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.     

Intermetallics and alloys of transplutonium elements with metals of the platinum group

Americium and curium alloys with palladium and platinum containing up to 20% of actinide were prepared by the coupled reduction technique. The alloys obtained were investigated by X-ray, differential thermal analysis and metallography. Phase diagram sections for Pd–Am, Pd–Cm, Pt–Am and Pt–Cm systems have been constructed. Intermetallics Pt₅An (An=²⁴³Am,²⁴⁴Cm,²⁴⁹Bk,²⁴⁹Cf), Ir₂ ²⁴⁹Bk and Rh₃ ²³⁹Bk were obtained as thin layers on the surfaces of metallic substrates. X-ray investigation has shown that Pt₅An compounds have hexagonal structures of the Cu₅Ca-type, Ir₂Bk- cubic lattice of the Cu₂Mg-type and Rh₃Bk intermetallic has fcc lattice of the Cu₃Au-type. The influence of intensive -decay of transplutonium nuclides on the crystal structure of the intermetallics prepared has been investigated.     

Preparation of actinide targets for the synthesis of the heaviest elements

The heaviest elements are synthesized in heavy-ion induced hot fusion reactions with various actinide targets. Because the actinide material is often available only in very limited amounts, a deposition method with high yields (~90 %) is needed. We report on the production of ²⁴⁴Pu, ²⁴³Am, ²⁴⁸Cm, ²⁴⁹Bk, and ²⁴⁹Cf targets on thin Ti backings by molecular plating. Different chemical purification steps using ion chromatographic techniques were applied for the purification of ²⁴⁹Cf and ²⁴⁴Pu. The deposition procedure applied for the production of ~0.4–0.8 mg/cm² thick targets is described. The deposition yield was determined either by α-particle or γ-ray spectroscopy. Furthermore, neutron activation analysis has been applied in the case of ²⁴⁴Pu, ²⁴³Am, and ²⁴⁸Cm. Information about the spatial distribution and homogeneity of the target layer was obtained by radiographic imaging.     

Maximum filling principle and sublattices of actinide atoms in crystal structures

The most important characteristics of the Voronoi-Dirichlet polyhedra (VDP) of A atoms (A is actinide) in chemically homogeneous sublattices in the crystal structures of 3479 inorganic, coordination, and organometallic compounds are determined. The effect of the actinide nature on the A-A interatomic distances in the crystal structures is considered. In the Th, U, Np, or Pu sublattices, VDP have most often 14 faces and the Fedorov cuboctahedron is the most abundant type of VDP, whereas in Ac, Pa, Am, Cm, Bk, or Cf sublattices, the VDP have mainly 12 faces and are shaped like rhomobododecahedra. In A sublattices that typically form VDP with 14 faces, the actinide atoms occupy, most often, sites with C ₁ symmetry (47 to 59% of the sample size). In the case of actinides whose A sublattices tend to form VDP with 12 faces, the C ₁ site symmetry is found either very rarely (Pa, Am, Cf) or not at all (Ac, Cm, Bk).     

Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

The chemistry of trivalent transplutonium ions (Am³⁺, Cm³⁺, Bk³⁺, Cf³⁺, Es³⁺…) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. Herein, we present the first extended X‐ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest‐neighbor bond lengths in the case of Cf³⁺. Corroborating those results, density functional theory calculations, extended to Es³⁺, suggest that the shorter Cf?O and Es?O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [M^IIIDTPA(H₂O)]^2? (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.     

O NMR studies of local structure and phase evolution for materials in the Y2Ti2O7-ZrTiO4 binary system

¹⁷O MAS NMR and XRD studies of precursor-derived Y_1.6Zr_0.4Ti₂O_7.2 and Y_1.2Zr_0.8Ti₂O_7.4 have been performed to investigate the development of local and long-range order in these materials as they evolve from a metastable amorphous state upon heating. Zirconium titanate (ZrTiO₄) was also investigated to help interpret the ¹⁷O NMR spectra of the ternary compositions. Consistent with earlier studies, crystallization was observed at 800 °C to form a fluorite structure and a small amount of rutile; weak broad reflections were also observed which were ascribed to the presence of small pyrochlore-like ordered domains or particles within the fluorite phase. As the temperature was increased further, the sizes of these domains grew along with the concentration of rutile. At the highest temperature studied (1300 °C), the reflections of the thermodynamic phases, pyrochlore and zirconium titanate (ZrTiO₄), dominated the XRD pattern. The ¹⁷O NMR spectra revealed a series of different peaks that were assigned to different 3- and 4-coordinate O local environments. The data were consistent with the formation of a metastable phase Y_2−xZr_xTi_2−yZr_yO_7+x with pyrochlore-like ordering but with Zr substitution on both cation sites of the pyrochlore structure. At low temperatures, doping on the A (Y³⁺) sites predominates (i.e., x>y), consistent with the fact that the pyrochlore develops out of a more disordered fluorite-like, phase. As the temperature is raised, the Zr doping on the A site decreases and the metastable phase at this temperature can now be written as Y_2−x′Zr_x′Ti_2−y′Zr_y′O_7+x′ (i.e., x′<y′); TiO₂ is also observed, consistent with this suggestion. At high temperatures, doping on the B site decreases and the resonances due to the stoichiometric pyrochlore yttrium titanate (Y₂Ti₂O₇) dominate the NMR spectra. Weaker ¹⁷O NMR resonances due zirconium titanate (ZrTiO₄) are also observed.     

Order-disorder transition in the Nd2−yYyZr2O7 system: Probed by X-ray diffraction and Raman spectroscopy

A series of compositions having the general formula Nd_2−yY_yZr₂O₇ have been synthesized by heating of mixtures of oxides of the components cation and characterized by X-ray diffraction and Raman spectroscopy. Rietveld analysis on the XRD data of all the compositions has been performed which revealed a decrease in lattice parameter as a function of y in the series Nd_2−yY_yZr₂O₇ (y=0.0-0.8). Subsequently, a biphasic region starts which continues for y=1.2 and 1.6. The other end member, i.e. Y₂Zr₂O₇ is found to be defect fluorite. On the other hand, Nd³⁺ has been used as surrogate material for Am³⁺, which is a minor actinide found in spent nuclear fuel. In the pyrochlore range, the increasing trend of the x-parameter of 48f oxygen indicates the enhancement of disorder in the system. Raman spectroscopy has been employed to validate the data obtained from XRD. The involvement of 48f oxygen in disorder has also been verified by Raman spectroscopic investigation.     

The fluorite-pyrochlore transformation of Ho2−yNdyZr2O7

Twelve members of the Ho_2−yNd_yZr₂O₇ series, prepared using conventional solid state methods, have been characterised by neutron powder diffraction. Ho₂Zr₂O₇ has a defect fluorite structure whereas Nd₂Zr₂O₇ is found to adopt the ordered pyrochlore structure with the composition induced fluorite-pyrochlore transformation occurring near y=1. Rietveld analysis on the neutron data for all the compositions reveals an increase in lattice parameter as a function of y across the entire series, with a small discontinuity associated with the transformation. The neutron profile results suggest that domains of pyrochlore-type initially begin to form before crystallising into a separate phase, and therefore that anion and cation ordering processes are distinct. There is a strong correlation between the extent of disorder in the anion sublattice and the x-parameter of 48f oxygen. These results point the way to a better understanding of the stability observed in pyrochlore structures.     

Order-disorder transition in Nd2−yGdyZr2O7 pyrochlore solid solution: An X-ray diffraction and Raman spectroscopic study

Powder X-ray diffraction (XRD) and Raman spectroscopic study of order-disorder-phase transition with increase in the content of Gd in Nd_2−yGd_yZr₂O₇ solid solution is being reported. It has been observed from Rietveld analysis that with increase in concentration of Gd in Nd_2−yGd_yZr₂O₇, the value of the x parameter of the 48f oxygen changes from 0.332(1) to 0.343(1) with a sudden change in the slope for y=1.8, which indicates that the structure is transforming from ordered pyrochlore to disordered pyrochlore. In addition to that a sudden and drastic change in the Raman spectra including changes in the position and width of several Raman modes beyond y?1.8 has also been observed which has been correlated with increasing disorder. Based on these studies, it is suggested that there is a discontinuous order-disorder transition from ‘perfect pyrochlore’ to ‘defect pyrochlore’ phase in Nd_2−yGd_yZr₂O₇ solid solution.     

Preparation of rare metallic actinides (248Cm,249Bk,249Cf) and investigation of their crystal structure

²⁴⁸Cm and²⁴⁹Bk metals were prepared by thermal reduction of their oxides with thorium and metallic²⁴⁹Cf with metallic lanthanum. These rare actinide samples of 1.0 mg in mass were thin layers on a flat substrate and were investigated by X-ray technique. Dhcp lattice parameters of -Cm, -Bk and -Cf as main phases in X-ray diagrams are presented. The effect of impurities on the -Cm lattice parameters is shown. Fcc lattices for the high temperature form of Cm metal (-Cm) with a=0.4933 nm, and of Cm and Bk monoxides (a=0.502–0.504 nm and a=0.5002 nm, respectively) have been observed. Thermal expansion coefficients for -Cm and -Bk at 80–300 K were calculated. Identification problems of fcc lattices and oxidation features of metals prepared are discussed.     

Correlation of crystal structures with electric field gradients in the fluorite- and pyrochlore-type compounds in the Gd2O3-ZrO2 system

Correlation of crystal structure with electric field gradient (EFG) in the fluorite- and pyrochlore-type compounds in the Gd₂O₃-ZrO₂ system Gd_xZr_1−xO_2−x/2 with 0.18?x?0.62 were investigated by ¹⁵⁵Gd Mössbauer spectroscopy, powder X-ray diffraction and point-charge model (PCM) calculation. An intermediate ordered pyrochlore phase forms for 0.45?x?0.55, sandwiched with a disordered fluorite phase for 0.18?x<0.45 and 0.55<x?0.62. Some ¹⁵⁵Gd Mössbauer parameters, especially the quadrupole coupling constant (e²qQ), were found to exhibit a characteristic maximum around the ideal-pyrochlore Gd₂Zr₂O₇ (x=0.50) composition. The validity of the proposed pyrochlore-based structural model was examined by comparing the experimental values of EFG at the Gd sites with those calculated by the PCM calculations.     

Lanthanum pyrochlores and the effect of yttrium addition in the systems La2−xYxZr2O7 and La2−xYxHf2O7

The crystal structures of the compounds La_2−xY_xZr₂O₇ and La_2−xY_xHf₂O₇ with x=0.0, 0.4, 0.8, 1.2, 1.6, and 2.0 have been studied using neutron powder diffraction and electron microscopy to determine the stability fields of the pyrochlore and fluorite solid solutions. The limits of pyrochlore stability in these solid solutions are found to be close to La_0.8Y_1.2Zr₂O₇ and La_0.4Y_1.6Hf₂O₇, respectively. In both systems the unit cell parameter is found to vary linearly with Y content across those compositions where the pyrochlore phase is stable, as does the x-coordinate of the oxygen atoms on the 48f (x,,) sites. In both systems, linear extrapolations of the pyrochlore data suggest that the disordering is accompanied by a small decrease in the lattice parameter of approximately 0.4%. After the pyrochlore solid solution limit is reached, a sharp change is observed from x∼0.41 to 0.375 as the disordered defect fluorite structure is favoured. Electron diffraction patterns illustrate that some short-range order remains in the disordered defect fluorite phases.     

Neutron diffraction studies of Gd2Zr2O7 pyrochlore

The structure of Gd₂Zr₂O₇ pyrochlore over the temperature range 4-300 K has been refined from powder neutron diffraction data. The sample was enriched in ¹⁶⁰Gd to avoid the high neutron absorption of naturally occurring Gd. The diffraction pattern showed well resolved superlattice reflections indicative of the pyrochlore structure and no evidence is found for anion-disorder from the structural refinements.     

First Principles Study of Uranium Solubility in Gd2Zr2O7 Pyrochlore

Ab initio calculation is performed to investigate the uranium solubility in different sites of Gd₂Zr₂O₇ pyrochlore. The Gd₂Zr₂O₇ maintains its pyrochlore structure at low uranium dopant levels, and the lattice constants of Gd₂(Zr_{2-y}U_y)O₇ and (Gd_{2-y}Uy)Zr₂O₇ are gen-erally expressed as being linearly related to the uranium content y. Uranium is found to be a preferable substitute for the B-site gadolinium atoms in cation-disordered Gd₂Zr₂O₇ (where gadolinium and zirconium atoms are swapped) over the A-site gadolinium atoms in orderedGd₂Zr₂O₇ due to the lower total energy of (Gd_{2-y}Zr_y)(Zr_{2-y}U_y)O₇.     

Ce4+替代Pu4+的模拟固化体(Gd1-xCex)2Zr2O7+x的合成及结构演变

Gd₂Zr₂O₇中Gd具有很大的中子吸收截面, 其烧绿石结构-缺陷萤石结构的转变能较低, 使其成为理想的核废料固化基材. 使用硝酸盐为原料, 添加少量NaF作助熔剂, 在较低温度下(和传统高温固相反应相比), 合成了烧绿石型Gd₂Zr₂O₇. 以Ce⁴⁺模拟Pu⁴⁺, 研究了Gd₂Zr₂O₇对锕系核素的固化, 并合成了系列模拟固化体(Gd_1-xCe_x)₂Zr₂O_7+x (0≤x≤0.6). 采用粉末X射线衍射(XRD)对系列样品进行了表征. 结果表明: 随着x值的增大,样品从烧绿石结构向缺陷萤石结构转变, 且晶胞大小基本保持恒定, 但当x=0.6时, 衍射峰明显宽化, 晶格畸变比较严重, 晶格稳定性降低. 当x=1时, 即用Ce⁴⁺完全取代Gd³⁺进行合成, 不能得到Ce₂Zr₂O₈, 产物发生了相分离, 为四方结构的(Zr_0.88Ce_0.12)O₂和萤石结构的(Ce_0.75Zr_0.25)O₂的混合物. 模拟固化体的浸出率测试表明: 当x≤0.2时, 各元素浸出率均很低, 但当x≥0.4时, 各元素的浸出率明显升高, 说明以Gd₂Zr₂O₇作为固化Pu⁴⁺的基材, Pu⁴⁺掺入量不宜高于40%.     

Solid solubilities of (La Nd,)2(Zr,Ti)2O7 phases deduced by neutron diffraction

Time-of-flight powder neutron diffraction has been performed on oxides with composition (La_1−xNd_x)₂Zr₂O₇ and Nd₂(Zr_1−xTi_x)₂O₇, where x=0, 0.2, 0.4,…1.0, in order to determine the solid solution behaviour across each series. Between La₂Zr₂O₇ and Nd₂Zr₂O₇, a cubic pyrochlore phase is observed (, Z=8). A linear decrease in the lattice parameter from 10.8047 to 10.6758 Å indicates complete miscibility of the two end-members. For the same series, the 48f oxygen x-parameter increases from 0.3313 to 0.3348, suggesting increased distortion of the 6 coordinate B sites and reduced distortion of the 8 coordinate A sites. There is limited solubility of Nd₂Ti₂O₇ in Nd₂Zr₂O₇. Exsolution of a monoclinic phase (P2₁, Z=8) rich in Nd₂Ti₂O₇ is observed at approximately x=0.56. The compositional range over which a solid solution exists is more extensive than that which has been previously reported. The solubility of Nd₂Zr₂O₇ in Nd₂Ti₂O₇ is very low.     

Separation of Am(III), Cm(III) and Eu(III) by electro-spun polystyrene-immobilized CyMe4-BTPhen

The synthesis of a novel 5-(4-vinylphenyl)-CyMe₄-BTPhen actinide selective ligand using selenium free synthetic procedures is reported. For the first time, we report the electrospinning of this actinide selective ligand into a polystyrene fiber and investigate its selective removal of Am(III) from Eu(III) and Am(III) from Cm(III). At 4?M HNO₃, the resulting fibrous solid extractant produced separation factors of SF_Am/Eu?≈?57 and a small, but significant separation of SF_Am/Cm?≈?2.9.     

Structural changes of (K,Gd)2Ta2O7 pyrochlore at high pressure

The structure of K-bearing tantalate pyrochlore (K_2-xGd_x)Ta₂O_6+x(x∼0.4) was studied at high pressures using in situ X-ray diffraction and Raman scattering methods. Experimental results indicated that (K_2-xGd_x)Ta₂O_6+x(x∼0.4) retains the pyrochlore structure up to 40 GPa, but partial amorphization occurred at pressures above 23 GPa. The amorphous phase was also confirmed in the quenched sample by means of transmission electron microscopy. The tantalate pyrochlore lattice is more stable than pyrochlore compounds in other systems, such as rare earth titanates, zirconates and stannates. The structural stability of pyrochlore tantalate may be mainly related to the size ratio of cations on the 16d and 16c sites in the lattice.     

Synthesis and solid state studies on Mb2Sb2O7 and (Mn1−xCdx)2Sb2O7 pyrochlores

Pyrochlore oxides of the type Mn₂Sb₂O₇ and (Mn_1?xCd_x)₂Sb₂O₇ have been synthesized by high-temperature solid state reactions and characterized by X-ray diffraction and chemical analysis. X-Ray diffraction studies showed that the compound Mn₂Sb₂O₇ has a rhombohedrally distorted pyrochlore structure. In the solid solutions (Mn_1?xCd_x)₂Sb₂O₇, the phases with x ≥ 0.6 are cubic. Magnetic and ¹²¹Sb Mössbauer studies indicate that all the Mn and Sb are present in the +2 and +5 state occupying A and B sites, respectively, in the pyrochlore structure. Electrical measurements indicate that the compounds are insulators or semiconductors exhibiting p-type behavior. The stoichiometry and probable cause of the rhombohedral distortion in Mn₂Sb₂O₇ and solid solutions are discussed.     

Phase relation studies in the CeO2-Gd2O3-ZrO2 system

The phase relations in the CeO₂-Gd₂O₃-ZrO₂ system have been established after slowly cooling the samples from 1400 °C. Ceria has been used as a surrogate material in place of plutonia. About 80 compositions in Zr_1−xGd_xO_2−x/2, Ce_1−xGd_xO_2−x/2, Ce_1−xZr_xO_2.00, (Zr_0.5Ce_0.5)_1−xGd_xO_2−x/2, (Ce_0.5Gd_0.5)_1−xZr_xO_1.75+x/4, (Zr_0.5Gd_0.5)_1−xCe_xO_1.75+x/4, and (Ce_0.8Zr_0.2)_xGd_1−xO_1.5+x/2 were prepared by a three steps heating protocol. Based on the refinement of the XRD data, several phase regions namely; cubic fluorite type solid solution, C-type solid solution, and various biphasic regions could be delineated. This system showed the existence of a very wide cubic phase field. About 17.5 mol% GdO_1.5 was found to fully stabilize the cubic zirconia. On the other hand ceria did not stabilize the cubic zirconia. The anion-excess gadolinia, i.e., Gd_1−xCe_xO_1.5+x was found to retain the C-type lattite unlike pure gadolinia. The ternary phase relations were mainly characterized by the presence of wide homogeneity ranges of fluorite type or C-type phases.