UxTh1-x(C2O4)2 Solid Characterisation Studies

Many advanced reprocessing schemes under development are aimed at co-processing and co-conversion of actinides, unlike current reprocessing plants that produce separate uranium and plutonium products. The most well developed option for the co-conversion stage is probably oxalate co-precipitation, followed by the thermal co-conversion to a mixed oxide product. It is thus envisaged that future processes will avoid separation of plutonium from uranium and instead allow part of the uranium to flow with the plutonium, resulting in co-precipitation as the oxalate, and finally co-conversion to a mixed uranium-plutonium oxide (MOX), which can be fabricated into recycled nuclear fuel for further energy generation.The co-crystallisation of uranium (IV) and plutonium (III) into a single oxalate structure ensures the homogenous distribution of the two actinides at the molecular scale. The joint conversion of uranium and plutonium to the oxide form makes it possible to remove the complicated step of blending and grinding the two distinct oxide powders, as currently employed for the purposes of MOX fuel fabrication. This concept can also be extended to other actinides, including minor actinides from partitioning processes such as SANEX (Selective Actinide Extraction) and GANEX (Grouped Actinide Extraction) processes or even a thorium containing product from recycle of thorium based fuels.A selection of U_xTh_1-x(C₂O₄)₂ solids at varying concentrations of uranium and thorium were prepared by oxalate co-precipitation. Uranium (VI) was conditioned electrochemically at -0.7 V to uranium (IV), in the presence of hydrazine. The reduced uranium (IV) in nitric acid was mixed with thorium nitrate solutions at different concentration ratios with oxalic acid. The mixed tetravalent uranium-thorium oxalate solid products have been characterised by Raman and IR spectroscopies. The influence of thorium substituted into the uranium oxalate structure was evaluated. Several vibrational modes were found to be affected by the variation in ionic radius appearing to be metal sensitive and therefore, provide the initial indication in the evaluation of the chemical composition.     

Structural relationships,crystal chemistry and anion substitution processes for M(III)X3 systems of the lanthanides and actinides

An examination of data for lanthanide and actinide phases with UCl₃-type and PuBr₃-type M(III)X₃ structures has shown that these systems are conveniently described by alternating layers of [MX₂]ⁿ⁺_n and [X]^n?_n. The relationships between the UCl₃- and PuBr₃-type structures are described and expanded to include a variety of anion substitution systems, M(III)X_3?xY_x. The two different types of [MX₂]ⁿ⁺_n layers observed in these systems are consistent with the existence of a novel structural unit, [M₂X₄]²⁺. The effects of radius ratio constraints and layering mechanisms on the phase equilibria and anionic substitution processes, polymorphism and crystal growth in the MX_3?xY_x systems are discussed.     

Quantitation of major elements with secondary ion mass spectrometry by using M 2 + -molecular ions

A new quantitation method, based on the detection of M ₂ ⁺ molecular ions, is presented. It has been shown that M ₂ ⁺ molecular ions are formed by a recombination process between independently sputtered M and M⁺ particles. Based on this formation mechanism, it will be demonstrated that M ₂ ⁺ molecular ions can be used to quantitate major elements. The method will be used for quantitation of an Al _x Ga_1?x As multilayer. Furthermore, it will be shown that some matrix effects can be explained by the energy dependence of instrument transmission.     

U(IV)/Ln(III) unexpected mixed site in polymetallic oxalato complexes. Part I. Substitution of Ln(III) for U(IV) from the new oxalate (NH4)2U2(C2O4)5·0.7H2O

A new ammonium uranium (IV) oxalate (NH₄)₂U₂(C₂O₄)₅·0.7H₂O (1) and three mixed uranium (IV)-lanthanide (III) oxalates, (N₂H₅)_2.6U_1.4M_0.6(C₂O₄)₅·xH₂O (M=Nd (2) and M=Sm (3)), Na_2.56U_1.44Nd_0.56(C₂O₄)₅·7.6H₂O (4) and Na₃UCe(C₂O₄)₅·10.4H₂O (5), have been prepared. The crystal structures of compounds 1, 4 and 5 have been determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least square method on the basis of F² for all unique reflections. Compounds 2 and 3 are isotypic with 1. Crystallographic data: 1, hexagonal, space group P6₃/mmc, a=19.177(3), c=12.728(4) Å, Z=6, R₁=0.0575 for 52 parameters with 1360 reflections with I?2σ(I); 2, hexagonal, space group P6₃/mmc, a=19.243(4), c=12.760(5) Å, Z=6; 3, hexagonal, space group P6₃/mmc, a=19.211(3), c=12.274(4) Å, Z=6; 4, orthorhombic, space group Pbcn, a=18.79(3), b=11.46(1), c=12.77(2) Å, Z=4, R₁=0.0511 for 183 parameters with 3026 reflections with I?2σ(I); 5, monoclinic, space group C2/c, a=18.878(6), b=11.684(4), c=12.932(4) Å, β=95.97(1)°, Z=4, R₁=0.0416 for 213 parameters with 4060 reflections with I?2σ(I). The honeycomb-like structure of the five compounds is built from the same three-dimensional arrangement of metallic and oxalate ions. Similar hexagonal rings of alternating metallic and oxalate ions form layers parallel to the (001) plane that are pillared by another oxalate ion. Indeed, some torsions or rotations of the bridging oxalate ligands led to modifications of the network symmetry. The monovalent cations and the water molecules occupy the hexagonal tunnels running down the [001] direction. Starting from the uranium (IV) compound A₂U₂(C₂O₄)₅·0.7H₂O with A=NH₄⁺ (1), the mixed U(IV)/Ln(III) oxalates are obtained by partial substitution of U(IV) by Ln(III) in a ten-coordinated site, the charge deficit being compensated by intercalation of supplementary monovalent ions within the tunnels. The distortion of the arrangement in the [001] direction for the Na-containing compounds allows the accommodation of a greater number of water molecules that insure an octahedral coordination of the Na atoms.     

Kinetics of replacement of bridging ligands in a diruthenium(II,III) cation

Tetrakis-μ-propionatodiruthenium(II,III) cation reacts with oxalate, in acidic aqueous solution (0.10 M LiCF₃SO₃, [H⁺] 0.01 M at 29.4°C) in a two-phase process. An initial rapid change results in a small decrease in absorbance. This is ascribed to replacement of one propionate ligand by oxalate. A subsequent slower reaction, of which the rate is proportional to added oxalate concentration (k_bi 1.3 M⁻¹ s⁻¹), corresponds to a relatively large increase of absorbance at 475 nm, the absorbance maximum of the product. The data indicate formation of a bis(μ-oxalato)bis(μ-propionato)diruthenium(II,III) anion with a formation constant K_f > 2 x 10⁴ M⁻¹ and an extinction coefficient of 1.3 x 10³ M⁻¹ cm⁻¹ at 475 nm. A third, much slower, change results in decomposition of that product. The occurrence of replacement of bridging ligands under mild conditions indicates that tris-μ-carboxylatodiruthenium(II,Ill) species (otherwise unknown) function as kinetic intermediates.     

Fe x Ti1−2x M x O2 (M=Nb,Ta) rutile solid solutions from gels

In this study, Fe _x Ti_1–2x M _x O₂ (M=Nb, Ta) rutile solid solutions have been synthesized from gels made from Fe(III) acetylacetonate, NbCl₅, TaCl₅, Ta(V) ethoxide, TiCl₄ and Ti(IV) isopropoxide. The results obtained are compared with those obtained by the ceramic method. The solid solutions synthesized from gels were obtained at lower temperatures than these synthesized by the ceramic method.     

Ion polarisation-assisted hydrogen-bonded ferroelectrics in liquid crystalline domains

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal. The introduction of simple M⁺X⁻ salts such as Na⁺PF₆⁻ and K⁺I⁻ into the ionic channel of 1 enhanced the ionic conductivity of the Col_h phase of the M⁺·(1)·X⁻ salts, with the highest ionic conductivity reaching ∼10⁻⁶ S cm⁻¹ for K⁺·(1)·I⁻ and Na⁺·(1)·PF₆⁻ at 460 K, which was approximately 5 orders of magnitude higher than that of 1. The introduction of non-ferroelectric 1 into the ferroelectric N,N′,N′′-tri(tetradecyl)-1,3,5-benzenetricarboxamide (3BC) elicited a ferroelectric response from the mixed Col_h phase of (3BC)_x(1)_1−x with x = 0.9 and 0.8. The further doping of M⁺X⁻ into the ferroelectric Col_h phase of (3BC)_0.9(1)_0.1 enhanced the ferroelectric polarisation assisted by ion displacement in the half-filled ionic channel for the vacant dibenzo[18]crown-6 of (3BC)_0.9[(M⁺)_0.5·(1)·(X⁻)_0.5]_0.1.

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal.     

Evaluation of cation influence on the formation of M(II)Cr2O4 during the thermal decomposition of mixed carboxylate type precursors

This paper reports an investigation regarding the influence of the cation M(II) (M = Zn, Ni, Mg) on the formation of MCr₂O₄ by thermal decomposition of the corresponding M(II),Cr(III)-carboxylates (precursors) obtained by redox reaction between the corresponding metal nitrates and 1,3-propanediol. The decomposition products at different temperatures have been characterized by FT-IR spectroscopy and thermal analysis. Thus, we have evidenced that by thermal decomposition of the studied precursors in the range 250–300 °C, different amorphous oxidic phases mixtures form depending on the nature of metalic cation: (Cr₂O_3+x + ZnO) (Cr₂O_3+x + Ni/NiO) and (Cr₂O_3+x+MgO). In case of M = Zn, around 400 °C when the transition Cr₂O_3+x to Cr₂O₃ takes place, zinc chromite nuclei form by the interaction ZnO with Cr₂O₃. In case of M = Ni, due to the partial reduction of Ni(II) at Ni(0) during the thermal decomposition of the precursor the formation of nickel chromite by the reaction NiO + Cr₂O₃ is shifted toward 500 °C, when Ni is oxidized at NiO. The thermal evolution of the mixture (MgO + CrO₃) is different due to the formation as intermediary phase of MgCrO₄, which decomposes to MgCr₂O₄ around 560 °C. In order to investigate the chromites formation mechanism, we have studied the mechanical mixtures of single oxides obtained from the corresponding carboxylates. These mixtures (MO + Cr₂O₃) have been annealed at 400, 500, and 600 °C to study the evolution of the crystalline phases. It results in the prepared mixture behaving different from the mixtures obtained by thermal decomposition of the binary M(II),Cr(III)-carboxylates, recommending our synthesis method for obtaining binary oxides.     

Lithium-substituted cobalt oxide spinels LixM1−xCo2O4 (M = Co2+, Zn2+; 0 ≤ x ≤ 0.4)

Substitution of Li⁺ into Co₃O₄ and ZnCo₂O₄ gives rise to the solid solution series Li_xM_1?xCo₂O₄ (M = Co²⁺ or Zn²⁺) having the spinel structure upto x = 0.4. X-Ray diffraction intensities show that the spinel solid solutions are likely to have the following cation distributions: (Co²⁺)_t[Li⁺_xCo³⁺_2?3xCo⁴⁺_2x]₀O₄ and (Zn²⁺_1?xCo²⁺_x)_t[Li⁺_xCo³⁺_2?3xCo⁴⁺_2x]₀O₄. Electrical resistivity and Seebeck coefficient data indicate that the electron transport in these systems occurs by a small-polaron hopping mechanism.     

Two Hexagonal Series of Lanthanoid(III) Oxide Fluoride Selenides: M6O2F8Se3 (M = La – Nd) and M2OF2Se (M = Nd,Sm, Gd – Ho)

Two hexagonal series of lanthanoid(III) oxide fluoride selenides with similar structure types can be obtained by the reaction of the components MF₃, M₂O₃, M, and Se in sealed niobium tubes at 850 °C using CsI as fluxing agent. The compounds with the lighter and larger representatives (M = La – Nd) occur with the formula M₆O₂F₈Se₃, whereas with the heavier and smaller ones (M = Nd, Sm, Gd – Ho) their composition is M₂OF₂Se. For both systems single‐crystal determinations were used in all cases. The compounds crystallize in the hexagonal crystal system (space group: P6₃/m) with lattice parameters of a = 1394–1331 pm and c = 403–372 pm (Z = 2 for M₆O₂F₈Se₃ and Z = 6 for M₂OF₂Se). The (M1)³⁺ cations show different square antiprismatic coordination spheres with or without an extra capping fluoride anion. All (M2)³⁺ cations exhibit a ninefold coordination environment shaped as tricapped trigonal prism. In both structure types the Se^2– anions are sixfold coordinated as trigonal prisms of M³⁺ cations, being first condensed by edges to generate trimeric units and then via faces to form strands running along [001]. The light anions reside either in threefold triangular or in fourfold tetrahedral cationic coordination. For charge compensation, both structures have to contain a certain amount of oxide besides fluoride anions. Since F^– and O^2– can not be distinguished by X‐ray diffraction, bond‐valence calculations were used to address the problem of their adjunction to the available crystallographic sites.     

Cation transport at 25°c from binary Tl+Mn+ and K+Mn+ nitrate mixtures in a H2OCHCl3H2O liquid membrane system containing a series of macrocyclic polyether carriers

Carrier-mediated cation fluxes were determined using a H₂OCHC1₃H₂O liquid merebrane system for TlNO₃ and for binary mixtures of either TlNO₃ or KNO₃ with alkali metal ions, alkaline earth metal ions, and Pb²⁺ (in the case of TlNO₃). Both macrocyclic polyether and cryptand ligands were used as carriers. In Tl⁺Mⁿ⁺ mixtures, selective transport of Tl⁺ was found over all cations studied, except in the cases of Ag⁺ by 2.2 and of Pb²⁺ by 18C6, DC18C6, ClDKP18C6, and 2.2. Generally, K⁺ was transported selectively from K⁺Mⁿ⁺ mixtures, except in the cases of K⁺Tl⁺ mixtures in which Tl⁺ was transported selectively in all cases. A model relating cation flux to log K(CH₃OH) for Mⁿ⁺—macrocycle interaction and to ion-partitioning between the organic and aqueous phases was successful in rationalizing selective cation transport in most of the systems studied.     

Hexagonal-spinel transitions in antimonates Li2Cr3−xMIIIxSbO8 (MIII = Al,Fe, Ga)

A new family of antimonates Li₂Cr_3?xM^III_xSbO₈ (M^III = Al, Fe, Ga) was synthesized and studied by X-ray diffraction and ir spectroscopy. The Al-containing compounds exhibit a hexagonal close-packed structure similar to that of LiFeSnO₄ ($\text{a ? 5.8, c ? 9.5}$ Å. For M = Fe or Ga, two structural forms are isolated: a low-temperature hexagonal form which is isotypic with LiFeSnO₄ and a high-temperature cubic form isotypic with the spinel structure. The hexagonal spinel transformation was observed for the first time, while the reverse transformation cannot be obtained.     

Thermodynamic Model for the Solubility of TcO2· xH2O(am) in the Aqueous Tc(IV) – Na+ – Cl− – H+ – OH− – H2O System

Solubility studies of TcO₂· xH₂O(am) have been conducted as a function of H⁺ concentration from 1 × 10^{– 5} to 6 M HCl and as a function of chloride concentration from 1 × 10^{– 3} to 5 M NaCl. These experiments were conducted under carefully controlled reducing conditions such that the preponderance of Tc present in solution is in the reduced oxidation state and was determined to be Tc(IV) by XANES analysis. The aqueous species and solid phases were characterized using a combination of techniques including thermodynamic analyses of solubility data, XRD, and XANES, EXAFS, and UV-vis spectroscopies. Chloride was found to significantly affect Tc(IV) concentrations through (1) the formation of Tc(IV) chloro complexes [i.e., TcCl₄(aq) and TcCl₆ ^{2 –}] and a stable compound [data suggests this compound to be TcCl₄(am)] in highly acidic and relatively concentrated chloride solutions, and (2) its interactions with the positively charged hydrolyzed Tc(IV) species in solutions of relatively low acidity and high chloride concentrations. A thermodynamic model was developed that included hitherto unavailable chemical potentials of the Tc(IV)–chloro species and Pitzer ion-interaction parameters for Tc(IV) hydrolyzed species with bulk electrolyte ions used in this study. The thermodynamic model presented in this paper is consistent with the extensive data reported in this study and with the reliable literature data and is applicable to a wide range of H⁺ and Cl^– concentrations and ionic strengths.     

Substitution mechanism and structural study of Ag-doped LiCu2O2

Plate-like stoichiometric crystals of Ag-doped LiCu₂O₂ have been grown by slowly cooling Li₂CO₃·4(1 – x)CuO·4xAgNO₃ (0 ≤ x ≤ 0.5) melts. X-ray single crystal diffraction has shown that the crystals are isostructural with LiCu₂O₂ and contain around 5 at % Ag (relative to the Cu atoms). The addition of silver to lithium cuprate crystals significantly increases their electrical conductivity but has little effect on the temperature behavior of their magnetic moment. The possible substitution mechanism is determined which supports Ag⁺ ↔ Cu⁺, rather than Ag⁺ ↔ Li⁺ in the Ag-doped LiCu₂O₂ crystals.     

The Crystal Chemistry of Lithium in the Alluaudite Structure: A Study of the (Na1−xLix)CdIn2(PO4)3 Solid Solution (x=0 to 1)

Several compounds of the (Na_1−xLi_x)CdIn₂(PO₄)₃ solid solution were synthesized by a solid-state reaction in air, and pure alluaudite-like compounds were obtained for x=0.00, 0.25, and 0.50. X-ray Rietveld refinements indicate the occurrence of Cd²⁺ in the M(1) site, and of In³⁺ in the M(2) site of the alluaudite structure. This non-disordered cationic distribution is confirmed by the sharpness of the infrared absorption bands. The distribution of Na⁺ and Li⁺ on the A(1) and A(2)′ crystallographic sites cannot be accurately assessed by the Rietvled method, probably because the electronic densities involved in the Na⁺→Li⁺ substitution are very small. A comparison with the synthetic alluaudite-like compounds, (Na_1−xLi_x)MnFe₂(PO₄)₃, indicates the influence of the cations occupying the M(1) and M(2) sites on the coordination polyhedra morphologies of the A(1) and A(2)′ crystallographic sites.     

Influence of a doubly charged cation nature on the formation and properties of mixed oxides MAlO x (M = Mg2+, Zn2+, Ni2+) obtained from the layered hydroxide precursors

Influence of the nature of a doubly charged cation in the layered double hydroxides (LDH) on the conditions of formation and properties of mixed oxide phase MAlO _x (M = Mg²⁺, Zn²⁺ and Ni²⁺), its ability to reconstruct the structure of the original precursor under contact with water has been studied. Hydrotalcite-like compounds and corresponding oxides with different M²⁺: M³⁺ ratio were investigated by XRD, TEM, TG-DTG-DTA, ²⁷Al NMR, N₂ adsorption, and differentiating dissolution. It has been found that the nature of the cation M²⁺ influences the conditions of LDH thermal decomposition, structural and textural characteristics of the formed mixed oxides. The obtained data can be used to synthesize the oxide supports with desired acid-base and adsorption properties.     

The influence of Ni2+ lons on the distribution of Mg2+ and Cu2+ lons in spinel ferrites

Cation distribution in quenched and furnace-cooled samples of composition Ni_xM_1?xFe₂O₄ (where M is either Mg²⁺ or Cu²⁺) has been studied through magnetization measurements. It has been found that cation distribution in these mixed ferrites cannot be predicted by site preference energies. In magnesium-nickel ferrites, cation distribution is controlled by heat treatment up to x = 0.5, beyond which the effect of heat treatment diminishes. Addition of Ni²⁺ ions in copper ferrite reduces the diffusibility of Cu²⁺ ions and the distribution tends toward inverse spinel in the high-nickel region.     

Actinide incorporation in a zirconia based pyrochlore (Nd1.8An0.2)Zr2O7+x (An=Th, U, Np, Pu, Am)

Actinides (thorium, uranium, neptunium, plutonium, and americium) were infiltrated into a porous Nd_1.8Zr₂O_6.7 matrix, prepared by gel-supported precipitation. (Nd_1.8An_0.2)Zr₂O_7+x pyrochlores were formed after sintering in Ar/H₂ and the pyrochlore structure remains during oxidation at 800 °C in air. X-ray diffraction reveals a linear relationship between the pyrochlore lattice parameter and the ionic radii of the actinides. EXAFS measurements on actinide L₃-edge show a split shell of nearest neighbour oxygen atoms similar to that surrounding of Nd. The actinide-oxygen bond distances decrease with the actinide ionic radii, which verifies that these actinides adopt the Nd site in the (Nd_1.8An_0.2)Zr₂O_7+x pyrochlore. The oxidation susceptibility of Np is related to the availability of oxygen vacancies and in contrast to stabilised zirconia Np(V) can be obtained in zirconia based pyrochlore.     

Comparative analysis of solubility in CuCl-MCl-H2O systems at 25°C (M+ = Li+, Cs+, NH 4 + )

Solubility in the ternary system CuCl-NH₄Cl-H₂O at 25°C was determined by the method of isothermal lifting of oversaturation. A comparative analysis of solubility in this system and the previously studied systems CuCl-MCl-H₂O (M⁺ = Li⁺, Na⁺, K⁺, Cs⁺) was made. The results obtained were interpreted in terms of competition between hydration, association, and complexation processes in water-salt systems.     

Studies regarding the formation from metal nitrates and diol of NiM 2 III O4 spinels, inside a silica matrix

The present study deals with preparation and characterization of spinel mixed oxide systems NiM ₂ ^III O₄, where M^III?=?Fe^III, Cr^III. In order to obtain 50% NiFe₂O₄/50% SiO₂ and 50% NiCr₂O₄/50% SiO₂ nanocomposite, we have used a versatile route based on the thermal decomposition inside the SiO₂ matrix, of some particular precursors, coordination compounds of the involved M^II and M^III cations with dicarboxylate ligands. The ligands form in the redox reaction between metal nitrates mixture and 1,3-propanediol at the heating around 140?°C of the gels (tetraethylorthosilicate?Cmetal nitrates?C1,3-propanediol?Cwater). The as-obtained precursors, embedded in silica gels, have been characterized by FT-IR spectrometry and thermal analysis. Both precursors thermally decompose up to 350?°C leading to the formation of the corresponding metal oxides inside the silica matrix. X-ray diffraction of the annealed powders have evidenced the formation of NiFe₂O₄ starting with 600?°C, and NiCr₂O₄ starting with 400?°C. This behavior can be explained by the fact that, by thermal decomposition of the Fe(III) carboxylate at 300?°C, the spinelic phase ??-Fe₂O₃ is formed, which interacts with the NiO, forming the ferrite nuclei. By thermal decomposition of chromium carboxylate, a nonstoichiometric chromium oxide (Cr₂O_3+x ) is formed. In the range 380?C400?°C, Cr₂O_3+x turns into Cr₂O₃ which immediately interacts with NiO leading to the formation of nickel chromites nuclei inside the pores of silica matrix. Both spinels have been obtained as nanocrystalites homogenously dispersed as resulted from XRD and TEM data.