel particles containing oxygen getters are summarized. Uranium carbide addition in the 3% to 15% range reduces the CO release by factors between 25 and 80, up to burn-up levels as high as 70% FIMA. Unintentional gettering by SiC in TRISO coated particles with failed inner pyrocarbon layers results in CO reduction factors between 15 and 110. For ZrC, ambiguous results are obtained; ZrC probably results in CO reduction by a factor of 40; Ce2O3 and La2O3 seem less effective than the carbides; for Ce2O3, reduction factors between 3 and 15 are found. However, the results are possibly incorrect due to premature oxidation of the getter already during fabrication. Addition of SiO2 + Al2O3 has no influence on CO release.

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.

Rapid dating of recent aquatic sediments using Pu activities and 240Pu/239Pu as determined by quadrupole inductively coupled plasma mass spectrometry.

PubMed

Ketterer, Michael E; Watson, Bridgette R; Matisoff, Gerald; Wilsont, Christopher G

2002-03-15

Quadrupole inductively coupled plasma mass spectrometry has been used to rapidly establish the chronology of recent aquatic sediments via measurements of the activities of 239Pu, 240Pu, and the atom ratio 240Pu/239Pu. Following addition of 0.007 Bq of a 242Pu spike isotope, Pu is leached from 3-20 g aliquots of dry-ashed sediments with HNO3. A selective anion exchanger is used to preconcentrate Pu into approximately 2 mL aliquots, which are directly analyzed using a pneumatic nebulizer and double-pass spraychamber operating at 60 microL/min solution uptake rate. The ICPMS data collection is performed for 10 min per sample. The U concentrations were 0.01-0.05 microg/L in the analyzed solutions, and the interference of 238U1H+ upon 239Pu+ was negligible. The method has been applied to determining Pu activities, inventory, and 240Pu/239Pu in a complete sediment core from Old Woman Creek (Huron, OH). The Pu activity profiles, obtained in approximately 6 h of instrumental measurement time, are in agreement with a y spectrometric 137Cs profile. Peak 239+240Pu and 137Cs activities in the core were 1.60 +/- 0.02 and 47.8 +/- 0.8 Bq/kg, respectively; inventories were 108 +/- 2 Bq/m2 239+240Pu and 2710 +/- 40 Bq/m2 137Cs. Detection limits, based upon the analysis of 20 g samples, were 0.004 Bq/kg 239Pu, 0.012 Bq/kg 240Pu, and 0.012 Bq/kg 239+240Pu. 240Pu/239Pu atom ratios of 0.16-0.19 were obtained for all core intervals containing detectable Pu, which indicates that global fallout is the source of these radionuclides.

In vivo canine studies of a Sinkhole valve and vascular graft coated with biocompatible PU-PEO-SO3.

PubMed

Han, D K; Lee, K B; Park, K D; Kim, C S; Jeong, S Y; Kim, Y H; Kim, H M; Min, B G

1993-01-01

PU-PEO-SO3 was applied as a coating material over a newly designed Sinkhole bileaflet PU heart valve and a porous PU vascular graft. Performance and biocompatibility were evaluated using an in vivo canine shunt system between the right ventricle and pulmonary artery. The survival periods in three implantations were 14, 24, and 39 days, during which no mechanical failure occurred in any Sinkhole valve or vascular graft. Scanning electron microscopy (SEM) studies demonstrated much less platelet adhesion and thrombus formation on PU-PEO-SO3 grafts than on PU vascular grafts. Cracks in the valve leaflet were occasionally observed on PU surfaces, but not on PU-PEO-SO3. After a 39 day implantation, calcium deposition on vascular grafts was decreased as compared with valve leaflets, and calcification on PU-PEO-SO3 was much lower than on PU. These results suggest that Sinkhole valves and vascular grafts are promising, and PU-PEO-SO3 as a coating material is more blood compatible, biostable, and calcification resistant in vivo than in untreated PU.

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

Burke, J. T.; Alan, B. S.; Akindele, O. A.

The goal of this project was to develop a new approach to measuring (n,2n) reactions for isotopes of interest. We set out to measure the 239Pu(n,2n) and 241Pu(n,2n) cross sections by directly detecting the 2n neutrons that are emitted. With the goal of improving the 239Pu(n,2n) cross section and to measure the 241Pu(n,2n) cross section for the first time. To that end, we have constructed a new neutron-charged-particle detector array called NeutronSTARS. It has been described extensively in Casperson et al. [1] and in Akindele et al. [2]. We have used this new neutron-charged-particle array to measure the 241Pu andmore » 239Pu fission neutron multiplicity as a function of equivalent incident-neutron energy from 100 keV to 20 MeV. We have made a preliminary determination of the 239Pu(n,2n) and 241Pu(n,2n) cross sections from the surrogate 240Pu(α,α’2n) and 242Pu(α,α’2n) reactions respectively. The experimental approach, detector array, data analysis, and results to date are summarized in the following sections.« less

PRESSURIZED WATER REACTOR (PWR) PROJECT TECHNICAL PROGRESS REPORT FOR THE PERIOD DECEMBER 24, 1959 TO FEBRUARY 23, 1960

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

None

< 9 A < 2 6 < 7 4 8 9 6 2 6 equalizing vent valves on air locks 2, 4, and 5 was completed. An evaluation of the failed main coolant pump No. 1-80-F-737 was completed. The design for installing combination ball check and manual stop valves on the boiler water level sight glasses, to prevent the escape of steam should a defective sight glass develop, was completed. The main coolant pumps No. 80 and No. 79 were modified by increasing the radial clearance of the impeller wear ring and by removing the upper labyrinth ring. A designmore » for relocating the cooling water flow orifice 17-J4-17 was completed. Metallurgy: Preliminary data from the Bett 69-1 in-pile thermal conductivity capsules indicate that the thermal conductivity of as-sintered ZrO/sub 2/ 34 wt.% UO/sub 2/ appears to decrease from an initial value of about 1.6 Btu/hr-ft- deg F to about 0.7 Btu/hr-ft- deg F after 17 days irradiation in an estimated perturbed flux of 4 x 10/sup 13/. The thermal conductivities of UO/sub 2/ and BeO 51 wt.% UO/sub 2/ fuel remained unchanged during this time. Examination of the two failed X-3-1 fuel plates and the two failed CR-V-m fuel plates showed that a definite burnup limitation exists for bulk UO/sub 2/i of about 16 x 10/sup 20/ to 21.5 x 10/sup 20/ fissions/cc at which point the fuel increases in volume about 4- -5%. Irradiation of both fine and coarse dis-persions of 28 wt.% UO/sub 2/in BeO to exposures of about 11 x 10/sup 20/ fissions/cc shows this material has very poor dimensional stabllity and poor fission gas retention ability. The fine particles dispersion showed approximately 4.8 times the thickness increase as did the coarse particles. Interim examination of a bulk B/sub 4/ burnable poison plate irradiated in the HB-1 loop to about 60 at.% B/sup 10/ burnup showed a 17% increase in plate thickness. The technical feasibility of fabricating blanket receptacles with full length fuel channels and an integral cover plate by form rolling was established. Hack-pressure-bonding appears to be a suitable means of incorporating void volume in fuel compartments of oxide plates. High density (99% T.D.) and improved microstructure of B/sub 4/C-SiC burnable poisons are achieved when small (2 micron) B/sub 4/C particle size powder is used ia hot pressing compacts. Measurements of the self-diffusion coefficients of uranium in UO/sub 2/ by the method of surface activity decrease were completed. Experiments on the diffusion of Xe/sup 133/ in Core 2--type UO/sup 2/ fuel platelets were completed. Diffusion anaeals carried out at 1000 deg C on samples from the X-3-1 and the 14-28 irradiation tests show that the apparent diffusion coefficient for Kr/sup 85/ incresses considerably with burnup. An average activation energy for thoron emanation in UO/sub 2/ was estimated to be 44 kcal/mole. An initial experiment on the release of helium from slightly irradiated B/sub 4/C at 900 deg C resulted in a diffusion coefficient for helium of 3.5 x 10/sup -8/ Physics: Calculatad values for seed-blanket power sharing as a function of PWR-1 Seed 1 life were compared with measured data obtained from thermal instrumentation at Shippingport. Two-dimensional depletion studies in the PWR-2 "composite cell" geometry were completed for seed assembly configurations having different radial fuel zoning. An eighth core representation is being employed for a two- dimensional depletion calculation of PWR-2. An analysis of the effect on the axial power distribution of the nonuniform temperature distribution in an 8 ft PWR-2 core loaded with 295 kg of U/sup 235/ indicated that local variations in power density of as much as 15% may occur, relative to the distribution that would exist if the axial temperature distribution were uniform. A technique was developed which makes possible an approximately correct description of the neutron capture rate within small rectangular boron wafers in diffusion theory calculations. Seed peaking factors measured in a five-cluster slab of PWR-2 mock- up materials were measured and compared with calculated peaking factors obtained using the nuclear« less

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

Miao, Yinbin; Mo, Kun; Yao, Tiankai

Here coordinated experimental efforts to quantitatively correlate crystallographic orientation and surface faceting features in UO2 are reported upon. A sintered polycrystalline UO2 sample was thermally etched to induce the formation of surface faceting features. Synchrotron Laue microdiffraction was used to obtain a precise crystallographic orientation map for the UO2 surface grains. Scanning electron microscopy (SEM) was utilized to collect the detailed information on the surface morphology of the sample. The surface faceting features were found to be highly dependent on the crystallographic orientation. In most cases, Triple-plane structures containing one {100} plane and two {111} planes were found to dominatemore » the surface of UO2. The orientation-faceting relationship established in this study revealed a practical and efficient method of determining crystallographic orientation based on the surface features captured by SEM images.« less

Electrolytic process for preparing uranium metal

DOEpatents

Haas, Paul A.

1990-01-01

An electrolytic process for making uranium from uranium oxide using Cl.sub.2 anode product from an electrolytic cell to react with UO.sub.2 to form uranium chlorides. The chlorides are used in low concentrations in a melt comprising fluorides and chlorides of potassium, sodium and barium in the electrolytic cell. The electrolysis produces Cl.sub.2 at the anode that reacts with UO.sub.2 in the feed reactor to form soluble UCl.sub.4, available for a continuous process in the electrolytic cell, rather than having insoluble UO.sub.2 fouling the cell.

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 parameters has been completed, and the established procedures have been applied to determination of PWR reference design parameters. Critical experiments and primary loop shielding analyses are described. (D.E.B.)« less

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.

Comparative uptake of plutonium from soils by Brassica juncea and Helianthus annuus.

PubMed

Lee, J H; Hossner, L R; Attrep, M; Kung, K S

2002-01-01

Plutonium uptake by Brassica juncea (Indian mustard) and Helianthus annuus (sunflower) from soils with varying chemical composition and contaminated with Pu complexes (Pu-nitrate [239Pu(NO3)4], Pu-citrate [239Pu(C6H5O7)], and Pu-diethylenetriaminepentaacetic acid (Pu-DTPA [239Pu-C14H23O10N3]) was investigated. Sequential extraction of soils incubated with applied Pu was used to determine the distribution of Pu in the various soil fractions. The initial Pu activity levels in soils were 44.40-231.25 Bq g(-1) as Pu-nitrate Pu-citrate, or Pu-DTPA. A difference in Pu uptake between treatments of Pu-nitrate and Pu-citrate without chelating agent was observed only with Indian mustard in acidic Crowley soil. The uptake of Pu by plants was increased with increasing DTPA rates, however, the Pu concentration of plants was not proportionally increased with increasing application rate of Pu to soil. Plutonium uptake from Pu-DTPA was significantly higher from the acid Crowley soil than from the calcareous Weswood soil. The uptake of Pu from the soils was higher in Indian mustard than in sunflower. Sequential extraction of Pu showed that the ion-exchangeable Pu fraction in soils was dramatically increased with DTPA treatment and decreased with time of incubation. Extractability of Pu in all fractions was not different when Pu-nitrate and Pu-citrate were applied to the same soil. More Pu was associated with the residual Pu fraction without DTPA application. Consistent trends with time of incubation for other fractions were not apparent. The ion-exchangeable fraction, assumed as plant-available Pu, was significantly higher in acid soil compared with calcareous soil with or without DTPA treatment. When the calcareous soil was treated with DTPA, the ion-exchangeable Pu was comparatively less influenced. This fraction in the soil was more affected with time of incubation. The lowest extractable Pu was from a pH 6.55 Crockett soil that contained the highest clay compared to the other two soils. Extractable soil Pu was largely affected by soil pH and the amounts of clay, salt, metal oxide, and carbonate.

A Study of the Factors Associated with Risk for Development of Pressure Ulcers: A Longitudinal Analysis.

PubMed

Thomas, Elizebeth; Vinodkumar, Sudhaya; Mathew, Silvia; Setia, Maninder Singh

2015-01-01

Pressure ulcers (PUs) are prevalent in hospitalized patients; they may cause clinical, psychological, and economic problems in these patients. Previous studies are cross-sectional, have used pooled data, or cox-regression models to assess the risk for developing PU. However, PU risk scores change over time and models that account for time varying variables are useful for cohort analysis of data. The present longitudinal study was conducted to compare the risk of PU between surgical and nonsurgical patients, and to evaluate the factors associated with the development of these ulcers over a period of time. We evaluated 290 hospitalized patients over a 4 months period. The main outcomes for our analysis were: (1) Score on the pressure risk assessment scale; and (2) the proportion of individuals who were at severe risk for developing PUs. We used random effects models for longitudinal analysis of the data. The mean PU score was significantly higher in the nonsurgical patients compared with surgical patients at baseline (15.23 [3.86] vs. 9.33 [4.57]; P < 0.01). About 7% of the total patients had a score of >20 at baseline and were considered as being at high-risk for PU; the proportion was significantly higher among the nonsurgical patients compared with the surgical patients (14% vs. 4%, P = 0.003). In the adjusted models, there was no difference for severe risk for PU between surgical and nonsurgical patients (odds ratios [ORs]: 0.37, 95% confidence interval [CI]: 0.01-12.80). An additional day in the ward was associated with a significantly higher likelihood of being at high-risk for PU (OR: 1.47, 95% CI: 1.16-1.86). There were no significant differences between patients who were admitted for surgery compared with those who were not. An additional day in the ward, however, is important for developing a high-risk score for PU on the monitoring scale, and these patients require active interventions.

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.

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

Experiments on the high-temperature behaviour of neutron-irradiated uranium dioxide and fission products, volume 8, number 1

NASA Astrophysics Data System (ADS)

Tanke, R. H. J.

The release rate of fission products from overheated UO2, the chemical form of these fission products, and the transport mechanism inside the nuclear fuel are determined. UO spheres of approximately 1 mm diameter, irradiated in a high-flux reactor were used for the experiments. The chemical forms of the particles released from the spheres during evaporation were determined by mass spectrometry and the release rate of the mission products was determined by gamma spectrometry. A gamma topographer was developed to determine the change with temperature in the three dimensional distribution of radioactive fission products in the spheres. No clear relationship between the stoichiometry of the spheres and uranium consumption were shown. A diffusion model was used to determine the activation energy for the diffusion of fission products. It is concluded that the microstructure of the nuclear fuel greatly affects the number of free oxygen atoms, the release rate and the chemical form of the fission products. The evaporation of the UO2 matrix is the main mechanism for the release of all fission products at temperatures above 2300 K. Barium can be as volatile as iodine. Niobium and lanthenum can be volatile. Molecular combinations of the fission products, iodine, cesium and tellurium, are highly unlikely to be present inside the fuel. Barium and nobium may form compounds with oxygen and are then released as simple oxides. Fission products are released from overheated UO2 or as oxides. A new model is proposed for describing the behavior of oxygen in irradiated nuclear fuel.

The heat of formation of gaseous PuO(2)2+ from relativistic density functional calculations.

PubMed

Moskaleva, Lyudmila V; Matveev, Alexei V; Dengler, Joachim; Rösch, Notker

2006-08-28

Using a set of model reactions, we estimated the heat of formation of gaseous PuO2(2+) from quantum-chemical reaction enthalpies and experimental heats of formation of reference species. To this end, we carried out relativistic density functional calculations on the molecules PuO(2)2+, PuO2, PuF6, and PuF4. We used a revised variant (PBEN) of the Perdew-Burke-Ernzerhof gradient-corrected exchange-correlation functional, and we accounted for spin-orbit interaction in a self-consistent fashion. As open-shell Pu species with two or more unpaired 5f electrons are involved, spin-orbit interaction significantly affects the energies of the model reactions. Our theoretical estimate for the heat of formation DeltafH degree 0(PuO2(2+),g), 418+/-15 kcal mol-1, evaluated using plutonium fluorides as references, is in good agreement with a recent experimental result, 413+/-16 kcal mol-1. The theoretical value connected to the experimental heat of formation of PuO2(g) has a notably higher uncertainty and therefore was not included in the final result.

Endothelialization of polyurethanes: Surface silanization and immobilization of REDV peptide.

PubMed

Butruk-Raszeja, Beata A; Dresler, Magdalena S; Kuźmińska, Aleksandra; Ciach, Tomasz

2016-08-01

The paper presents method for chemical immobilization of arginine-glutamic acid-aspartic acid-valine (REDV) peptide on polyurethane surface. The peptide has been covalently bonded using silanes as a spacer molecules. The aim of this work was to investigate the proposed modification process and assess its biological effectiveness, especially in contact with blood and endothelial cells. Physicochemical properties were examined in terms of wettability, atomic composition and density of introduced functional groups and peptide molecules. Experiments with blood showed that material coating reduced number of surface-adhered platelets and fibrinogen molecules. In contrast to polyurethane (PU), there were no blood components deposited on REDV-modified materials (PU-REDV); fibrinogen adsorption on PU-REDV surface has been strongly reduced compared to PU. Analysis of cell adhesion after 1, 2, 3, 4, and 5 days of culture showed a significant increase of the cell-coated area on PU-REDV compared to PU. However, an intense cell growth appeared also on the control surface modified without the addition of REDV. Thus, the positive effect of REDV peptide on the adhesion of HUVEC could not be unequivocally confirmed. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

DOE PAGES

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; ...

2016-09-30

Studies of the complexation of new promising ligands with uranyl (UO 2 2+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO 2 2+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO 2 2+, VO 2+, and VO 2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques,more » along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO 2 2+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO 2 2+, VO 2+, and VO 2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO 2 2+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

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

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

Studies of the complexation of new promising ligands with uranyl (UO 2 2+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO 2 2+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO 2 2+, VO 2+, and VO 2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques,more » along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO 2 2+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO 2 2+, VO 2+, and VO 2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO 2 2+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Polyuria and impaired renal blood flow after asphyxia in preterm fetal sheep.

PubMed

Quaedackers, J S; Roelfsema, V; Hunter, C J; Heineman, E; Gunn, A J; Bennet, L

2004-03-01

Renal impairment is common in preterm infants, often after exposure to hypoxia/asphyxia or other circulatory disturbances. We examined the hypothesis that this association is mediated by reduced renal blood flow (RBF), using a model of asphyxia induced by complete umbilical cord occlusion for 25 min (n = 13) or sham occlusion (n = 6) in chronically instrumented preterm fetal sheep (104 days, term is 147 days). During asphyxia there was a significant fall in RBF and urine output (UO). After asphyxia, RBF transiently recovered, followed within 30 min by a secondary period of hypoperfusion (P < 0.05). This was mediated by increased renal vascular resistance (RVR, P < 0.05); arterial blood pressure was mildly increased in the first 24 h (P < 0.05). RBF relatively normalized between 3 and 24 h, but hypoperfusion developed again from 24 to 60 h (P < 0.05, analysis of covariance). UO significantly increased to a peak of 249% of baseline between 3 and 12 h (P < 0.05), with increased fractional excretion of sodium, peak 10.5 +/- 1.4 vs. 2.6 +/- 0.6% (P < 0.001). Creatinine clearance returned to normal after 2 h; there was a transient reduction at 48 h to 0.32 +/- 0.02 ml.min(-1).g(-1) (vs. 0.45 +/- 0.04, P < 0.05) corresponding with the time of maximal depression of RBF. No renal injury was seen on histological examination at 72 h. In conclusion, severe asphyxia in the preterm fetus was associated with evolving renal tubular dysfunction, as shown by transient polyuria and natriuresis. Despite a prolonged increase in RVR, there was only a modest effect on glomerular function.

Structural, spectroscopic and redox properties of uranyl complexes with a maleonitrile containing ligand.

PubMed

Hardwick, Helen C; Royal, Drew S; Helliwell, Madeleine; Pope, Simon J A; Ashton, Lorna; Goodacre, Roy; Sharrad, Clint A

2011-06-14

The reaction of uranyl nitrate hexahydrate with the maleonitrile containing Schiff base 2,3-bis[(4-diethylamino-2-hydroxybenzylidene)amino]but-2-enedinitrile (salmnt((Et(2)N)(2))H(2)) in methanol produces [UO(2)(salmnt((Et2N)2))(H(2)O)] (1) where the uranyl equatorial coordination plane is completed by the N(2)O(2) tetradentate cavity of the (salmnt((Et(2)N)(2)))(2-) ligand and a water molecule. The coordinated water molecule readily undergoes exchange with pyridine (py), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) and triphenylphosphine oxide (TPPO) to give a series of [UO(2)(salmnt((Et(2)N)(2)))(L)] complexes (L = py, DMSO, DMF, TPPO; 2-5, respectively). X-Ray crystallography of 1-5 show that the (salmnt((Et(2)N)(2)))(2-) ligand is distorted when coordinated to the uranyl moiety, in contrast to the planar structure observed for the free protonated ligand (salmnt((Et(2)N)(2))H(2)). The Raman spectra of 1-5 only display extremely weak bands (819-828 cm(-1)) that can be assigned to the typically symmetric O=U=O stretch. This stretching mode is also observed in the infrared spectra for all complexes 1-5 (818-826 cm(-1)) predominantly caused by the distortion of the tetradentate (salmnt((Et(2)N)(2)))(2-) ligand about the uranyl equatorial plane resulting in a change in dipole for this bond stretch. The solution behaviour of 2-5 was studied using NMR, electronic absorption and emission spectroscopy, and cyclic voltammetry. Complexes 2-5 exhibit intense absorptions in the visible region of the spectrum due to intramolecular charge transfer (ICT) transitions and the luminescence lifetimes (< 5 ns) indicate the emission arises from ligand-centred excited states. Reversible redox processes assigned to the {UO(2)}(2+)/{UO(2)}(+) couple are observed for complexes 2-5 (2: E(1/2) = -1.80 V; 3,5: E(1/2) = -1.78 V; 4: E(1/2) = -1.81 V : vs. ferrocenium/ferrocene {Fc(+)/Fc}, 0.1 M Bu(4)NPF(6)) in dichloromethane (DCM). These are some of the most negative half potentials for the {UO(2)}(2+)/{UO(2)}(+) couple observed to date and indicate the strong electron donating nature of the (salmnt((Et(2)N)(2)))(2-) ligand. Multiple uranyl redox processes are clearly seen for [UO(2)(salmnt((Et(2)N)(2)))(L)] in L (L = py, DMSO, DMF; 2-4: 0.1 M Bu(4)NPF(6)) indicating the relative instability of these complexes when competing ligands are present, but the reversible {UO(2)}(2+)/{UO(2)}(+) couple for the intact complexes can still be assigned and shows the position of this couple can be modulated by the solvation environment. Several redox processes were also observed between +0.2 and +1.2 V (vs. Fc(+)/Fc) that prove the redox active nature of the maleonitrile-containing ligand.

Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

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

Miskowiec, A., E-mail: miskowiecaj@ornl.gov; Trowbridge, L.; Anderson, B.

2016-03-07

The structural phase diagram of uranyl fluoride (UO{sub 2}F{sub 2}), while incomplete, contains at least one anhydrous crystal structure and a second, zeolite-like structure with the formula [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} that can be produced by adding water to the anhydrous structure. While traditional diffraction measurements can easily differentiate these crystals, additional aqueous structures (in general of the form UO{sub 2}F{sub 2} + xH{sub 2}O) have been proposed as well. We present results using a novel sample environment setup to intercalate water during a quasielastic neutron scattering measurement over the course of 86 h. Our sample environment allows low-pressure (<2 atm)more » humid air flow across the sample coupled with a system to control the relative humidity of this air flow between 10% and 70%. The water dynamics in UO{sub 2}F{sub 2} and [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} are sufficiently different to distinguish them, with water in the latter executing a restricted diffusion (D = 2.7 × 10{sup −6} cm{sup 2}/s) within the structure's accessible pores (r = 3.17 Å) such that the dynamics can be used as a fingerprinting tool. We confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4}, and we demonstrate the feasibility of extending this approach to aqueous forms of UO{sub 2}F{sub 2} + xH{sub 2}O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.« less

Evaluation of the association between quantitative mammographic density and breast cancer occurred in different quadrants.

PubMed

Chan, Siwa; Chen, Jeon-Hor; Li, Shunshan; Chang, Rita; Yeh, Darh-Cherng; Chang, Ruey-Feng; Yeh, Lee-Ren; Kwong, Jessica; Su, Min-Ying

2017-04-17

To investigate the relationship between mammographic density measured in four quadrants of a breast with the location of the occurred cancer. One hundred and ten women diagnosed with unilateral breast cancer that could be determined in one specific breast quadrant were retrospectively studied. Women with previous cancer/breast surgery were excluded. The craniocaudal (CC) and mediolateral oblique (MLO) mammography of the contralateral normal breast were used to separate a breast into 4 quadrants: Upper-Outer (UO), Upper-Inner (UI), Lower-Outer (LO), and Lower-Inner (LI). The breast area (BA), dense area (DA), and percent density (PD) in each quadrant were measured by using the fuzzy-C-means segmentation. The BA, DA, and PD were compared between patients who had cancer occurring in different quadrants. The upper-outer quadrant had the highest BA (37 ± 15 cm 2 ) and DA (7.1 ± 2.9 cm 2 ), with PD = 20.0 ± 5.8%. The order of BA and DA in the 4 separated quadrants were: UO > UI > LO > LI, and almost all pair-wise comparisons showed significant differences. For tumor location, 67 women (60.9%) had tumor in UO, 16 (14.5%) in UI, 7 (6.4%) in LO, and 20 (18.2%) in LI quadrant, respectively. The estimated odds and the 95% confidence limits of tumor development in the UO, UI, LO and LI quadrants were 1.56 (1.06, 2.29), 0.17 (0.10, 0.29), 0.07 (0.03, 0.15), and 0.22 (0.14, 0.36), respectively. In these 4 groups of women, the order of quadrant BA and DA were all the same (UO > UI > LO > LI), and there was no significant difference in BA, DA or PD among them (all p > 0.05). Breast cancer was most likely to occur in the UO quadrant, which was also the quadrant with highest BA and DA; but for women with tumors in other quadrants, the density in that quadrant was not the highest. Therefore, there was no direct association between quadrant density and tumor occurrence.

Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes.

PubMed

Tecmer, Paweł; Gomes, André Severo Pereira; Knecht, Stefan; Visscher, Lucas

2014-07-28

We present a study of the electronic structure of the [UO2](+), [UO2](2 +), [UO2](3 +), NUO, [NUO](+), [NUO](2 +), [NUN](-), NUN, and [NUN](+) molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin-orbit coupling and Gaunt interactions are compared to results obtained with the Dirac-Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity).

Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

NASA Astrophysics Data System (ADS)

Tecmer, Paweł; Severo Pereira Gomes, André; Knecht, Stefan; Visscher, Lucas

2014-07-01

We present a study of the electronic structure of the [UO2]+, [UO2]2 +, [UO2]3 +, NUO, [NUO]+, [NUO]2 +, [NUN]-, NUN, and [NUN]+ molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin-orbit coupling and Gaunt interactions are compared to results obtained with the Dirac-Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity).

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.

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.

Galactosylated pullulan-curcumin conjugate micelles for site specific anticancer activity to hepatocarcinoma cells.

PubMed

Sarika, P R; James, Nirmala Rachel; Nishna, N; Anil Kumar, P R; Raj, Deepa K

2015-09-01

Galactosylated pullulan-curcumin conjugate (LANH2-Pu Ald-Cur SA) is developed for target specific delivery of curcumin to hepatocarcinoma cells by five step synthetic strategy, which includes oxidation of pullulan (Pu Ald), introduction of amino group to the targeting ligand (LANH2), grafting of the LANH2 to Pu Ald, modification of curcumin (Cur SA) and conjugation of Cur SA to pullulan. Nongalactosylated pullulan-curcumin conjugate (Pu-Cur SA) is also prepared to compare the enhancement in cytotoxicity offered by the targeting group. Both LANH2-Pu Ald-Cur SA and Pu-Cur SA conjugates could self assemble to micelle in water with hydrodynamic diameters of 355±9nm and 363±10nm, respectively. Both conjugates show spherical morphology and enhance stability of curcumin in physiological pH. Compared to Pu-Cur SA, LANH2-Pu Ald-Cur SA exhibits higher toxicity and internalization towards HepG2 cells. This indicates the enhanced uptake of LANH2-Pu Ald-Cur SA conjugate via ASGPR (asialoglycoprotein receptor) mediated endocytosis into HepG2 cells. Copyright © 2015 Elsevier B.V. All rights reserved.

First-principles study on oxidation effects in uranium oxides and high-pressure high-temperature behavior of point defects in uranium dioxide

NASA Astrophysics Data System (ADS)

Geng, Hua Y.; Song, Hong X.; Jin, K.; Xiang, S. K.; Wu, Q.

2011-11-01

Formation Gibbs free energy of point defects and oxygen clusters in uranium dioxide at high-pressure high-temperature conditions are calculated from first principles, using the LSDA+U approach for the electronic structure and the Debye model for the lattice vibrations. The phonon contribution on Frenkel pairs is found to be notable, whereas it is negligible for the Schottky defect. Hydrostatic compression changes the formation energies drastically, making defect concentrations depend more sensitively on pressure. Calculations show that, if no oxygen clusters are considered, uranium vacancy becomes predominant in overstoichiometric UO2 with the aid of the contribution from lattice vibrations, while compression favors oxygen defects and suppresses uranium vacancy greatly. At ambient pressure, however, the experimental observation of predominant oxygen defects in this regime can be reproduced only in a form of cuboctahedral clusters, underlining the importance of defect clustering in UO2+x. Making use of the point defect model, an equation of state for nonstoichiometric oxides is established, which is then applied to describe the shock Hugoniot of UO2+x. Furthermore, the oxidization and compression behavior of uranium monoxide, triuranium octoxide, uranium trioxide, and a series of defective UO2 at 0 K are investigated. The evolution of mechanical properties and electronic structures with an increase of the oxidation degree are analyzed, revealing the transition of the ground state of uranium oxides from metallic to Mott insulator and then to charge-transfer insulator due to the interplay of strongly correlated effects of 5f orbitals and the shift of electrons from uranium to oxygen atoms.

Solid state reactions of CeO 2, PuO 2, (U,Ce)O 2 and (U,Pu)O 2 with K 2S 2O 8

NASA Astrophysics Data System (ADS)

Keskar, Meera; Kasar, U. M.; Mudher, K. D. Singh; Venugopal, V.

2004-09-01

Solid state reactions of CeO 2, PuO 2 and mixed oxides (U,Ce)O 2 and (U,Pu)O 2 containing different mol.% of Ce and Pu, were carried out with K 2S 2O 8 at different temperatures to identify the formation of various products and to investigate their dissolution behaviour. X-ray, chemical and thermal analysis methods were used to characterise the products formed at various temperatures. The products obtained by heating two moles of K 2S 2O 8 with one mole each of CeO 2, PuO 2, (U,Ce)O 2 and (U,Pu)O 2 at 400 °C were identified as K 4Ce(SO 4) 4, K 4Pu(SO 4) 4, K 4(U,Ce)(SO 4) 4 and K 4(U,Pu)(SO 4) 4, respectively. K 4Ce(SO 4) 4 further decomposed to form K 4Ce(SO 4) 3.5 at 600 °C and mixture of K 2SO 4 and CeO 2 at 950 °C. Thus the products formed during the reaction of 2K 2S 2O 8 + CeO 2 show that cerium undergoes changes in oxidation state from +4 to +3 and again to +4. XRD data of K 4Ce(SO 4) 4 and K 4Ce(SO 4) 3.5 were indexed on triclinic and monoclinic system, respectively. PuO 2 + 2K 2S 2O 8 reacts at 400 °C to form K 4Pu(SO 4) 4 which was stable upto 750 °C and further decomposes to form K 2SO 4 + PuO 2 at 1000 °C. The products formed at 400 °C during the reactions of the oxides and mixed oxides were found to be readily soluble in 1-2 M HNO 3.

PREPARATION OF UO$sub 2$ FOR NUCLEAR REACTOR FUEL PELLETS

DOEpatents

Googin, J.M.

1962-06-01

A method is given for preparing high-density UO/sub 2/ compacts. An aqueous uranyl fluoride solution is contacted with an aqueous ammonium hydroxide solution at an ammonium to-uranium ratio of 25: 1 to 30:1 to form a precipitate. The precipitate is separated from the- mother liquor, dried, and contacted with steam at a uniform temperature within the range of 400 to 650 deg C to produce U/ sub 3/O/sub 8/. The U/sub 3/O/sub 8/ is red uced to UO/sub 2/ with hydrogen at a uniform temperature within the range of 550 to 600 deg C. The UO/sub 2/ is then compressed into compacts and sintered. High-density compacts are fabricated to close tolerances without use of a binder and without machining or grinding. (AEC)

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 total water content of 17-18H2O per formula unit. The MgCa3F2[UO2(CO3)3]ṡ8H2O layers are pseudosymmetric according to plane group symmetry cmm. The remaining constituents do not sustain this pseudosymmetry and make the entire structure truly triclinic. A characteristic paddle-wheel motif Ca[UO2(CO3)3]4Ca relates the structure of albrechtschraufite partly to that of andersonite and two synthetic alkali calcium uranyl tricarbonates.

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

Biotic and abiotic reduction and solubilization of Pu(IV)O₂•xH₂O(am) as affected by anthraquinone-2,6-disulfonate (AQDS) and ethylenediaminetetraacetate (EDTA).

PubMed

Plymale, Andrew E; Bailey, Vanessa L; Fredrickson, James K; Heald, Steve M; Buck, Edgar C; Shi, Liang; Wang, Zheming; Resch, Charles T; Moore, Dean A; Bolton, Harvey

2012-02-21

This study measured reductive solubilization of plutonium(IV) hydrous oxide (Pu(IV)O(2)·xH(2)O((am))) with hydrogen (H(2)) as electron donor, in the presence or absence of dissimilatory metal-reducing bacteria (DMRB), anthraquinone-2,6-disulfonate (AQDS), and ethylenediaminetetraacetate (EDTA). In PIPES buffer at pH 7 with excess H(2), Shewanella oneidensis and Geobacter sulfurreducens both solubilized <0.001% of 0.5 mM Pu(IV)O(2)·xH(2)O((am)) over 8 days, with or without AQDS. However, Pu((aq)) increased by an order of magnitude in some treatments, and increases in solubility were associated with production of Pu(III)((aq)). The solid phase of these treatments contained Pu(III)(OH)(3(am)), with more in the DMRB treatments compared with abiotic controls. In the presence of EDTA and AQDS, PuO(2)·xH(2)O((am)) was completely solubilized by S. oneidensis and G. sulfurreducens in ∼24 h. Without AQDS, bioreductive solubilization was slower (∼22 days) and less extensive (∼83-94%). In the absence of DMRB, EDTA facilitated reductive solubilization of 89% (without AQDS) to 98% (with AQDS) of the added PuO(2)·xH(2)O((am)) over 418 days. An in vitro assay demonstrated electron transfer to PuO(2)·xH(2)O((am)) from the S. oneidensis outer-membrane c-type cytochrome MtrC. Our results (1) suggest that PuO(2)·xH(2)O((am)) reductive solubilization may be important in reducing environments, especially in the presence of complexing ligands and electron shuttles, (2) highlight the environmental importance of polynuclear, colloidal Pu, (3) provide additional evidence that Pu(III)-EDTA is a more likely mobile form of Pu than Pu(IV)-EDTA, and (4) provide another example of outer-membrane cytochromes and electron-shuttling compounds facilitating bioreduction of insoluble electron acceptors in geologic environments.

Laser Doppler imager (LDI) scanner and intradermal injection for in vivo pharmacology in human skin microcirculation: responses to acetylcholine, endothelin-1 and their repeatability

PubMed Central

Saez, Anabelle M Opazo; Mosel, Frank; Nürnberger, Jens; Rushentsova, U; Gössl, Mario; Mitchell, Anna; Schäfers, Rafael F; Philipp, Thomas; Wenzel, René R

2005-01-01

Aims The purpose of this study was to evaluate the repeatability of forearm skin blood flow responses to intradermal injections of acetylcholine (ACh) and endothelin-1 (ET-1) using a double injection technique (DIT) and a laser Doppler imager (LDI) scanner in the human skin microcirculation. Methods We used a laser Doppler imager (Moor LDI V3.01) to continuously monitor the change in skin blood flow during intradermal administration of physiological saline (0.9% NaCl), acetylcholine (ACh 10−7, 10−8, 10−9 M) and endothelin-1 (ET-1 10−14, 10−16, 10−18 M) in 10 healthy male subjects. Subjects were examined on 3 different days for assessment of interday and interobserver repeatability. Injections of either drug were randomly placed on different sites of the forearm. Laser Doppler images were collected before and after injection at 2.5 min intervals for 30 min. Data were analysed after the completion of each experiment using Moor Software V.3.01. Results are expressed as changes from baseline in arbitrary perfusion units (PU). Results ACh caused a significant vasodilation (P< 0.0001 anova, mean ± SE: 766 ± 152 PU, ACh 10−9 M; 1868 ± 360 PU, ACh 10−8 M; 4188 ± 848 PU, ACh 10−7 M; mean of days 1 and 2, n = 10), and ET-1 induced a significant vasoconstrictive response (P< 0.0001 anova, −421 ± 83 PU, ET-1 10−18 M; −553 ± 66 PU, ET-1 10−16 M; −936 ± 90 PU, ET-1 10−14 M; mean of days 1 and 2, n = 10). There was no difference on the response to either drug on repeated days. Bland-Altman analyses showed a close agreement of responses between days with repeatability coefficients of 1625.4 PU for ACh, and 386.0 PU for ET-1 (95% CI: ACh, −1438 to 1747 PU, ET-1, −399 to 358 PU) and between observers with repeatability coefficients of 1057.2 PU for ACh and 255.8 PU for ET-1 (95% CI: ACh, −1024 to 1048 PU, ET-1, −252 to 249 PU). The variability between these responses was independent of average flux values for both ACh and ET-1. There was a significant correlation between responses measured in the same site, in the same individual on two different days by the same observer (ACh, r = 0.94, P < 0.0001; ET-1, r = 0.90, P < 0.0006), and between responses measured by two different observers (ACh, r = 0.94, P < 0.0001; ET-1, r = 0.91, P < 0.0003). Conclusion We have shown that interday and intraobserver responses to intradermal injections of ET-1 and ACh, assessed using the DIT in combination with an LDI scanner, exhibited good reproducibility and may be a useful tool for studying the skin microcirculation in vivo. PMID:15842548

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

Probing the Oxygen Environment in UO22+ by Solid-State O-17 Nuclear Magnetic Resonance Spectroscopy and Relativistic Density Functional Calculations

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

Cho, Herman M.; De Jong, Wibe A.; Soderquist, Chuck Z.

A combined theoretical and solid-state O-17 NMR study of the electronic structure of the uranyl ion UO22+ in (NH4)4UO2(CO3)3 and rutherfordine UO2CO3 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. A fully relativistic ab initio treatment reveals unique features of the U-O covalent bond, including the finding of O-17 chemical shift anisotropies that are among the largest 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 O-17 NMR measurementsmore » 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 O-17 echo signal of UO22+. The William R. Wiley environmental Molecular Sciences Laboratory is a US Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. PNNL is operated by Battelle for the US Department of Energy.« less

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.

Reductive Dissolution of PuO2(am): The Effect of Fe(II) and Hydroquinone

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

Rai, Dhanpat; Gorby, Yuri A.; Fredrickson, Jim K.

2002-06-01

SYNOPIS-Reducing agents commonly present in geologic environments can increase solubility of PuO2(am), which is otherwise very insoluble, by many orders of magnitude through reduction of Pu(IV) to Pu(III). The reduction reactions involving Fe(II) and hydroquinone, hitherto unquantified under environmental pH values, were found to be relatively fast and controlled the extent of PuO2(am) dissolution: a decrease in redox potential (pe + pH) resulted in concomitant increase in PuO2(am) solubility.

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.

Pu isotopes in the western North Pacific Ocean before the accident at Fukushima Dai-ichi Nuclear Power Station

NASA Astrophysics Data System (ADS)

Yamada, M.; Zheng, J.; Aono, T.

2011-12-01

Anthropogenic radionuclides such as Pu-239 (half-life: 24100 yr), Pu-240 (half-life: 6560 yr) and Pu-241 (half-life: 14.325 yr) mainly have been released into the environment as the result of atmospheric nuclear weapons testing. In the North Pacific Ocean, two distinct sources of Pu isotopes can be identified; i.e., the global stratospheric fallout and close-in tropospheric fallout from nuclear weapons testing at the Pacific Proving Grounds in the Marshall Islands. The atom ratio of Pu-240/Pu-239 is a powerful fingerprint to identify the sources of Pu in the ocean. The Pu-240/Pu-239 atom ratios in seawater and marine sediment samples collected in the western North Pacific before the accident at Fukushima Dai-ichi Nuclear Power Station will provide useful background data for understanding the process controlling Pu transport and for distinguishing future Pu sources. The atom ratios of Pu-240/Pu-239 in water columns from the Yamato and Tsushima Basins in the Japan Sea were significantly higher than the mean global fallout ratio of 0.18; however, there were no temporal variation of atom ratios during the period from 1984 to 1993 in the Japan Sea. The total Pu-239+240 inventories in the whole water columns were approximately doubled during the period from 1984 to 1993 in the two basins. The atom ratio of Pu-240/Pu-239 in surface water from Sagami Bay, western North Pacific Ocean, was 0.224 and showed no notable variation from the surface to the bottom with the mean atom ratio being 0.234. The atom ratios for the Pacific coast, near the Rokkasho nuclear fuel reprocessing plant, were approximately the same as the 0.224 ratio obtained from Sagami Bay, western North Pacific margin. The atom ratios in the surficial sediments from Sagami Bay ranged from 0.229 to 0.247. The mean atom ratio in the sediment columns in the East China Sea ranged from 0.248 for the Changjiang estuary to 0.268 for the shelf edge. The observed atom ratios were significantly higher than the mean global fallout ratio of 0.180, proving the existence of close-in fallout Pu originating from the Pacific Proving Grounds. The North Equatorial Current and Kuroshio Current were proposed as pathways for transporting Pacific Proving Grounds-origin Pu to the western North Pacific Ocean.

Pu-erh Tea Reduces Nitric Oxide Levels in Rats by Inhibiting Inducible Nitric Oxide Synthase Expression through Toll-Like Receptor 4

PubMed Central

Xu, Yang; Wang, Guan; Li, Chunjie; Zhang, Min; Zhao, Hang; Sheng, Jun; Shi, Wei

2012-01-01

Pu-erh tea undergoes a unique fermentation process and contains theabrownins, polysaccharides and caffeine; although it is unclear about which component is associated with the down regulation of nitric oxide levels or how this process is mediated. To address this question we examined the effects of pu-erh tea on nitric oxide synthase (NOS) genes. Cohorts of rats were separately given four-week treatments of water as control, pu-erh tea, or the tea components: theabrownins, caffeine or polysaccharides. Five experimental groups were injected with lipopolysaccharides (LPS) to induce nitric oxide (NO) production, while the corresponding five control groups were injected with saline as a negative control. The serum and liver NO concentrations were examined and the NOS expression of both mRNA and protein was measured in liver. The results showed that the rats which were fed pu-erh tea or polysaccharides had lower levels of NO which corresponded with the down-regulation of inducible nitric oxide synthase (iNOS) expression. We further demonstrate that this effect is mediated through reduction of Toll-like receptor 4 (TLR4) signaling. Thus we find that the polysaccharide components in pu-erh tea reduce NO levels in an animal model by inhibiting the iNOS expression via signaling through TLR4. PMID:22837686

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.

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)).

NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

PubMed

Schreckenbach, Georg

2002-12-16

In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

Hydrothermal synthesis of (C6N2H14)2(UVI2UIVO4F12), a mixed-valent one-dimensional uranium oxyfluoride.

PubMed

Allen, S; Barlow, S; Halasyamani, P S; Mosselmans, J F; O'Hare, D; Walker, S M; Walton, R I

2000-08-21

A new hybrid organic-inorganic mixed-valent uranium oxyfluoride, (C6N2H14)2(U3O4F12), UFO-17, has been synthesized under hydrothermal conditions using uranium dioxide as the uranium source, hydrofluoric acid as mineralizer, and 1,4-diazabicyclo[2.2.2]octane as template. The single-crystal X-ray structure was determined. Crystals of UFO-17 belonged to the orthorhombic space group Cmcm (no. 63), with a = 14.2660(15) A, b = 24.5130(10) A, c = 7.201(2) A, and Z = 4. The structure reveals parallel uranium-containing chains of two types: one type is composed of edge-sharing UO2F5 units; the other has a backbone of edge-sharing UF8 units, each sharing an edge with a pendant UO2F5 unit. Bond-valence calculations suggest the UF8 groups contain UIV, while the UO2F5 groups contain UVI. EXAFS data give results consistent with the single-crystal X-ray structure determination, while comparison of the uranium LIII-edge XANES of UFO-17 with that of related UIV and UVI compounds supports the oxidation-state assignment. Variable-temperature magnetic susceptibility measurements on UFO-17 and a range of related hybrid organic-inorganic uranium(IV) and uranium(VI) fluorides and oxyfluorides further support the formulation of UFO-17 as a mixed-valent UIV/UVI compound.

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.

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 POLYURETHANE/NANO-SiO2 Composites Coating on Thermo-Mechanical Properties of Polyethylene Film

NASA Astrophysics Data System (ADS)

Ching, Yern Chee; Yaacob, Iskandar Idris

2011-06-01

Polyethylene (PE) film was coated with polyurethane/nanosilica composite layer using rod Mayer process. The polyurethane/nanosilica system was prepared by dispersing nanosilica powder into solvent borne polyurethane (PU) binder under vigorous stirring. The silica nanoparticle used has an average diameter of 16 nm, and their weight fraction were varied from 0 % to 14 %. Two different thicknesses of the PU/nanosilica coating layer were fabricated which were about 4 μm and 8 μm. The structure and thermal mechanical features of the nanocomposite coated PE film were characterized by scanning electron microscope (SEM), dynamic mechanical analyzer (DMA), thermogravimetric analyzer (TGA) as well as tensile tests. The results showed that thin layer coating of the PU/nanosilica composite reduced tensile strength of PE substrate slightly. However, the nanocomposite coating of up to 8 μm reduced the elongation % of PE substrate significantly. PU/nanosilica composite coating layer increased the tensile modulus and stiffness of PE substrate. There was no influence of the PU/nanosilica composite coating to the thermal degradation rate of PE film.

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

Measurement of UO2 surface oxidation using grazing-incidence x-ray diffraction: Implications for nuclear forensics

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Chen, Chien-Hung; Park, Sulgiye; Davisson, M. Lee; Ewing, Rodney C.

2018-04-01

Nuclear forensics involves determination of the origin and history of interdicted nuclear materials based on the detection of signatures associated with their production and trafficking. The surface oxidation undergone by UO2 when exposed to air is a potential signature of its atmospheric exposure during handling and transport. To assess the sensitivity of this oxidation to atmospheric parameters, surface sensitive grazing-incidence x-ray diffraction (GIXRD) measurements were performed on UO2 samples exposed to air of varying relative humidity (34%, 56%, and 95% RH) and temperature (room temperature, 50 °C, and 100 °C). Near-surface unit cell contraction was observed following exposure, indicating oxidation of the surface and accompanying reduction of the uranium cation ionic radii. The extent of unit cell contraction provides a measure of the extent of oxidation, allowing for comparison of the effects of various exposure conditions. No clear influence of relative humidity on the extent of oxidation was observed, with samples exhibiting similar degrees of unit cell contraction at all relative humidities investigated. In contrast, the thickness of the oxidized layers increased substantially with increasing temperature, such that differences on the order of 10 °C yielded readily observable crystallographic signatures of the exposure conditions.

Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

NASA Astrophysics Data System (ADS)

Carter, Korey P.; Kerr, Andrew T.; Taydakov, Ilya V.; Cahill, Christopher L.

2018-02-01

A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.

Compositional changes at the interface between thorium-doped uranium dioxide and zirconium due to high-temperature annealing

NASA Astrophysics Data System (ADS)

Youn, Young-Sang; Lee, Jeongmook; Kim, Jandee; Kim, Jong-Yun

2018-06-01

Compositional changes at the interface between thorium-doped uranium dioxide (U0.97Th0.03O2) and Zr before and after annealing at 1700 °C for 18 h were studied by X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy. At room temperature, the U0.97Th0.03O2 pellet consisted of hyperstoichiometric UO2+x with UO2 and ThO2, and the Zr sample contained Zr with ZrO2. After annealing, the former contained stoichiometric UO2 with ThO2 and the latter consisted of ZrO2 along with ZrO2·2H2O.

METHOD FOR PREPARATION OF SPHERICAL UO$sub 4$

DOEpatents

Gregory, J.F. Jr.; Levey, R.P. Jr.

1962-06-01

A method is given for continuously precipitating ura nium peroxide in the form of spherical particles. Seed crystals are formed in a first reaction zone by introducing an acidified aqueous uranyl nitrate solution and an aqueous hydrogen peroxide solution at a ratio of 5 to 20 per cent of the stoichiometric amount required for complete precipitation. After a mean residence time of 2 to 5 minutes in the first reaction zone, the resulting mixture is introduced into a second reaction zone, together with a large excess of hydrogen peroxide solution. The resulting UO4 is rapidly separated from the mother liquor after an over-all residence time of 5 to 11 minutes. The first reaction is maintained at a temperature of 85 to 90 deg C and the second zone above 50 deg C. Additional reaction zones may be employed for further crystal growth. The UO/sub 4/ is converted to U/sub 3/O/sub 8/ or UO/sub 2/ by heating in air or hydrogen atmosphere. This method is particularly useful for the preparation of spherical UO/sub 2/ particles 10 to 25 microns in diameter. (AEC)

PREVENTION OF POLYURETHANE OXIDATIVE DEGRADATION WITH PHENOLIC-ANTIOXIDANTS COVALENTLY ATTACHED TO THE HARD SEGMENTS: STRUCTURE FUNCTION RELATIONSHIPS

PubMed Central

Stachelek, Stanley J; Alferiev, Ivan; Ueda, Masako; Eckels, Edward C.; Gleason, Kevin T.; Levy, Robert J

2010-01-01

Oxidative degradation of the polyurethane elastomeric (PU) components greatly reduces the efficacy of PU containing cardiovascular devices. Covalently appending the phenol-based antioxidant, 4-substituted 2,6-di-tert-butylphenol (DBP), to PU hard segments effectively reduced oxidative degradation of the PU in vivo and in vitro in prior studies by our group. In these experiments we analyze the contribution of the tethering molecule to the antioxidant capabilities of the DBP modified PU. Bromoalkylation chemistry was used to link DBP to the hard segment of the polyether polyurethane, Tecothane, via our original linker (PU-DBP), or variants containing side chains with 1 (PU-C-DBP) or 3 (PU-3C-DBP) carbons. Two additional DBP variants were fabricated in which the DBP group was appended to the alkyl chain via an oxygen atom (PU-O-DBP) or an amide linkage in the middle of the tether (PU-NHCO-DBP). All DBP variant films and unmodified control films were subject to oxidative degradation via 15 day immersion in a solution of 20% H2O2 + 0.1 M CoCl2. At the end of the oxidation protocol films were analyzed for the presence of oxidation related endpoints via scanning electron microscopy, contact angle measurements and Fourier transformation infrared spectroscopy (FTIR). All DBP containing variants resisted oxidation damage significantly better than the unmodified control PU. SEM analysis of oxidized PU-C-DBP and PU-O-DBP showed evidence of surface cracking consistent with oxidative degradation of the PU surfaces. Similarly there was a trend in increased ether cross-linking, a marker for oxidative degradation, in PU-C-DBP and PU-NHCO-DBP films. Consistent with these FTIR results, both PU-C-DBP and PU-NHCO-DBP had significant reductions in measured surface hydrophobicity as a result of oxidation. These data show for the first time that the choice of linker molecule significantly affects the efficiency of the linked phenolic antioxidant. PMID:20306526

Spermicidal activity of some halides.

PubMed

Narayan, J P; Singh, J N

1979-01-01

Though most of the metallic ions are spermicidal in action, the present investigation emphasises the spermicidal activity of anions. Among the inorganic compounds screened at 4 concentrations (0.01%, 0.1%, 1% and 5%) halides are mainly spermicidal, except NaCl, KCl & CsCl which are spermiostatic; sulphates and nitrates are mainly spermiostatic except ZnSO4 at 1% concentration and above; CuSO4, Al2 (SO4)3, Uo2(NO3)2.6H2O and AgNO3 at 5% concentration where they become spermicidal.

Canadian experience in irradiation and testing of MOX fuel

NASA Astrophysics Data System (ADS)

Yatabe, S.; Floyd, M.; Dimayuga, F.

2018-04-01

Experimental irradiation and performance testing of Mixed OXide (MOX) fuel at the Canadian Nuclear Laboratories (CNL) has taken place for more than 40 years. These experiments investigated MOX fuel behaviour and compared it with UO2 behaviour to develop and verify fuel performance models. This article compares the performance of MOX of various concentrations and homogeneities, under different irradiation conditions. These results can be applied to future fuel designs. MOX fuel irradiated by CNL was found to be comparable in performance to similarly designed and operated UO2 fuel. MOX differs in behaviour from UO2 fuel in several ways. Fission-gas release, grain growth and the thickness of zirconium oxide on the inner sheath appear to be related to MOX fuel homogeneity. Columnar grains formed at the pellet centre begin to develop at lower powers in MOX than in UO2 fuel.