Improvements in the characterization of actinide targets by low solid-angle counting

In a paper presented in the Proceedings of the 19th World Conference of the INTDS, 1998, the results of a blind comparison between groups at NIST and the IRMM showed excellent agreement in characterization of actinide targets by alpha-particle counting with low solid-angle geometry. At that time the most accurate NIST results estimated an uncertainty of 0.03 % for the solid-angle determination. The NIST Neutron Physics Group now has improved the accuracy of its solid-angle determination by about a factor of 4, based on an improved aperture design, improved metrology, and comparisons among independent metrology techniques at NIST. Applications of this improved technology are expected to include improved NIST measurements of the free neutron lifetime and a recalibration of the NIST standard for neutron emission rate, NBS-I.     

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.     

New radiochemical procedures for environmental actinide measurements and data quality control

Suitable separation techniques were prepared for actinide,⁹⁰Sr and²²⁶Ra determinations in environmental and industrial samples. Extraction chromatography with tri-n-octylphosphine oxide (TOPO) and di(2-ethylhexyl) phosphoric acid (HDEHP) solutions was used. IN some cases, a powder of Microthene (Microporous polyethylene) supporting solid TOPO was prepared thus obtaining a material showing better storing and column preparation features.Uranium and²²⁶Ra were determined in phosphorites, phosphoric acid and phosphogypsum.Uranium, thorium and²²⁶Ra were also measured in the low specific activity scales of hydrocarbon production equipment:²²⁶Ra was found to concentrate in some parts of the plant so causing a radiation protection problem.Plutonium and⁹⁰Sr were measured either in some Mediterranean Sea samples or in environmental samples collected in Antarctica. Some interesting sea sediment profiles were also obtained.All the chemical methods were verified by: a) adding some yield tracers (²³²U,²²⁸Th,²⁴²Pu); b) analyzing some certified samples supplied by IAEA and NIST; c) participating in some international intercomparison runs; d) using, when possible, both an analytical and a radiometric method and e) following the radioactivity decay or growth (⁹⁰Y and²²⁶Ra).     

Radiochemistry and actinide chemistry

The paper deals with radiochemistry of tracer amounts of radionucli des with N=1 to 100 or several hundreds of species/cm³.     

Progress in actinide extraction chemistry

Progress in actinide extraction chemistry for period 1985–1989 is discussed.     

人造岩石固wx 包容锕系核素废物

研究了富钙钛锆石型和富烧绿石型两种人造岩石固化体包容锕系核素的配方设计和固化产品的鉴定评价,包括物理性能、抗浸出性能和耐辐照性能。采用了X射线衍射(XRD)、扫描电镜/能谱分析(SEM/EDS)和透射电镜/能谱分析(TEM/EDS)研究了矿相组合、元素分布和矿相化学组成等。研究表明,富钙钛锆石和富烧绿石型人造岩石都能很好地固化包容锕系核素废物。     

First structurally characterized actinide isocyanates

The synthesis and characterization of the neutral uranylisocyanate UO(2)(NCO)(2)(OP(NMe(2))(3))(2) [crystal data: monoclinic, P2(1)/c, a = 8.512(2) A, b = 10.931(2) A, c = 14.329(3) A, beta = 103.923(3) degrees , V = 1294.0(4) A(3), Z = 2] and isocyanato uranate (Et(4)N)(6)[(UO(2))(2)(NCO)(5)O](2) x 2CH(3)CN x H(2)O [crystal data: monoclinic, P2(1)/c, a = 17.2787(2) A, b = 15.560(1) A, c = 32.7619(4) A, beta = 94.0849(5) degrees , V = 8786.5(2) A(3), Z = 4] are reported. Not only are these compounds the first unambiguously characterized uranium isocyanates regardless of the oxidation state for uranium, but they are also the first structurally characterized actinide isocyanates. Both compounds show coordination of the OCN moiety through nitrogen to uranium and were characterized using IR and (1)H, (13)C, (14)N, and (31)P NMR spectroscopy and X-ray diffraction.     

Production and characterization of actinide metallofullerenes

We have, previously, reported on the HPLC elution behavior of the Th, Pa, U, Np, and Am metallofullerenes and the UV/vis/NIR absorption spectra of the Th@C₈₄ and U@C₈₂ species. In this paper, the followings are reported: (1) Pu metallofullerenes were produced and their HPLC elution behavior was investigated using a radiotracer technique. The HPLC chromatogram of this metallofullerene was found to be almost the same as that of the Np and Am metallofullerenes. (2) The oxidation states of Th@C₈₄ and U@C₈₂ produced in macroscopic quantities were examined by XANES (X-ray absorption near edge structure) measurements. The oxidation state of the U atom in the C₈₂ fullerene cage was estimated to be 3+ with the formal charge of the ionic molecule being U³⁺@C₈₂ ^3-.     

Recent progress in actinide borate chemistry

The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.     

Recent developments in computational actinide chemistry

This review describes recent computational investigations into the electronic and geometric structures of molecular actinide compounds. Following brief introductions to (i) the effects of relativity in chemistry and (ii) ab initio and density functional quantum chemical methods, four areas of contemporary research are discussed. These are pi backbonding in uranium complexes, the geometric structures of bis benzene actinide compounds, the valence electronic structure of the uranyl ion, and the inverse trans influence in pseudo-octahedral [AnOX5]n-. Comparisons are made with experimental studies, and similarities and differences between d- and f-block chemistry are highlighted.     

Periodic trends in hexanuclear actinide clusters

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.     

Strong correlations in actinide redox reactions

Reduction-oxidation (redox) reactions of the redox couples An(VI)/An(V), An(V)/An(IV), and An(IV)/An(III), where An is an element in the family of early actinides (U, Np, and Pu), as well as Am(VI)/Am(V) and Am(V)/Am(III), are modeled by combining density functional theory with a generalized Anderson impurity model that accounts for the strong correlations between the 5f electrons. Diagonalization of the Anderson impurity model yields improved estimates for the redox potentials and the propensity of the actinide complexes to disproportionate.     

Photoelectron spectroscopy of actinide organometallic compounds I. Bis(cyclooctatetraene)actinide(IV) complexes

The He(I) photoelectron spectra of the antinocene species Th(cot)₂ and U(cot)₂ (cot = cyclooctatetraene) have been determined. The 5f metal ionization has been detected at the onset of the uranocene spectrum. The low ionization energy region of both spectra is discussed in terms of simple qualitative molecular orbital scheme.     

Sructural parameters of the nearest surrounding of tri- and tetravalent actinide ions in aqueous solutions of actinide salts

Published data are generalized on different research methods for structural characterization of the nearest surrounding of trivalent and tetravalent actinide ions in aqueous solutions of their salts under standard conditions. The structural parameters such as coordination numbers, interparticle distances, the parameters of the second coordination sphere, and the types of ionic association are discussed. The quantitative characteristics of hydrated complexes of poorly known trivalent actinide ions are determined on the basis of comparative analysis with lanthanide ions.     

Multicoordinate ligands for actinide/lanthanide separations

In nuclear waste treatment processes there is a need for improved ligands for the separation of actinides (An(III)) and lanthanides (Ln(III)). Several research groups are involved in the design and synthesis of new An(III) ligands and in the confinement of these and existing An(III) ligands onto molecular platforms giving multicoordinate ligands. The preorganization of ligands considerably improves the An(III) extraction properties, which are largely dependent on the solubility and rigidity of the platform. This tutorial review summarizes the most important An(III) ligands with emphasis on the preorganization strategy using (macrocyclic) platforms.     

Reactions of actinide ions with ethylene oxide

Naked and oxo-ligated actinide (An) monopositive ions were reacted with ethylene oxide, cyclo-C(2)H(4)O (EtO). Along with An = U, Np, Pu and Am, ions of two lanthanide (Ln) elements, Ln = Tb and Tm, were studied for comparison. Metal and metal oxide ions, M(+), MO(+) and MO(2)(+), were generated by laser ablation and immediately reacted with EtO. Unreacted and product ions were detected by time-of-flight mass spectrometry. It was apparent that the overall reaction cross-sections decreased in the order U(+) > or = Np(+) > Pu(+) > Am(+). A primary reaction channel for each studied metal was the formation of MO(+) from M(+), in accord with the expected exothermicity of oxygen abstraction from EtO. For U, Np and Pu, the dioxides were also major products, indicating OAn(+)--O dissociation energies of at least 350 kJ mol(-1), the energy required for O-atom abstraction from EtO. For Am, Tb and Tm, the dioxides were only very minor products, reflecting the stabilities of the trivalent states and resistance to oxidation to higher valence states; the structures/bonding in these MO(2)(+) are intriguing given that the formal pentavalent bonding state is effectively unattainable. It was demonstrated that EtO, unlike more thermochemically favorable but kinetically restricted O-donors, is effective at achieving facile oxidation of actinide metal ions to the monoxide, and to the dioxide if the second O-abstraction reaction is exothermic. Several intriguing minor products were also identified, most of which incorporate metal--oxygen bonding and are attributed to the oxophilicity of the f-block elements; the contrast to the behavior of first-row d-block transition elements is striking in this regard. Particularly noteworthy was the formation of MH(4)(+) (and MOH(4)(+)), evidently via abstraction of all four H atoms from a single C(2)H(4)O molecule; the structures/bonding in these novel 'hydride' species are indeterminate and warrant further attention.     

From extended solids to nano-scale actinide clusters

Selected highlights of more than a decade of research efforts concerning the structural chemistry of actinyl materials at the University of Notre Dame is reviewed, with an emphasis on complex topological arrangements of polyhedra to form extended structures and frameworks. Earlier work focused on structures of uranyl minerals and synthetic compounds, with increasing emphasis on neptunyl materials and the importance of cation–cation interactions in their structural details and properties. Much of the research over the past 5 years has examined a growing family of nano-scale clusters of uranyl peroxide polyhedra containing from 16 to 60 polyhedra. These clusters contain topological squares, pentagons and hexagons, and six have adopted fullerene topologies with 12 pentagons and an even number of hexagons.     

Chemistry of tetravalent actinide phosphates—Part II

The chemistry and crystal structure of tetravalent cation phosphates, including that of actinides was reviewed several times until 1985. Later, new compounds were synthesized and characterized. In more recent studies it was found that some of previously reported phases, especially those of thorium, uranium, and neptunium, were wrongly identified. In the light of these new facts, an update review and classification of tetravalent actinides phosphates is proposed in this two-part paper. Their crystal structure and some chemical properties are compared to non-actinide cation phosphates.