Science.gov

Sample records for neptunium borides

  1. Neptunium

    NASA Astrophysics Data System (ADS)

    Yoshida, Zenko; Johnson, Stephen G.; Kimura, Takaumi; Krsul, John R.

    The first report on the discovery of neptunium was in 1940 by McMillan and Abelson (1940), although McMillan did the preliminary work in 1939 and published his findings (McMillan, 1939). He did not claim that a new element had been discovered until confirmatory measurements had been undertaken in the following year. The production of neptunium was accomplished by placing a layer of uranium trioxide on paper with several aluminum or paper foils and then exposing this to neutrons from a cyclotron. Examination of the uranium paper sample containing the non-recoiling fraction displayed that two new radioactive components had been created. One component displayed a 23 min half-life, later identified as U-239, while the second exhibited a 2.3 day half-life. Both components decayed via β particle emission. Preliminary chemical analysis was performed to determine the behavior of the 2.3 day component and resulted in the contradictory assignment of this component as that exhibiting an atomic number of 93, but not being transuranic in nature (Segrè, 1939). Segrè noted in his paper that his conclusions were contradictory. However, the following quotation is from his paper, “The necessary conclusion seems to be that the 23 minute uranium decays into a very long-lived 93 and that transuranic elements have not yet been observed.” The primary stumbling block to the proper assignment of the material as transuranic in nature was the lack of observation of any alpha decay activity that would emanate from the daughter product of the beta decay of this new material with an atomic number 93. It was this work by Segrè (1939) that led McMillan and Abelson to revisit the chemical analysis and determine its properties in greater depth.

  2. NEPTUNIUM SOLVENT EXTRACTION PROCESS

    DOEpatents

    Dawson, L.R.; Fields, P.R.

    1959-10-01

    The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

  3. Gradient boride layers formed by diffusion carburizing and laser boriding

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Makuch, N.; Dziarski, P.; Mikołajczak, D.; Przestacki, D.

    2015-04-01

    Laser boriding, instead of diffusion boriding, was proposed to formation of gradient borocarburized layers. The microstructure and properties of these layers were compared to those-obtained after typical diffusion borocarburizing. First method of treatment consists in diffusion carburizing and laser boriding only. In microstructure three zones are present: laser borided zone, hardened carburized zone and carburized layer without heat treatment. However, the violent decrease in the microhardness was observed below the laser borided zone. Additionally, these layers were characterized by a changeable value of mass wear intensity factor thus by a changeable abrasive wear resistance. Although at the beginning of friction the very low values of mass wear intensity factor Imw were obtained, these values increased during the next stages of friction. It can be caused by the fluctuations in the microhardness of the hardened carburized zone (HAZ). The use of through hardening after carburizing and laser boriding eliminated these fluctuations. Two zones characterized the microstructure of this layer: laser borided zone and hardened carburized zone. Mass wear intensity factor obtained a constant value for this layer and was comparable to that-obtained in case of diffusion borocarburizing and through hardening. Therefore, the diffusion boriding could be replaced by the laser boriding, when the high abrasive wear resistance is required. However, the possibilities of application of laser boriding instead of diffusion process were limited. In case of elements, which needed high fatigue strength, the substitution of diffusion boriding by laser boriding was not advisable. The surface cracks formed during laser re-melting were the reason for relatively quickly first fatigue crack. The preheating of the laser treated surface before laser beam action would prevent the surface cracks and cause the improved fatigue strength. Although the cohesion of laser borided carburized layer was

  4. ELECTRODEPOSITION OF NEPTUNIUM

    DOEpatents

    Seaborg, G.T.; Wahl, A.C.

    1960-08-30

    A process of electrodepositing neptunium from solutions is given which comprises conducting the electrodeposition from an absolute alcohol bath containing a neptunium nitrate and lanthanum nitrate at a potential of approximately 50 volts and a current density of between about 1.8 and 4.7 ma/dm/ sup 2/.

  5. NEPTUNIUM OXIDE PROCESSING

    SciTech Connect

    Jordan, J; Watkins, R; Hensel, S

    2009-05-27

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty nine cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. The neptunium campaign was divided into two parts: Part 1 which consisted of oxide made from H-Canyon neptunium solution which did not require any processing prior to conversion into an oxide, and Part 2 which consisted of oxide made from additional H-Canyon neptunium solutions which required processing to purify the solution prior to conversion into an oxide. The neptunium was received as a nitrate solution and converted to oxide through ion-exchange column extraction, precipitation, and calcination. Numerous processing challenges were encountered in order make a final neptunium oxide product that could be shipped in a 9975 shipping container. Among the challenges overcome was the issue of scale: translating lab scale production into full facility production. The balance between processing efficiency and product quality assurance was addressed during this campaign. Lessons learned from these challenges are applicable to other processing projects.

  6. Neptunium storage at Hanford

    SciTech Connect

    Alderman, C.J.; Shiraga, S.S.; Schwartz, R.A.; Smith, R.J.; Wootan, D.W.

    1993-06-01

    A decision must be made regarding whether the United State`s stockpile of neptunium should be discarded into the waste stream or kept for the production of Pu-238. Although the cost of long term storage is not inconsequential, to dispose of the material means the closing of our option to maintain control over our Pu-238 stockpile. Within the Fuels and Materials Examination Facility at Hanford there exists a remotely operated facility that can be converted for neptunium storage. This paper describes the facility and the anticipated handling requirements.

  7. SOLVENT EXTRACTION OF NEPTUNIUM

    DOEpatents

    Butler, J.P.

    1958-08-12

    A process is described for the recovery of neptuniunn from dissolver solutions by solvent extraction. The neptunium containing solution should be about 5N, in nitric acid.and about 0.1 M in ferrous ion. The organic extracting agent is tributyl phosphate, and the neptuniunn is recovered from the organic solvent phase by washing with water.

  8. METHOD OF SEPARATING NEPTUNIUM

    DOEpatents

    Seaborg, G.T.

    1961-10-24

    plutonium in an aqueous solution containing sulfate ions. The process consists of contacting the solution with an alkali metal bromate, digesting the resulting mixture at 15 to 25 deg C for a period of time not more than that required to oxidize the neptunium, adding lanthanum ions and fluoride ions, and separating the plutonium-containing precipitate thus formed from the supernatant solution. (AEC)

  9. Results of Neptunium Disposal Testing

    SciTech Connect

    Walker, D.D.

    2003-10-07

    Researchers investigated the neutralization of neptunium solution from H-Canyon Tank 16.4 and the properties of the resulting slurry. This work investigated slurry properties from a single neutralization protocol and limited storage times.

  10. Kinetics of electrochemical boriding of low carbon steel

    NASA Astrophysics Data System (ADS)

    Kartal, G.; Eryilmaz, O. L.; Krumdick, G.; Erdemir, A.; Timur, S.

    2011-05-01

    In this study, the growth kinetics of the boride layers forming on low carbon steel substrates was investigated during electrochemical boriding which was performed at a constant current density of 200 mA/cm 2 in a borax based electrolyte at temperatures ranging from 1123 K to 1273 K for periods of 5-120 min. After boriding, the presence of both FeB and Fe 2B phases were confirmed by the X-ray diffraction method. Cross-sectional microscopy revealed a very dense and thick morphology for both boride phases. Micro hardness testing of the borided steel samples showed a significant increase in the hardness of the borided surfaces (i.e., up to (1700 ± 200) HV), while the hardness of un-borided steel samples was approximately (200 ± 20) HV. Systematic studies over a wide range of boriding time and temperature confirmed that the rate of the boride layer formation is strongly dependent on boriding duration and has a parabolic character. The activation energy of boride layer growth for electrochemical boriding was determined as (172.75 ± 8.6) kJ/mol.

  11. Beta cell device using icosahedral boride compounds

    DOEpatents

    Aselage, Terrence L.; Emin, David

    2002-01-01

    A beta cell for converting beta-particle energies into electrical energy having a semiconductor junction that incorporates an icosahedral boride compound selected from B.sub.12 As.sub.2, B.sub.12 P.sub.2, elemental boron having an .alpha.-rhombohedral structure, elemental boron having a .beta.-rhombohedral structure, and boron carbides of the chemical formula B.sub.12-x C.sub.3-x, where 0.15boride compound self-heals, resisting degradation from radiation damage.

  12. The fracture toughness of borides formed on boronized cold work tool steels

    SciTech Connect

    Sen, Ugur; Sen, Saduman

    2003-06-15

    In this study, the fracture toughness of boride layers of two borided cold work tool steels have been investigated. Boriding was carried out in a salt bath consisting of borax, boric acid, ferro-silicon and aluminum. Boriding was performed at 850 and 950 deg. C for 2 to 7 h. The presence of boride phases were determined by X-ray diffraction (XRD) analysis. Hardness and fracture toughness of borides were measured via Vickers indenter. Increasing of boriding time and temperature leads to reduction of fracture toughness of borides. Metallographic examination showed that boride layer formed on cold work tool steels was compact and smooth.

  13. Direct chemical reduction of neptunium oxide to neptunium metal using calcium and calcium chloride

    NASA Astrophysics Data System (ADS)

    Squires, Leah N.; Lessing, Paul

    2016-04-01

    A process of direct reduction of neptunium oxide to neptunium metal using calcium metal as the reducing agent is discussed. After reduction of the oxide to metal, the metal is separated by density from the other components of the reaction mixture and can be easily removed upon cooling. The direct reduction technique consistently produces high purity (98%-99% pure) neptunium metal.

  14. Fracture Microindentation on boride layers on AISI 1020 steel

    NASA Astrophysics Data System (ADS)

    Prince, M.; Thanu, A. Justin; Arjun, S. L.; Velmurugan, U.; Gopalakrishnan, P.

    2016-02-01

    In this paper, an attempt has been made to enhance the fracture toughness (Kc) of boride layer using multi-component (Ni, Cr and B) laser bonding. The fracture toughness of continuously pack borided, interrupted pack borided and multi-component (Ni, Cr and B) laser borided steel specimens was measured using Vickers microindentation fracture toughness test as per ASTM E384 standard. The fracture toughness of continuously pack borided layer was - 3.3 MPa.m1/2. The fracture toughness of interrupted boride layer was in the range of - 4.9 MPa.m1/2. The fracture toughness of multi-component (Ni, Cr and B) laser borided layer was in the range of 13.8 - 18.3 MPa.m1/2. A significant improvement in fracture toughness of laser treated specimens was observed from the experimental results. This may be due to better distribution of boron, nickel, chromium and other alloying elements due to laser treatment and relatively more uniform boride layer as compared with continuously pack borided layer and interrupted pack borided layer.

  15. Investigation of the fracture mechanics of boride composites

    NASA Technical Reports Server (NTRS)

    Kaufman, L.; Clougherty, E. V.; Nesor, H.

    1971-01-01

    Fracture energies of WC-6Co, Boride 5 (ZrB2+SiC), Boride 8(ZrB2+SiC+C) and Boride 8-M2(ZrB2+SiC+C) were measured by slow bend and impact tests of notched charpy bars. Cobalt bonded tungsten carbide exhibited impact energies of 0.76 ft-lb or 73.9 in-lb/square inch. Boride 5 and the Boride 8 exhibit impact energies one third and one quarter of that observed for WC-6Co comparing favorably with measurements for SiC and Si3N4. Slow bend-notched bar-fracture energies for WC-6Co were near 2.6 in-lb/square inch or 1/20 the impact energies. Slow bend energies for Boride 8-M2, Boride 8 and Boride 5 were 58%, 42% and 25% of the value observed for WC-6Co. Fractograph showed differences for WC-6Co where slow bend testing resulted in smooth transgranular cleavage while samples broken by impact exhibited intergranular failures. By contrast the boride fractures showed no distinction based on testing method. Fabrication studies were conducted to effect alteration of the boride composites by alloying and introduction of graphite cloth.

  16. OXIDATIVE METHOD OF SEPARATING PLUTONIUM FROM NEPTUNIUM

    DOEpatents

    Beaufait, L.J. Jr.

    1958-06-10

    A method is described of separating neptunium from plutonium in an aqueous solution containing neptunium and plutonium in valence states not greater than +4. This may be accomplished by contacting the solution with dichromate ions, thus oxidizing the neptunium to a valence state greater than +4 without oxidizing any substantial amount of plutonium, and then forming a carrier precipitate which carries the plutonium from solution, leaving the neptunium behind. A preferred embodiment of this invention covers the use of lanthanum fluoride as the carrier precipitate.

  17. Electrochemical Evaluation of Corrosion on Borided and Non-borided Steels Immersed in 1 M HCl Solution

    NASA Astrophysics Data System (ADS)

    Mejía-Caballero, I.; Martínez-Trinidad, J.; Palomar-Pardavé, M.; Romero-Romo, M.; Herrera-Hernández, H.; Herrera-Soria, O.; Campos Silva, I.

    2014-08-01

    In this study the corrosion resistances of AISI 1018 and AISI 304 borided and non-borided steels were estimated using polarization resistance and electrochemical impedance spectroscopy (EIS) techniques. Boriding of the steel samples was conducted using the powder-pack method at 1223 K with 6 h of exposure. Structural examinations of the surfaces of the borided steels showed the presence of a Fe2B layer with isolated FeB teeth on the AISI 1018 steel, whereas a compact layer of FeB/Fe2B was formed on the AISI 304 steel. Polarization resistance and EIS of the borided and non-borided steels surfaces were performed in a corrosive solution of 1 M HCl. The EIS data were analyzed during 43 days of exposure to the acid solution. Impedance curves obtained during this period for the borided and non-borided steels were modeled using equivalent electrical circuits. The results of both electrochemical techniques indicated that boride layers formed at the steel surfaces effectively protect the samples from the corrosive effects of HCl. The main corrosion processes observed on the boride layers were pitting and crevice corrosion.

  18. Phonon dynamics of neptunium chalcogenides

    NASA Astrophysics Data System (ADS)

    Aynyas, Mahendra; Rukmangad, Aditi; Arya, Balwant S.; Sanyal, Sankar P.

    2012-06-01

    We have performed phonon calculations of Neptunium Chalcogenides (NpX) (X= S, Se, Te) based on breathing shell model (BSM) which includes breathing motion of electron of the Np-atoms due to f-d hybridization. The model predicts that the short range breathing phenomenon play a dominant role in the phonon properties. We also report, for the first time specific heat for these compounds.

  19. Radiotoxicity of neptunium(V) and neptunium(V)-nitrilotriacetic acid (NTA) complexes towards Chelatobacter heintzii

    SciTech Connect

    Banaszak, J.E. |; Reed, D.T.; Rittmann, B.E.

    1997-03-10

    The objective of this work was to investigate the toxicity mechanisms of neptunium and the neptunium-NTA complex towards Chelatobacter heintzii. The results show that metal toxicity of aquo NpO{sub 2}{sup +} may significantly limit growth of Cl heintzii at free metal ion concentrations greater than {approx} 10{sup {minus}5} M. However, neptunium concentrations {ge} 10{sup {minus}4} M do not cause measurable radiotoxicity effects in C. heintzii when present in the form of a neptunium-NTA complex or colloidal/precipitated neptunium-phosphate. The neptunium-NTA complex, which is stable under aerobic conditions, is destabilized by microbial degradation of NTA. When phosphate was present, degradation of NTA led to the precipitation of a neptunium-phosphate phase.

  20. Colloidal nickel boride catalyst for hydrogenation of olefins

    SciTech Connect

    Nakao, Y.; Fujishige, S.

    1981-04-01

    Colloidal nickel boride was prepared from nickel(II) chloride by reduction with sodium borohydride in the presence of polyvinylpyrrolidone in ethanol. Hydrogenation of various olefins was examined over the colloidal catalyst at 30/sup 0/C and atmospheric pressure. The colloidal nickel boride was much more effective than the precipitated nickel boride prepared in the absence of polyvinylpyrrolidone as a hydrogenation catalyst, especially for isopropenyl compounds. Additional amines and sodium acetate were slightly inhibitive to the colloidal catalyst, while, being strongly promotive to the precipitated catalyst. The colloidal nickel boride was superior to the charcoal-supported metals of the platinum group in catalytic activity for ..cap alpha..-methylstyrene.

  1. Packaging and Transportation of Additional Neptunium Oxide

    SciTech Connect

    Watkins, R.; Jordan, J.; Hensel, S.

    2010-05-05

    The Savannah River Site's HB-Line Facility completed a second neptunium oxide production campaign in which nine (9) additional cans of neptunium oxide were produced and shipped to the Idaho National Laboratory and Oak Ridge National Laboratory in the 9975 shipping container. These additional cans were from a different feed solution than the first fifty (50) cans of neptunium oxide that were previously produced and shipped via a Letter of Amendment to the 9975 Safety Analysis Report for Packaging (SARP) content table. This paper will address the challenges associated with demonstrating the neptunium oxide produced from the additional feed solution was equivalent to the original neptunium oxide and within the content description of the Letter of Amendment.

  2. Mechanism of boriding from pastes in a glow discharge

    SciTech Connect

    Isakov, S.A.; Al'tshuler, S.A.

    1987-09-01

    The authors investigate the boridation of steel 45 from the standpoint of the glow-discharge dissociation of a borax paste and the plasma arc spraying of the resulting boron into the steel. The effects of process parameters on the impregnation of boron into the steel and its phase behavior in the boridation process are discussed.

  3. Neptunium uptake by serum transferrin.

    PubMed

    Llorens, Isabelle; Den Auwer, Christophe; Moisy, Philippe; Ansoborlo, Eric; Vidaud, Claude; Funke, Harld

    2005-04-01

    Although of major impact in terms of biological and environmental hazards, interactions of actinide cations with biological molecules are only partially understood. Human serum transferrin (Tf) is one of the major iron carriers in charge of iron regulation in the cell cycle and consequently contamination by actinide cations is a critical issue of nuclear toxicology. Combined X-ray absorption spectroscopy (XAS) and near infrared absorption spectrometry were used to characterize a new complex between Tf and Np (IV) with the synergistic nitrilotriacetic acid (NTA) anion. Description of the neptunium polyhedron within the iron coordination site is given.

  4. PRECIPITATION METHOD OF SEPARATION OF NEPTUNIUM

    DOEpatents

    Magnusson, L.B.

    1958-07-01

    A process is described for the separation of neptunium from plutonium in an aqueous solution containing neptunium ions in a valence state not greater than +4, plutonium ioms in a valence state not greater than +4, and sulfate ions. The Process consists of adding hypochlorite ions to said solution in order to preferentially oxidize the neptunium and then adding lanthanum ions and fluoride ions to form a precipitate of LaF/sub 3/ carrying the plutonium, and thereafter separating the supernatant solution from the precipitate.

  5. Organometallic neptunium(III) complexes

    NASA Astrophysics Data System (ADS)

    Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  6. Organometallic neptunium(III) complexes.

    PubMed

    Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  7. Organometallic neptunium(III) complexes

    NASA Astrophysics Data System (ADS)

    Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal–ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  8. Organometallic neptunium(III) complexes.

    PubMed

    Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements. PMID:27442286

  9. Boriding of high carbon high chromium cold work tool steel

    NASA Astrophysics Data System (ADS)

    Muhammad, W.

    2014-06-01

    High-carbon high-chromium cold work tool steels are widely used for blanking and cold forming of punches and dies. It is always advantageous to obtain an increased wear resistant surface to improve life and performance of these steels. In this connection boriding of a high-carbon high-chromium cold work die steel, D3, was conducted in a mixture of 30% B4C, 70% borax at 950 °C for two, four and six hours. Case depth of the borided layer obtained was between 40 to 80 μm. After boriding, the surface hardness achieved was between 1430 to 1544 HV depending upon the process time. X-ray diffraction studies confirmed the formation of a duplex compound layer consisting of FeB and Fe2B. It is generally considered that FeB is undesirable because of its inherent brittleness. Post boriding treatment (homogenization) transformed the compound layer into single-phase layer of Fe2B, while surface hardness decreased to 1345-1430 HV. Pin-on-disc wer test showed that wear resistance of the borided samples was superior as compared to non-borided material and increased with boriding time.

  10. Synthesis and properties of nanoscale titanium boride

    NASA Astrophysics Data System (ADS)

    Efimova, K. A.; Galevskiy, G. V.; Rudneva, V. V.

    2015-09-01

    This work reports the scientific and technological grounds for plasma synthesis of titanium diboride, including thermodynamic and kinetic conditions of boride formation when titanium and titanium dioxide are interacting with products resulting from boron gasification in the nitrogen - hydrogen plasma flow, and two variations of its behavior using the powder mixtures: titanium - boron and titanium dioxide - boron. To study these technology variations, the mathematical models were derived, describing the relation between element contents in the synthesized products of titanium and free boron and basic parameters. The probable mechanism proposed for forming titanium diboride according to a "vapour - melt - crystal" pattern was examined, covering condensation of titanium vapour in the form of aerosol, boriding of nanoscale melt droplets by boron hydrides and crystallization of titanium - boron melt. The comprehensive physical - chemical certification of titanium diboride was carried out, including the study of its crystal structure, phase and chemical composition, dispersion, morphology and particle oxidation. Technological application prospects for use of titanium diboride nanoscale powder as constituent element in the wettable coating for carbon cathodes having excellent physical and mechanical performance and protective properties.

  11. Method of making an icosahedral boride structure

    DOEpatents

    Hersee, Stephen D.; Wang, Ronghua; Zubia, David; Aselage, Terrance L.; Emin, David

    2005-01-11

    A method for fabricating thin films of an icosahedral boride on a silicon carbide (SiC) substrate is provided. Preferably the icosahedral boride layer is comprised of either boron phosphide (B.sub.12 P.sub.2) or boron arsenide (B.sub.12 As.sub.2). The provided method achieves improved film crystallinity and lowered impurity concentrations. In one aspect, an epitaxially grown layer of B.sub.12 P.sub.2 with a base layer or substrate of SiC is provided. In another aspect, an epitaxially grown layer of B.sub.12 As.sub.2 with a base layer or substrate of SiC is provided. In yet another aspect, thin films of B.sub.12 P.sub.2 or B.sub.12 As.sub.2 are formed on SiC using CVD or other vapor deposition means. If CVD techniques are employed, preferably the deposition temperature is above 1050.degree. C., more preferably in the range of 1100.degree. C. to 1400.degree. C., and still more preferably approximately 1150.degree. C.

  12. Plasma metallurgical production of nanocrystalline borides and carbides

    NASA Astrophysics Data System (ADS)

    Galevsky, G. V.; Rudneva, V. V.; Cherepanov, A. N.; Galevsky, S. G.; Efimova, K. A.

    2016-09-01

    he experience in production and study of properties of nanocrystalline borides and chromium carbides, titanium, silicon was summarized. The design and features of the vertical three-jet once-through reactor with power 150 kW, used in the plasma metallurgical production, was described. The technological, thermotechnical and resource characteristics of the reactor were identified. The parameters of borides and carbides synthesis, their main characteristics in the nanodispersed state and equipment-technological scheme of production were provided. Evaluation of engineering-and-economical performance of the laboratory and industrial levels of borides and carbides production and the state corresponding to the segment of the world market was carried out.

  13. Pack-boriding of Fe-Mn binary alloys: Characterization and kinetics of the boride layers

    SciTech Connect

    Bektes, M.; Calik, A.; Ucar, N.; Keddam, M.

    2010-02-15

    In this work, the boronizing of Fe-Mn binary alloys at 0.42, 0.76 and 0.94 wt.% Mn was carried out in a solid medium using the powder pack method. In this method, commercial Ekabor-II boron source and activator (ferro-silicon) were thoroughly mixed to form the boriding medium. The samples were boronized in an electrical resistance furnace for exposure times of 2, 4, 6 and 8 h at 1173 K under atmospheric pressure and a series of boronized samples in the temperature range 1073-1373 K for 3 h. After the furnace process, boronized samples were removed from the furnace and cooled in air. Afterwards, the boride layers generated by the pack-boronizing process were characterized by optical microscopy, scanning electron microscopy, XRD analysis, Vickers microhardness and tensile testing. The generated boride layers, showing a saw-tooth morphology, had a surface microhardness in the range 1400-1270 HV0.1. It was shown that the values of yield stresses and ultimate tensile stresses were increased as the Mn content increases in the boronized Fe-Mn binary alloys. In contrast, the values of elongations determined from the stress-strain curves were decreased. Furthermore, it was found that the calculated mean value of the activation energy of boron diffusion was close to 119 J/mol.

  14. NMR studies of borates and borides

    NASA Astrophysics Data System (ADS)

    Bray, P. J.

    1986-04-01

    Nuclear magnetic resonance (NMR) has been employed for some 25 years to study the structure of boron-containing compounds.1-3 The earliest works employed the 11B nuclear isotope in a study of glasses containing boron oxide. Many additional NMR studies3-10 of boron-containing glasses have utilized both the 11B and 10B isotopes. Crystalline materials were also studied2,3 at an early date, with particular attention given to borides and boron carbide. After a discussion of the features of NMR spectroscopy particularly pertinent for the study of boron-containing compounds, highlights of the early work and more recent studies will be summarized to indicate the usefulness of 10B and 11B NMR for structural studies.

  15. Certain physical properties of cobalt and nickel borides

    NASA Technical Reports Server (NTRS)

    Kostetskiy, I. I.; Lvov, S. N.

    1981-01-01

    The temperature dependence of the electrical resistivity, the thermal conductivity, and the thermal emf of cobalt and nickel borides were studied. In the case of the nickel borides the magnetic susceptibility and the Hall coefficient were determined at room temperature. The results are discussed with allowance for the current carrier concentration, the effect of various mechanisms of current-carrier scattering and the location of the Fermi level in relation to the 3d band.

  16. Dehydration of plutonium or neptunium trichloride hydrate

    DOEpatents

    Foropoulos, Jr., Jerry; Avens, Larry R.; Trujillo, Eddie A.

    1992-01-01

    A process of preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride is provided.

  17. PACKAGING AND TRANSPORTATION OF NEPTUNIUM OXIDE

    SciTech Connect

    Watkins, R; Steve Hensel, S; Jeffrey Jordan, J

    2009-03-03

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty (50) cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. This shipping campaign involved the addition of neptunium oxide to the 9975 Safety Analysis Report for Packaging (SARP) as a new content and subsequently a Letter of Amendment to the SARP content table. This paper will address the proper steps which should be taken to add a new content table to a SARP. It will also address the importance of product sampling and understanding the material shipping requirements of a SARP.

  18. Dehydration of plutonium or neptunium trichloride hydrate

    DOEpatents

    Foropoulos, J. Jr.; Avens, L.R.; Trujillo, E.A.

    1992-03-24

    A process is described for preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride.

  19. Neptunium dioxide precipitation kinetics in aqueous systems

    NASA Astrophysics Data System (ADS)

    Johnsen, Amanda Melia

    The proposed Yucca Mountain nuclear waste repository poses questions about the behavior of nuclear materials stored underground for thousands of years. Chemical and transport behaviors of 237Np in such a repository are of particular interest because of 237Np's 2.14 million year half-life. Previous neptunium solubility studies in Yucca Mountain ground waters supersaturated with NpO+2aq reacted below 100°C for up to a year reported various Np(V) solid phases. However, recent studies with NpO+2aq under similar conditions at 200°C reported precipitation of NpO 2(cr), suggesting Np(IV) solid phases were previously unobserved due to kinetic limitations. The aim of this thesis is to better understand the NpO+2aq -NpO2(cr) reduction-precipitation system by conducting experiments to obtain first-order answers concerning effects of temperature, ionic strength, and O2 and CO2. Unfiltered experiments conducted at 10-4M Np(V), pH 6-6.5, ˜ 10-4-10 -3M ionic strength, and 200°C indicated colloids might effect precipitation kinetics, necessitating solution filtration. Subsequent filtered experiments at 200, 212, and 225°C showed consistent and distinctive temperature dependent behavior at short reaction times. At long times, 200°C experiments showed unexpected dissolution of neptunium solids, but 212°C and 225°C experiments demonstrated quasi steady-state neptunium concentrations of ˜ 3x10-6M and ˜ 6x10-6M, respectively. Steady-state 212°C and 225°C experiments were then "adjusted" to their original neptunium and hydrogen ion concentrations before continuing at temperature, creating additional neptunium precipitates; these experiments showed less consistent neptunium behavior, suggesting kinetic dependence on solids from the initial precipitation. Solids from a 225°C experiment analyzed by X-ray diffraction were NpO2(cr). A 200°C experiment with a NaCl concentration of 0.05 M showed a drastic increase in neptunium loss and hydrogen ion gain rates. Another 200

  20. DEVELOPMENT OF NDA METHODS FOR NEPTUNIUM METAL

    SciTech Connect

    C. MOSS; ET AL

    2000-10-01

    Many techniques have been developed and applied in the US and other countries for the control of the special nuclear materials (SNM) plutonium and uranium, but no standard methods exist for the determination of neptunium in bulk containers. Such methods are needed because the U.S. Department of Energy requires all Government-owned {sup 237}Np be treated as if it were SNM and the International Atomic Energy Agency is considering how to monitor this material. We present the results of the measurements of several samples of neptunium metal with a variety of techniques. Analysis of passive gamma-ray spectra uniquely identifies the material, provides isotopic ratios for contaminants, such as {sup 243}Am, and may provide information about the shielding, mass, and time since processing. Active neutron interrogation, using the delayed neutron technique in a package monitor, provides useful data even if the neptunium is shielded. The tomographic gamma scanner yields a map of the distribution of the neptunium and shielding in a container. Active photon interrogation with pulses from a 10-MeV linac produces delayed neutrons between pulses, even when the container is heavily shielded. Data from one or more of these techniques can be used to identify the material and estimate a mass in a bulk container.

  1. Valence of neptunium in intermetallic compounds

    SciTech Connect

    Spitsyn, V.I.; Ionova, G.V.

    1987-07-01

    The authors use Moessbauer spectroscopy and quantum chemical calculations to determine the valence and electronic structure of neptunium in its intermetallic forms with a variety of alloys. The isomeric shifts are measured on Np 237 nuclei. Quantum electronic properties and population density estimates are calculated within the framework of the Hartree-Fock-Slater method.

  2. Insertion of neptunium in borosilicate glasses

    NASA Astrophysics Data System (ADS)

    Petit-Maire, D.; Petiau, J.; Calas, G.; Jacquet-Francillon, N.

    1989-06-01

    Neptunium environment are studied in borosilicate glasses modelling those used to confine the high-level radioactive waste solution of fission products. Valence states III, IV and V are analysed and the local structures are compared to those of uranium and thorium in the same glasses.

  3. Neptunium_Oxide_Precipitation_Kinetics_AJohnsen

    SciTech Connect

    Johnsen, A M; Roberts, K E; Prussin, S G

    2012-06-08

    We evaluate the proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation system at elevated temperatures to obtain primary information on the effects of temperature, ionic strength, O{sub 2} and CO{sub 2}. Experiments conducted on unfiltered solutions at 10{sup -4} M NpO{sub 2}{sup +}(aq), neutral pH, and 200 C indicated that solution colloids strongly affect precipitation kinetics. Subsequent experiments on filtered solutions at 200, 212, and 225 C showed consistent and distinctive temperature-dependent behavior at reaction times {le} 800 hours. At longer times, the 200 C experiments showed unexpected dissolution of neptunium solids, but experiments at 212 C and 225 C demonstrated quasi steady-state neptunium concentrations of 3 x 10{sup -6} M and 6 x 10{sup -6} M, respectively. Solids from a representative experiment analyzed by X-ray diffraction were consistent with NpO{sub 2}(cr). A 200 C experiment with a NaCl concentration of 0.05 M showed a dramatic increase in the rate of neptunium loss. A 200 C experiment in an argon atmosphere resulted in nearly complete loss of aqueous neptunium. Previously proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation mechanisms in the literature specified a 1:1 ratio of neptunium loss and H{sup +} production in solution over time. However, all experiments demonstrated ratios of approximately 0.4 to 0.5. Carbonate equilibria can account for only about 40% of this discrepancy, leaving an unexpected deficit in H+ production that suggests that additional chemical processes are occurring.

  4. Corrosion behavior of boride layers evaluated by the EIS technique

    NASA Astrophysics Data System (ADS)

    Campos, I.; Palomar-Pardavé, M.; Amador, A.; VillaVelázquez, C.; Hadad, J.

    2007-09-01

    The corrosion behavior of boride layers at the AISI 304 steel surface is evaluated in the present study. Electrochemical impedance spectroscopy (EIS) technique was used for the evaluation of the polarization resistance at the steel surface, with the aid of AUTOLAB potentiostat. Samples were treated with boron paste thickness of 4 and 5 mm, in the range of temperatures 1123 ≤ T ≤ 1273 K and exposed time of 4 and 6 h. The electrochemical technique employed 10 mV AC with a frequency scan range from 8 kHz to 3 mHz in deaerated 0.1 M NaCl solution. Nyquist diagrams show that the highest values of corrosion resistance are present in the samples borided at the temperature of 1273 K, with treatment time of 4 h and 4 mm of boron paste thickness. The values of corrosion resistance on borided steels are compared with the porosity exhibited in the layers.

  5. The characterization of boride layer on the St37 iron

    NASA Astrophysics Data System (ADS)

    Sutrisno, Soegijono, Bambang

    2012-06-01

    The property such as microhardness of boride layer formed on St37 iron was investigated. Boronizing was carried out in a solid medium consisting of nano size powders of 50% B4C as a donor, 45% SiC as a diluent, and 5% KBF4 as an activator treated at the temperature of 1000°C for 8 hours. The phases that were formed on the substrate was found as Fe2B and FeB layer that had smooth and flate shape morphology. The hardness of boride layer on St37 was over 2000 HV, while the hardness of untreated St37 iron was about 123,82 HV. Depending on process time and temperature, the depth of boride layer ranges from 20 to 60 μm, leading to a diffusion controlled process.

  6. DISSOLUTION OF NEPTUNIUM OXIDE RESIDUES

    SciTech Connect

    Kyser, E

    2009-01-12

    This report describes the development of a dissolution flowsheet for neptunium (Np) oxide (NpO{sub 2}) residues (i.e., various NpO{sub 2} sources, HB-Line glovebox sweepings, and Savannah River National Laboratory (SRNL) thermogravimetric analysis samples). Samples of each type of materials proposed for processing were dissolved in a closed laboratory apparatus and the rate and total quantity of off-gas were measured. Samples of the off-gas were also analyzed. The quantity and type of solids remaining (when visible) were determined after post-dissolution filtration of the solution. Recommended conditions for dissolution of the NpO{sub 2} residues are: Solution Matrix and Loading: {approx}50 g Np/L (750 g Np in 15 L of dissolver solution), using 8 M nitric acid (HNO{sub 3}), 0.025 M potassium fluoride (KF) at greater than 100 C for at least 3 hours. Off-gas: Analysis of the off-gas indicated nitric oxide (NO), nitrogen dioxide (NO{sub 2}) and nitrous oxide (N{sub 2}O) as the only identified components. No hydrogen (H{sub 2}) was detected. The molar ratio of off-gas produced per mole of Np dissolved ranged from 0.25 to 0.4 moles of gas per mole of Np dissolved. A peak off-gas rate of {approx}0.1 scfm/kg bulk oxide was observed. Residual Solids: Pure NpO{sub 2} dissolved with little or no residue with the proposed flowsheet but the NpCo and both sweepings samples left visible solid residue after dissolution. For the NpCo and Part II Sweepings samples the residue amounted to {approx}1% of the initial material, but for the Part I Sweepings sample, the residue amounted to {approx}8 % of the initial material. These residues contained primarily aluminum (Al) and silicon (Si) compounds that did not completely dissolve under the flowsheet conditions. The residues from both sweepings samples contained minor amounts of plutonium (Pu) particles. Overall, the undissolved Np and Pu particles in the residues were a very small fraction of the total solids.

  7. New neptunium(V) borates that exhibit the alexandrite effect.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2012-01-01

    A new neptunium(V) borate, K[(NpO(2))B(10)O(14)(OH)(4)], was synthesized using boric acid as a reactive flux. The compound possesses a layered structure in which Np(V) resides in triangular holes, creating a hexagonal-bipyramidal environment around neptunium. This compound is unusual in that it exhibits the Alexandrite effect, a property that is typically restricted to neptunium(IV) compounds.

  8. Investigation of Neptunium Precipitator Cleanout Options

    SciTech Connect

    Hill, B.C.

    2003-09-08

    Oxalate precipitation followed by filtration is used to prepare plutonium oxalate. Historically, plutonium oxalate has tended to accumulate in the precipitation tanks. These solids are periodically removed by flushing with concentrated (64 percent) nitric acid. The same precipitation tanks will now be used in the processing of neptunium. Literature values indicate that neptunium oxalate may not be as soluble as plutonium oxalate in nitric acid. Although a wide variety of options is available to improve neptunium oxalate solubility for precipitator flushing, most of these options are not practical for use. Many of these options require the use of incompatible or difficult to handle chemicals. Other options would require expensive equipment modifications or are likely to lead to product contamination. Based on review of literature and experimental results, the two best options for flushing the precipitator are (1) 64 percent nitric acid and (2) addition of sodium permanganate follow ed by sodium nitrite. Nitric acid is the easiest option to implement. It is already used in the facility and will not lead to product contamination. Experimental results indicate that neptunium oxalate can be dissolved in concentrated nitric acid (64 percent) at 60 degree C to a concentration of 2.6 to 5.6 grams of Np/liter after at least three hours of heating. A lower concentration (1.1 grams of Np/liter) was measured at 60 degree C after less than two hours of heating. These concentrations are acceptable for flushing if precipitator holdup is low (approximately 100-250 grams), but a second method is required for effective flushing if precipitator holdup is high (approximately 2 kilograms). The most effective method for obtaining higher neptunium concentrations is the use of sodium permanganate followed by the addition of sodium nitrite. There is concern that residual manganese from these flushes could impact product purity. Gas generation during permanganate addition is also a concern

  9. Incorporation of neptunium(VI) into a uranyl selenite.

    PubMed

    Meredith, Nathan A; Polinski, Matthew J; Lin, Jian; Simonetti, Antonio; Albrecht-Schmitt, Thomas E

    2012-10-15

    The incorporation of neptunium(VI) into the layered uranyl selenite Cs[(UO(2))(HSeO(3))(SeO(3))] has yielded the highest level of neptunium uptake in a uranyl compound to date with an average of 12(±3)% substitution of Np(VI) for U(VI). Furthermore, this is the first case in nearly 2 decades of dedicated incorporation studies in which the oxidation state of neptunium has been determined spectroscopically in a doped uranyl compound and also the first time in which neptunium incorporation has resulted in a structural transformation.

  10. Neptunium flow-sheet verification at reprocessing plants

    SciTech Connect

    Rance, P.; Chesnay, B.; Killeen, T.; Murray, M.; Nikkinen, M.; Petoe, A.; Plumb, J.; Saukkonen, H.

    2007-07-01

    Due to their fissile nature, neptunium and americium have at least a theoretical potential application as nuclear explosives and their proliferation potential was considered by the IAEA in studies in the late 1990's. This work was motivated by an increased awareness of the proliferation potential of americium and neptunium and a number of emerging projects in peaceful nuclear programmes which could result in an increase in the available quantities of these minor actinides. The studies culminated in proposals for various voluntary measures including the reporting of international transfers of separated americium and neptunium, declarations concerning the amount of separated neptunium and americium held by states and the application of flow-sheet verification to ensure that facilities capable of separating americium or neptunium are operated in a manner consistent with that declared. This paper discusses the issue of neptunium flowsheet verification in reprocessing plants. The proliferation potential of neptunium is first briefly discussed and then the chemistry of neptunium relevant to reprocessing plants described with a view to indicating a number of issues relevant to the verification of neptunium flow-sheets. Finally, the scope of verification activities is discussed including analysis of process and engineering design information, plant monitoring and sampling and the potential application of containment and surveillance measures. (authors)

  11. Neptunium concentrations in solutions contacting actinide-doped glass

    SciTech Connect

    Rai, D.; McVay, G.L.; Strickert, R.G.

    1982-07-01

    To help predict concentrations of neptunium leached from nuclear waste repositories in geologic environments, the solubility of neptunium in a neptunium-doped borosilicate glass, which simulates a high-level waste glass, was investigated. The concentrations of neptunium in solutions contacting the crushed doped glass were found to be controlled by a neptunium solid phase that is similar to crystalline(c) NpO/sub 2/ in solubility. Thus, the maximum concentration of the neptunium leached from this waste form can be predicted from the solubility of NpO/sub 2/(c). This conclusion is based on similar neptunium concentrations in solutions contacting neptunium-doped glass, neptunium-doped glass plus NpO/sub 2/(c), and NpO/sub 2/(c) alone, under controlled redox potentials and a range of pH values. The quinhydrone used in this study was found to be a very effective redox buffer (the approximate pe + pH = 11.8). The predictions based on the thermodynamic data and the solvent extraction tests showed Np(V) to be the primary oxidation state in solution.

  12. Subminiature eddy current transducers for studying boride coatings

    NASA Astrophysics Data System (ADS)

    Dmitriev, S. F.; Ishkov, A. V.; Malikov, V. N.; Sagalakov, A. M.

    2016-07-01

    Strengthening of parts and units of machines, increased reliability and longer service life is an important task of modern mechanical engineering. The main objects of study in the work were selected steel 65G and 50HGA, wear-resistant boride coatings ternary system Fe-B-Fe n B which were investigated by scanning electron microscopy and eddy-current nondestructive methods.

  13. Development and application of high strength ternary boride base cermets

    SciTech Connect

    Takagi, Ken-ichi . E-mail: u4381@toyokohan.co.jp

    2006-09-15

    Reaction boronizing sintering is a novel strategy to form a ternary boride coexisting with a metal matrix in a cermet during liquid phase sintering. This new sintering technique has successfully developed world first ternary boride base cermets with excellent mechanical properties such as Mo{sub 2}FeB{sub 2}, Mo{sub 2}NiB{sub 2} and WCoB base ones. In these cermets Mo{sub 2}FeB{sub 2} and Mo{sub 2}NiB{sub 2} base ones consist of a tetragonal M {sub 3}B{sub 2} (M: metal)-type complex boride as a hard phase and a transition metal base matrix. The cermets have already been applied to wear resistant applications such as injection molding machine parts, can making tools, and hot copper extruding dies, etc. This paper focuses on the characteristics, effects of the additional elements on the mechanical properties and structure, and practical applications of the ternary boride base cermets. - Graphical abstract: TRS and hardness of Ni-5B-51Mo-17.5Cr and Ni-5B-51Mo-12.5Cr-5V-xMn mass% cermets as functions of Mn content (Fig. 17)

  14. Dissolution of Neptunium Oxide in Unirradiated Mark 53 Targets

    SciTech Connect

    Rudisill, T.S.

    2002-12-06

    Nine unirradiated Mark 53 targets currently stored at the K-Reactor must be dissolved to allow recovery of the neptunium content. The Mark 53 targets are an aluminum clad, neptunium oxide (NpO2)/aluminum metal cermet used for the production of plutonium-238. The targets will be dissolved in H-Canyon and blended with solutions generated from routine fuel dissolutions for purification by solvent extraction. The increased neptunium concentration should not have a significant effect on the neptunium decontamination factor achieved by the 1st cycle of solvent extraction; however, the neptunium content of the uranium product (1CU) will likely increase in proportion to the increase in the neptunium feed concentration. The recovered neptunium will be combined with the existing inventory of neptunium solution currently stored in H-Canyon. The combined inventory will undergo subsequent purification and conversion to an oxide for shipment to the Oak Ridge National Laboratory where plutonium- 238 will be manufactured using the High Flux Isotope Reactor.

  15. Comparison of neptunium sorption results using batch and column techniques

    SciTech Connect

    Triay, I.R.; Furlano, A.C.; Weaver, S.C.; Chipera, S.J.; Bish, D.L.

    1996-08-01

    We used crushed-rock columns to study the sorption retardation of neptunium by zeolitic, devitrified, and vitric tuffs typical of those at the site of the potential high-level nuclear waste repository at Yucca Mountain, Nevada. We used two sodium bicarbonate waters (groundwater from Well J-13 at the site and water prepared to simulate groundwater from Well UE-25p No. 1) under oxidizing conditions. It was found that values of the sorption distribution coefficient, Kd, obtained from these column experiments under flowing conditions, regardless of the water or the water velocity used, agreed well with those obtained earlier from batch sorption experiments under static conditions. The batch sorption distribution coefficient can be used to predict the arrival time for neptunium eluted through the columns. On the other hand, the elution curves showed dispersivity, which implies that neptunium sorption in these tuffs may be nonlinear, irreversible, or noninstantaneous. As a result, use of a batch sorption distribution coefficient to calculate neptunium transport through Yucca Mountain tuffs would yield conservative values for neptunium release from the site. We also noted that neptunium (present as the anionic neptunyl carbonate complex) never eluted prior to tritiated water, which implies that charge exclusion does not appear to exclude neptunium from the tuff pores. The column experiments corroborated the trends observed in batch sorption experiments: neptunium sorption onto devitrified and vitric tuffs is minimal and sorption onto zeolitic tuffs decreases as the amount of sodium and bicarbonate/carbonate in the water increases.

  16. Environmental monitoring for uranium and neptunium at Yucca Mountain

    SciTech Connect

    Riggle, K.J.

    1992-11-01

    In this paper Epithermal Neutron Activation Analysis (ENAA) is investigated as an analysis method for uranium and neptunium in environmental samples from Yucca Mountain. The design and construction of a facility for this technique are described. Theoretical improvements in sensitivity for ENAA over thermal Neutron Activation Analysis (NAA) are discussed and compared to experimental results for different sample types. Uranium is analyzed in eight different sample matrices, including samples from Yucca Mountain. To date, neptunium has been studied only in AGV-1 Granite. As predicted by theory, uranium shows a high sensitivity improvement factor (average = 7.76), while neptunium has a factor of only 0.49. Detection limits for uranium using ENAA range from 6 to 52 ppb (2.6 to 17 ng). neptunium shows a detection limit of 57 ppb (6.2 ng). Using thermal NAA, neptunium can be analyzed to 35 ppb (3.4 ng).

  17. PERFORMANCE OF THE SAVANNAH RIVER SITE COULOMETER FOR NEPTUNIUM PROCESSACCOUNTABILITY AND NEPTUNIUM OXIDE PRODUCT CHARACTERIZATION

    SciTech Connect

    Holland, M; Patterson Nuessle, P; Sheldon Nichols, S; Joe Cordaro, J; George Reeves, G

    2008-06-04

    The Savannah River Site's (SRS) H-Area B-Line (HB-Line) nuclear facility is processing neptunium solutions for stabilization as an oxide. The oxide will eventually be reprocessed and fabricated into target material and the 237Np irradiated to produce {sup 238}Pu in support of National Aeronautics and Space Administration space program missions. As part of nuclear materials accountability, solution concentrations were measured using a high-precision controlled-potential coulometer developed and manufactured at the SRS for plutonium accountability measurements. The Savannah River Site Coulometer system and measurement methodology for plutonium meets performance standards in ISO 12183-2005, 'Controlled-Potential Coulometric Assay of Plutonium'. The Department of Energy (DOE) does not produce or supply a neptunium metal certified reference material, which makes qualifying a measurement method and determining accuracy and precision difficult. Testing and performance of the Savannah River Site Coulometer indicates that it can be used to measure neptunium process solutions and dissolved neptunium oxide without purification for material control and accountability purposes. Savannah River Site's Material Control and Accountability organization has accepted the method uncertainty for accountability and product characterization measurements.

  18. Nanosize cobalt boride particles: Control of the size and properties

    NASA Astrophysics Data System (ADS)

    Petit, C.; Pileni, M. P.

    1997-02-01

    Cobalt boride is obtained by the reduction of cobalt (2-ethyl hexyl) sulfosuccinate, Co(AOT) 2, by sodium borohydride either in reverse micelles or in a diphasic system. In Co(AOT) 2/Na(AOT)/H 2O reverse micellar solution, the size and polydispersity of the Co 2B particles is controlled by the size of the water droplets, which increases from 4 to 7.5 nm by increasing the water content. In a diphasic system of Co(AOT) 2/isooctane and sodium borohydride in aqueous solution, large and polydisperse particles of cobalt boride are formed (˜ 10 nm), and their magnetization properties are presented. The smallest particles are in a superparamagnetic regime at room temperature, whereas the largest particles show ferromagnetic behavior.

  19. Structural and Magnetic Properties of Ni Rich Amorphous Boride Nanoparticles

    SciTech Connect

    Singh, Vidyadhar; Banerjee, Progna; Srinivas, V.; Babu, N. H.

    2011-06-30

    The Ni rich amorphous boride nanoparticles can be prepared very easily by the solid-solid reaction of the NiCl{sub 2} and NaBH{sub 4} powders at room temperature. XRD, DTA-TG, FESEM, TEM, and selected-area electron diffraction characterize the resultant nanoparticles. The results show that the resultant is mainly composed of the amorphous Ni-B alloy nanoparticles with an average diameter of 15-25 nm.

  20. Neptunium Binding Kinetics with Arsenazo(III)

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Stephen P. Mezyk

    2014-08-01

    This document has been prepared to meet FCR&D level 2 milestone M2FT-14IN0304021, “Report on the results of actinide binding kinetics with aqueous phase complexants” This work was carried out under the auspices of the Thermodynamics and Kinetics of Advanced Separations Systems FCR&D work package. The report details kinetics experiments that were performed to measure rates of aqueous phase complexation for pentavalent neptunium with the chromotropic dye Arsenazo III (AAIII). The studies performed were designed to determine how pH, ionic strength and AAIII concentration may affect the rate of the reaction. A brief comparison with hexavalent neptunium is also made. It was identified that as pH was increased the rate of reaction also increased, however increasing the ionic strength and concentration of AAIII had the opposite effect. Interestingly, the rate of reaction of Np(VI) with AAIII was found to be slower than that of the Np(V) reaction.

  1. Neptunium(III) application in extraction chromatography.

    PubMed

    Guérin, Nicolas; Nadeau, Kenny; Larivière, Dominic

    2011-12-15

    This paper describes a novel strategy for actinide separation by extraction chromatography with Np(III) valence adjustment. Neptunium(IV) was reduced to Np(III) using Cr(II) and then selectively separated from uranium (IV) on a TEVA resin. After elution, Np(III) was retained on a DGA resin in order to remove any detrimental chromium impurities. Neptunium(III) formation was demonstrated by the complete and selective elution of Np from TEVA resin (99 ± 7%) in less than 12 mL of 9M HCl from U(IV) (0.7 ± 0.7%). It was determined by UV-visible and kinetic studies that Cr(II) was the only species responsible for the elution of Np(IV) as Np(III) and that the Cr(II) solution could be prepared from 2 to 30 min before its use without the need of complex degassing systems to prevent the oxidation of Np(III) by oxygen. The methodology proposed here with TEVA/DGA resins provides removal of Cr(III) impurities produced at high decontamination factors (2.8 × 10(3) and 7.3 × 10(4) respectively).

  2. The production of Neptunium-236g.

    PubMed

    Jerome, S M; Ivanov, P; Larijani, C; Parker, D J; Regan, P H

    2014-12-01

    Radiochemical analysis of (237)Np is important in a number of fields, such as nuclear forensics, environmental analysis and measurements throughout the nuclear fuel cycle. However analysis is complicated by the lack of a stable isotope of neptunium. Although various tracers have been used, including (235)Np, (239)Np and even (236)Pu, none are entirely satisfactory. However, (236g)Np would be a better candidate for a neptunium yield tracer, as its long half-life means that it is useable as both a radiometric and mass spectrometric measurements. This radionuclide is notoriously difficult to prepare, and limited in scope. In this paper, we examine the options for the production of (236g)Np, based on work carried out at NPL since 2011. However, this work was primarily aimed at the production of (236)Pu, and not (236g)Np and therefore the rate of production are based on the levels of (236)Pu generated in the irradiation of (i) (238)U with protons, (ii) (235)U with deuterons, (iii) (236)U with protons and (iv) (236)U with deuterons. The derivation of a well-defined cross section is complicated by the relevant paucity of information on the variation of the (236m)Np:(236g)Np production ratio with incident particle energy. Furthermore, information on the purity of (236g)Np so produced is similarly sparse. Accordingly, the existing data is assessed and a plan for future work is presented.

  3. Surface Complexation of Neptunium(V) with Goethite

    SciTech Connect

    Jerden, James L.; Kropf, A. Jeremy

    2007-07-01

    Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH less than 5.0 to greater than 10,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np

  4. Dissolution of Neptunium Oxide in Unirradiated Mark 53 Targets

    SciTech Connect

    Rudisill, T.S.

    2002-06-07

    Nine unirradiated Mark 53 targets currently stored at the K-Reactor must be dissolved to allow recovery of the neptunium content. The Mark 53 targets are an aluminum clad neptunium oxide (NpO2)/aluminum metal cermet used for the production of plutonium-238. The targets will be dissolved in H-Canyon and blended with solutions generated from routine fuel dissolutions for purification by solvent extraction

  5. Neptunium Disposal to the Savannah River Site Tank Farm

    SciTech Connect

    Walker, D.D.

    2004-02-26

    Researchers investigated the neutralization of an acidic neptunium solution from a Savannah River Site (SRS) processing canyon and the properties of the resulting slurry to determine the feasibility of disposal in the SRS tank farm. The acidic solution displayed no properties that precluded the proposed disposal route. Neutralization of the acidic neptunium forms a 4 wt per cent slurry of precipitated metal hydroxides. The insoluble solids consist largely of iron (92 per cent) and neptunium hydroxides (2 per cent). The concentration of soluble neptunium remaining after neutralization equaled much less than previous solubility measurements predicted. Researchers used an apparatus similar to an Ostwald-type viscometer to estimate the consistency of the neptunium slurry with the solids present. The yield stress and consistency of the 4 wt per cent slurry will allow transfer through the tank farm, although concentration of the insoluble solids above 4 wt per cent may cause significant problems due to increased consistency and yield stress. The consistency of the 4 wt per cent slurry is 7.6 centipoise (cP) with a yield stress less than 1 Pascal (Pa). The neptunium slurry, when combined with actual washed radioactive sludge, slightly reduces the yield stress and consistency of the sludge and produces a combined slurry with acceptable rheological properties for vitrification.

  6. Characterisation of titanium-titanium boride composites processed by powder metallurgy techniques

    SciTech Connect

    Selva Kumar, M.; Chandrasekar, P.; Chandramohan, P.; Mohanraj, M.

    2012-11-15

    In this work, a detailed characterisation of titanium-titanium boride composites processed by three powder metallurgy techniques, namely, hot isostatic pressing, spark plasma sintering and vacuum sintering, was conducted. Two composites with different volume percents of titanium boride reinforcement were used for the investigation. One was titanium with 20% titanium boride, and the other was titanium with 40% titanium boride (by volume). Characterisation was performed using X-ray diffraction, electron probe micro analysis - energy dispersive spectroscopy and wavelength dispersive spectroscopy, image analysis and scanning electron microscopy. The characterisation results confirm the completion of the titanium boride reaction. The results reveal the presence of titanium boride reinforcement in different morphologies such as needle-shaped whiskers, short agglomerated whiskers and fine plates. The paper also discusses how mechanical properties such as microhardness, elastic modulus and Poisson's ratio are influenced by the processing techniques as well as the volume fraction of the titanium boride reinforcement. - Highlights: Black-Right-Pointing-Pointer Ti-TiB composites were processed by HIP, SPS and vacuum sintering. Black-Right-Pointing-Pointer The completion of Ti-TiB{sub 2} reaction was confirmed by XRD, SEM and EPMA studies. Black-Right-Pointing-Pointer Hardness and elastic properties of Ti-TiB composites were discussed. Black-Right-Pointing-Pointer Processing techniques were compared with respect to their microstructure.

  7. Reactive Boride Brazing on Low-Alloy Automotive Grade Steel

    NASA Astrophysics Data System (ADS)

    Palanisamy, B.; Upadhyaya, A.

    2011-11-01

    Brazing is a widely used process to improve the performance of steels used in automotive applications. The substrate material is often exposed to harsh conditions in these applications and may affect the service life of the component. Reactive boride brazing aims to improve the mechanical properties of the substrate material by forming a ceramic-metal composite coating in a single-step process in situ. In this study, sintered Ancor 4300 low-alloy steel is used as the substrate with chromium-rich braze and chromium-lean braze materials. The mechanical properties of the brazed samples were studied in detail using microindentation hardness measurements and the transverse rupture test. The results indicate that the brazed superlayer has a 10 times higher hardness. There was a significant improvement in the transverse rupture strength of the steel brazed with the chromium-rich boride as compared to the pure substrate material. In an effort to reduce processing time, green compacts of the substrate were also directly brazed and yielded favorable results.

  8. Discovery of elusive structures of multifunctional transition-metal borides.

    PubMed

    Liang, Yongcheng; Wu, Zhaobing; Yuan, Xun; Zhang, Wenqing; Zhang, Peihong

    2016-01-14

    A definitive determination of crystal structures is an important prerequisite for designing and exploiting new functional materials. Even though tungsten and molybdenum borides (TMBx) are the prototype for transition-metal light-element compounds with multiple functionalities, their elusive crystal structures have puzzled scientists for decades. Here, we discover that the long-assumed TMB2 phases with the simple hP3 structure (hP3-TMB2) are in fact a family of complex TMB3 polytypes with a nanoscale ordering along the axial direction. Compared with the energetically unfavorable and dynamically unstable hP3-TMB2 phase, the energetically more favorable and dynamically stable TMB3 polytypes explain the experimental structural parameters, mechanical properties, and X-ray diffraction (XRD) patterns better. We demonstrate that such a structural and compositional modification from the hP3-TMB2 phases to the TMB3 polytypes originates from the relief of the strong antibonding interaction between d electrons by removing one third of metal atoms systematically. These results resolve the longstanding structural mystery of this class of metal borides and uncover a hidden family of polytypic structures. Moreover, these polytypic structures provide an additional hardening mechanism by forming nanoscale interlocks that may strongly hinder the interlayer sliding movements, which promises to open a new avenue towards designing novel superhard nanocomposite materials by exploiting the coexistence of various polytypes.

  9. Gas Generation Testing of Neptunium Oxide at Elevated Temperature

    SciTech Connect

    Duffey, JM

    2004-01-30

    Elevated temperature gas generation tests have been conducted using neptunium dioxide produced on a laboratory scale using the HB-Line Phase II flowsheet. These tests were performed to determine what effect elevated temperatures would have on the neptunium dioxide in comparison to neptunium dioxide tested at ambient temperature. The headspace gas compositions following storage at elevated temperatures associated with normal conditions of transport (NCT) have been measured. These test results show an increase in hydrogen generation rate at elevated temperature and significant removal of oxygen from the headspace gas. The elevated temperature gas generation tests described in this report involved heating small test vessels containing neptunium dioxide and measuring the headspace gas pressure and composition at the end of the test period. Four samples were used in these tests to evaluate the impact of process variables on the gas generation rate. Two samples were calcined to 600 degrees Celsius and two were calcined to 650 degrees Celsius. Each test vessel contained approximately 9.5 g of neptunium dioxide. Following exposure to 75 per cent relative humidity (RH) for five days, these samples were loaded in air and then heated to between 105 and 115 degrees Celsius for about one month. At the conclusion of the test period, the headspace gas of each container was analyzed using a micro-gas chromatograph installed in the glovebox where the experiments were conducted. The pressure, volume, and composition data for the headspace gas samples were used to calculate average H2 generation rates.

  10. Neptunium interaction with uranium dioxide in aqueous solution

    NASA Astrophysics Data System (ADS)

    Batuk, O. N.; Kalmykov, St. N.; Petrov, V. G.; Zakharova, E. V.; Teterin, Yu. A.; Teterin, A. Yu.; Shapovalov, V. I.; Haire, M. J.

    2007-05-01

    Neptunium, Np(V) and Np(IV), sorption onto uranium dioxide surface was studied at various values of pH. Sorption was studied in two sets of experiments with different redox conditions that correspond to either Np(V) (Set 1) or Np(IV) (Set 2) in solution. In Set 1 the reduction of Np(V) was established when low pH solution covered a UO2 surface. When the pH increased, the sorption of neptunium is decreased. At pH > 5.5 neptunium sequestration from solution is governed by Np(V) sorption onto UO2.25. In Set 2 (the more anoxic conditions) complete neptunium sorption is established at pH > 2: it is present in the tetravalent form over the whole pH range. The proposed mechanisms of neptunium sorption was suggested by using pH sorption edges of Th(IV) as an analog to Np(IV) onto UO2 and Np(V) onto ThO2. The UO2 surface was characterized by X-ray photoelectron spectroscopy (XPS) after equilibration with aqueous solutions at different pH values.

  11. Neptunium(V) Incorporation/Sorption with Uranium(VI) Alteration Products

    SciTech Connect

    Friese, Judah I.; Douglas, Matthew; Buck, Edgar C.; Clark, Susan B.; Hanson, Brady D.

    2004-04-01

    An initial uranium phase that has been observed to form during the corrosion of spent nuclear fuel is the uranium oxy-hydroxide metaschoepite. It has been proposed that neptunium(V) solubility can be limited by its association with this uranium phase. Metaschoepite has been synthesized in the presence of neptunium(V) over the pH range modeled in the proposed Yucca Mountain geologic repository. Uranium (VI) phaseswere synthesized by varying pH and neptunium concentrations. Results of neptunium association with the uranium alteration phases are presented and the relationship to dissolved neptunium concentrations discussed.

  12. Modified Purex first-cycle extraction for neptunium recovery

    SciTech Connect

    Dinh, Binh; Moisy, Philippe; Baron, Pascal; Calor, Jean-Noel; Espinoux, Denis; Lorrain, Brigitte; Benchikouhne-Ranchoux, Magali

    2008-07-01

    A new PUREX first-cycle flowsheet was devised to enhance the extraction yield of neptunium at the extraction step of this cycle. Simulation results (using a qualified process-simulation tool), le d to raising the nitric acid concentration of the feed from 3 M to 4.5 M to allow extraction of more than 99% of the neptunium. This flowsheet was operated in the shielded process cell of ATALANTE facility using pulsed columns and mixer-settlers banks. A 15 kg quantity of genuine oxide fuel of average burn up of 52 GWd/t with cooling time of nearly five years was treated, and the neptunium extraction yield obtained was greater than 99.6%. (authors)

  13. [Selective localization of neptunium-237 in nuclei of mammalian cells].

    PubMed

    Galle, P; Boulahdour, H; Metivier, H

    1992-01-01

    After injection in the rat of soluble neptunium salt, the distribution of this element was studied at the subcellular level by electron microscopy and electron probe microanalysis. Abnormal structures have been observed by electron microscopy in the nuclei of hepatocytes, and the same structures have also been observed in the nuclei of the proximal tubules cells of the kidney. These structures are formed of clusters of very small and dense particles, several nanometers in diameter. The clusters are localized in the central part of the nuclei and they are separate from nucleoli and heterochromatin. Electron probe X-ray analysis of this cluster have shown that they contain neptunium associated with phosphorus. In the cell containing neptunium inclusions, other non specific lesions are also observed (nuclear pycnosis, mitochondrial depletion).

  14. Ultrastructural lesions induced by neptunium-237: apoptosis or necrosis?

    PubMed

    Pusset, D; Fromm, M; Poncy, J L; Kantelip, B; Galle, P; Chambaudet, A; Baud, M; Boulahdour, H

    2002-07-01

    In this study, we are concerned with the 237 isotope of neptunium (237Np), which is a by-product of uranium in nuclear reactors. To study ultrastructural lesions induced by this element, a group of rats were injected with a solution of 237Np-nitrate once a day for 14 weeks. Lesions observed in liver and kidney are described using electron microscopy. Ultrastructural alterations of cellular membranes and intracellular organelles demonstrated the existence of neptunium toxicity. This toxicity was characterized by various lesions, such as cytoplasmic clarification, disappearance of mitochondrial cristae, swollen mitochondria, abnormal condensation of nuclear chromatin, and nuclear fragmentations. This study demonstrated the probable induction of apoptosis by neptunium both in liver and kidneys.

  15. Microstructure and properties of laser-borided composite layers formed on commercially pure titanium

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Makuch, N.; Dziarski, P.; Piasecki, A.; Miklaszewski, A.

    2014-03-01

    Laser-boriding was proposed in order to produce composite boride layers on commercially pure titanium. Three zones were observed in the microstructure: laser-borided re-melted zone (TiB, TiB2 and Tiα'-phase), heat affected zone (Tiα'-phase) and the substrate without heat treatment (Tiα-phase). The stick-like titanium borides occurred in the re-melted zone. In some areas, the tubular nature of titanium borides was visible. Among the sticks of titanium borides the needles of Tiα'-phase appeared. The high overlapping of multiple laser tracks (86%) caused the formation of uniform laser-alloyed layer in respect of the thickness. The microcracks and pores were not detected in the laser-borided composite layer. The high hardness of the re-melted zone (1250-1650 HV) was obtained. The hardness gradually decreased up to 250-300 HV in heat affected zone and up to about 200 HV in the substrate. In case of higher laser beam power used (1.95 kW), the re-melted zone was thicker and more homogeneous in respect of the microstructure and hardness. The craters obtained at the surface after the Rockwell C indentation test evidently revealed ideal cohesion of the laser-borided layer (HF1 standard). The significant increase in wear resistance of laser-borided composite layers was observed in comparison with commercially pure titanium. The lower mass wear intensity factors were obtained for laser-alloyed layers. The measurements of relative mass loss were also used in order to evaluate wear behavior of the investigated materials. The tests of laser-borided layers showed the catastrophic wear of the counter-specimens. The separated particles of counter-sample caused the accelerated wear of the laser-alloyed specimen. The longer duration of the tests, carried out without the change in a counter-specimen, caused the adhesion of counter-sample particles on the laser-borided specimen. The increased contact surface was the reason for the higher temperature and created the favourable

  16. Deposition and characterization of aluminum magnesium boride thin film coatings

    NASA Astrophysics Data System (ADS)

    Tian, Yun

    Boron-rich borides are a special group of materials possessing complex structures typically comprised of B12 icosahedra. All of the boron-rich borides sharing this common structural unit exhibit a variety of exceptional physical and electrical properties. In this work, a new ternary boride compound AlMgB14, which has been extensively studied in bulk form due to its novel mechanical properties, was fabricated into thin film coatings by pulsed laser deposition (PLD) technology. The effect of processing conditions (laser operating modes, vacuum level, substrate temperature, and postannealing, etc.) on the composition, microstructure evolution, chemical bonding, and surface morphology of AlMgB14 thin film coatings has been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectrometry; the mechanical, electrical, and optical properties of AlMgB14 thin films have been characterized by nanoindentation, four-point probe, van der Pauw Hall measurement, activation energy measurement, and UV-VIS-NIR spectrophotometer. Experimental results show that AlMgB14 films deposited in the temperature range of 300 K - 873 K are amorphous. Depositions under a low vacuum level (5 x 10-5 Torr) can introduce a significant amount of C and O impurities into AlMgB14 films and lead to a complex oxide glass structure. Orthorhombic AlMgB14 phase cannot be obtained by subsequent high temperature annealing. By contrast, the orthorhombic AlMgB 14 crystal structure can be attained via high temperature-annealing of AlMgB14 films deposited under a high vacuum level (< 3 x 10-6 Torr), accompanied by strong texture formation. Low vacuum level-as deposited AlMgB14 films have low hardness (10 GPa), but high vacuum level-as deposited AlMgB14 films exhibit an extremely high hardness (45 GPa - 51 GPa), and the higher deposition temperature results in still higher hardness

  17. An alternative method of gas boriding applied to the formation of borocarburized layer

    SciTech Connect

    Kulka, M. Makuch, N.; Pertek, A.; Piasecki, A.

    2012-10-15

    The borocarburized layers were produced by tandem diffusion processes: carburizing followed by boriding. An alternative method of gas boriding was proposed. Two-stage gas boronizing in N{sub 2}-H{sub 2}-BCl{sub 3} atmosphere was applied to the formation of iron borides on a carburized substrate. This process consisted in two stages, which were alternately repeated: saturation by boron and diffusion annealing. The microstructure and microhardness of produced layer were compared to those-obtained in case of continuous gas boriding in H{sub 2}-BCl{sub 3} atmosphere, earlier used. The first objective of two-stage boronizing, consisting in acceleration of boron diffusion, has been efficiently implemented. Despite the lower temperature and shorter duration of boronizing, about 1.5 times larger iron borides' zone has been formed on carburized steel. Second objective, the absolute elimination of brittle FeB phase, has failed. However, the amount of FeB phase has been considerably limited. Longer diffusion annealing should provide the boride layer with single-phase microstructure, without FeB phase. - Highlights: Black-Right-Pointing-Pointer Alternative method of gas boriding in H{sub 2}-N{sub 2}-BCl{sub 3} atmosphere was proposed. Black-Right-Pointing-Pointer The process consisted in two stages: saturation by boron and diffusion annealing. Black-Right-Pointing-Pointer These stages of short duration were alternately repeated. Black-Right-Pointing-Pointer The acceleration of boron diffusion was efficiently implemented. Black-Right-Pointing-Pointer The amount of FeB phase in the boride zone was limited.

  18. [Mechanism of distribution of neptunium and plutonium in rats].

    PubMed

    Zhuravleva, A K

    1984-01-01

    Neptunium administered intravenously together with the high molecular weight protein fraction of blood serum was almost completely accumulated by the liver after 60 min. Then neptunium left the liver and was partially deposited in the skeleton. Plutonium, being a component of a nonprotein and a low molecular weight protein fractions, was mainly found in the skeleton where it had been accumulated throughout the entire period of observation (14 days, 52-58%); as to the nonprotein fraction, the value of accumulation was somewhat higher.

  19. Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth

    NASA Astrophysics Data System (ADS)

    Johnston, Jamin M.; Jubinsky, Matthew; Catledge, Shane A.

    2015-02-01

    Chemical vapor deposited (CVD) diamond coatings can potentially improve the wear resistance of cobalt-chromium medical implant surfaces, but the high cobalt content in these alloys acts as a catalyst to form graphitic carbon. Boriding by high temperature liquid baths and powder packing has been shown to improve CVD diamond compatibility with cobalt alloys. We use the microwave plasma-enhanced (PE) CVD process to deposit interlayers composed primarily of the borides of cobalt and chromium. The use of diborane (B2H6) in the plasma feedgas allows for the formation of a robust boride interlayer for suppressing graphitic carbon during subsequent CVD of nano-structured diamond (NSD). This metal-boride interlayer is shown to be an effective diffusion barrier against elemental cobalt for improving nucleation and adhesion of NSD coatings on a CoCrMo alloy. Migration of elemental cobalt to the surface of the interlayer is significantly reduced and undetectable on the surface of the subsequently-grown NSD coating. The effects of PECVD boriding are compared for a range of substrate temperatures and deposition times and are evaluated using glancing-angle X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and micro-Raman spectroscopy. Boriding of CoCrMo results in adhered nanostructured diamond coatings with low surface roughness.

  20. Neptunium redox speciation at the illite surface

    NASA Astrophysics Data System (ADS)

    Marsac, Rémi; Banik, Nidhu lal; Lützenkirchen, Johannes; Marquardt, Christian Michael; Dardenne, Kathy; Schild, Dieter; Rothe, Joerg; Diascorn, Alexandre; Kupcik, Tomas; Schäfer, Thorsten; Geckeis, Horst

    2015-03-01

    Neptunium (Np(V)) sorption onto a purified illite is investigated as a function of pH (3-10) and [NpVO2+]tot(3 × 10-8-3 × 10-4 M) in 0.1 M NaCl under Ar atmosphere. After about one week reaction time, only insignificant variation of Np sorption is observed and the establishment of reaction equilibrium can be assumed. Surprisingly, solid-liquid distribution ratios (Rd) are clearly higher than those measured for Np(V) sorption onto illite under aerobic conditions. The observation that Rd increases with decreasing pe (pe = -log ae-) suggests partial reduction to Np(IV), although measured redox potentials (pe values) at a first glance suggest the predominance of Np(V). Reduction to Np(IV) at the illite surface could indeed be confirmed by X-ray absorption near-edge spectroscopy (XANES). Np speciation in presence of the purified Na-illite under given conditions is consistently described by applying the 2 sites protolysis non-electrostatic surface complexation and cation exchange model. Measured pe data are taken to calculate Np redox state and surface complexation constants for Np(IV) are derived by applying a data fitting procedure. Constants are very consistent with results obtained by applying an existing linear free energy relationship (LFER). Taking Np(IV) surface complexation constants into account shifts the calculated Np(V)/Np(IV) redox borderline in presence of illite surfaces by 3-5 pe units (0.2-0.3 V) towards redox neutral conditions. Our study suggests that Np(V) reduction in presence of a sorbing mineral phase is thermodynamically favored.

  1. Morphology and structure of borides in as-cast titanium and gamma-titanium aluminide-based alloys

    NASA Astrophysics Data System (ADS)

    Kitkamthorn, Usanee

    In this study, the morphology and structure of the borides in boron-modified Ti- and gamma-TiAl-based alloys have been investigated using SEM, TEM, and HRTEM. A variety of different boride morphologies was observed including plates, needles, and ribbons. For the plate and needle borides, the major boride phase is B27 TiB. The needle borides have their major axis parallel to [010], and are bounded by (100) and {101} type-facets. The plate borides develop the same types of facets as the needles and have habit planes parallel to the (100). There are high densities of intrinsic stacking faults on (100) in these borides and these correspond to thin embedded layers of the Bf structure. The plate borides do not exhibit well-defined ORs with respect to the surrounding phases, suggesting that they develop in the liquid melt and were then trapped by the growing solid. Needle borides are observed mostly at boundaries between lamellar colonies: these needles tend to occur in groups lying nearly parallel to one another and, in some cases, to adopt well-defined ORs with respect to the surrounding phases. Cored borides with metallic phases such as beta, alpha, o and alpha 2+gamma in the center are frequently observed, especially in the Ti-based alloy. These core phases usually adopt well-defined ORs with respect to the surrounding boride which enable low-energy coherent interfaces to form between the phases. The ribbon borides are comprised of thin boride flakes interspersed with thin metallic layers. The major boride phase in these flakes is Bf TiB. The habit plane of the flakes is (010) and there are high densities of faults on this plane corresponding to intergrowths of the Ti3B 4 and TiB2 phases, together with thin layers or occluded pockets of metallic B2 phase. Occasional faults are observed on {110} corresponding to embedded slabs of B27 TiB. There is a well-defined OR between the boride flakes and the B2 phase within the ribbons, but not with the surrounding matrix. The

  2. Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet

    SciTech Connect

    Laurinat, J. E.

    2006-04-01

    A flowsheet has been proposed to separate neptunium from solutions in H-Canyon Tanks 16.4, 12.5, and 11.7 in the First Cycle solvent extraction banks, in which cerium(IV) (Ce(IV)) serves as an agent to oxidize neptunium to neptunium(VI) (Np(VI)). A SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction) spreadsheet model indicates that the proposed flowsheet is a feasible method for separating neptunium and uranium from sulfates, thorium, and other metal impurities. The proposed flowsheet calls for stripping the sulfates, thorium, and other metal impurities into the 1AW stream and extracting and then stripping the neptunium and uranium into the 1BP stream. SASSE predicts that separation of thorium from the other actinides can be accomplished with actinide losses of 0.01% or less. It is assumed that other metal impurities such as iron, aluminum, and fission products will follow the thorium into 1AW. Due to an organic/aqueous distribution coefficient that is close to one, SASSE predicts that plutonium(VI) (Pu(VI)) is split between the A Bank and B Bank aqueous output streams, with 27% going to 1AW and 73% going to 1BP. An extrapolated distribution coefficient based on unvalidated Ce(IV) distribution measurements at a single nitrate concentration and a comparison with thorium(IV) (Th(IV)) distributions indicates that Ce(IV) could reflux in 1B Bank. If the Ce(IV) distribution coefficient is lower than would be predicted by this single point extrapolation, but still higher than the distribution coefficient for Th(IV), then Ce(IV) would follow Np(VI) and uranium(VI) (U(VI)) into 1BP. The SASSE model was validated using data from a 1964 oxidizing flowsheet for the recovery of Np(VI) in Second Cycle. For the proposed flowsheet to be effective in recovering neptunium, the addition of approximately 0.025 M ceric ammonium nitrate (Ce(NH4)2(NO3)6) to both the 1AF and 1AS streams is required to stabilize the neptunium in the +6

  3. Precipitation of neptunium dioxide from aqueous solution

    SciTech Connect

    Roberts, K E

    1999-12-01

    Tens of thousands of metric tons of highly radioactive, nuclear waste have been generated in the US. Currently, there is no treatment or disposal facility for these wastes. Of the radioactive elements in high-level nuclear waste, neptunium (Np) is of particular concern because it has a long half-life and may potentially be very mobile in groundwaters associated with a proposed underground disposal site at Yucca Mountain, Nevada. Aqueous Np concentrations observed in previous, short-term solubility experiments led to calculated potential doses exceeding proposed long-term regulatory limits. However, thermodynamic data for Np at 25 C showed that these observed aqueous Np concentrations were supersaturated with respect to crystalline NpO{sub 2}. It was hypothesized that NpO{sub 2} is the thermodynamically stable solid phase in aqueous solution, but it is slow to form in an aqueous solution of NpO{sub 2}{sup +} on the time scale of previous experiments. The precipitation of NpO{sub 2} would provide significantly lower aqueous Np concentrations leading to calculated doses below proposed regulatory limits. To test this hypothesis, solubility experiments were performed at elevated temperature to accelerate any slow precipitation kinetics. Ionic NpO{sub 2}{sup +} (aq) was introduced into very dilute aqueous solutions of NaCl with initial pH values ranging from 6 to 10. The reaction vessels were placed in an oven and allowed to react at 200 C until steady-state aqueous Np concentrations were observed. In all cases, aqueous Np concentrations decreased significantly from the initial value of 10{sup {minus}4} M. The solids that formed were analyzed by x-ray powder diffraction, x-ray absorption spectroscopy, and scanning electron microscopy. The solids were determined to be high-purity crystals of NpO{sub 2}. This is the first time that crystalline NpO{sub 2} has been observed to precipitate from NpO{sub 2}{sup +}(aq) in near-neutral aqueous solutions. The results obtained

  4. The Growth Behavior of Titanium Boride Layers in α and β Phase Fields of Titanium

    NASA Astrophysics Data System (ADS)

    Lv, Xiaojun; Hu, Lingyun; Shuang, Yajing; Liu, Jianhua; Lai, Yanqing; Jiang, Liangxing; Li, Jie

    2016-07-01

    In this study, the commercially pure titanium was successfully electrochemical borided in a borax-based electrolyte. The process was carried out at a constant cathodic current density of 300 mA cm-2 and at temperatures of 1123 K and 1223 K (850 °C and 950 °C) for 0.5, 1, 2, 3, and 5 hours. The growth behavior of titanium boride layers in the α phase field of titanium was compared with that in the β phase field. After boriding, the presence of both the TiB2 top layer and TiB whisker sub-layer was confirmed by the X-ray diffraction (XRD) and scanning electron microscope. The relationship between the thickness of boride layers and boriding time was found to have a parabolic character in both α and β phase fields of titanium. The TiB whiskers showed ultra-fast growth rate in the β phase field. Its growth rate constant was found to be as high as 3.2002 × 10-13 m2 s-1. Besides, the chemical resistance of the TiB2 layer on the surface of titanium substrate was characterized by immersion tests in molten aluminum.

  5. Metal boride catalysts for indirect liquefaction. Quarterly technical progress report, December 1, 1983-February 29, 1984

    SciTech Connect

    Bartholomew, C.H.

    1984-04-12

    During the sixth quarter four boron-promoted cobalt catalysts were prepared by a new boriding process using diborane gas as the boriding agent. These catalysts were characterized by chemical analysis, BET, H/sub 2/ chemisorption, and x-ray diffraction. Temperature-programmed desorption spectra of H/sub 2/ were obtained for a sodium-promoted cobalt boride and a sodium-promoted Co/SiO/sub 2/. Four cobalt catalysts (unsupported, boron-promoted, sodium-promoted, and doubly-promoted) were tested for CO hydrogenation activity and selectivity at 1 atm and 3 to 4 temperatures in the range of 190 to 240/sup 0/C. About 10% of the surface of cobalt boride consists of reduced metallic cobalt. The addition of sodium to cobalt increases its binding energy with H/sub 2/ and its activation energy for H/sub 2/ adsorption. Boron does not affect the activity of cobalt; sodium decreases it by a factor of 10. Cobalt boride produces lighter hydrocarbon products relative to cobalt; sodium-promoted cobalt produces heavier products, more alcohols, and more CO/sub 2/. 29 references, 10 figures, 4 tables.

  6. Neptunium (VI) and neptunium (VI/V) mixed valence cluster compounds

    SciTech Connect

    May, Iain

    2008-01-01

    Neptunium has three readily accessible oxidation states, IV, V and VI, which can coexist under certain conditions, with the aqueous soluble neptunyl(V) moiety, {l_brace}NpO{sub 2}{r_brace}{sup +}, of most environmental relevance. Careful control of Np chemistry is required during actinide separation processes. In addition, the long half life of the major alpha emitting isotope ({sup 237}Np, t{sub 1/2} = 2.144 x 10{sup 6} years) renders Np a major contributor to the radiotoxicity of nuclear waste as a function of time. Significant quantities of neptunium are generated in nuclear reactors and the current surge in interest in nuclear power will lead to an increase in our need to further understand the chemistry of this element. It is clearly of importance that Np chemistry is well understood and there have been several recent investigations into the structural, spectroscopic and magnetic properties of Np compounds. However, the vast majority of this chemistry has been performed in aqueous solution, prohibiting the use of air and moisture sensitive ligands. This is in stark contrast to uranium and thorium where inert atmosphere chemistry with moisture sensitive donor ligands has flourished, yielding greater insight into the structural and electronic properties of these early actinides. For the uranyl(VI) moiety, {l_brace}UO{sub 2}{r_brace}{sup 2+}, UO{sub 2}Cl{sub 2}(thf){sub 3} (and the desolvated dimer [UO{sub 2}Cl{sub 2}(thf)]{sub 2}) have proven to be excellent moisture-free reagents for inert atmosphere uranyl chemistry. These starting reagents have been used extensively within our group to study soft donor ligand coordination in the uranyl equatorial plane and oxo-activation to Lewis acid coordination. However, until now the absence of such a starting reagent for Np has limited our ability to extend this chemistry any further across the actinide series, which is required if we are to gain a more complete understanding of 5f element chemistry. The synthesis of [Np

  7. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold.

    PubMed

    Brown, Jessie L; Gaunt, Andrew J; King, David M; Liddle, Stephen T; Reilly, Sean D; Scott, Brian L; Wooles, Ashley J

    2016-04-01

    The syntheses and characterisation of isostructural neptunium(iv) and plutonium(iv) complexes [An(IV)(TREN(TIPS))(Cl)] [An = Np, Pu; TREN(TIPS) = {N(CH2CH2NSiPr(i)3)3}(3-)] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(iii) and plutonium(iii) products [An(III)(TREN(TIPS))]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(iv) molecule is the first structurally characterised neptunium(iv)-amide complex. PMID:27009799

  8. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold

    DOE PAGESBeta

    Brown, Jessie L.; Gaunt, Andrew J.; King, David M.; Liddle, Stephen T.; Reilly, Sean D.; Scott, Brian L.; Wooles, Ashley J.

    2016-03-11

    Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [MIV(TRENTIPS)(Cl)] [An = Np, Pu; TRENTIPS = {N(CH2CH2NSiPri3)3}3] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [MIII(TRENTIPS)]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.

  9. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold.

    PubMed

    Brown, Jessie L; Gaunt, Andrew J; King, David M; Liddle, Stephen T; Reilly, Sean D; Scott, Brian L; Wooles, Ashley J

    2016-04-01

    The syntheses and characterisation of isostructural neptunium(iv) and plutonium(iv) complexes [An(IV)(TREN(TIPS))(Cl)] [An = Np, Pu; TREN(TIPS) = {N(CH2CH2NSiPr(i)3)3}(3-)] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(iii) and plutonium(iii) products [An(III)(TREN(TIPS))]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(iv) molecule is the first structurally characterised neptunium(iv)-amide complex.

  10. Speciation-dependent toxicity of neptunium(V) toward chelatobacter heintzii.

    SciTech Connect

    Banaszak, J. E.; Reed, D. T.; Rittmann, B. E.; Chemical Engineering; Northwestern Univ.

    1998-04-15

    This work investigates how chemical speciation controls the toxicity of neptunium and the neptunium-NTA complex toward Chelatobacter heintzii. We studied the effect of aquo and complexed/precipitated neptunium on the growth of C. heintzii in noncomplexing glucose and phosphate-buffered nitrilotriacetic acid (NTA) growth media. Equilibrium chemical speciation modeling and absorption spectroscopy were used to link neptunium speciation to biological growth inhibition. Our results show that metal toxicity of aquo NpO{sub 2}{sup +} significantly limits the growth of C. heintzii at free metal ion concentrations greater than {approx}10{sup -5} M. However, neptunium concentrations {ge}10{sup -4} M do not cause measurable radiotoxicity effects in C. heintzii when present in the form of a neptunium-NTA complex or colloidal/precipitated neptunium phosphate. The neptunium-NTA complex, which is stable under aerobic conditions, is destabilized by microbial degradation of NTA. When phosphate was present, degradation of NTA led to the precipitation of a neptunium-phosphate phase.

  11. Sorption behavior of neptunium on bentonite -- Effect of calcium ion on the sorption

    SciTech Connect

    Kozai, Naofumi; Ohnuki, Toshihiko; Muraoka, Susumu

    1995-12-31

    The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca{sup 2+} (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (K{sub d}) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite K{sub d} increased below pH 5 due to specific sorption of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca{sup 2+} in solution, an effect most pronounced at pH < 5. These results show that Ca{sup 2+} limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca{sup 2+} was solubilized to depress neptunium sorption. This investigation demonstrates that Ca{sup 2+} contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium.

  12. Nano-Disperse Borides and Carbides: Plasma Technology Production, Specific Properties, Economic Evaluation

    NASA Astrophysics Data System (ADS)

    Galevskii, G. V.; Rudneva, V. V.; Galevskii, S. G.; Tomas, K. I.; Zubkov, M. S.

    2016-04-01

    The experience of production and study on properties of nano-disperse chromium and titanium borides and carbides, and silicon carbide has been generalized. The structure and special service aspects of utilized plasma-metallurgical complex equipped with a three-jet direct-flow reactor with a capacity of 150 kW have been outlined. Processing, heat engineering and service life characteristics of the reactor are specified. The synthesis parameters of borides and carbides, as well as their basic characteristics in nano-disperse condition and their production flow diagram are outlined. Engineering and economic performance of synthesizing borides in laboratory and industrial conditions is assessed, and the respective segment of the international market as well. The work is performed at State Siberian Industrial University as a project part of the State Order of Ministry of Science and Education of the Russian Federation No. 11.1531/2014/K.

  13. Boride-based nano-laminates with MAX-phase-like behaviour

    SciTech Connect

    Telle, Rainer . E-mail: telle@ghi.rwth-aachen.de; Momozawa, Ai; Music, Denis; Schneider, Jochen M.

    2006-09-15

    MAX-phases being usually composed of transition metals, group A elements and carbon/nitrogen are considered interesting materials for many applications because of their tremendous bulk modulus, 'reversible' plasticity, and machinability. This is mainly due to their unique kind of bonding comprising covalent, ionic as well as metallic bonds providing 'easy' planes of rupture and deformability due to the layered crystal structures. In transition metal boride systems, similar types of bonding are available. In particular the W{sub 2}B{sub 5}-structure type and its stacking variations allow the synthesis of strongly layered crystal structures exhibiting unique delamination phenomena. The paper presents ab initio calculations showing the similarities of bonding between the ternary carbides and the corresponding ternary or quaternary borides. Formation of boride-based nano-laminates from auxiliary liquid phases, from the melt as well as during sintering and precipitation from supersaturated solid solutions will be discussed by means of SEM and TEM studies. The role of impurities weakening the interlayer bonding will be addressed in particular. The pronounced cleavage parallel to the basal plane gives rise for crack deflection and pull-out mechanisms if the laminates are dispersed in brittle matrices such as boron carbide, silicon carbide or other transition metal borides. - Graphical abstract: Some transition metal borides crystallise in a layered structure of alternating stacks of metal and boron atoms giving rise for strongly anisotropic properties. Their preferred cleavage parallel and the deformability perpendicular to the basal plan are similar to the peculiar mechanical behaviour recently described for MAX-phases. Ab initio calculations of the crystal structure prove the weak bonds between the layers for a variety of borides which can be used to reinforce ceramic materials on a nano-scale level.

  14. Extraction of Uranium, Neptunium and Plutonium from Caustic Media

    SciTech Connect

    Delmau, Laetitia H.; Bonnesen, Peter V.; Engle, Nancy L.; Raymond, Kenneth N.; Xu, Jade

    2004-03-28

    5 Fundamental research on uranium, neptunium and plutonium separation from alkaline media using solvent extraction is being conducted. Specific extractants for these actinides from alkaline media have been synthesized to investigate the feasibility of selective removal of these elements. Two families of extractants have been studied: terephthalamide and tetra(hydroxybenzyl)ethylene diamine derivatives. Fundamental studies were conducted to characterize their extraction behavior from a wide variety of aqueous conditions. The terephthalamide derivatives exhibit a significant extraction strength along with a discriminatory behavior among the actinides, plutonium being extracted the most strongly. Quantitative extraction of plutonium and moderate extraction of neptunium and uranium was achieved from a simple caustic solution. Interestingly, strontium is also quantitatively extracted by these derivatives. However, their stability to highly caustic solutions still needs to be imp roved. Tetra(hydroxybenzyl)ethylene diamine derivatives exhibit a very good stability to caustic conditions and are currently being studied.

  15. Syntheses of neptunium trichloride and measurements of its melting temperature

    NASA Astrophysics Data System (ADS)

    Hayashi, Hirokazu; Takano, Masahide; Kurata, Masaki; Minato, Kazuo

    2013-09-01

    Neptunium trichloride (NpCl3) of high purity was synthesized by the solid state reaction of neptunium nitride with cadmium chloride. Lattice parameters of hexagonal NpCl3 were determined from the powder X-ray diffraction pattern to be a = 0.7428 ± 0.0001 nm and c = 0.4262 ± 0.0003 nm, which fairly agree with the reported values. The melting temperature of NpCl3 was measured on a sample of about 1 mg, hermetically encapsulated in a gold crucible with a differential thermal analyzer. The value determined was 1070 ± 3 K which is close to the recommended value (1075 ± 30 K) derived from the mean value of the melting temperature of UCl3 and of PuCl3.

  16. RAPID MEASUREMENTS OF NEPTUNIUM OXIDATION STATES USING CHROMATOGRAPHIC RESINS

    SciTech Connect

    Diprete, D; C Diprete, C; Mira Malek, M; Eddie Kyser, E

    2009-03-24

    The Savannah River Site's (SRS) H-Canyon facility uses ceric ammonium nitrate (CAN) to separate impure neptunium (Np) from a high sulfate feed stream. The material is processed using a two-pass solvent extraction purification which relies on CAN to oxidize neptunium to Np(VI) during the first pass prior to extraction. Spectrophotometric oxidation-state analyses normally used to validate successful oxidation to Np(VI) prior to extraction were compromised by this feed stream matrix. Therefore, a rapid chromatographic method to validate successful Np oxidation was developed using Eichrom Industries TRU and TEVA{reg_sign} resins. The method was validated and subsequently transferred to existing operations in the process analytical laboratories.

  17. Plutonium, americium, and neptunium speciation in selected groundwaters

    USGS Publications Warehouse

    Cleveland, J.M.; Rees, T.F.; Nash, K.L.

    1985-01-01

    Speciation was determined at 25 and 90 degree C in four groundwaters from diverse sources: the Sparta aquifer in Louisiana, near the Vacherie salt dome; Mansfield No. 2 well in the Palo Duro Basin, Texas; the Stripa mine in Sweden; and the Waste Isolation Pilot Plant in New Mexico. Neptunium generally was soluble in all waters and was present exclusively as Np(V) and Np(VI), regardless of initial oxidation state. The results indicated that plutonium and neptunium solubilities were determined by the oxidation-reduction properties of the waters, i. e. , their abilities to convert these elements to soluble oxidation states. This was not the case for americium, however; Am(IV) was not detected, and the solubility of this element was determined entirely by the chemical properties of Am(III).

  18. Possible Incorporation of Neptunium in Uranyl (VI) Alteration Phases

    SciTech Connect

    Buck, Edgar C.; McNamara, Bruce K.; Douglas, Matthew; Hanson, Brady D.

    2003-11-25

    This study examines existing data on Np behavior from both spent fuel and borosilicate glass tests in effort to resolve issues concerning the selection of possible solubility limiting phases for neptunium and the methods for detecting neptunium at low levels in spent fuel. These issues were raised in a recent report by Finch and Fortner (2002) that argues that the Np analysis with Electron Energy-Loss Spectroscopy (EELS) reported by Buck et al., (1998) is incorrect and that based on a series of experiments with Np-doped U3O8, NpO2 should be adopted as the solubility controlling phase for Np, in the Yucca Mountain performance assessment model. In this report, we will refute the claim that EELS is unable to detect Np and will suggest that the use of NpO2 as the Np solubility controlling phase is not supported by available scientific data from both spent fuel and borosilicate glass.

  19. Surface hardening of steel by boriding in a cold rf plasma

    NASA Technical Reports Server (NTRS)

    Finberg, I.; Avni, R.; Grill, A.; Spalvins, T.; Buckley, D. H.

    1985-01-01

    Scanning electron spectroscopy, X-ray diffractometry, Auger electron spectroscopy, and microhardness measurements, are used to study the surfaces of 4340-steel samples that have been borided in a cold RF plasma which had been initiated in a gas mixture of 2.7 percent diborane in Ar. As a result of the dislocation of the diborane in the plasma, boron is deposited on the surface of the steel substrate and two crystalline phases, tetragonal Fe2B and orthorhombic FeB, are formed. The formation of boride phases then increases the surface microhardness from 2650 MPa to a maximum value of 7740 MPa.

  20. Geologic migration potentials of technetium-99 and neptunium-237.

    PubMed

    Bondietti, E A; Francis, C W

    1979-03-30

    Relatively mobile TcO(+)(-) and NpO(2)(+) can be chemically reduced to less soluble oxidation states in the presence of igneous rocks, as predicted by oxidation-reduction measurements. Current risk assessments, which consider technetium and neptunium as potentially capable of migrating from high-level radioactive waste repositories, may be overestimating their potential hazard to the public since the Fe(II) content of many subsurface waters may maintain these elements in less soluble oxidation states.

  1. SEPARATION OF NEPTUNIUM FROM PLUTONIUM BY CHLORINATION AND SUBLIMATION

    DOEpatents

    Fried, S.M.

    1958-11-18

    A process is described for separating neptunium from plutonium. The method consists in chlorinating a mixture of the oxides of Np and Pu by contacting the mixture with carbon tetrachloride at about 500 icient laborato C. ln this manner the Np is converted to the tetrachlorlde and the Pu converted to the trichloride. Since NpCl/sub 4/ is more latile than PuCl/sub 3/, the separation ls effected by vaporing sad subsequently condenslng the NpCl/sub 4/.

  2. XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

    PubMed

    Maloubier, Melody; Solari, Pier Lorenzo; Moisy, Philippe; Monfort, Marguerite; Den Auwer, Christophe; Moulin, Christophe

    2015-03-28

    Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data.

  3. Uranium and Neptunium Desorption from Yucca Mountain Alluvium

    SciTech Connect

    C.D. Scism; P.W. Reimus; M. Ding; S.J. Chipera

    2006-03-16

    Uranium and neptunium were used as reactive tracers in long-term laboratory desorption studies using saturated alluvium collected from south of Yucca Mountain, Nevada. The objective of these long-term experiments is to make detailed observations of the desorption behavior of uranium and neptunium to provide Yucca Mountain with technical bases for a more realistic and potentially less conservative approach to predicting the transport of adsorbing radionuclides in the saturated alluvium. This paper describes several long-term desorption experiments using a flow-through experimental method and groundwater and alluvium obtained from boreholes along a potential groundwater flow path from the proposed repository site. In the long term desorption experiments, the percentages of uranium and neptunium sorbed as a function of time after different durations of sorption was determined. In addition, the desorbed activity as a function of time was fit using a multi-site, multi-rate model to demonstrate that different desorption rate constants ranging over several orders of magnitude exist for the desorption of uranium from Yucca Mountain saturated alluvium. This information will be used to support the development of a conceptual model that ultimately results in effective K{sub d} values much larger than those currently in use for predicting radionuclide transport at Yucca Mountain.

  4. Evaluation of the Effects of Tank 50H Solids on Dissolved Uranium, Plutonium and Neptunium

    SciTech Connect

    Oji, L.N.

    2003-12-02

    The study of the effects of contacting a simulated salt solution spiked with uranium, plutonium, and neptunium with Tank 50H solids. General findings include: There is no evidence for interaction between Tank 50H solids and uranium from the spiked salt solution. Lack of uranium removal may reflect prior removal of uranium. There is evidence for interaction between Tank 50H solids with plutonium and neptunium as evidenced by loss of these two actinides from the salt solution. The amount of plutonium and neptunium lost from solution increased with an increase in the quantity of Tank 50H solids for a fixed simulant volume. The removal of plutonium and neptunium fit typical sorption isotherms allowing development of loading curves for estimating maximum solids loading. The maximum loading capacities for plutonium and neptunium in the simulants are, respectively, 2.01 and 4.48 micrograms per gram of Tank 50H solids. The oxalate in the Tank 50H solids is not directly responsible for the loss of plutonium and neptunium from the salt solution. The removal of plutonium and neptunium may be attributed to other minor components of the Tank 50H solids. We recommend additional testing to identify the component responsible for the plutonium and neptunium removal.

  5. Re-evaluating neptunium in uranyl phases derived from corroded spent fuel.

    SciTech Connect

    Fortner, J. A.; Finch, R. J.; Kropf, A. J.; Cunnane, J. C.; Chemical Engineering

    2004-11-01

    Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O+2]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest-a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-MV energy.

  6. Re-Evaluating Neptunium in Uranyl Phases Derived from Corroded Spent Fuel

    SciTech Connect

    Fortner, Jeffrey A.; Finch, Robert J.; Kropf, A. Jeremy; Cunnane, James C.

    2004-11-15

    Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O{sub 2}{sup +}]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-M{sub V} energy.

  7. Neptunium and americium speciation in selected basalt, granite, shale, and tuff ground waters.

    PubMed

    Cleveland, J M; Rees, T F; Nash, K L

    1983-07-15

    Neptunium and americium are relatively insoluble in ground waters containing high sulfate concentrations, particularly at 90 degrees C. The insoluble neptunium species is Np(IV); hence reducing waters should enhance its formation. Americium can exist only in the trivalent state under these conditions, and its solubility also should be representative of that of curium.

  8. Neptunium and americium speciation in selected basalt, granite, shale, and tuff ground waters

    USGS Publications Warehouse

    Cleveland, J.M.; Rees, T.F.; Nash, K.L.

    1983-01-01

    Neptunium and americium are relatively insoluble in ground waters containing high sulfate concentrations, particularly at 90??C. The insoluble neptunium species is Np(IV); hence reducing waters should enhance its formation. Americium can exist only in the trivalent state under these conditions, and its solubility also should be representative of that of curium.

  9. Metal-boride phase formation on tungsten carbide (WC-Co) during microwave plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Johnston, Jamin M.; Catledge, Shane A.

    2016-02-01

    Strengthening of cemented tungsten carbide by boriding is used to improve the wear resistance and lifetime of carbide tools; however, many conventional boriding techniques render the bulk carbide too brittle for extreme conditions, such as hard rock drilling. This research explored the variation in metal-boride phase formation during the microwave plasma enhanced chemical vapor deposition process at surface temperatures from 700 to 1100 °C. We showed several well-adhered metal-boride surface layers consisting of WCoB, CoB and/or W2CoB2 with average hardness from 23 to 27 GPa and average elastic modulus of 600-730 GPa. The metal-boride interlayer was shown to be an effective diffusion barrier against elemental cobalt; migration of elemental cobalt to the surface of the interlayer was significantly reduced. A combination of glancing angle X-ray diffraction, electron dispersive spectroscopy, nanoindentation and scratch testing was used to evaluate the surface composition and material properties. An evaluation of the material properties shows that plasma enhanced chemical vapor deposited borides formed at substrate temperatures of 800 °C, 850 °C, 900 °C and 1000 °C strengthen the material by increasing the hardness and elastic modulus of cemented tungsten carbide. Additionally, these boride surface layers may offer potential for adhesion of ultra-hard carbon coatings.

  10. Neptunium multipoles and resonant x-ray Bragg diffraction by neptunium dioxide (NpO2)

    NASA Astrophysics Data System (ADS)

    Lovesey, S. W.; Detlefs, C.; Rodríguez-Fernández, A.

    2012-06-01

    The low-temperature ordered state of neptunium dioxide (NpO2) remains enigmatic. After decades of experimental and theoretical efforts, long-range order of a time-odd (magnetic) high-order atomic multipole moment is now generally considered to be the fundamental order parameter, the most likely candidate being a magnetic triakontadipole (rank 5). To date, however, direct experimental observation of the primary order parameter remains outstanding. In the light of new experimental findings, we re-examine the effect of crystal symmetry on the atomic multipoles and the resulting x-ray resonant scattering signature. Our simulations use the crystallographic point group \\bar {3}m (D3d), because corresponding magnetic groups \\bar {3}{m}^{\\prime}, {\\bar {3}}^{\\prime}{m}^{\\prime} and {\\bar {3}}^{\\prime}m are shown by us to be at odds with a wealth of experimental results. In addition to the previously observed (secondary) quadrupole order, we derive expressions for higher-order multipoles that might be observed in future experiments. In particular, magnetic octupole moments are predicted to contribute to Np M2,3 and L2,3 resonant scattering via E2-E2 events. The Lorentzian-squared lineshape observed at the M4 resonance is shown to be the result of the anisotropy of the 3p3/2 core levels. Quantitative comparison of our calculations to the measured data yields a core-hole width Γ = 2.60(7) eV and a core-state exchange energy \\vert \\varepsilon (\\frac{1}{2})\\vert =0.7 6(2) eV.

  11. Neptunium multipoles and resonant x-ray Bragg diffraction by neptunium dioxide (NpO2).

    PubMed

    Lovesey, S W; Detlefs, C; Rodríguez-Fernández, A

    2012-06-27

    The low-temperature ordered state of neptunium dioxide (NpO(2)) remains enigmatic. After decades of experimental and theoretical efforts, long-range order of a time-odd (magnetic) high-order atomic multipole moment is now generally considered to be the fundamental order parameter, the most likely candidate being a magnetic triakontadipole (rank 5). To date, however, direct experimental observation of the primary order parameter remains outstanding. In the light of new experimental findings, we re-examine the effect of crystal symmetry on the atomic multipoles and the resulting x-ray resonant scattering signature. Our simulations use the crystallographic point group ̅3m (D(3d)), because corresponding magnetic groups ̅3m', ̅3'm', and ̅3'm are shown by us to be at odds with a wealth of experimental results. In addition to the previously observed (secondary) quadrupole order, we derive expressions for higher-order multipoles that might be observed in future experiments. In particular, magnetic octupole moments are predicted to contribute to Np M(2,3) and L(2,3) resonant scattering via E2–E2 events. The Lorentzian-squared lineshape observed at the M(4) resonance is shown to be the result of the anisotropy of the 3p(3/2) core levels. Quantitative comparison of our calculations to the measured data yields a core–hole width Γ = 2.60(7) eV and a core-state exchange energy [absolute value]ε(1/2)[absolute value] = 0.76(2) eV.

  12. Niobium boride layers deposition on the surface AISI D2 steel by a duplex treatment

    SciTech Connect

    Kon, O.; Pazarlioglu, S.

    2015-03-30

    In this paper, we investigated the possibility of deposition of niobium boride layers on the surface of AISI D2 steel by a duplex treatment. At the first step of duplex treatment, boronizing was performed on AISI D2 steel samples at 1000{sup o}C for 2h and then pre-boronized samples niobized at 850°C, 900°C and 950°C using thermo-reactive deposition method for 1–4 h. The presence of the niobium boride layers such as NbB, NbB{sub 2} and Nb{sub 3}B{sub 4} and also iron boride phases such as FeB, Fe{sub 2}B were examined by X-ray diffraction analysis. Scanning electron microscope (SEM) and micro-hardness measurements were realized. Experimental studies showed that the depth of the coating layers increased with increasing temperature and times and also ranged from 0.42 µm to 2.43 µm, depending on treatment time and temperature. The hardness of the niobium boride layer was 2620±180 HV{sub 0.005}.

  13. Superabrasive boride and a method of preparing the same by mechanical alloying and hot pressing

    DOEpatents

    Cook, Bruce A.; Harringa, Joel L.; Russell, Alan M.

    2002-08-13

    A ceramic material which is an orthorhombic boride of the general formula: AlMgB.sub.14 :X, with X being a doping agent. The ceramic is a superabrasive, and in most instances provides a hardness of 40 GPa or greater.

  14. Chemical Speciation of Neptunium in Spent Fuel. 1st Progress Report

    SciTech Connect

    Czerwinski, Ken; Sherman, Christi; Reed, Don

    2000-03-02

    This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste.

  15. Additive-assisted synthesis of boride, carbide, and nitride micro/nanocrystals

    SciTech Connect

    Chen, Bo; Yang, Lishan; Heng, Hua; Chen, Jingzhong; Zhang, Linfei; Xu, Liqiang; Qian, Yitai; Yang, Jian

    2012-10-15

    General and simple methods for the syntheses of borides, carbides and nitrides are highly desirable, since those materials have unique physical properties and promising applications. Here, a series of boride (TiB{sub 2}, ZrB{sub 2}, NbB{sub 2}, CeB{sub 6}, PrB{sub 6}, SmB{sub 6}, EuB{sub 6}, LaB{sub 6}), carbide (SiC, TiC, NbC, WC) and nitride (TiN, BN, AlN, MgSiN{sub 2}, VN) micro/nanocrystals were prepared from related oxides and amorphous boron/active carbon/NaN{sub 3} with the assistance of metallic Na and elemental S. In-situ temperature monitoring showed that the reaction temperature could increase quickly to {approx}850 Degree-Sign C, once the autoclave was heated to 100 Degree-Sign C. Such a rapid temperature increase was attributed to the intense exothermic reaction between Na and S, which assisted the formation of borides, carbides and nitrides. The as-obtained products were characterized by XRD, SEM, TEM, and HRTEM techniques. Results in this report will greatly benefit the future extension of this approach to other compounds. - Graphical abstract: An additive-assisted approach is successfully developed for the syntheses of borides, carbides and nitrides micro/nanocrystals with the assistance of the exothermic reaction between Na and S. Highlights: Black-Right-Pointing-Pointer An additive-assisted synthesis strategy is developed for a number of borides, carbides and nitrides. Black-Right-Pointing-Pointer The reaction mechanism is demonstrated by the case of SiC nanowires. Black-Right-Pointing-Pointer The formation of SiC nanowires is initiated by the exothermic reaction of Na and S.

  16. Potential and limitations of microanalysis SEM techniques to characterize borides in brazed Ni-based superalloys

    SciTech Connect

    Ruiz-Vargas, J.; Siredey-Schwaller, N.; Noyrez, P.; Mathieu, S.; Bocher, P.; and others

    2014-08-15

    Brazed Ni-based superalloys containing complex phases of different Boron contents remain difficult to characterize at the micrometer scale. Indeed Boron is a light element difficult to measure precisely. The state-of-the-art microanalysis systems have been tested on a single crystal MC2 based metal brazed with BNi-2 alloy to identify boride precipitates. Effort has been made to evaluate the accuracy in Boron quantitation. Energy-dispersive and wavelength-dispersive X-ray spectroscopy attached to a Scanning Electron Microscope have first been used to determine the elemental composition of Boron-free phases, and then applied to various types of borides. Results have been compared to the ones obtained using a dedicated electron probe microanalysis, considered here as the reference technique. The most accurate method to quantify Boron using EDS is definitely by composition difference. A precision of 5 at.% could be achieved with optimized data acquisition and post-processing schemes. Attempts that aimed at directly quantifying Boron with various standards using EDS or coupled EDS/WDS gave less accurate results. Ultimately, Electron Backscatter Diffraction combined with localized EDS analysis has proved invaluable in conclusively identifying micrometer sized boride precipitates; thus further improving the characterization of brazed Ni-based superalloys. - Highlights: • We attempt to accurately identify Boron-rich phases in Ni-based superalloys. • EDS, WDS, EBSD systems are tested for accurate identification of these borides. • Results are compared with those obtained by electron probe microanalysis. • Boron was measured with EDS by composition difference with a precision of 5 at. %. • Additional EBSD in phase identification mode conclusively identifies the borides.

  17. Selection of peptides binding to metallic borides by screening M13 phage display libraries

    PubMed Central

    2014-01-01

    Background Metal borides are a class of inorganic solids that is much less known and investigated than for example metal oxides or intermetallics. At the same time it is a highly versatile and interesting class of compounds in terms of physical and chemical properties, like semiconductivity, ferromagnetism, or catalytic activity. This makes these substances attractive for the generation of new materials. Very little is known about the interaction between organic materials and borides. To generate nanostructured and composite materials which consist of metal borides and organic modifiers it is necessary to develop new synthetic strategies. Phage peptide display libraries are commonly used to select peptides that bind specifically to metals, metal oxides, and semiconductors. Further, these binding peptides can serve as templates to control the nucleation and growth of inorganic nanoparticles. Additionally, the combination of two different binding motifs into a single bifunctional phage could be useful for the generation of new composite materials. Results In this study, we have identified a unique set of sequences that bind to amorphous and crystalline nickel boride (Ni3B) nanoparticles, from a random peptide library using the phage display technique. Using this technique, strong binders were identified that are selective for nickel boride. Sequence analysis of the peptides revealed that the sequences exhibit similar, yet subtle different patterns of amino acid usage. Although a predominant binding motif was not observed, certain charged amino acids emerged as essential in specific binding to both substrates. The 7-mer peptide sequence LGFREKE, isolated on amorphous Ni3B emerged as the best binder for both substrates. Fluorescence microscopy and atomic force microscopy confirmed the specific binding affinity of LGFREKE expressing phage to amorphous and crystalline Ni3B nanoparticles. Conclusions This study is, to our knowledge, the first to identify peptides that

  18. Improving the Adhesion Resistance of the Boride Coatings to AISI 316L Steel Substrate by Diffusion Annealing

    NASA Astrophysics Data System (ADS)

    Campos-Silva, I.; Bernabé-Molina, S.; Bravo-Bárcenas, D.; Martínez-Trinidad, J.; Rodríguez-Castro, G.; Meneses-Amador, A.

    2016-07-01

    In this study, new results about the practical adhesion resistance of boride coating/substrate system formed at the surface of AISI 316 L steel and improved by means of a diffusion annealing process are presented. First, the boriding of AISI 316 L steel was performed by the powder-pack method at 1173 K with different exposure times (4-8 h). The diffusion annealing process was conducted on the borided steels at 1273 K with 2 h of exposure using a diluent atmosphere of boron powder mixture. The mechanical behavior of the boride coating/substrate system developed by both treatments was established using Vickers and Berkovich tests along the depth of the boride coatings, respectively. Finally, for the entire set of experimental conditions, the scratch tests were performed with a continuously increasing normal force, in which the practical adhesion resistance of the boride coating/substrate system was represented by the critical load. The failure mechanisms developed over the surface of the scratch tracks were analyzed; the FeB-Fe2B/substrate system exhibited an adhesive mode, while the Fe2B/substrate system obtained by the diffusion annealing process showed predominantly a cohesive failure mode.

  19. Improving the Adhesion Resistance of the Boride Coatings to AISI 316L Steel Substrate by Diffusion Annealing

    NASA Astrophysics Data System (ADS)

    Campos-Silva, I.; Bernabé-Molina, S.; Bravo-Bárcenas, D.; Martínez-Trinidad, J.; Rodríguez-Castro, G.; Meneses-Amador, A.

    2016-09-01

    In this study, new results about the practical adhesion resistance of boride coating/substrate system formed at the surface of AISI 316 L steel and improved by means of a diffusion annealing process are presented. First, the boriding of AISI 316 L steel was performed by the powder-pack method at 1173 K with different exposure times (4-8 h). The diffusion annealing process was conducted on the borided steels at 1273 K with 2 h of exposure using a diluent atmosphere of boron powder mixture. The mechanical behavior of the boride coating/substrate system developed by both treatments was established using Vickers and Berkovich tests along the depth of the boride coatings, respectively. Finally, for the entire set of experimental conditions, the scratch tests were performed with a continuously increasing normal force, in which the practical adhesion resistance of the boride coating/substrate system was represented by the critical load. The failure mechanisms developed over the surface of the scratch tracks were analyzed; the FeB-Fe2B/substrate system exhibited an adhesive mode, while the Fe2B/substrate system obtained by the diffusion annealing process showed predominantly a cohesive failure mode.

  20. The biodistribution and toxicity of plutonium, americium and neptunium.

    PubMed

    Taylor, D M

    1989-07-15

    In the nuclear fuel cycle the transuranic radionuclides plutonium-239, americium-241 and neptunium-237 would probably present the most serious hazard to human health if released into the environment. Despite differences in their solution chemistry the three elements exhibit remarkable similarity in their biochemical behaviour, apparently sharing similar transport pathways in blood and cells. After entering the blood the elements deposit predominantly in liver and skeleton, where retention appears to be prolonged, with half-times of the order of years. The principal late effects of all three radionuclides are the induction of cancers of bone, lung or liver. For the latter tumours the induction risk per unit radiation dose appears similar for the three radionuclides. But in bone there are indications that, due to microscopic differences in the distribution of the alpha-particle radiation dose, the efficiency of bone cancer induction may increase in the order americium-241 less than plutonium-239 less than neptunium-237. No case of human cancer induced by these radionuclides is known.

  1. Adsorption of micelle-forming surfactants from aqueous solutions on disperse titanium boride

    SciTech Connect

    Grodskii, A.S.; Komleva, E.A.; Frolov, Yu.G.

    1988-08-10

    Adsorption studies showed that nonionogenic and cationic surfactants are adsorbed on the surface of disperse titanium boride. Anionic surfactants are virtually not adsorbed due to the negative charge of the particles. It was found that in the region of low concentrations of surfactants in the solution, adsorption of Sintanols takes place in lyophobic regions and the surface of the particles becomes hydrophilic. The Sintamid molecules are adsorbed on the entire interface, including both hydrophobic and hydrophilic sections, with subsequent formation of bimolecular layers by adsorption on hydrophobic sections. Catamine-AB is adsorbed on hydrophilic sections of the surface also with the formation of bimolecular layers. Developed polymolecular layers up to 10-15 nm thick are formed on titanium boride particles from micellar solutions of nonionigenic and cationic surfactants.

  2. A Crossover from High Stiffness to High Hardness: The Case of Osmium and Its Borides

    NASA Astrophysics Data System (ADS)

    Bian, Yongming; Liu, Xiaomei; Li, Anhu; Liang, Yongcheng

    2016-09-01

    Transition-metal light-element compounds are currently raising great expectations for hard and superhard materials. Using the widely attracting osmium (Os) and its borides (OsB, Os2B3 and OsB2) as prototypes, we demonstrate by first-principles calculations that heavy transition metals, which possess high stiffness but low hardness, can be converted into highly hard materials by incorporating of light elements to form compounds. Such a crossover is a manifestation that the underlying sources of high stiffness and high hardness are fundamentally different. The stiffness is related to elastic deformation that is closely associated with valence electron density, whereas the hardness depends strongly on plastic deformation that is determined by bonding nature. Therefore, the incorporation of light atoms into transition metal should be a valid pathway of designing hard and superhard materials. This strategy is in principle also applicable to other transition-metal borides, carbides, and nitrides.

  3. Friction and wear of radiofrequency-sputtered borides, silicides, and carbides

    NASA Technical Reports Server (NTRS)

    Brainard, W. A.; Wheeler, D. R.

    1978-01-01

    The friction and wear properties of several refractory compound coatings were examined. These compounds were applied to 440 C bearing steel surfaces by radiofrequency (RF) sputtering. The refractory compounds were the titanium and molybdenum borides, the titanium and molybdenum silicides, and the titanium, molybdenum, and boron carbides. Friction testing was done with a pin-on-disk wear apparatus at loads from 0.1 to 5.0 newtons. Generally, the best wear properties were obtained when the coatings were bias sputtered onto 440 C disks that had been preoxidized. Adherence was improved because of the better bonding of the coatings to the iron oxide formed during preoxidation. As a class the carbides provided wear protection to the highest loads. Titanium boride coatings provided low friction and good wear properties to moderate loads.

  4. Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB

    NASA Astrophysics Data System (ADS)

    Kota, Sankalp; Zapata-Solvas, Eugenio; Ly, Alexander; Lu, Jun; Elkassabany, Omar; Huon, Amanda; Lee, William E.; Hultman, Lars; May, Steve J.; Barsoum, Michel W.

    2016-05-01

    The ‘MAlB’ phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, mostly amorphous, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36–0.49 μΩm) and – like a metal – drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm‑1K‑1 at 26 °C). In the 25–1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10‑6 K‑1. Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures.

  5. Direct Hydrogenation Magnesium Boride to Magnesium Borohydride: Demonstration of >11 Weight Percent Reversible Hydrogen Storage

    SciTech Connect

    Severa, Godwin; Ronnebro, Ewa; Jensen, Craig M.

    2010-11-16

    We here for the first time demonstrate direct hydrogenation of magnesium boride, MgB2, to magnesium borohydride, Mg(BH4)2 at 900 bar H2-pressures and 400°C. Upon 14.8wt% hydrogen release, the end-decomposition product of Mg(BH4)2 is MgB2, thus, this is a unique reversible path here obtaining >11wt% H2 which implies promise for a fully reversible hydrogen storage material.

  6. Studies of refractory carbides, nitrides, and borides as the thermionic emitters for electron microscopy.

    PubMed

    Yada, K; Masaoka, H; Shoji, Y; Tanji, T

    1989-07-01

    Thermionic emission properties of several kinds of refractory carbides, nitrides, and borides of the transition metals in the form of powder were investigated with a newly developed measuring device and evaluated by the figure of merit defined as the ratio of the effective work function to the working temperature at which the vapor pressure becomes 1 x 10(-5) Torr. There are several materials whose thermionic emission properties are better than those of tungsten or compatible to those of tungsten among the carbides and borides, such as TaC, HfC, ZrC, LaB6, and CeB6, as judged by the figure of merit. New preparation methods for carburization, nitriding, and boriding of the wires of matrix metals and alloys were successfully developed for using these materials as the cathode of the electron microscope. Other necessary techniques such as spot welding and electrolytic etching were also developed. From the brightness characteristics, it was found that some of carbides, carbide solid solutions, and borides such as HfC, ZrC (Ta0.8-0.7Hf0.2-0.3)C, TaB2, and HfB2 are very good emitters comparable to LaB6. It is emphasized that the work functions of the carbide-solid solutions (Ta0.8Hf0.2)C and (Ta0.7Hf0.3)C, which have low rates of evaporation at high temperature, show no remarkable rise as compared with that of HfC, so that their figures of merit are better than that of HfC. Feasibility of providing good cathodes with HfC and (Ta0.8Hf0.2)C tips was demonstrated by taking high-resolution electron micrographs.

  7. Heat capacity and thermal expansion of icosahedral lutetium boride LuB66

    SciTech Connect

    Novikov, V V; Avdashchenko, D V; Matovnikov, A V; Mitroshenkov, N V; Bud’ko, S L

    2014-01-07

    The experimental values of heat capacity and thermal expansion for lutetium boride LuB66 in the temperature range of 2-300 K were analysed in the Debye-Einstein approximation. It was found that the vibration of the boron sub-lattice can be considered within the Debye model with high characteristic temperatures; low-frequency vibration of weakly connected metal atoms is described by the Einstein model.

  8. Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB

    PubMed Central

    Kota, Sankalp; Zapata-Solvas, Eugenio; Ly, Alexander; Lu, Jun; Elkassabany, Omar; Huon, Amanda; Lee, William E.; Hultman, Lars; May, Steve J.; Barsoum, Michel W.

    2016-01-01

    The ‘MAlB’ phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, mostly amorphous, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36–0.49 μΩm) and – like a metal – drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm−1K−1 at 26 °C). In the 25–1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10−6 K−1. Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures. PMID:27220751

  9. Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB.

    PubMed

    Kota, Sankalp; Zapata-Solvas, Eugenio; Ly, Alexander; Lu, Jun; Elkassabany, Omar; Huon, Amanda; Lee, William E; Hultman, Lars; May, Steve J; Barsoum, Michel W

    2016-01-01

    The 'MAlB' phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, mostly amorphous, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36-0.49 μΩm) and - like a metal - drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm(-1)K(-1) at 26 °C). In the 25-1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10(-6 )K(-1). Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures. PMID:27220751

  10. Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB.

    PubMed

    Kota, Sankalp; Zapata-Solvas, Eugenio; Ly, Alexander; Lu, Jun; Elkassabany, Omar; Huon, Amanda; Lee, William E; Hultman, Lars; May, Steve J; Barsoum, Michel W

    2016-05-25

    The 'MAlB' phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, mostly amorphous, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36-0.49 μΩm) and - like a metal - drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm(-1)K(-1) at 26 °C). In the 25-1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10(-6 )K(-1). Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures.

  11. Structure of superhard tungsten tetraboride: A missing link between MB2 and MB12 higher borides

    PubMed Central

    Lech, Andrew T.; Turner, Christopher L.; Mohammadi, Reza; Tolbert, Sarah H.; Kaner, Richard B.

    2015-01-01

    Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten—often referred to as WB4 and sometimes as W1–xB3—is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961—a fact that severely limits our understanding of its structure–property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray–only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedra—slightly distorted boron cuboctahedra—appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals. PMID:25733870

  12. Structure of superhard tungsten tetraboride: a missing link between MB2 and MB12 higher borides.

    PubMed

    Lech, Andrew T; Turner, Christopher L; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

    2015-03-17

    Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten--often referred to as WB4 and sometimes as W(1-x)B3--is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961--a fact that severely limits our understanding of its structure-property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray-only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedral--slightly distorted boron cuboctahedra--appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals.

  13. Distinct surface hydration behaviors of boron-rich boride thin film coatings

    NASA Astrophysics Data System (ADS)

    Lu, Xinhong; Liu, Wei; Ouyang, Jun; Tian, Yun

    2014-08-01

    In this work, the surface boron chemical states and surface hydration behaviors of the as-deposited and annealed boron-rich boride thin film coatings, including AlMgB14, TiB2 and AlMgB14-TiB2, were systematically studied by use of X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS results indicate that boron at annealed AlMgB14 film surface can be oxidized; surprisingly, such oxidation does not lead to the formation of boric acid in ambient air. Instead, boric acid can be produced at the surface of annealed TiB2 film and AlMgB14-TiB2 film. It is shown, via the water contact angle measurements, that these boride films exhibit distinct surface wettability characteristics, which are believed to result in the observed surface hydration processes. Furthermore, we found anatase TiO2 formation plays a major role in the surface wetting behaviors for these boride films.

  14. Dose rate dependence of the speciation of neptunium in irradiated solutions of nitric acid

    SciTech Connect

    Precek, M.; Paulenova, A.; Mincher, B.J.; Mezyk, S.P.

    2013-07-01

    The effects of radiation on the redox speciation of neptunium are of interest due to their impact on the performance of separation of neptunium from highly radioactive solutions of dissolved used nuclear fuel. In this study, the influence of dose rate change from 0.4 kGy/h to 6 kGy/h was examined during irradiation of solutions of initially hexavalent 2.0-2.5 mM neptunium in nitric acid of two different concentrations (0.5 and 1 M). Results indicate that the immediate radiolytic steady-state concentration of neptunium(V) were depressed and its initial radiolytic yield was up to 2-times lower (in 1 M HNO{sub 3} solutions)during irradiations with the higher dose rate. The finding is explained on the basis of the enhancement of the role of oxidizing radicals during the radiolytic process. (authors)

  15. Existing Evidence for the Fate of Neptunium in the Yucca Mountain Repository

    SciTech Connect

    Friese, Judah I. ); Buck, Edgar C. ); McNamara, Bruce K. ); Hanson, Brady D. ); Marschman, Steven C. )

    2003-06-18

    Neptunium, because of its long half life, is an element of long-term interest to the Yucca Mountain repository. The fate of neptunium under repository settings is unknown. This report provides a review and new interpretation of past tests on commercial spent nuclear fuel and experimental evidence on the fate of neptunium. Tests on commercial spent nuclear fuel preformed previously at Pacific Northwest National Laboratory (PNNL) used a bathtub setup by immersing spent fuel in either deionized water or a groundwater typical of those at Yucca Mountain. The main goal of the tests was to determine the different concentrations of radionuclides in solution with different types of cladding defects. Neptunium was not the focus of these tests, nor were the tests designed to study neptunium. Drip tests performed at Argonne National Laboratory (ANL) are unsaturated tests that drip water at different rates on spent fuel. Relatively new tests at ANL examine the corrosion of Np-doped U3O8 in humid air at various temperatures. This review concludes that all tests reported here have analytical problems (i.e., relatively high detection limits for Np) and have been configured such that they limit the ability to interpret the available neptunium data. Past tests on spent nuclear fuel do not unambiguously describe neptunium chemistry as there are multiple mechanisms that may explain the observed behavior in each test. One apparently major shortcoming of most tests is that the extent of fuel reaction was limited by the amount of oxygen present in the system. Further detailed studies under repository-relevant conditions, which include the assumption of a constant 20 percent oxygen atmosphere, are needed to provide the data necessary for the development and validation of models used to predict the long-term fate of neptunium and other radionuclides at Yucca Mountain.

  16. Corrosion behavior of titanium boride composite coating fabricated on commercially pure titanium in Ringer's solution for bioimplant applications.

    PubMed

    Sivakumar, Bose; Singh, Raghuvir; Pathak, Lokesh Chandra

    2015-03-01

    The boriding of commercially pure titanium was performed at 850°C, 910°C, and 1050°C for varied soaking periods (1, 3 and 5h) to enhance the surface properties desirable for bioimplant applications. The coating developed was characterized for the evolution of phases, microstructure and morphology, microhardness, and consequent corrosion behavior in the Ringer's solution. Formation of the TiB2 layer at the outermost surface followed by the TiB whiskers across the borided CpTi is unveiled. Total thickness of the composite layer on the substrates borided at 850, 910, and 1050°C for 5h was found to be 19.1, 26.4, and 18.2μm respectively which includes <3μm thick TiB2 layer. The presence of TiB2 phase was attributed to the high hardness ~2968Hv15gf of the composite coating. The anodic polarization studies in the simulated body fluid unveiled a reduction in the pitting corrosion resistance after boriding the CpTi specimens. However, this value is >0.55VSCE (electrochemical potential in in-vivo physiological environment) and hence remains within the safe region. Both the untreated and borided CpTi specimens show two passive zones associated with different passivation current densities. Among the CpTi borided at various times and temperatures, a 3h treated shows better corrosion resistance. The corrosion of borided CpTi occurred through the dissolution of TiB2. PMID:25579920

  17. Corrosion behavior of titanium boride composite coating fabricated on commercially pure titanium in Ringer's solution for bioimplant applications.

    PubMed

    Sivakumar, Bose; Singh, Raghuvir; Pathak, Lokesh Chandra

    2015-03-01

    The boriding of commercially pure titanium was performed at 850°C, 910°C, and 1050°C for varied soaking periods (1, 3 and 5h) to enhance the surface properties desirable for bioimplant applications. The coating developed was characterized for the evolution of phases, microstructure and morphology, microhardness, and consequent corrosion behavior in the Ringer's solution. Formation of the TiB2 layer at the outermost surface followed by the TiB whiskers across the borided CpTi is unveiled. Total thickness of the composite layer on the substrates borided at 850, 910, and 1050°C for 5h was found to be 19.1, 26.4, and 18.2μm respectively which includes <3μm thick TiB2 layer. The presence of TiB2 phase was attributed to the high hardness ~2968Hv15gf of the composite coating. The anodic polarization studies in the simulated body fluid unveiled a reduction in the pitting corrosion resistance after boriding the CpTi specimens. However, this value is >0.55VSCE (electrochemical potential in in-vivo physiological environment) and hence remains within the safe region. Both the untreated and borided CpTi specimens show two passive zones associated with different passivation current densities. Among the CpTi borided at various times and temperatures, a 3h treated shows better corrosion resistance. The corrosion of borided CpTi occurred through the dissolution of TiB2.

  18. Reduction and precipitation of neptunium(V) by sulfate-reducing bacteria.

    SciTech Connect

    Banaszak, J. E.; Rittmann, B. E.; Reed, D. T.

    1999-10-21

    Migration of neptunium, as NpO{sub 2}{sup +}, has been identified as a potentially important pathway for actinide release at nuclear waste repositories and existing sites of subsurface contamination. Reduction of Np(V) to Np(IV) will likely reduce its volubility, resulting in lowered subsurface migration. The ability of sulfate-reducing bacteria (SRB) to utilize Np(V) as an electron acceptor was investigated, because these bacteria are active in many anaerobic aquifers and are known to facilitate the reduction of metals and radionuclides. Pure and mixed cultures of SRB were able to precipitate neptunium during utilization of pyruvate, lactate, and hydrogen as electron donors in the presence and absence of sulfate. The neptunium in the precipitate was identified as Np(IV) using X-ray absorption near edge spectroscopy (XANES) analysis. In mixed-culture studies, the addition of hydrogen to consortia grown by pyruvate fermentation stimulated neptunium reduction and precipitation. Experiments with pure cultures of Desulfovibrio vulgaris, growing by lactate fermentation in the absence of sulfate or by sulfate reduction, confirm that the organism is active in neptunium reduction and precipitation. Based on our results, the activity of SRB in the subsurface may have a significant, and potentially beneficial, impact on actinide mobility by reducing neptunium volubility.

  19. Thermodynamics of neptunium in LiCl-KCl eutectic/liquid bismuth systems

    SciTech Connect

    Sakamura, Y.; Shirai, O.; Iwai, T.; Suzuki, Y.

    2000-02-01

    Thermodynamic properties of neptunium in LiCl-KCl eutectic/liquid bismuth systems in the temperature range 400--500 C have been studied using a galvanic cell method for the pyrometallurgical reprocessing of nuclear spent fuels. The standard potential of the Np/Np(III) couple vs. the Ag/AgCl (1 wt% AgCl) reference electrode in LiCl-KCl eutectic was measured and given by the equation E{sub Np/Np(III)}{sup 0} = {minus}2.0667 + 0.0007892 T ({sigma} = 0.0009), where E is in volts, T is in kelvin, and {sigma} is the standard deviation. The potential of neptunium-bismuth alloy, E{sub Np-Bi}, was measured as a function of neptunium concentration, X{sub Np in Bi}. The curves for E{sub Bi-Np} vs. log X{sub Np in Bi} indicated the neptunium solubility in liquid bismuth to be 0.34 {+-} 0.02, 0.61 {+-} 0.08, and 1.06 {+-} 0.09 ({+-}{sigma}) atom % at 400, 450, and 500 C, respectively. The excess partial free energy of neptunium in liquid bismuth was represented by the equation, {Delta}{bar G}{sub Np}{sup xs} (kcal/g atom) = {minus}32.5 ({+-}0.7) + 0.0072 ({+-}0.0010) T. The values of the solubility and excess partial free energy for neptunium were closer to those for plutonium rather than uranium.

  20. SORPTION OF URANIUM, PLUTONIUM AND NEPTUNIUM ONTO SOLIDS PRESENT IN HIGH CAUSTIC NUCLEAR WASTE STORAGE TANKS

    SciTech Connect

    Oji, L; Bill Wilmarth, B; David Hobbs, D

    2008-05-30

    Solids such as granular activated carbon, hematite and sodium phosphates, if present as sludge components in nuclear waste storage tanks, have been found to be capable of precipitating/sorbing actinides like plutonium, neptunium and uranium from nuclear waste storage tank supernatant liqueur. Thus, the potential may exists for the accumulation of fissile materials in such nuclear waste storage tanks during lengthy nuclear waste storage and processing. To evaluate the nuclear criticality safety in a typical nuclear waste storage tank, a study was initiated to measure the affinity of granular activated carbon, hematite and anhydrous sodium phosphate to sorb plutonium, neptunium and uranium from alkaline salt solutions. Tests with simulated and actual nuclear waste solutions established the affinity of the solids for plutonium, neptunium and uranium upon contact of the solutions with each of the solids. The removal of plutonium and neptunium from the synthetic salt solution by nuclear waste storage tank solids may be due largely to the presence of the granular activated carbon and transition metal oxides in these storage tank solids or sludge. Granular activated carbon and hematite also showed measurable affinity for both plutonium and neptunium. Sodium phosphate, used here as a reference sorbent for uranium, as expected, exhibited high affinity for uranium and neptunium, but did not show any measurable affinity for plutonium.

  1. Nuclear forensics of a non-traditional sample: Neptunium

    DOE PAGESBeta

    Doyle, Jamie L.; Schwartz, Daniel; Tandon, Lav

    2016-05-16

    Recent nuclear forensics cases have focused primarily on plutonium (Pu) and uranium (U) materials. By definition however, nuclear forensics can apply to any diverted nuclear material. This includes neptunium (Np), an internationally safeguarded material like Pu and U, that could offer a nuclear security concern if significant quantities were found outside of regulatory control. This case study couples scanning electron microscopy (SEM) with quantitative analysis using newly developed specialized software, to evaluate a non-traditional nuclear forensic sample of Np. Here, the results of the morphological analyses were compared with another Np sample of known pedigree, as well as other traditionalmore » actinide materials in order to determine potential processing and point-of-origin.« less

  2. Gamma-ray measurements of a 6-kilogram neptunium sphere

    SciTech Connect

    Moss, C. E.; Frankle, C. M.

    2002-01-01

    In order to better determine the properties of {sup 237}Np for criticality safety and nuclear nonproliferation, especially its critical mass, 6070-gram solid sphere was cast on 15 May 2001 in a hot cell. The casting sprue was cut off on a lathe and the casting ground to a final diameter of 8.29 cm. The sphere was enclosed in a spherical tungsten shell 0.523-cm thick to reduce the gamma-ray dose. The neptunium and the tungsten were doubly encapsulated in welded, spherical nickel shells, each 0.381-cm thick. The sprue material was analyzed by mass spectrometry. Here we report the results of the first gamma-ray measurements of this unique item.

  3. Thermodynamics of neptunium(V) fluoride and sulfate at elevatedtemperatures

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin; Xia, Yuanxian; Friese, Judah I.

    2006-10-31

    Complexation of neptunium(V) with fluoride and sulfate at elevated temperatures was studied by microcalorimetry. Thermodynamic parameters, including the equilibrium constants and enthalpy of protonation of fluoride and sulfate, and the enthalpy of complexation between Np(V) and fluoride and sulfate at 25 - 70 C were determined. Results show that the complexation of Np(V) with fluoride and sulfate is endothermic and that the complexation is enhanced by the increase in temperature - a three-fold increase in the stability constants of NpO{sub 2}F(aq) and NpO{sub 2}SO{sub 4}{sup -} as the temperature is increased from 25 to 70 C.

  4. Complexation of Neptunium(V) with Fluoride at Elevated Temperatures

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin; Xia, Yuanxian; Friese, Judah I.

    2008-06-16

    Complexation of neptunium(V) with fluoride at elevated temperatures was studied by spectrophotometry and microcalorimetry. Two successive complexes, NpO{sub 2}F(aq) and NpO{sub 2}F{sub 2}{sup -}, were identified by spectrophotometry in the temperature range of 10-70 C. Thermodynamic parameters, including the equilibrium constants and enthalpy of complexation between Np(V) and fluoride at 10-70 C were determined. Results show that the complexation of Np(V) with fluoride is endothermic and that the complexation is enhanced by the increase in temperature - a two-fold increase in the stability constants of NpO{sub 2}F(aq) and more than five-fold increase in the stability constants of NpO{sub 2}F{sub 2}{sup -} as the temperature is increased from 10 to 70 C.

  5. Geomicrobiological redox cycling of the transuranic element neptunium.

    PubMed

    Law, Gareth T W; Geissler, Andrea; Lloyd, Jonathan R; Livens, Francis R; Boothman, Christopher; Begg, James D C; Denecke, Melissa A; Rothe, Jörg; Dardenne, Kathy; Burke, Ian T; Charnock, John M; Morris, Katherine

    2010-12-01

    Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management. PMID:21047117

  6. Neptunium and Plutonium Sorption to Snake River Plain, Idaho Soil

    SciTech Connect

    Mincher, Bruce Jay; Fox, Robert Vincent; Cooper, David Craig; Groenewold, Gary Steven

    2003-07-01

    The behavior of Np and Pu on soil collected from the subsurface disposal area at the Idaho National Engineering and Environmental Laboratory was investigated by performing short-duration, sorption experiments to measure sorption isotherms. Neptunium sorption can be described with a Freundlich isotherm; however, Pu sorption can only be described in this fashion as a conservative estimate of minimum sorption. Geochemical modeling predictions suggest that initial sorption of Np is controlled predominantly by surface complexation on clay minerals, while Pu is controlled by a competition between complexation with iron oxyhydroxides and the precipitation of hydrolysis products. Longer-term sorption is governed by the transformation of these species to oxide minerals. Solution ionic strength and carbonate alkalinity did not significantly affect Np or Pu soil sorption.

  7. Application of the underscreened Kondo lattice model to neptunium compounds

    NASA Astrophysics Data System (ADS)

    Thomas, Christopher; da Rosa Simoes, Acirete S.; Iglesias, J. R.; Lacroix, C.; Coqublin, B.

    2012-12-01

    The coexistence of Kondo effect and ferromagnetic order has been observed in many uranium and neptunium compounds such as UTe or Np2PdGa3. This coexistence can be described within the underscreened Anderson lattice model with two f-electrons and S = 1 spins on each site. After performing the Schrieffer-Wolff transformation on this model, we have obtained an effective Hamiltonian with a f-band term in addition to the Kondo interaction for S = 1 spins. The results indicate a coexistence of Kondo effect and ferromagnetic order, with different relative values of the Kondo TK and Curie TC temperatures. We emphasize here especially the case TK < TC where there is a Kondo behavior below TC and a clear decrease of the magnetization below TK. Such a behavior has been observed in the magnetization curves of NpNiSi2 at low temperatures.

  8. Geomicrobiological redox cycling of the transuranic element neptunium.

    PubMed

    Law, Gareth T W; Geissler, Andrea; Lloyd, Jonathan R; Livens, Francis R; Boothman, Christopher; Begg, James D C; Denecke, Melissa A; Rothe, Jörg; Dardenne, Kathy; Burke, Ian T; Charnock, John M; Morris, Katherine

    2010-12-01

    Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

  9. Metabolism and gastrointestinal absorption of neptunium and protactinium in adult baboons

    SciTech Connect

    Ralston, L.G.; Cohen, N.; Bhattacharyya, M.H.; Larsen, R.P.; Ayres, L.; Oldham, R.D.; Moretti, E.S.

    1985-01-01

    The metabolism of neptunium and protactinium was studied in adult female baboons following intravenous injection and intragastric intubation. Immediately following intravenous injection (10/sup -1/ to 10/sup -10/ mg Np per kg body wt), neptunium cleared rapidly from blood, deposited primarily in the skeleton (54 +- 5%) and liver (3 +- 0.2%), and was excreted predominantly via urine (40 +- 3%). For the first year post injection, neptunium was retained with a biological half-time of approx.100 days in liver and 1.5 +- 0.2 yr in bone. In comparison, injected protactinium (10/sup -9/ mg/kg) was retained in blood in higher concentrations and was initially eliminated in urine to a lesser extent (6 +- 3%). In vivo measurements indicated that protactinium was retained in bone (65 +- 0.3%) with a half-time of 3.5 +- 0.6 yr. Differences in the physicochemical states of the neptunium or protactinium solutions injected did not alter the metabolic behavior of these nuclides. The gastrointestinal absorption value for neptunium in two fasted baboons, sacrificed at 1 day post administration, was determined to be 0.92 +- 0.04%. Of the total amount of neptunium absorbed, 52 +- 3% was retained in bone, 6 +- 2% was in liver, and 42 +- 0.1% was excreted in urine. A method was developed to estimate GI absorption values for both nuclides in baboons which were not sacrificed. Absorption values calculated by this method for neptunium and protactinium in fasted baboons were 1.8 +- 0.8% and 0.65 +- 0.01%, respectively. Values for fed animals were 1 to 2 orders of magnitude less than those for fasted animals. 14 refs., 3 figs., 4 tabs. (DT)

  10. Neptunium Solubility in the Near-Field Environment of A Proposed Yucca Mountain Repository

    SciTech Connect

    D.C. Sassani

    2004-05-14

    For representing the source-term of a proposed repository at Yucca Mountain, NV, total system performance assessment models evaluate the disequilibrium degradation of the waste forms to capture a bounding rate for radionuclide source-term availability and use solubility constraints that are more representative of longer-term, equilibrium processes to limit radionuclide mass transport from the source-term. These solubility limits capture precipitation processes occurring either as the waste forms alter, or in the near-field environment as chemical conditions evolve. A number of alternative models for solubility controls on dissolved neptunium concentrations have been evaluated. These include idealized models based on precipitation of neptunium as separate oxide minerals and more complex considerations of trace amounts of neptunium being incorporated into the secondary uranyl phases from waste form alteration. Thermodynamic models for neptunium under oxidizing conditions indicate that tetravalent neptunium (NpO{sub 2}) solids are more stable relative to pentavalent (Np{sub 2}O{sub 5}) phases, and thereby set lower dissolved concentrations of neptunyl species. Data on solids and solutions from slow flow through (dripping) tests on spent fuel grains indicate that neptunium is tetravalent in the spent fuel and that over {approx}9 years the neptunium concentrations are near to or below calculated NpO{sub 2} solubility. The possibility of kinetic rate limitations to NpO{sub 2} precipitation has led to temperature-dependent studies of NpO{sub 2} precipitation kinetics and solubility to reduce uncertainties and confirm application of the model.

  11. A reactive transport model of neptunium migration from the potential repository at Yucca Mountain

    NASA Astrophysics Data System (ADS)

    Viswanathan, Hari S.; Robinson, Bruce A.; Valocchi, Albert J.; Triay, Ines R.

    1998-08-01

    Characterization and performance assessment studies for the potential high-level nuclear waste repository at Yucca Mountain have identified 237Np as a radionuclide of concern for the proposed repository. To predict the migration of neptunium after a repository breach, an understanding of the relevant hydrologic and geochemical processes is required. The hydrologic flow in the unsaturated zone at Yucca Mountain is dependent on the infiltration rate, the stratigraphy of the vadose zone, and the heat generated by the decaying radioactive waste. The geochemical processes that strongly affect 237Np migration include: solubility-limited release of 237Np from the near-field environment, aqueous speciation of neptunium into non-sorbing carbonate/hydroxy complexes and the sorbing NpO 2+ cation, sorption of neptunium onto the zeolitic tuffs via an ion exchange mechanism, and radioactive decay. The finite element heat and mass transfer (FEHM) code was used to investigate the coupled effects of chemical interactions and heat on neptunium transport from the potential repository to the water table. The selective coupling method is introduced to solve these reactive transport problems. The simulations indicate that in the absence of irreversible changes in the hydrologic and transport properties, the heat pulse does not significantly affect the migration of neptunium, as the time scale of heat pulse propagation is shorter than the time scales associated with neptunium release and migration. Water chemistry, particularly pH, calcium, and sodium concentration significantly affect the retardation of neptunium by the zeolitic rocks between the repository and the water table.

  12. PREFACE: The 16th International Symposium on Boron, Borides and Related Materials (ISBB 2008)

    NASA Astrophysics Data System (ADS)

    Tanaka, Takaho

    2009-07-01

    This volume of Journal of Physics: Conference Series contains invited and contributed peer-reviewed papers that were presented at the 16th International Symposium on Boron, Borides and Related Materials (ISBB 2008), which was held on 7-12 September 2008, at Kunibiki Messe, Matsue, Japan. This triennial symposium has a half-century long history starting from the 1st meeting in 1959 at Asbury Park, New Jersey. We were very pleased to organize ISBB 2008, which gathered chemists, physicists, materials scientists as well as diamond and high-pressure researchers. This meeting had a strong background in the boron-related Japanese research history, which includes the discovery of superconductivity in MgB2 and development of Nd-Fe-B hard magnets and of YB66 soft X-ray monochromator. The scope of ISBB 2008 spans both basic and applied interdisciplinary research that is centered on boron, borides and related materials, and the collection of articles defines the state of the art in research on these materials. The topics are centered on: 1. Preparation of new materials (single crystals, thin films, nanostructures, ceramics, etc) under normal or extreme conditions. 2. Crystal structure and chemical bonding (new crystal structures, nonstoichiometry, defects, clusters, quantum-chemical calculations). 3. Physical and chemical properties (band structure, phonon spectra, superconductivity; optical, electrical, magnetic, emissive, mechanical properties; phase diagrams, thermodynamics, catalytic activity, etc) in a wide range of temperatures and pressures. 4. Applications and prospects (thermoelectric converters, composites, ceramics, coatings, etc) There were a few discoveries of new materials, such as nanomaterials, and developments in applications. Many contributions were related to 4f heavy Fermion systems of rare-earth borides. Exotic mechanisms of magnetism and Kondo effects have been discussed, which may indicate another direction of development of boride. Two special sessions

  13. Boride Zone Formation in Transient Liquid Phase Bonding of Pairings of Parent Superalloy Materials with Different Compositions and Grain Structures

    NASA Astrophysics Data System (ADS)

    Steuer, S.; Singer, R. F.

    2013-05-01

    Two nickel-base superalloys are joined via transient liquid phase (TLP) bonding with boron as the MPD. Boride formation is observed in the parent materials at some distance from the solid/liquid interface. The boron concentration profile over the joint is measured with glow discharge optical emission spectroscopy (GDOES). Boron concentration peaks are observed corresponding to the boride formation. Boron distribution is discussed on the basis of theoretical predictions in the literature. It is concluded that diffusion of another element is necessary to explain the results with the second element influencing the solubility of boron.

  14. The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

    NASA Astrophysics Data System (ADS)

    Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

    2013-06-01

    The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering

  15. Infiltration processing of boron carbide-, boron-, and boride-reactive metal cermets

    DOEpatents

    Halverson, Danny C.; Landingham, Richard L.

    1988-01-01

    A chemical pretreatment method is used to produce boron carbide-, boron-, and boride-reactive metal composites by an infiltration process. The boron carbide or other starting constituents, in powder form, are immersed in various alcohols, or other chemical agents, to change the surface chemistry of the starting constituents. The chemically treated starting constituents are consolidated into a porous ceramic precursor which is then infiltrated by molten aluminum or other metal by heating to wetting conditions. Chemical treatment of the starting constituents allows infiltration to full density. The infiltrated precursor is further heat treated to produce a tailorable microstructure. The process at low cost produces composites with improved characteristics, including increased toughness, strength.

  16. Neptunium as a Tool for Reducing Proliferation Risks with Plutonium: A Technical Analysis of its Efficiency and its Drawbacks

    SciTech Connect

    Greneche, Dominique; Ng, Selena; Guesdon, Bernard; Vinoche, Richard; Delpech, Marc; Golfier, Herve; Dolci, Florence; Poinot-Salanon, Christine

    2006-07-01

    Introducing neptunium into the nuclear fuel cycle has been proposed in the past as a way to impede the diversion or the direct use of plutonium to fabricate a nuclear explosive device. This paper aims to technically analyze the industrial consequences should this proposal be implemented. Two scenarios are considered: 1) adding neptunium to fresh uranium oxide (UOX) fuel before irradiation in a light water reactor; 2) separating neptunium together with plutonium from used UOX fuel and using this combined oxide to fabricate mixed oxide (MOX) fuel before subsequent irradiation in a light water reactor. In both cases, assembly calculations for a pressurized water reactor using fresh fuel doped with neptunium are presented for a wide range of neptunium proportions. Consequences on core and fuel performances and the fuel cycle are analyzed. These are weighed against the potential proliferation resistance benefits of adding neptunium due to the increased quantity of the plutonium isotope {sup 238}Pu in the discharged fuel, or due to the potentially increased detectability through gamma ray emissions of a plutonium-neptunium oxide mixture. Finally, the proliferation risk presented by neptunium itself is discussed. (authors)

  17. Batch sorption results for neptunium transport through Yucca Mountain tuffs. Yucca Mountain Site Characterization Program milestone 3349

    SciTech Connect

    Triay, I.R.; Cotter, C.R.; Huddleston, M.H.; Leonard, D.E.

    1996-09-01

    We studied the sorption of neptunium onto tuffs characteristic of the proposed nuclear waste repository at Yucca Mountain, Nevada. The neptunium was in the Np(V) oxidation state under oxidizing conditions in groundwaters from two wells located close to the repository site (J-13 and UE-25 p No.1). We used devitrified, vitric, zeolitic (with emphasis on clinoptilolite-rich samples), and calcite-rich tuffs characteristic of the geology of the site. Neptunium sorbed well onto calcite and calcite-rich tuffs, indicating that a significant amount of neptunium retardation can be expected under fractured-flow scenarios because of calcite coating of the fractures. Neptunium sorption onto clinoptilolite-rich zeolitic tuffs in J-13 well water (pH from 7 to 8.5) was moderate, increased with decreasing pH, and correlated to surface area and amount of clinoptilolite. Neptunium sorbed poorly onto zeolitic tuffs from UE-25 p No.1 groundwater (pH from 7 to 9) and onto devitrified and vitric tuffs from J-13 and UE-25 p No.1 waters (pH from 7 to 9). Iron oxides appeared to be passivated in tuffs, not seeming to contribute to the observed neptunium sorption, even though neptunium sorption onto synthetic iron oxide is significant.

  18. Environmental monitoring for uranium and neptunium at Yucca Mountain using epithermal neutron activation analysis

    SciTech Connect

    Riggle, K.J.

    1992-12-31

    Epithermal Neutron Activation Analysis (ENAA) is investigated as an analysis method for uranium and neptunium in environmental samples from Yucca Mountain. The design and construction of a facility for this technique are described. Theoretical improvement in sensitivity for ENAA over thermal NAA (TNAA) is discussed and compared to experimental results for different sample types. Uranium is analyzed in eight different sample matrices, including samples from Yucca Mountain. Neptunium has been studied only in AGV-1 Granite. As predicted by theory, uranium shows a high experimental sensitivity improvement factor (average = 7.76), while neptunium has a factor of only 0.49. Detection limits for uranium using ENAA range from 6 to 52 ppb by weight (2.6 to 17 ng in sample) for the different matrices. Neptunium shows a detection limit of 57 ppb by weight (6.2 ng in sample) in AGV-1 Granite using ENAA. Using TNAA, neptunium can be analyzed to 35 ppb by weight (3.4 ng in sample).

  19. Effect of Precipitation Conditions on the Specific Surface Area of Neptunium Oxide

    SciTech Connect

    HILL, BENJAMINC.

    2004-06-01

    Neptunium oxalate was precipitated under nominal and bounding HB-Line flowsheet conditions. The nominal case represents expected normal HB-Line operation. The bounding case represents process flowsheet extremes that could occur which are anticipated to decrease particle size and increase surface area. The neptunium oxalate produced under bounding conditions was used to validate the effectiveness of HB-Line calcination conditions. The maximum specific surface area of the neptunium oxide (NpO2) used in gas generation testing was 5.34 m2/g. Experiments were conducted to verify that even under bounding precipitation conditions the SSA of NpO2 produced would remain within the range evaluated during gas generation testing. The neptunium oxalate from nominal and bounding precipitation conditions was calcined at 600 degrees Celsius and 625 degrees Celsius, respectively, to form NpO2. Samples from each batch of neptunium oxalate were calcined for one, two, or four hours. Results indicate that the SSA of NpO2 continues to decrease between one and four hours. After two hours of calcination at 625 degrees Celsius, the SSA of NpO2 from the bounding case meets the surface area requirements for limiting moisture uptake.

  20. Report on neptunium speciation by NMR and optical spectroscopies

    SciTech Connect

    Tait, C.D.; Palmer, P.D.; Ekberg, S.A.; Clark, D.L.

    1995-11-01

    Hydrolysis and carbonate complexation reactions were examined for NpO{sub 2}{sup 2+} and NpO{sub 2}{sup +} ions by a variety of techniques including potentiometric titration, UV-Vis-NIR and NMR spectroscopy. The equilibrium constant for the reaction 3NpO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} + 3H{sup +} {rightleftharpoons} (NpO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} + 3HCO{sub 3}{sup {minus}} was determined to be logK = 19.7 ({plus_minus} 0.8) (I = 2.5 m). {sup 17}O NMR spectroscopy of NpO{sub 2}{sup n+} ions (n = 1,2) reveals a readily observable {sup 17}O resonance for n = 2, but not for n = 1. The first hydrolysis constant for NpO{sub 2}{sup +} was studied as a function of temperature, and the functional form for the temperature-dependent equilibrium constant for the reaction written as NpO{sub 2}{sup +} + H{sub 2}O {rightleftharpoons} NpO{sub 2}OH + H{sup +} was found to be logK = 2.28 {minus} 3780/T, where T is in {degree}K. Finally, the temperature dependence of neptunium(V) carbonate complexation constants was studied. For the first carbonate complexation constant, the appropriate functional form was found to be log{beta}{sub 01} = 1.47 + 786/T.

  1. Gastrointestinal absorption of protactinium, uranium, and neptunium in the hamster

    SciTech Connect

    Harrison, J.D.; Stather, J.W.

    1981-10-01

    The gastrointestinal absorption of protactinium, uranium, and neptunium in adult hamsters was measured. The actinide preparations were administered intragastrically and animals were kept 2 to 4 weeks prior to the radiochemical analysis of selected tissue samples. Total absorption was estimated using data for the distribution of the actinides after intravenous injection in soluble form. The values obtained were 3.9 and 0.22% for /sup 231/Pa citrate and /sup 231/Pa fluoride, respectively; 0.77 and 0.11% for /sup 233/U (uranyl) nitrate and /sup 233/U dioxide, respectively; and 0.06 and 0.05% for /sup 237/Np citrate and /sup 237/Np nitrate, respectively. The absorption factors recommended by the International Commission on Radiological Protection for use in calculating annual limits on intake for occupationally exposed workers are: 0.1% for all compounds of Pa; 5 and 0.2% for soluble hexavalent and relatively insoluble tetravalent forms of U, respectively; and 1.0% for all chemical forms of Np. The experimental basis for these values is discussed.

  2. Speciation of neptunium during sorption and diffusion in natural clay

    NASA Astrophysics Data System (ADS)

    Reich, T.; Amayri, S.; Bӧrner, P. J. B.; Drebert, J.; Frӧhlich, D. R.; Grolimund, D.; Kaplan, U.

    2016-05-01

    In argillaceous rocks, which are considered as a potential host rock for nuclear waste repositories, sorption and diffusion processes govern the migration behaviour of actinides like neptunium. For the safety analysis of such a repository, a molecular-level understanding of the transport and retardation phenomena of radioactive contaminants in the host rock is mandatory. The speciation of Np during sorption and diffusion in Opalinus Clay was studied at near neutral pH using a combination of spatially resolved synchrotron radiation techniques. During the sorption and diffusion experiments, the interaction of 8 μM Np(V) solutions with the clay lead to the formation of spots at the clay-water interface with increased Np concentrations as determined by μ-XRF. Several of these spots are correlated with areas of increased Fe concentration. Np L3-edge μ-XANES spectra revealed that up to 85% of the initial Np(V) was reduced to Np(IV). Pyrite could be identified by μ-XRD as a redox-active mineral phase responsible for the formation of Np(IV). The analysis of the diffusion profile within the clay matrix after an in-diffusion experiment for two months showed that Np(V) is progressively reduced with diffusion distance, i.e. Np(IV) amounted to ≈12% and ≈26% at 30 μm and 525 μm, respectively.

  3. Purification of Simulated Neptunium Filtrate Solution by Anion Exchange

    SciTech Connect

    Crowder, Mark L.; Kyser, Edward A. III

    2007-07-01

    Full text of publication follows: Anion exchange was investigated as a means to recover and purify neptunium (Np) from solutions containing significant plutonium (Pu), sodium (Na), and manganese (Mn) impurities and a high nitrate concentration. The solution being evaluated resulted from lean filtrate and precipitator clean-out solutions which were generated during Np processing at the Savannah River Site. Prior to anion exchange, valence adjustment of the Np using ferrous sulfamate (i.e., Fe{sub 2}(SO{sub 3}NH{sub 2}){sub 2} or FS) was evaluated. For testing, a simulated filtrate solution was made with {approx}1.5 g Np/L and slightly elevated levels of impurities. Two anion exchange column runs were performed. In both runs, Np was loaded onto Reillex HPQ resin in high nitric acid (HNO{sub 3}) solution, typical for Np processing. The resin wash step differed in the two runs, but the elution step was the same. In the first column run, 12 column bed volumes (BV) of reductive or partition wash with 6.4 M nitric acid / 0.05 M FS were used. In the second run, six BV of 5 M HNO{sub 3} / 0.05 M FS were used as the reductive wash. Reported results will include Pu rejection, Np losses and decontamination factors for Na and Mn. (authors)

  4. Fate of neptunium in an anaerobic, methanogenic microcosm.

    SciTech Connect

    Banaszak, J. E.

    1998-12-21

    Neptunium is found predominantly as Np(IV) in reducing environments, but Np(V) in aerobic environments. However, currently it is not known how the interplay between biotic and abiotic processes affects Np redox speciation in the environment. In order to evaluate the effect of anaerobic microbial activity on the fate of Np in natural systems, Np(V) was added to a microcosminoculated with anaerobic sediments from a metal-contaminated fresh water lake. The consortium included metal-reducing, sulfate-reducing, and methanogenic microorganisms, and acetate was supplied as the only exogenous substrate. Addition of more than 10{sup {minus}5} M Np did not inhibit methane production. Total Np volubility in the active microcosm, as well as in sterilized control samples, decreased by nearly two orders of magnitude. A combination of analytical techniques, including VIS-NIR absorption spectroscopy and XANES, identified Np(IV) as the oxidation state associated with the sediments. The similar results from the active microcosm and the abiotic controls suggest that microbian y produced Mn(II/HI) and Fe(II) may serve as electron donors for Np reduction.

  5. Fate of neptunium in an anaerobic, methanogenic microcosm

    SciTech Connect

    Banaszak, J.E.; Webb, S.M.; Rittmann, B.E.; Gaillard, J.F.; Reed, D.T.

    1999-07-01

    Neptunium is found predominantly as Np(IV) in reducing environments, but as Np(V) in aerobic environments. Currently, it is not known how the interplay between biotic and abiotic processes affects Np redox speciation in the environment. To evaluate the effect of anaerobic microbial activity on the fate of Np in natural systems, Np(V) was added to a microcosm inoculated with anaerobic sediments from a metal-contaminated freshwater lake. The consortium included metal-reducing, sulfate-reducing, and methanogenic microorganisms, and acetate was supplied as the only exogenous substrate. Addition of more than 10{sup {minus}5} M Np did not inhibit methane production. Total Np solubility in the active microcosm, as well as in sterilized control samples, decreased by nearly two orders of magnitude. A combination of analytical techniques, including VIS-NIR absorption spectroscopy and XANES, identified Np(IV) as the oxidation state associated with the sediments. The similar results from the active microcosm and the abiotic controls suggest that microbially produced Mn(II/III) and Fe(II) may serve as electron donors for Np reduction.

  6. Evidence for Neptunium Incorporation into Uranium (VI) Phases

    SciTech Connect

    Buck, Edgar C.; Hanson, Brady D.; Friese, Judah I.; Douglas, Matthew; McNamara, Bruce K.

    2004-12-01

    This paper examines the ability of Electron Energy-Loss Spectroscopy (EELS) on the Transmission Electron Microscope (TEM) to both detect low levels of neptunium (Np) in a uranium matrix and to provide evidence for incorporation of Np in U6+ phases. The case for using U6+ secondary minerals as solubility-controlling phases for Np in repository performance assessment models has not been established. Direct evidence for incorporation rather than sorption has been difficult to obtain. The detection of Np in a matrix of uranium (U) can be impeded by the occurrence of a plural scattering event from U (U-M5 + U-O4,5) that results in severe overlap on the Np-M5 edge at 3665 eV. By examining the energy gap between the Np-M5 and Np-M4 edges (184 eV), a method for observing Np independently of the plural scattering event has been established. Clear evidence of Np incorporation into studtite, [(UO2)(O2)(H2O)2](H2O)2 and uranophane, Ca(UO2)2(SiO3OH)2(H2O)5 has been found in laboratory tests using TEM-EELS. This data suggests that U6+ phases, if present, may control Np solubility in a repository environment.

  7. Oxidation behaviour of uranium and neptunium in stabilised zirconia

    NASA Astrophysics Data System (ADS)

    Walter, Marcus; Somers, Joseph; Bouëxière, Daniel; Gaczyński, Piotr; Brendebach, Boris

    2009-12-01

    Yttria stabilised zirconia (YSZ) based (Zr,Y,U)O 2-x and (Zr,Y,Np)O 2-x solid solutions with 6 and 20 mol% actinide were prepared with Y/Zr ratios ranging from 0.2 to 2.0 to investigate uranium and neptunium oxidation behaviour depending on the oxygen vacancies in the defect fluorite lattice. Sintering at 1600 °C in Ar/H 2 yields a cubic, fluorite-type structure with U(IV) and Np(IV). Annealing (Zr,Y,U)O 2-x with Y/Zr=0.2 at 800 °C in air results in a tetragonal phase, whereas (Zr,Y,U)O 2-x with higher Y/Zr ratios and (Zr,Y,Np)O 2-x retain the cubic structure. XANES and O/ M measurements indicate mixed U(V)-U(VI) and Np(IV)-Np(V) oxidation states after oxidation. Based on X-ray diffraction, O/ M and EXAFS measurements, different oxidation mechanisms are identified for U- and Np-doped stabilised zirconia. In contrast to U, excess oxygen vacancies are needed to oxidise Np in (Zr,Y,Np)O 2-x as the oxidation process competes with Zr for oxygen vacancies. As a consequence, U(VI) and Np(V) can only be obtained in stabilised zirconia with Y/Zr=1 but not in YSZ with Y/Zr=0.2.

  8. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

    PubMed

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

  9. Amorphous nickel boride membrane on a platinum–nickel alloy surface for enhanced oxygen reduction reaction

    PubMed Central

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum–nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum–nickel catalyst, and this composite catalyst composed of crystalline platinum–nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

  10. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-08-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

  11. Investigation of composition and chemical state of elements in iron boride by the method of X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Alyoshin, V. G.; Kharlamov, A. I.; Prokopenko, V. M.

    1981-06-01

    The composition and chemical state of iron and boron in the surface layer of iron boride under different kinds of pretreatment of samples have been investigated by the method of X-ray photo-electron spectroscopy. It has been found that in the initial sample there is oxygen chemically combined with iron and boron atoms. Upon heating (450°C) in hydrogen, in argon, and in vacuo there occurs removal of oxygen only from iron atoms (no pure iron was found to be formed). Boron oxidizes and there probably appears a new surface combination of boron with oxygen in which the bonding energy of 1 s electrons is higher than that in B 2O 3. Treatment of the iron boride surface with argon ions and with protons ensures uniform removal of oxygen from iron and boron atoms. It has been found that thermal treatment of iron boride leads to depletion of iron atoms from the sample surface layer, and pickling with argon ions and with protons leads to strong enrichment. Iron boride samples subjected to Ar + and H + bombardment tend to undergo significant oxidation when subsequently exposed to air at room temperature.

  12. Factors Controlling Redox Speciation of Plutonium and Neptunium in Extraction Separation Processes

    SciTech Connect

    Paulenova, Alena; Vandegrift, III, George F.

    2013-09-24

    The objective of the project was to examine the factors controlling redox speciation of plutonium and neptunium in UREX+ extraction in terms of redox potentials, redox mechanism, kinetics and thermodynamics. Researchers employed redox-speciation extractions schemes in parallel to the spectroscopic experiments. The resulting distribution of redox species w studied uring spectroscopic, electrochemical, and spectro-electrochemical methods. This work reulted in collection of data on redox stability and distribution of redox couples in the nitric acid/nitrate electrolyte and the development of redox buffers to stabilize the desired oxidation state of separated radionuclides. The effects of temperature and concentrations on the redox behavior of neptunium were evaluated.

  13. Apparent diffusion coefficients and chemical species of neptunium (V) in compacted Na-montmorillonite.

    PubMed

    Kozai, N; Inada, K; Kozaki, T; Sato, S; Ohashi, H; Banba, T

    2001-02-01

    Diffusion of neptunium (V) in compacted Na-montmorillonite was studied through the non-steady state diffusion method. In this study, two experimental attempts were carried out to understand the diffusion mechanism of neptunium. One was to establish the diffusion activation energy, which was then used to determine the diffusion process in the montmorillonite. The other was the measurement of the distribution of neptunium in the montmorillonite by a sequential batch extraction. The apparent diffusion coefficients of neptunium in the montmorillonite at a dry density of 1.0 Mg m-3 were from 3.7 x 10(-12) m2 s-1 at 288 K to 9.2 x 10(-12) m2 s-1 at 323 K. At a dry density of 1.6 Mg m-3, the apparent diffusion coefficients ranged between 1.5 x 10(-13) m2 s-1 at 288 K and 8.7 x 10(-13) m2 s-1 at 323 K. The activation energy for the diffusion of neptunium at a dry density of 1.0 Mg m-3 was 17.5 +/- 1.9 kJ mol-1. This value is similar to those reported for diffusion of other ions in free water, e.g., 18.4 and 17.4 kJ mol-1 for Na+ and Cl-, respectively. At a dry density of 1.6 Mg.m-3, the activation energy was 39.8 +/- 1.9 kJ mol-1. The change in the activation energy suggests that the diffusion process changes depending on the dry density of the compacted montmorillonite. A characteristic distribution profile was obtained by the sequential extraction procedure for neptunium diffused in compacted montmorillonite. The estimated fraction of neptunium in the pore water was between 3% and 11% at a dry density of 1.6 Mg m-3 and at a temperature of 313 K. The major fraction of the neptunium in the montmorillonite was identified as neptunyl ions sorbed on the outer surface of the montmorillonite. These findings suggested that the activation energy for diffusion and the distribution profile of the involved nuclides could become powerful parameters in understanding the diffusion mechanism.

  14. Ultrastructural apoptotic lesions induced in bone marrow after neptunium-237 contamination.

    PubMed

    Pusset, D; Boulahdour, H; Fromm, M; Poncy, J L; Kantelip, B; Griffond, B; Baud, M; Galle, P

    2003-01-01

    This study describes the ultrastructure of lesions induced by neptunium-237 (237Np), a by-product of uranium in nuclear reactors, in the bone marrow. A group of rats were given a single injection of 237Np-nitrate solution in order to observe the acute toxicity effects of this actinide. Electron microscopy was used to describe the different lesions. Observations included the swelling of the cell membrane, nuclear membrane lyses, abnormal chromatin condensation or nucleus convolution. These ultrastructural alterations of the nucleus and the cellular membrane appeared shortly after treatment. This study demonstrates the toxic effects of neptunium and its implication in the induction of apoptosis in bone marrow.

  15. Intrinsic formation of nanocrystalline neptunium dioxide under neutral aqueous conditions relevant to deep geological repositories.

    PubMed

    Husar, Richard; Hübner, René; Hennig, Christoph; Martin, Philippe M; Chollet, Mélanie; Weiss, Stephan; Stumpf, Thorsten; Zänker, Harald; Ikeda-Ohno, Atsushi

    2015-01-25

    The dilution of aqueous neptunium carbonate complexes induces the intrinsic formation of nanocrystalline neptunium dioxide (NpO2) particles, which are characterised by UV/Vis and X-ray absorption spectroscopies and transmission electron microscopy. This new route of nanocrystalline NpO2 formation could be a potential scenario for the environmental transport of radionuclides from the waste repository (i.e. under near-field alkaline conditions) to the geological environment (i.e. under far-field neutral conditions).

  16. Characterization of Neptunium Oxide Generated Using the HB-Line Phase II Flowsheet

    SciTech Connect

    Duffey, J

    2003-08-29

    Approximately 98 grams of neptunium(IV) oxide (NpO{sub 2}) were produced at the Savannah River Technology Center (SRTC) for use in gas generation tests to support the neptunium stabilization program at the Savannah River Site (SRS). The NpO{sub 2} was produced according to the anticipated HB-Line flowsheet consisting of anion exchange, oxalate precipitation, filtration, and calcination. Characterization of the NpO{sub 2} product to be used in gas generation tests included bulk and tap density measurements, X-ray diffraction, particle size distribution, specific surface area measurements, and moisture analysis.

  17. Neptunium(V) and neptunium(VI) solubilities in synthetic brines of interest to the Waste Isolation Pilot Plant (WIPP)

    SciTech Connect

    Novak, C.F.; Nitsche, H. |; Silber, H.B. |

    1996-12-31

    The solubility of Np(V) and Np(VI) has been measured in three synthetic Na-K-Mg-Cl brines in the presence of CO{sub 2}(g). Experiments were prepared from oversaturation by adding an excess of NpO{sub 2}{sup +} or NpO{sub 2}{sup 2+} to the brines and allowing the neptunium solids to precipitate. Vessels were maintained in contact with fixed CO{sub 2}(g) partial pressures at constant pH and 24 {+-} 1 C. Dissolved Np(V) concentrations decreased several orders of magnitude within the first 100 days of the experiment, while dissolved Np(VI) concentrations decreased initially but then remained relatively constant for more than 400 days. The solid phases formed in all experiments were identified by X-ray powder diffraction as KNpO{sub 2}CO{sub 3}{center_dot}xH{sub 2}O(s). Steady state concentrations for Np(V) are similar to those observed for Pu(V) in the same brines under the same conditions, where Pu occurs predominantly as Pu(V). Similarly, steady state concentrations for Np(VI), which was not reduced over a two year period, compare well with measured Pu(VI) concentrations in the same brines before the Pu(VI) was reduced to Pu(V).

  18. Neptunium - Uranium - Plutonium Co-Extraction in TBP-based Solvent Extraction Processes for Spent Nuclear Fuel Recycling

    SciTech Connect

    Arm, S.T.; Abrefah, J.; Lumetta, G.J.; Sinkov, S.I.

    2007-07-01

    The US, through the Global Nuclear Energy Partnership, is currently engaged in efforts aimed at closing the nuclear fuel cycle. Neptunium behavior is important to understand for transuranic recycling because of its complex oxidation chemistry. The Pacific Northwest National Laboratory is investigating neptunium oxidation chemistry in the context of the PUREX process. Neptunium extraction in the PUREX process relies on maintaining either IV or V oxidation states. Qualitative conversion of neptunium(V) to neptunium(VI) was achieved within 5 hours in 6 M nitric acid at 95 deg. C. However, the VI state was not maintained during a batch contact test simulating the PUREX process and neptunium reduced to the V state, rendering it inextractable. Vanadium(V) was found to be effective in maintaining neptunium(VI) by adding it to a simulated irradiated nuclear fuel feed in 6 M nitric acid and to the scrub acid in the batch contact simulation of the PUREX process. Computer simulations of the PUREX process with a typical irradiated nuclear fuel in 6 M nitric acid as feed indicated little impact of the higher acid concentration on the behavior of fission products of moderate extractability. We plan to perform countercurrent tests of this modified PUREX process in the near future. (authors)

  19. Spectroscopic investigations of neptunium`s and plutonium`s oxidation states in sol-gel glasses as a function of initial valance and thermal history

    SciTech Connect

    Stump, N.A.; Haire, R.G.; Dai, S.

    1996-12-01

    Several oxidation states of neptunium and plutonium, Pu(III),Pu (IV), PU(VI), Np(IV), Np(V) and Np (VI), were studied in glasses prepared by a sol-gel technology. The oxidation state of these actinides was determined primarily by absorption spectrometry and followed as a function of the solidification process, subsequent aging and thermal treatments. It was determined that the initial oxidation state of the actinides in the starting solutions was essentially maintained through the solidification process to form the glasses. However, during densification and removal of residual solvents at elevated temperatures, both actinides in the different sol-gel products converted completely to their tetravalent states. These results are discussed in terms of our findings in comparable studies that only the tetravalent states of plutonium and neptunium are formed in glasses prepared by dissolving their dioxides in different molten- glass formulations.

  20. Sensitive redox speciation of neptunium by CE-ICP-MS.

    PubMed

    Stöbener, Nils; Amayri, Samer; Gehl, Aaron; Kaplan, Ugras; Malecha, Kurtis; Reich, Tobias

    2012-11-01

    Capillary electrophoresis (CE) was used to separate the neptunium oxidation states Np(IV) and Np(V), which are the only oxidation states of Np that are stable under environmental conditions. The CE setup was coupled to an inductively coupled plasma mass spectrometer (Agilent 7500ce) using a Mira Mist CE nebulizer and a Scott-type spray chamber. The combination of the separation capacity of CE with the detection sensitivity of inductively coupled plasma mass spectrometry (ICP-MS) allows identification and quantification of Np(IV) and Np(V) at the trace levels expected in the far field of a nuclear waste repository. Limits of detection of 1 × 10(-9) and 5 × 10(-10) mol L(-1) for Np(IV) and Np(V), respectively, were achieved, with a linear range from 10(-9) to 10(-6) mol L(-1). The method was applied to study the redox speciation of the Np remaining in solution after interaction of 5 × 10(-7) mol L(-1) Np(V) with Opalinus Clay. Under mildly oxidizing conditions, a Np sorption of 31% was found, with all the Np remaining in solution being Np(V). A second sorption experiment performed in the presence of Fe(2+) led to complete sorption of the Np onto the clay. After desorption with HClO(4), a mixture of Np(IV) and Np(V) was found in solution by CE-ICP-MS, indicating that some of the sorbed Np had been reduced to Np(IV) by Fe(2+).

  1. Experimental study on neptunium migration under in situ geochemical conditions

    NASA Astrophysics Data System (ADS)

    Kumata, M.; Vandergraaf, T. T.

    1998-12-01

    Results are reported for migration experiments performed with Np under in situ geochemical conditions over a range of groundwater flow rates in columns of crushed rock in a specially designed facility at the 240-level of the Underground Research Laboratory (URL) near Pinawa, Manitoba, Canada. This laboratory is situated in an intrusive granitic rock formation, the Lac du Bonnet batholith. Highly altered granitic rock and groundwater were obtained from a major subhorizontal fracture zone at a depth of 250 m in the URL. The granite was wet-crushed and wet-sieved with groundwater from this fracture zone. The 180-850-μm size fraction was selected and packed in 20-cm long, 2.54-cm in diameter Teflon™-lined stainless steel columns. Approximately 30-ml vols of groundwater containing 3HHO and 237Np were injected into the columns at flow rates of 0.3, 1, and 3 ml/h, followed by elution with groundwater, obtained from the subhorizontal fracture, at the same flow rates, for a period of 95 days. Elution profiles for 3HHO were obtained, but no 237Np was detected in the eluted groundwater. After terminating the migration experiments, the columns were frozen, the column material was removed and cut into twenty 1-cm thick sections and each section was analyzed by gamma spectrometry. Profiles of 237Np were obtained for the three columns. A one-dimensional transport model was fitted to the 3HHO breakthrough curves to obtain flow parameters for this experiment. These flow parameters were in turn applied to the 237Np concentration profiles in the columns to produce sorption and dispersion coefficients for Np. The results show a strong dependence of retardation factors ( Rf) on flow rate. The decrease in the retarded velocity of the neptunium ( Vn) varied over one order of magnitude under the geochemical conditions for these experiments.

  2. Uranium (VI) and Neptunium (V) Transport Fractured, Hydrothermally Altered Concrete

    SciTech Connect

    Matzen, S.L.; Beiriger, J.M.; Torretto, P.C.; Zhao, P.

    1999-11-04

    In a high level waste repository in which temperatures are elevated due to waste decay, concrete structures will be subjected to hydrothermal conditions that will alter their physical and chemical properties. Virtually no studies have examined the interaction of hydrothermally altered concrete with radionuclides. We present the results of experiments in which soluble and colloid-associated actinides, uranium (U) and neptunium (Np), were eluted into a fractured, hydrothermally altered concrete core. Although the fluid residence time in the fracture was estimated to be on the order of 1 minute, U and Np were below detection (10{sup -9}-10{sup -8} M) in the effluent from the core, for both soluble and colloid-associated species. Inorganic colloids and latex microspheres were similarly immobilized within the core. Post-test analysis of the core identified the immobilized U and Np at or near the fracture surface, with a spatial distribution similar to that of the latex microspheres. Because hydrothermal alteration followed fracturing, the growth of crystalline calcium silicate hydrate and clay mineral alteration products on, and possibly across the fracture, resulted in a highly reactive fracture that was effective at capturing both soluble and colloidal radionuclides. Comparison of results from batch experiments [1] with these experiments indicate that partitioning of U and Np to the solid phase, and equilibration of the incoming fluid with the concrete, occurs rapidly in the fractured system. Transport of U through the concrete may be solubility and/or sorption limited; transport of Np appears to be limited primarily by sorption.

  3. Boronic acid flux synthesis and crystal growth of uranium and neptunium boronates and borates: a low-temperature route to the first neptunium(V) borate.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Miller, Hannah M; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2010-11-01

    Molten methylboronic acid has been used as a reactive flux to prepare the first neptunium(V) borate, NpO(2)[B(3)O(4)(OH)(2)] (NpBO-1), and the first actinide boronate, UO(2)(CH(3)BO(2))(H(2)O) (UCBO-1). NpBO-1 contains cation-cation interactions between the neptunyl units. In contrast, the presence of the methyl groups in the uranyl boronate leads to a one-dimensional structure.

  4. Mixed-valent neptunium(IV/V) compound with cation-cation-bound six-membered neptunyl rings.

    PubMed

    Jin, Geng Bang

    2013-11-01

    A new mixed-valent neptunium(IV/V) compound has been synthesized by evaporation of a neptunium(V) acidic solution. The structure of the compound features cation-cation-bound six-membered neptunyl(V) rings. These rings are further connected by Np(IV) ions through cation-cation interactions (CCIs) into a three-dimensional neptunium cationic open framework. This example illustrates the possibility of isolating neptunyl(V) CCI oligomers in inorganic systems using other cations to compete with Np(V) in bonding with the neptunyl oxygen.

  5. Gastrointestinal absorption of neptunium in primates: effect of ingested mass, diet, and fasting

    SciTech Connect

    Metivier, H.; Bourges, J.; Fritsch, P.; Nolibe, D.; Masse, R.

    1986-05-01

    Absorption and retention of neptunium were determined in baboons after intragastric administration of neptunium nitrate solutions at pH 1. The effects of mass, diet, and fasting on absorption were studied. At higher mass levels (400-800 micrograms Np/kg), absorption was about 1%; at lower mass intakes (0.0009-0.005 micrograms Np/kg), absorption was reduced by 10- to 20-fold. The addition of an oxidizing agent (Fe3+) increased gastrointestinal absorption and supported the hypothesis of a reduction of Np (V) when loss masses were ingested. Diets depleted of or enriched with hydroxy acids did not modify retention of neptunium but increased urinary excretion with increasing hydroxy acid content. The diet enriched with milk components reduced absorption by a factor of 5. Potatoes increased absorption and retention by a factor 5, not necessarily due to the effect of phytate. Fasting for 12 or 24 h increased retention and absorption by factors of about 3 and 10, respectively. Data obtained in baboons when low masses of neptunium were administered suggest that the f1 factor used by ICRP should be decreased. However, fasting as encountered in certain nutritional habits is a factor to be taken into consideration.

  6. Gastrointestinal absorption of neptunium in primates: effect of ingested mass, diet, and fasting.

    PubMed

    Metivier, H; Bourges, J; Fritsch, P; Nolibe, D; Masse, R

    1986-05-01

    Absorption and retention of neptunium were determined in baboons after intragastric administration of neptunium nitrate solutions at pH 1. The effects of mass, diet, and fasting on absorption were studied. At higher mass levels (400-800 micrograms Np/kg), absorption was about 1%; at lower mass intakes (0.0009-0.005 micrograms Np/kg), absorption was reduced by 10- to 20-fold. The addition of an oxidizing agent (Fe3+) increased gastrointestinal absorption and supported the hypothesis of a reduction of Np (V) when loss masses were ingested. Diets depleted of or enriched with hydroxy acids did not modify retention of neptunium but increased urinary excretion with increasing hydroxy acid content. The diet enriched with milk components reduced absorption by a factor of 5. Potatoes increased absorption and retention by a factor 5, not necessarily due to the effect of phytate. Fasting for 12 or 24 h increased retention and absorption by factors of about 3 and 10, respectively. Data obtained in baboons when low masses of neptunium were administered suggest that the f1 factor used by ICRP should be decreased. However, fasting as encountered in certain nutritional habits is a factor to be taken into consideration.

  7. Criticality of a Neptunium-237 sphere surrounded with highly enriched uranium shells and an iron reflector

    SciTech Connect

    Sanchez, R. G.; Loaiza, D. J.; Hayes, D. K.; Kimpland, R. H.

    2004-01-01

    An additional experiment has been performed using the recently cast 6-kg {sup 237}Np sphere. The experiment consisted of surrounding the neptunium sphere with highly enriched uranium and an iron reflector. The purpose of the critical experiment is to provide additional criticality data that can be used to validate criticality safety evaluations involving the deposition of neptunium. It is well known that {sup 237}Np is primarily produced by successive neutron capture events in {sup 235}U or through the (n, 2n) reaction in {sup 238}U. These nuclear reactions lead to the production of {sup 237}U, which decays by beta emission into {sup 237}Np. In addition, in the spent fuel, {sup 241}Am decays by alpha emission into {sup 237}Np. Because {sup 237}Np is a threshold fissioner, the best reflectors for critical systems containing neptunium are those materials that exhibit good neutron scattering properties such as low carbon steel (99 wt % Fe). In this experiment, the iron reflector reduced the amount of uranium used in the critical experiment and increased the importance of the neptunium sphere.

  8. The influence of phonon anharmonicity on thermal and elastic properties of neptunium

    NASA Astrophysics Data System (ADS)

    Filanovich, A.; Povzner, A.

    2013-06-01

    A self-consistent thermodynamic model describing the thermal and elastic properties of α- and β-phases of neptunium was developed. The presence of strong phonon anharmonicity of Np is established. The obtained results are in good agreement with the experimental data and enable to predict the Np properties in wide temperature range.

  9. High-temperature X-ray diffraction study of uranium-neptunium mixed oxides.

    PubMed

    Chollet, Mélanie; Belin, Renaud C; Richaud, Jean-Christophe; Reynaud, Muriel; Adenot, Frédéric

    2013-03-01

    Incorporating minor actinides (MAs = Am, Np, Cm) in UO2 fertile blankets is a viable option to recycle them. Despite this applied interest, phase equilibria between uranium and MAs still need to be thoroughly investigated, especially at elevated temperatures. In particular, few reports on the U-Np-O system are available. In the present work, we provide for the first time in situ high-temperature X-ray diffraction results obtained during the oxidation of (U1-yNpy)O2 uranium-neptunium mixed oxides up to 1373 K and discuss subsequent phase transformations. We show that (i) neptunium stabilizes the UO2-type fluorite structure at high temperature and that (ii) the U3O8-type orthorhombic structure is observed in a wide range of compositions. We clearly demonstrate the incorporation of neptunium in this phase, which was a controversial question in previous studies up to now. We believe it is the particular stability of the tetravalent state of neptunium that is responsible for the observed phase relationships.

  10. Valence fluctuations of europium in the boride Eu4Pd(29+x)B8.

    PubMed

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A; Abd-Elmeguid, Mohsen M; Kvashnina, Kristina O; Tsirlin, Alexander A; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-23

    We synthesized a high-quality sample of the boride Eu4Pd(29+x)B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems.

  11. Valence fluctuations of europium in the boride Eu4Pd29+x B8

    NASA Astrophysics Data System (ADS)

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A.; Abd-Elmeguid, Mohsen M.; Kvashnina, Kristina O.; Tsirlin, Alexander A.; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-01

    We synthesized a high-quality sample of the boride Eu4Pd29+x B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems.

  12. Identification of delamination failure of boride layer on common Cr-based steels

    NASA Astrophysics Data System (ADS)

    Taktak, Sukru; Tasgetiren, Suleyman

    2006-10-01

    Adhesion is an important aspect in the reliability of coated components. With low-adhesion of interfaces, different crack paths may develop depending on the local stress field at the interface and the fracture toughness of the coating, substrate, and interface. In the current study, an attempt has been made to identify the delamination failure of coated Cr-based steels by boronizing. For this reason, two commonly used steels (AISI H13, AISI 304) are considered. The steels contain 5.3 and 18.3 wt.% Cr, respectively. Boriding treatment is carried out in a slurry salt bath consisting of borax, boric acid, and ferrosilicon at a temperature range of 800 950 °C for 3, 5, and 7 h. The general properties of the boron coating are obtained by mechanical and metallographic characterization tests. For identification of coating layer failure, some fracture toughness tests and the Daimler-Benz Rockwell-C adhesion test are used.

  13. Valence fluctuations of europium in the boride Eu4Pd(29+x)B8.

    PubMed

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A; Abd-Elmeguid, Mohsen M; Kvashnina, Kristina O; Tsirlin, Alexander A; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-23

    We synthesized a high-quality sample of the boride Eu4Pd(29+x)B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems. PMID:26895077

  14. Physics Among Lightweights: Boride Superconductors (Superconductivity in MgB2)

    SciTech Connect

    Canfield, Paul C.

    2001-06-13

    Recently there has been a great deal of excitement about the intermetallic superconductor MgB2. MgB2 has a superconducting transition temperature Tc {approx} 40 K, can be synthesized as single phase powders and wire segments, has a remarkably low normal state resistivity, and manifests a promising critical current density in the superconducting state. In this colloquium I will review recent discoveries associated with intermetallic borides and try to show how MgB2 fits into the basic gestalt of intermetallic compounds. In addition I will try to explain why anybody should care about this and why some physicists find the topic of novel states in intermetallic compounds to be an extremely interesting research topic.

  15. The aqueous geochemistry of neptunium: Dynamic control of soluble concentrations with applications to nuclear waste disposal

    SciTech Connect

    Kaszuba, J.P.; Runde, W.H.

    1999-12-15

    The valence state of neptunium, one of the most important radionuclides of concern for long-term emplacement of nuclear waste, primarily defines its geochemical reactions and migration behavior. The authors evaluate how redox potential and solid-phase stability interact and influence neptunium solubility and aqueous speciation in natural systems. Neptunium thermodynamic data for the most important valence states for natural waters, +IV and +V, are updated to correct database inconsistencies. The most significant changes are as follows: (1) Np{sub 2}O{sub 5}(cr) is 2 orders of magnitude more stable than reported previously, (2) the stability of NpO{sub 2}OH(aq) is reduced, (3) NpO{sub 2}(OH){sub 2}{sup {minus}} and mixed Np(V) hydroxo-carbonato species become important at high pH, and (4) Np(OH){sub 5{minus}} is disregarded as a valid species. As a result, Np{sub 2}O{sub 5} and Np(OH){sub 4}(am) are the stable solids in aquifers of low ionic strength, neptunium solubility decreases in the pH range 10--12 and increases at pH above 12, and both redox potential and Np(OH){sub 4}(am) solubility product control soluble neptunium concentrations at neutral pH and Eh between {minus}0.2 and 0.3. these relationships are important for effective nuclear waste package design, such as including cement as an engineered barrier and evaluating impacts of discharged solutions on natural waters in release scenarios at nuclear waste storage facilities.

  16. Refractory Boride Formation and Microstructure Evolution during Solidification of Titanium-Boron and Titanium Aluminum-Boron Alloys

    NASA Astrophysics Data System (ADS)

    Hyman, Mark Edward

    1990-01-01

    gamma-TiAl alloys targeted for use as a structural material in advanced aerospace applications lack adequate creep strength at high temperatures. Incorporation of hard refractory second phase particles (e.g. TiB _2) exhibiting large aspect ratios (i.e. needles) can increase creep strength by constraining the plastic flow of the matrix during high temperature service. Matrix microstructure evolution and refractory boride formation in binary Ti-B and Ti-(25-52) at% Al and <= ~ 6 at% B alloys during conventional solidification is examined. The effects of rapid solidification processing (RSP) on microstructure evolution and boride morphology in ternary alloys is examined in electromagnetically levitated droplets processed via gas and splat quenching. A liquidus projection near the Ti-Al edge binary is deduced from a combination of computer modelling efforts and experimental evidence. The primary fields of crystallization sequentially traversed with increasing Al content starting from the Ti-B edge binary are: TiB to Ti_3B_4 to TiB_2 and beta to alpha to gamma for B-rich (i.e. ~5 at% B) and dilute alloys, respectively. A monovariant line of the type, L to M + TiB_2 (where M = beta, alpha , and gamma) was found to run slightly below the ~1 at% B isoconcentration line near the equiatomic TiAl composition. Matrix microstructure evolution and boride formation in these ternary alloys can be explained using the proposed liquidus projection for the Ti-Al-B system. TiB_2 forms in Ti-Al-B alloys (i.e. >= 35 at% Al) with various morphologies--blocky, plate/needle and flakes--and are extensively characterized by TEM and SEM. Their growth mechanisms leading to their various morphologies is discussed. Aside from the boride phases formed, the solidification microstructures of the Ti-Al -B alloys of interest showed essentially the same constituent phases as those of binary Ti-Al alloys of similar composition. Characterization of supercooled ternary droplets dilute in B (i.e. <=1 at% B

  17. PLUTONIUM-238 RECOVERY FROM IRRADIATED NEPTUNIUM TARGETS USING SOLVENT EXTRACTION

    SciTech Connect

    Scott Herbst; Terry Todd; Jack Law; Bruce Mincher; Steve Frank; John Swanson

    2006-10-01

    The United States Department of Energy proposes to re-establish a domestic capability for producing plutonium-238 (238Pu) to fuel radioisotope power systems primarily in support of future space missions. A conceptual design report is currently being prepared for a new 238Pu, and neptunium-237 (237Np) target fabrication and processing facility tentatively to be built at the Idaho National Laboratory (INL) in the USA. The facility would be capable of producing at least 5 kg of 238Pu-oxide powder per year. Production of 238Pu requires fabrication of 237Np targets with subsequent irradiation in the existing Advanced Test Reactor (ATR) located at the INL. The targets are 237Np oxide dispersed in a compact of powdered aluminum and clad with aluminum metal. The 238Pu product is separated and purified from the residual 237Np, aluminum matrix, and fission products. The unconverted 237Np is also a valuable starting material and is separated, purified and recycled to the target fabrication process. The proposed baseline method for separating and purifying 238Pu and unconverted 237Np post irradiation is by anion exchange (IX). Separation of Pu from Np by IX was chosen as the baseline method because of the method’s proven ability to produce a quality Pu product and because it is amenable to the relatively small scale, batch type production methods used (small batches of ~200g 238Pu are processed at a time). Multiple IX cycles are required involving substantial volumes of nitric acid and other process solutions which must be cleaned and recycled or disposed of as waste. Acid recycle requires rather large evaporator systems, including one contained in a hot cell for remote operation. Finally, the organic based anion exchange resins are rapidly degraded due to the high a-dose and associated heat production from 238Pu decay, and must be regularly replaced (and disposed of as waste). In summary, IX is time consuming, cumbersome, and requires substantial tankage to accommodate the

  18. Interlayer utilization (including metal borides) for subsequent deposition of NSD films via microwave plasma CVD on 316 and 440C stainless steels

    NASA Astrophysics Data System (ADS)

    Ballinger, Jared

    Diamond thin films have promising applications in numerous fields due to the extreme properties of diamonds in conjunction with the surface enhancement of thin films. Biomedical applications are numerous including temporary implants and various dental and surgical instruments. The unique combination of properties offered by nanostructured diamond films that make it such an attractive surface coating include extreme hardness, low obtainable surface roughness, excellent thermal conductivity, and chemical inertness. Regrettably, numerous problems exist when attempting to coat stainless steel with diamond generating a readily delaminated film: outward diffusion of iron to the surface, inward diffusion of carbon limiting necessary surface carbon precursor, and the mismatch between the coefficients of thermal expansion yielding substantial residual stress. While some exotic methods have been attempted to overcome these hindrances, the most common approach is the use of an intermediate layer between the stainless steel substrate and the diamond thin film. In this research, both 316 stainless steel disks and 440C stainless steel ball bearings were tested with interlayers including discrete coatings and graded, diffusion-based surface enhancements. Titanium nitride and thermochemical diffusion boride interlayers were both examined for their effectiveness at allowing for the growth of continuous and adherent diamond films. Titanium nitride interlayers were deposited by cathodic arc vacuum deposition on 440C bearings. Lower temperature diamond processing resulted in improved surface coverage after cooling, but ultimately, both continuity and adhesion of the nanostructured diamond films were unacceptable. The ability to grow quality diamond films on TiN interlayers is in agreement with previous work on iron and low alloy steel substrates, and the similarly seen inadequate adhesion strength is partially a consequence of the lacking establishment of an interfacial carbide phase

  19. Effects of Hanford high-level waste components on the solubility of cobalt, strontium, neptunium, plutonium, and americium

    SciTech Connect

    Delegard, C.H.; Gallagher, S.A.

    1983-10-01

    Experiments have been performed to identify Hanford high-level waste (HLW) solution components that significantly affect the solubility of cobalt, strontium, neptunium, plutonium, and americium. Further tests which quantified the effects of the significant components on strontium, plutonium, and americium solubility were also performed. The compounds controlling radioelement solubility were not identified. Twelve HLW solution components were studied. The components HEDTA and EDTA increased cobalt, strontium, and americium solubility through complexation of the metal ions. Americium solubility was also increased through apparent complexation by hydroxyacetate and citrate. Sodium nitrite decreased neptunium solubility by reduction of Np(VI) to the less soluble Np(V) oxidation state. Sodium carbonate and HEDTA increased neptunium solubility through complexation while, unexpectedly, EDTA decreased the solubility of neptunium. The components NaNO/sub 3/, NaOH, and NaAlO/sub 2/ increased plutonium solubility through the formation of soluble complexes. 13 references, 3 figures, 5 tables.

  20. Pt-B System Revisited: Pt2B, a New Structure Type of Binary Borides. Ternary WAl12-Type Derivative Borides.

    PubMed

    Sologub, Oksana; Salamakha, Leonid; Rogl, Peter; Stöger, Berthold; Bauer, Ernst; Bernardi, Johannes; Giester, Gerald; Waas, Monika; Svagera, Robert

    2015-11-16

    On the basis of a detailed study applying X-ray single-crystal and powder diffraction, differential scanning calorimetry, and scanning electron microscopy analysis, it was possible to resolve existing uncertainties in the Pt-rich section (≥65 atom % Pt) of the binary Pt-B phase diagram above 600 °C. The formation of a unique structure has been observed for Pt2B [X-ray single-crystal data: space group C2/m, a = 1.62717(11) nm, b = 0.32788(2) nm, c = 0.44200(3) nm, β = 104.401(4)°, RF2 = 0.030]. Within the homogeneity range of "Pt3B", X-ray powder diffraction phase analysis prompted two structural modifications as a function of temperature. The crystal structure of "hT-Pt3B" complies with the hitherto reported structure of anti-MoS2 [space group P63/mmc, a = 0.279377(2) nm, c = 1.04895(1) nm, RF = 0.075, RI = 0.090]. The structure of the new "[Formula: see text]T-Pt3B" is still unknown. The formation of previously reported Pt∼4B has not been confirmed from binary samples. Exploration of the Pt-rich section of the Pt-Cu-B system at 600 °C revealed a new ternary compound, Pt12CuB6-y [X-ray single-crystal data: space group Im3̅, a = 0.75790(2) nm, y = 3, RF2 = 0.0129], which exhibits the filled WAl12-type structure accommodating boron in the interstitial trigonal-prismatic site 12e. The isotypic platinum-aluminum-boride was synthesized and studied. The solubility of copper in binary platinum borides has been found to attain ∼7 atom % Cu for Pt2B but to be insignificant for "[Formula: see text]T-Pt3B". The architecture of the new Pt2B structure combines puckered layers of boron-filled and empty [Pt6] octahedra (anti-CaCl2-type fragment) alternating along the x axis with a double layer of boron-semifilled [Pt6] trigonal prisms interbedded with a layer of empty tetrahedra and tetragonal pyramids (B-deficient α-T[Formula: see text]I fragment). Assuming boron vacancies ordering (space group R3), the Pt12CuB6-y structure exhibits serpentine-like columns of edge

  1. Pt-B System Revisited: Pt2B, a New Structure Type of Binary Borides. Ternary WAl12-Type Derivative Borides.

    PubMed

    Sologub, Oksana; Salamakha, Leonid; Rogl, Peter; Stöger, Berthold; Bauer, Ernst; Bernardi, Johannes; Giester, Gerald; Waas, Monika; Svagera, Robert

    2015-11-16

    On the basis of a detailed study applying X-ray single-crystal and powder diffraction, differential scanning calorimetry, and scanning electron microscopy analysis, it was possible to resolve existing uncertainties in the Pt-rich section (≥65 atom % Pt) of the binary Pt-B phase diagram above 600 °C. The formation of a unique structure has been observed for Pt2B [X-ray single-crystal data: space group C2/m, a = 1.62717(11) nm, b = 0.32788(2) nm, c = 0.44200(3) nm, β = 104.401(4)°, RF2 = 0.030]. Within the homogeneity range of "Pt3B", X-ray powder diffraction phase analysis prompted two structural modifications as a function of temperature. The crystal structure of "hT-Pt3B" complies with the hitherto reported structure of anti-MoS2 [space group P63/mmc, a = 0.279377(2) nm, c = 1.04895(1) nm, RF = 0.075, RI = 0.090]. The structure of the new "[Formula: see text]T-Pt3B" is still unknown. The formation of previously reported Pt∼4B has not been confirmed from binary samples. Exploration of the Pt-rich section of the Pt-Cu-B system at 600 °C revealed a new ternary compound, Pt12CuB6-y [X-ray single-crystal data: space group Im3̅, a = 0.75790(2) nm, y = 3, RF2 = 0.0129], which exhibits the filled WAl12-type structure accommodating boron in the interstitial trigonal-prismatic site 12e. The isotypic platinum-aluminum-boride was synthesized and studied. The solubility of copper in binary platinum borides has been found to attain ∼7 atom % Cu for Pt2B but to be insignificant for "[Formula: see text]T-Pt3B". The architecture of the new Pt2B structure combines puckered layers of boron-filled and empty [Pt6] octahedra (anti-CaCl2-type fragment) alternating along the x axis with a double layer of boron-semifilled [Pt6] trigonal prisms interbedded with a layer of empty tetrahedra and tetragonal pyramids (B-deficient α-T[Formula: see text]I fragment). Assuming boron vacancies ordering (space group R3), the Pt12CuB6-y structure exhibits serpentine-like columns of edge

  2. Synthesis and characterization of nitrogen-phosphorus-based fire retardants modified by boride/propanetriol flyeidyl ether complex

    NASA Astrophysics Data System (ADS)

    Kang, Haijiao; Ma, Linrong; Zhang, Shifeng; Li, Jianzhang

    2015-07-01

    A Boride/propanetriol glyeidyl ether (B/PTGE) complex was employed to intensify the fire resistance capabilities of nitrogen-phosphorus (NP) fire retardants by reacting with phosphoric acid and urea to yield nitrogen-phosphorus-boron-PTGE fire retardants. The effects of NPB-PTGE fire retardants on wooden properties were characterized by limit oxygen index (LOI), cone calorimetry, X-ray Diffraction (XRD) and scanning electron microscopy (SEM). The results depict that the fire resistance of the B/PTGE complex modified by NP-based fire retardants was improved significantly. The PTGE was at 10% boride at 2%, and the treated wood has the LOI of 52%, which is 11.46% higher compared with woods treated with NP fire retardant.

  3. Pre-irradiation spatial distribution and stability of boride particles in rapidly solidified boron-doped stainless steels

    SciTech Connect

    Kanani, N.; Arnberg, L.; Harling, O.K.

    1981-01-01

    The time temperature behavior of boride particles has been studied in rapidly solidified ultra low carbon and nitrogen modified 316 stainless steel with 0.088% boron and 0.45% zirconium. The results show that the as-splat-cooled specimens exhibit precipitates at the grain boundaries and triple junctions. For temperatures up to about 750/sup 0/C no significant microstructural changes occur for short heat treatment times. In the temperature range of 750 to 950/sup 0/C, however, particles typically 100 to 500 A in diameter containing Zr and B are formed within the grains. Higher temperatures enhance the formation of such particles and give rise to particle networks. The results show that a fine and uniform distribution of the boride particles almost exclusively within the grains can be achieved if proper annealing conditions are chosen. This type of distribution is an important requirement for the homogeneous production of helium during neutron irradiation in fast reactors.

  4. Structural and mechanical properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) under pressure

    NASA Astrophysics Data System (ADS)

    Li, Xiaofeng; Yan, Haiyan; Wei, Qun

    2016-10-01

    First-principle total energy calculations are employed to provide a fundamental understanding of the structural, mechanical, and electronic properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) within the tetragonal superstructure P4/mnc structure. The mechanically and dynamically stabilities of three borides have been demonstrated by the elastic constants and phonons calculations under pressure. Among these three compounds, Nb2TcB2 exhibits the biggest bulk and Young's modulus, smallest Poission's ratio, and highest harness. Density of states of them revealed that the strong B-B, Nb-B and M-B covalent bonds are major driving forces for their high bulk and shear moduli as well as small Poisson's ratio.

  5. A Structural Study of Neptunium-Bearing Uranium Oxides

    NASA Astrophysics Data System (ADS)

    Finch, R. J.

    2002-05-01

    Neptunium is an element of significant concern at several contaminated DOE sites, as well as being potentially the largest long-term contributor of radiation dose to people living near the high-level nuclear-waste repository recently recommended by the President for construction at Yucca Mountain, Nevada. In order to understand potential structural effects of Np substitution into uranium minerals, we have synthesized a series of Np-doped U oxides and present here results of a structural study of Np-doped U3O8 (NpxU3-xO8). Although not a mineral, U3O8 bears significant structural similarities to numerous uranyl minerals with both known and potential importance as radionuclide hosts in the environment (Burns et al., Can. Mineral. 34, 845, 1997). Qualitative chemical analyses of U3O8 powders by energy-dispersive x-ray emission spectroscopy (EDS) in a scanning electron microscope indicate that sample powders are homogeneous at the micrometer scale. Further examinations by electron energy-loss spectroscopy (EELS) and EDS in a transmission electron microscope do not reveal compositional inhomogeneities or discernable variability in the Np:U ratios within samples having Np:U ratios of 1:80 and 1:8. Bulk samples of Np-doped U3O8 powders having Np:U ratios of 1:160, 1:80, 1:25, and 1:8, were also analyzed by X-ray absorption near-edge spectroscopy (XANES), which indicates that Np occupies distorted U sites and is predominantly tetravalent. X-ray powder diffraction (XRD) analyses of pure U3O8 and Np-doped U3O8 show that incorporation of Np into U3O8 affects positions and intensities of diffraction peaks, but that all samples are isostructural with alpha-U3O8. No spurious diffraction peaks are observed in any powder patterns of U3O8 with Np:U from 1:160 to 1:8. Lattice parameters vary smoothly as a function of Np concentration. The c cell parameter (perpendicular to the plane of the structural sheets in U3O8) shows little or no dependence on Np concentration, whereas the a

  6. Chemical speciation of neptunium in spent fuel. Annual report for period 15 August 1999 to 15 August 2000

    SciTech Connect

    Ken Czerwinski; Don Reed

    2000-09-01

    (B204) This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste. Another important aspect of this project is the close cooperation between a university and a national laboratory. The PI has a transuranic laboratory at MIT where

  7. Boronic Acid Flux Synthesis and Crystal Growth of Uranium and Neptunium Boronates and Borates: A Low Temperature Route to the First Neptunium(V) Borate

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Miller, Hannah M.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2010-10-04

    Molten methylboronic acid has been used as a reactive flux to prepare the first neptunium(V) borate, NpO2[B3O4(OH)2] (NpBO-1), and the first actinide boronate, UO2(CH3BO2)(H2O) (UCBO-1). NpBO-1 contains cation-cation interactions between the neptunyl units. In contrast, the presence of the methyl groups in the uranyl boronate leads to a one-dimensional structure.

  8. Development of Defined, Minimal, and Complete Media for the Growth of Hyphomicrobium neptunium

    PubMed Central

    Havenner, Jeffrey A.; McCardell, Barbara A.; Weiner, Ronald M.

    1979-01-01

    A complete synthetic medium containing 15 amino acids, a minimal synthetic medium (GAMS) containing 4 amino acids, and a supplemented minimal medium (GAMS + calcium pantothenate) have been developed for the cultivation of Hyphomicrobium neptunium ATCC 15444. Depending on the complexity of the synthetic media, generation times were approximately 2 to 3 times longer, and maximum cell densities were 0.3 to 0.9 log10 lower than in ZoBell marine broth 2216. The fates of 14C-labeled amino acids in GAMS were monitored. Results suggested that H. neptunium was auxotrophic for methionine, utilized glutamic acid as a primary energy source, and readily anabolized and catabolized serine and aspartic acid. Individual amino acid concentrations above 125 mM induced prolonged lag periods, whereas only methionine was not growth limiting at a concentration as low as 2 mM. PMID:16345413

  9. Long-term desorption behavior of uranium and neptunium in heterogeneous volcanic tuff materials /

    SciTech Connect

    Dean, Cynthia A.

    2010-05-01

    Uranium and neptunium desorption were studied in long-term laboratory experiments using four well-characterized volcanic tuff cores collected from southeast of Yucca Mountain, Nevada. The objectives of the experiments were to 1. Demonstrate a methodology aimed at characterizing distributions of sorption parameters (attributes of multiple sorption sites) that can be applied to moderately-sorbing species in heterogeneous systems to provide more realistic reactive transport parameters and a more realistic approach to modeling transport in heterogeneous systems. 2. Focus on uranium and neptunium because of their high solubility, relatively weak sorption, and high contributions to predicted dose in Yucca Mountain performance assessments. Also, uranium is a contaminant of concern at many DOE legacy sites and uranium mining sites.

  10. Kinetics of oxidation of pentavalent neptunium by pentavalent vanadium in solutions of nitric acid

    NASA Astrophysics Data System (ADS)

    Precek, Martin; Paulenova, Alena

    2010-03-01

    Management of the oxidation state of neptunium in the reprocessing of spent nuclear fuel by solvent extraction is very important. The kinetics of the oxidation of neptunium(V) by vanadium(V) in solutions of nitrate acid was investigated at constant ionic strength 4M. The reaction rate is first order with respect to Np(V) and V(V). The effects of proton concentration on the apparent second order rate constant k1" was determined for temperature 25°C as k1" = (0.99±0.03)·[H+]1.21M-1s-1. Activation parameters associated with the overall reaction have been calculated; the standard reaction enthalpy and entropy were 52.6±0.9 kJ/mol and -55.8±0.9 J/K/mol respectively.

  11. Theoretical studies on level structures and transition properties of neptunium ions

    NASA Astrophysics Data System (ADS)

    Zhou, W. D.; Dong, C. Z.; Wang, Q. M.; Wang, X. L.; Saber, I. A.

    2012-10-01

    Multiconfiguration Dirac-Fock (MCDF) method was employed to calculate the ionization potentials, ionic radii, excitation energies and oscillator strengths for neptunium ions. In the calculations, main valence correlation effects, Breit interaction and QED effects were taken into account. The good consistency with other available theoretical values demonstrates the validity of the present calculations. These theoretical results therefore can be used to predict some physicochemical properties of Np and its oxides.

  12. Comparison of sample preparation methods for reliable plutonium and neptunium urinalysis using automatic extraction chromatography.

    PubMed

    Qiao, Jixin; Xu, Yihong; Hou, Xiaolin; Miró, Manuel

    2014-10-01

    This paper describes improvement and comparison of analytical methods for simultaneous determination of trace-level plutonium and neptunium in urine samples by inductively coupled plasma mass spectrometry (ICP-MS). Four sample pre-concentration techniques, including calcium phosphate, iron hydroxide and manganese dioxide co-precipitation and evaporation were compared and the applicability of different techniques was discussed in order to evaluate and establish the optimal method for in vivo radioassay program. The analytical results indicate that the various sample pre-concentration approaches afford dissimilar method performances and care should be taken for specific experimental parameters for improving chemical yields. The best analytical performances in terms of turnaround time (6h) and chemical yields for plutonium (88.7 ± 11.6%) and neptunium (94.2 ± 2.0%) were achieved by manganese dioxide co-precipitation. The need of drying ashing (≥ 7h) for calcium phosphate co-precipitation and long-term aging (5d) for iron hydroxide co-precipitation, respectively, rendered time-consuming analytical protocols. Despite the fact that evaporation is also somewhat time-consuming (1.5d), it endows urinalysis methods with better reliability and repeatability compared with co-precipitation techniques. In view of the applicability of different pre-concentration techniques proposed previously in the literature, the main challenge behind relevant method development is pointed to be the release of plutonium and neptunium associated with organic compounds in real urine assays. In this work, different protocols for decomposing organic matter in urine were investigated, of which potassium persulfate (K2S2O8) treatment provided the highest chemical yield of neptunium in the iron hydroxide co-precipitation step, yet, the occurrence of sulfur compounds in the processed sample deteriorated the analytical performance of the ensuing extraction chromatographic separation with chemical

  13. Comparison of sample preparation methods for reliable plutonium and neptunium urinalysis using automatic extraction chromatography.

    PubMed

    Qiao, Jixin; Xu, Yihong; Hou, Xiaolin; Miró, Manuel

    2014-10-01

    This paper describes improvement and comparison of analytical methods for simultaneous determination of trace-level plutonium and neptunium in urine samples by inductively coupled plasma mass spectrometry (ICP-MS). Four sample pre-concentration techniques, including calcium phosphate, iron hydroxide and manganese dioxide co-precipitation and evaporation were compared and the applicability of different techniques was discussed in order to evaluate and establish the optimal method for in vivo radioassay program. The analytical results indicate that the various sample pre-concentration approaches afford dissimilar method performances and care should be taken for specific experimental parameters for improving chemical yields. The best analytical performances in terms of turnaround time (6h) and chemical yields for plutonium (88.7 ± 11.6%) and neptunium (94.2 ± 2.0%) were achieved by manganese dioxide co-precipitation. The need of drying ashing (≥ 7h) for calcium phosphate co-precipitation and long-term aging (5d) for iron hydroxide co-precipitation, respectively, rendered time-consuming analytical protocols. Despite the fact that evaporation is also somewhat time-consuming (1.5d), it endows urinalysis methods with better reliability and repeatability compared with co-precipitation techniques. In view of the applicability of different pre-concentration techniques proposed previously in the literature, the main challenge behind relevant method development is pointed to be the release of plutonium and neptunium associated with organic compounds in real urine assays. In this work, different protocols for decomposing organic matter in urine were investigated, of which potassium persulfate (K2S2O8) treatment provided the highest chemical yield of neptunium in the iron hydroxide co-precipitation step, yet, the occurrence of sulfur compounds in the processed sample deteriorated the analytical performance of the ensuing extraction chromatographic separation with chemical

  14. Molecular Toolbox for Genetic Manipulation of the Stalked Budding Bacterium Hyphomonas neptunium

    PubMed Central

    Jung, Alexandra; Eisheuer, Sabrina; Cserti, Emöke; Leicht, Oliver; Strobel, Wolfgang; Möll, Andrea; Schlimpert, Susan; Kühn, Juliane

    2014-01-01

    The alphaproteobacterium Hyphomonas neptunium proliferates by a unique budding mechanism in which daughter cells emerge from the end of a stalk-like extension emanating from the mother cell body. Studies of this species so far have been hampered by the lack of a genetic system and of molecular tools allowing the regulated expression of target genes. Based on microarray analyses, this work identifies two H. neptunium promoters that are activated specifically by copper and zinc. Functional analyses show that they have low basal activity and a high dynamic range, meeting the requirements for use as a multipurpose expression system. To facilitate their application, the two promoters were incorporated into a set of integrative plasmids, featuring a choice of two different selection markers and various fluorescent protein genes. These constructs enable the straightforward generation and heavy metal-inducible synthesis of fluorescent protein fusions in H. neptunium, thereby opening the door to an in-depth analysis of polar growth and development in this species. PMID:25398860

  15. The effect of mass on the gastrointestinal absorption of plutonium and neptunium.

    PubMed

    Sullivan, M F; Miller, B M; Ryan, J L

    1983-04-01

    Absorption and retention of plutonium were determined in mice after intragastric administration of either 6 X 10(-4) or 1.5 mg/kg in bicarbonate, citrate, or nitrate media. At the higher concentration, absorption of the citrate was greater than that of the nitrate; at the lower concentration, chemical form was not an important factor in absorption. Concentration and chemical form had much less influence on absorption by the neonatal (versus the adult) rat. The transfer factor (f1) for neonates was between one and two orders of magnitude higher than for adults. Absorption and retention of neptunium were determined in rats and/or mice after intragastric administration at doses ranging from 2.2 X 10(-7) to 43 mg/kg in nitrate solutions of pH 1.5. At the higher concentrations, absorption was 1.5 to 2.7%. For lower concentrations, absorption was 25 to 65 times less. In contrast to results obtained in adult animals, absorption of neptunium by neonates decreased with increasing dose. The data obtained in adult animals suggest that the f1 factor recommended by the ICRP for plutonium should be increased by a factor of 10, but the neptunium f1 factor, in contrast, should be decreased by a factor of 10.

  16. Molecular toolbox for genetic manipulation of the stalked budding bacterium Hyphomonas neptunium.

    PubMed

    Jung, Alexandra; Eisheuer, Sabrina; Cserti, Emöke; Leicht, Oliver; Strobel, Wolfgang; Möll, Andrea; Schlimpert, Susan; Kühn, Juliane; Thanbichler, Martin

    2015-01-01

    The alphaproteobacterium Hyphomonas neptunium proliferates by a unique budding mechanism in which daughter cells emerge from the end of a stalk-like extension emanating from the mother cell body. Studies of this species so far have been hampered by the lack of a genetic system and of molecular tools allowing the regulated expression of target genes. Based on microarray analyses, this work identifies two H. neptunium promoters that are activated specifically by copper and zinc. Functional analyses show that they have low basal activity and a high dynamic range, meeting the requirements for use as a multipurpose expression system. To facilitate their application, the two promoters were incorporated into a set of integrative plasmids, featuring a choice of two different selection markers and various fluorescent protein genes. These constructs enable the straightforward generation and heavy metal-inducible synthesis of fluorescent protein fusions in H. neptunium, thereby opening the door to an in-depth analysis of polar growth and development in this species.

  17. Sorption kinetics of uranium-238 and neptunium-237 on a glacial sediment

    NASA Astrophysics Data System (ADS)

    Braithwaite, A.; Richardson, S.; Moyes, L. N.; Livens, F. R.; Bunker, D. J.; Hughes, C. R.; Smith, J. T.; Hilton, J.

    2000-02-01

    Studies of uptake of radionuclides by natural materials have shown that sorption may occur via fast equilibrium exchange and/or slow kinetic processes, which can be described using a series of box models. This paper describes the use of such models to evaluate the solid-solution partitioning of 238U and 237Np on a clay rich sediment. Experimental data are obtained using the batch sorption technique, which are then analysed using 1, 2, and 3 box kinetic models. Uptake of 238U is initially rapid, with approximately 90% sorbed within the first 30 minutes. Sorption continues, but at a slower rate. Uptake of 237Np is initially slower than U, with approximately 30% sorbed within the first 30 minutes. Sorption again continues, at a slower rate. Analysis of the experimental data indicates that sorption can be described using 2 and 3 box kinetic models. The results demonstrate that sorption of uranium and neptunium on clay rich sediments occurs via equilibrium and kinetically controlled pathways, with neptunium being controlled by kinetics to a greater extent than uranium. The 2 or 3 box model can describe sorption of neptunium, uranium requires the 3 box model.

  18. Effects of Titanium Doping in Titanomagnetite on Neptunium Sorption and Speciation.

    PubMed

    Wylie, E Miller; Olive, Daniel T; Powell, Brian A

    2016-02-16

    Neptunium-237 is a radionuclide of great interest owing to its long half-life (2.14 × 10(6) years) and relative mobility as the neptunyl ion (NpO2(+)) under many surface and groundwater conditions. Reduction to tetravalent neptunium (Np(IV)) effectively immobilizes the actinide in many instances due to its low solubility and strong interactions with natural minerals. One such mineral that may facilitate the reduction of neptunium is magnetite (Fe(2+)Fe(3+)2O4). Natural magnetites often contain titanium impurities which have been shown to enhance radionuclide sorption via titanium's influence on the Fe(2+)/Fe(3+) ratio (R) in the absence of oxidation. Here, we provide evidence that Ti-substituted magnetite reduces neptunyl species to Np(IV). Titanium-substituted magnetite nanoparticles were synthesized and reacted with NpO2(+) under reducing conditions. Batch sorption experiments indicate that increasing Ti concentration results in higher Np sorption/reduction values at low pH. High-resolution transmission electron microscopy of the Ti-magnetite particles provides no evidence of NpO2 nanoparticle precipitation. Additionally, X-ray absorption spectroscopy confirms the nearly exclusive presence of Np(IV) on the titanomagnetite surface and provides supporting data indicating preferential binding of Np to terminal Ti-O sites as opposed to Fe-O sites.

  19. Preliminary investigation of zirconium boride ceramals for gas-turbine blade applications

    NASA Technical Reports Server (NTRS)

    Hoffman, Charles A

    1953-01-01

    Zirconium boride ZrB2 ceramals were investigated for possible gas-turbine-blade application. Included in the study were thermal shock evaluations of disks, preliminary turbine-blade operation, and observations of oxidation resistance. Thermal shock disks of the following three compositions were studied: (a) 97.5 percent ZrB2 plus 2.5 percent B by weight; (b) 92.5 percent ZrB2 plus 7.5 percent B by weight; and (c) 100 percent ZrB2. Thermal shock disks were quenched from temperatures of 1800 degrees, 2000 degrees, 2200 degrees, and 2400 degrees F. The life of turbine blades containing 93 percent ZrB2 plus 7 percent B by weight was determined in gas-turbine tests. The blades were run at approximately 1600 degrees F and 15,000 to 26,000 rpm. The thermal shock resistance of the 97.5 percent ZrB2 plus 2.5 percent boron ceramals compares favorably with that of TiC plus Co and TiC plus Ni ceramals. Oxidation of the disks during the thermal shock evaluation was slight for the comparatively short time (8.3 hr) up through 2000 degrees F. Oxidation of a specimen was severe, however, after 100 hours at 2000 degrees F. The turbine blade performance evaluation of the 93 percent ZrB2 plus 7 percent B composition was preliminary in scope ; no conclusions can be drawn.

  20. Joining of zirconium boride based refractory ceramics to Ti6Al4V

    NASA Astrophysics Data System (ADS)

    Muolo, Maria Luigia; Ferrera, Elena; Morbelli, Luisa; Zanotti, Claudio; Passerone, Alberto

    2003-09-01

    The exploitation of the peculiar characteristics of ceramic refractory materials in extreme conditions (as for Thermal Protection Systems - TPS) often depends to a great extent on the ability to join different ceramics one to the other and to special metallic alloys. Joints may be achieved in a number of ways, but principally are made by either solid phase or liquid phase transformations (brazing). Brazed joints are difficult to realise in the presence of ceramic materials, due to the fact that they are not wet, in general, by liquid metals. This paper presents experimental results on the wettability characteristics of zirconium boride based materials (with Si3N4, Ni etc.) by an AgZr alloy, the microstructures and thermal tests of brazed joints with the special alloy Ti6Al4V. The wetting data will be examined in terms of interfacial characteristics and in terms of the kinetics of spreading. Thermal tests and models will be devoted to evaluate and measure the thermal insulation capacity of the ceramic layers in order to determine the optimal thickness as a function of the foreseen outer surface temperature.

  1. Reduction of boride enhanced diffusion in MeV-implanted silicon

    NASA Astrophysics Data System (ADS)

    Shao, Lin; Thompson, Phillip E.; Bleiler, Roger J.; Baumann, Scott; Wang, Xuemei; Chen, Hui; Liu, Jiarui; Chu, Wei-Kan

    2002-11-01

    We demonstrated that implantation of MeV Si ions into a Si substrate can suppress boride-enhanced diffusion (BED) normally associated with a high B concentration layer. In this study, a molecular-beam-epitaxy grown Si layer with a B concentration of 1021/cm3 over a 10 nm region capped with 100 nm Si was used as a source of BED. A sequence of four B delta-doped layers with 100 nm Si spacers was grown prior to the source layer to monitor the diffusion. Half of the sample was implanted with 1 MeV Si ions at a dose of 1016/cm2, followed by annealing at 800, 900, and 1000 °C for different periods of time. For control samples without the MeV Si implant, BED was observed with enhancements of around 40 while the MeV Si-implanted sample showed a reduced, yet nonvanishing, BED with an enhancement of around 8 after annealing at 800 °C for 1 h. Both BED and suppressed BED with MeV implant show transient behavior with decay after annealing for long periods of time. The effect of high energy implant on B diffusion from surface deposited B layer was also discussed.

  2. Complexation of neptunium(V) with fluoride in aqueous solutions at elevated temperatures

    SciTech Connect

    Tian, Guoxin; Rao, Linfeng; Xia, Yuanxian; Friese, Judah I.

    2009-02-01

    Over the past several decades, the production and testing of nuclear weapons in the U.S. have created significant amounts of high-level nuclear wastes (HLW) that are currently stored in underground tanks across the U.S. DOE (Department of Energy) sites. Eventually, the HLW will be made into the waste form and disposed of in geological repositories for HLW. Among the radioactive materials, neptunium is of great concern in the post-closure chemical environment in the repository because of the long half-life of 237Np (2.14•106 years) and the high mobility of Np(V), the most stable oxidation state of neptunium. It is estimated that 237Np, together with 129I and 99Tc, will be the major contributors to the potential total annual dose from the repository beyond 10000 years [1]. Due to the high radiation energy released from the HLW, the postclosure repository is expected to remain at elevated temperatures for thousands of years [1]. If the waste package is breached and becomes in contact with groundwater, neptunium, as well as other radioactive materials will be in aqueous solutions at elevated temperatures. Interactions of radioactive materials with the chemical components in groundwater play an important role in determining their migration in the repository. To predict the migration behavior of neptunium, it is necessary to have sufficient and reliable thermodynamic data on its complexation with the ligands that are present in the groundwater of the repository (e.g., OH–, F–, SO42– ,PO43– and CO32) at elevated temperatures. However, such data are scarce and scattered for 25°C, and nearly nonexistent for elevated temperatures [2]. To provide reliable thermodynamic data, we have conducted investigations of the complexation of actinides, including thorium, uranium, neptunium and plutonium, at elevated temperatures. Thermodynamic parameters, including formation constants, enthalpy and heat capacity of complexation are experimentally determined. This paper

  3. Combine Studies Pertaining to the Solubility of Neptunium in Oxidizing Aqueous Systems

    SciTech Connect

    Wolery, T.J; .Robert, K.E.; Wruck, D.A; Brachmann, A.; Palmer, C.E.A.

    2000-09-15

    The report combines two separate studies dealing with different aspects of the behavior of neptunium in oxidizing aqueous systems. The goal of both studies is to obtain a better understanding of what would control the concentration of neptunium in oxidizing groundwaters upon release from a geologic high-level waste repository. {sup 237}Np has a very long half-life, and consequently tends to appear as a component of concern in long-term dose calculations. Part A examines the formation of NpO{sub 2} [Np(IV) oxide] from aqueous Np(V) under oxidizing conditions, using elevated temperature as a means of accelerating putative slow kinetics. According to thermodynamic data, NpO{sub 2} should be the stable Np solid, even though Np is generally thought to be mainly some form of Np(V) under oxidizing conditions. The first observed precipitation of this solid from aqueous solution under any conditions is reported. This result suggests, but does not prove, that long-term very slow formation of NpO{sub 2} might be an important long-term control on neptunium migration. Even at 200{sup o}C, the kinetics can be sluggish on typical experimental time scales. Though not reported in Part A, a similar situation may exist for Pu, and NpO{sub 2} and PuO{sub 2} may potentially form solid solutions. Under reducing conditions, UO{sub 2} might join in. Part B examines the interaction of Np(V) with the uranium mineral schoepite. Is neptunium incorporated into the crystal structure as a solid-solution component, or does it just sorb onto the mineral surface? The results presented here suggest that it basically just sorbs onto the surface, which would be a less effective process in limiting neptunium migration. This is not a surprising result, as schoepite is a relatively simple solid of U(VI). There is no obvious means to compensate for the charge difference between U(VI) and Np(V) without introducing unfavorable energetics. However, the results reported here do not rule out a possible

  4. Mineralogic controls on aqueous neptunium(V) concentrations in silicate systems

    NASA Astrophysics Data System (ADS)

    Alessi, Daniel S.; Szymanowski, Jennifer E. S.; Forbes, Tori Z.; Quicksall, Andrew N.; Sigmon, Ginger E.; Burns, Peter C.; Fein, Jeremy B.

    2013-02-01

    The presence of radioactive neptunium in commercially spent nuclear fuel is problematic due to its mobility in environmental systems upon oxidation to the pentavalent state. As uranium is the major component of spent fuel, incorporation of neptunium into resulting U(VI) mineral phases would potentially influence its release into environmental systems. Alternatively, aqueous neptunium concentrations may be buffered by solid phase Np2O5. In this study, we investigate both of these controls on aqueous neptunium(V) concentrations. We synthesize two uranyl silicates, soddyite, (UO2)2SiO4·2H2O, and boltwoodite, (K, Na)(UO2)(SiO3OH)·1.5H2O, each in the presence of two concentrations of aqueous Np(V). Electron microscopy and electron diffraction analyses of the synthesized phases show that while significant neptunyl incorporation occurred into soddyite, the Np(V) in the boltwoodite systems largely precipitated as a secondary phase, Np2O5(s). The release of Np(V) from each system into aqueous solution was measured for several days, until steady-state concentrations were achieved. Using existing solubility constants (Ksp) for pure soddyite and boltwoodite, we compared predicted equilibrium aqueous U(VI) concentrations with the U(VI) concentrations released in the solubility experiments. Our experiments reveal that Np(V) incorporation into soddyite increases the concentration of aqueous U in equilibrium with the solid phase, perhaps via the formation of a metastable phase. In the mixed boltwoodite - Np2O5(s) system, the measured aqueous U(VI) activities are consistent with those predicted to be in equilibrium with boltwoodite under the experimental conditions, a result that is consistent with our conclusion that little Np(V) incorporation occurred into the boltwoodite. In the boltwoodite systems, the measured Np concentrations are likely controlled by the presence of Np2O5 nanoparticles, suggesting an additional potential mobility vector for Np in geologic systems. Our

  5. EVALUATING EFFECTS OF NEPTUNIUM ON THE SRS METHOD FOR CONTROLLED POTENTIAL COULOMETRIC ASSAY OF PLUTONIUM IN SULFURIC ACID SUPPORTING ELECTROLYTE

    SciTech Connect

    Holland, M; Sheldon Nichols, S

    2008-05-09

    A study of the impact of neptunium on the coulometric assay of plutonium in dilute sulfuric acid was performed. Weight aliquots of plutonium standard solutions were spiked with purified neptunium solution to evaluate plutonium measurement performance for aliquots with Pu:Np ratios of 50:1, 30:1, 20:1, 15:1, and 10:1. Weight aliquots of the pure plutonium standard solution were measured as controls. Routine plutonium instrument control standards were also measured. The presence of neptunium in plutonium aliquots significantly increases the random uncertainty associated with the plutonium coulometric measurement performed in accordance with ISO12183:2005.7 However, the presence of neptunium does not appear to degrade electrode performance and conditioning as aliquots of pure plutonium that were interspersed during the measurement of the mixed Pu:Np aliquots continued to achieve the historical short-term random uncertainty for the method. Lack of adequate control of the neptunium oxidation state is suspected to be the primary cause of the elevated measurement uncertainty and will be pursued in a future study.

  6. An X-ray absorption spectroscopy study of neptunium(V) reactions with Mackinawite (FeS).

    PubMed

    Moyes, Lesley N; Jones, Mark J; Reed, Wendy A; Livens, Francis R; Charnock, John M; Mosselmans, J Frederick W; Hennig, Christoph; Vaughan, David J; Pattrick, Richard A D

    2002-01-15

    Neptunium is a transuranium element, produced in tonne quantities in nuclear reactors. Because it has access to a range of oxidation states, neptunium may undergo redox transformations in the environment and these can have far-reaching effects on its environmental mobility. Here, the reaction of NpO2+ (the soluble and thermodynamically stable neptunium species in oxic systems) with microcrystalline mackinawite is studied. Uptake of neptunium from solution is relatively low (approximately 10% of the total initially present in solution) and independent of initial solution concentration over the range 0.27-2.74 mM and of equilibration time. X-ray absorption spectroscopy (XAS) of the solid sulfide samples indicates nearest neighbor oxygen atoms at distances around 2.25-2.26 A, sulfur atoms at around 2.61-2.64 A, and two more distant shells fitted with iron, at 3.91-3.95 A and 4.15-4.16 A. These observations suggest that on interaction with the sulfide surface reduction of Np(V) to Np(IV) occurs, accompanied by loss of axial oxygen atoms. Neptunium coordinates directly to surface sulfide atoms, in contrast to the behavior previously observed for uranium under similar conditions. These results demonstrate the importance and variability of the speciation of redox sensitive actinides under anoxic conditions.

  7. EFFECT OF COMPOSITION OF SELECTED GROUNDWATERS FROM THE BASIN AND RANGE PROVINCE ON PLUTONIUM, NEPTUNIUM, AND AMERICIUM SPECIATION.

    USGS Publications Warehouse

    Rees, Terry F.; Cleveland, Jess M.; Nash, Kenneth L.

    1984-01-01

    The speciation of plutonium, neptunium, and americium was determined in groundwaters from four sources in the Basin and Range Province: the lower carbonate aquifer, Nevada Test Site (NTS) (Crystal Pool); alluvial fill, Frenchman Flat, NTS (well 5C); Hualapai Valley, Arizona (Red Lake south well); and Tularosa Basin, New Mexico (Rentfrow well). The results were interpreted to indicate that plutonium and, to a lesser extent, neptunium are least soluble in reducing groundwaters containing a large concentration of sulfate ion and a small concentration of strongly complexing anions. The results further emphasize the desirability of including studies such as this among the other site-selection criteria for nuclear waste repositories.

  8. Crystal and electronic structures of neptunium nitrides synthesized using a fluoride route.

    PubMed

    Silva, G W Chinthaka; Weck, Philippe F; Kim, Eunja; Yeamans, Charles B; Cerefice, Gary S; Sattelberger, Alfred P; Czerwinski, Kenneth R

    2012-02-15

    A low-temperature fluoride route was utilized to synthesize neptunium mononitride, NpN. Through the development of this process, two new neptunium nitride species, NpN(2) and Np(2)N(3), were identified. The NpN(2) and Np(2)N(3) have crystal structures isomorphous to those of UN(2) and U(2)N(3), respectively. NpN(2) crystallizes in a face-centered cubic CaF(2)-type structure with a space group of Fm3m and a refined lattice parameter of 5.3236(1) Å. The Np(2)N(3) adopts the body-centered cubic Mn(2)O(3)-type structure with a space group of Ia3. Its refined lattice parameter is 10.6513(4) Å. The NpN synthesis at temperatures ≤900 °C using the fluoride route discussed here was also demonstrated. Previous computational studies of the neptunium nitride system have focused exclusively on the NpN phase because no evidence was reported experimentally on the presence of NpN(x) systems. Here, the crystal structures of NpN(2) and Np(2)N(3) are discussed for the first time, confirming the experimental results by density functional calculations (DFT). These DFT calculations were performed within the local-density approximation (LDA+U) and the generalized-gradient approximation (GGA+U) corrected with an effective Hubbard parameter to account for the strong on-site Coulomb repulsion between Np 5f electrons. The effects of the spin-orbit coupling in the GGA+U calculations have also been investigated for NpN(2) and NpN.

  9. The effect of concentration and chemical form on the gastrointestinal absorption of neptunium.

    PubMed

    Harrison, J D; Popplewell, D S; David, A J

    1984-09-01

    The gastrointestinal absorption of neptunium at low mass concentrations as 239Np nitrate (0.5-1 ng Np; 2-5 micrograms l-1) has been found to be 0.03, 0.02 and 0.18 per cent in adult rats, hamsters and rabbits, respectively. Administration as 239Np bicarbonate increased uptake in the rat to 0.15 per cent but had no significant effect on uptake in either the hamster or the rabbit. Absorption in the rat was also increased to 0.14 per cent for 239Np citrate but not for either 239Np phytate (0.04 per cent) or 239Np incorporated into rat liver (0.01 per cent). The fasting of rats for 8 hours increased their subsequent absorption of 239Np as the bicarbonate to 0.25 per cent. The absorption of neptunium at high mass concentrations as 237Np nitrate (0.5 mg Np, 5 g l-1) was increased to 0.26 per cent in the rat compared with the value of 0.03 per cent for 239Np (0.5 ng, 5 micrograms l-1) but a similar effect of concentration was not observed in the hamster. The results support the use of a value of absorption of 0.1 per cent instead of 1 per cent in calculations of annual limits on intake of radioisotopes of neptunium by workers and in estimates of radiation doses resulting from the ingestion of contaminated food and water by adult members of the public.

  10. Crystal and Electronic Structures of Neptunium Nitrides Synthesized Using a Fluoride Route

    SciTech Connect

    Silva, G W Chinthaka M; Weck, Dr. Phil F.; Eunja, Dr. Kim; Yeamans, Dr. Charles B.; Cerefice, Gary S.; Sattelberger, Alfred P; Czerwinski, Ken R.

    2012-01-01

    A low-temperature fluoride route was utilized to synthesize neptunium mononitride, NpN. Through the development of this process, two new neptunium nitride species, NpN{sub 2} and Np{sub 2}N{sub 3}, were identified. The NpN{sub 2} and Np{sub 2}N{sub 3} have crystal structures isomorphous to those of UN{sub 2} and U{sub 2}N{sub 3}, respectively. NpN{sub 2} crystallizes in a face-centered cubic CaF{sub 2}-type structure with a space group of Fm3m and a refined lattice parameter of 5.3236(1) {angstrom}. The Np{sub 2}N{sub 3} adopts the body-centered cubic Mn{sub 2}O{sub 3}-type structure with a space group of Ia{bar 3}. Its refined lattice parameter is 10.6513(4) {angstrom}. The NpN synthesis at temperatures {le} 900 C using the fluoride route discussed here was also demonstrated. Previous computational studies of the neptunium nitride system have focused exclusively on the NpN phase because no evidence was reported experimentally on the presence of NpN{sub x} systems. Here, the crystal structures of NpN{sub 2} and Np{sub 2}N{sub 3} are discussed for the first time, confirming the experimental results by density functional calculations (DFT). These DFT calculations were performed within the local-density approximation (LDA+U) and the generalized-gradient approximation (GGA+U) corrected with an effective Hubbard parameter to account for the strong on-site Coulomb repulsion between Np 5f electrons. The effects of the spin-orbit coupling in the GGA+U calculations have also been investigated for NpN{sub 2} and NpN.

  11. Gastrointestinal absorption of plutonium, uranium and neptunium in fed and fasted adult baboons: Application to humans

    SciTech Connect

    Bhattacharyya, M.H.; Larsen, R.P.; Oldham, R.D.; Moretti, E.S. ); Cohen, N.; Ralston, L.G.; Ayres, L. )

    1992-03-01

    Gastrointestinal (GI) absorption values of plutonium, uranium, and neptunium were determined in fed and fasted adult baboons. A dual isotope method of determining GI absorption, which does not require animal sacrifice, was validated and shown to compare well with the sacrifice method (summation of oral isotope in urine with that in tissues at sacrifice). For all three elements, mean GI absorption values were significantly high (5- to 50-fold) in 24-hour (h)-fasted animals than in fed animals, and GI absorption values for baboons agreed well with those for humans.

  12. Determination of neptunium in environmental samples by extraction chromatography after valence adjustment.

    PubMed

    Guérin, Nicolas; Langevin, Marc-Antoine; Nadeau, Kenny; Labrecque, Charles; Gagné, Alexandre; Larivière, Dominic

    2010-12-01

    Neptunium(V) ions are unstable in acid media, which limits their extraction on chromatographic resins. We developed a novel analytical method to measure Np by either α-spectrometry or inductively coupled plasma mass spectrometry (ICP-MS) after extraction chromatography as Np(VI). We investigated the reactivity of various oxidizing reagents, and determined the retention capacity of Np(IV, V, and VI) on various extraction chromatographic supports. A simple method using two UTEVA resins was used to rapidly detect Np in soil and sediment samples.

  13. Unusual redox stability of neptunium in the ionic liquid [Hbet][Tf(2)N].

    PubMed

    Long, Kristy; Goff, George; Runde, Wolfgang

    2014-07-25

    The behavior of neptunium in the ionic liquid betaine bistriflimide, [Hbet][Tf2N], has been studied spectroscopically at room temperature and 60 °C for the first time. An unprecedented complex redox chemistry is observed, with up to three oxidation states (iv, v and vi) and up to six Np species existing simultaneously. Both redox reactions and coordination of betaine are observed for Np(iv), (v) and (vi). Elevating the temperature accelerates the coordination of Np(v) with betaine and reduction reactions slow down.

  14. Subcellular and intranuclear localization of neptunium-237 (V) in rat liver.

    PubMed

    Paquet, F; Verry, M; Grillon, G; Landesman, C; Masse, R; Taylor, D M

    1995-08-01

    The present investigation was aimed at establishing the distribution of 237Np within the different structures of hepatocytes. Rats were contaminated experimentally by intravenous injection of 237Np (V) and the subcellular structures of the liver were separated by ultracentrifugation. Twenty-four hours after contamination, the nuclear and cytosolic fractions bound 54 and 32%, respectively, of the total radionuclide. Purification of the nuclei followed by dissociation of the protein components in medium of increasing ionic strength showed a specific binding of neptunium to the structural proteins of the nuclear matrix.

  15. The synthesis and characterization of neptunium hydroxysulfate, Np(OH) 2SO 4

    NASA Astrophysics Data System (ADS)

    Wester, D. W.; Mulak, J.; Banks, R.; Carnall, W. T.

    1982-11-01

    Neptunium (IV) hydroxysulfate, Np(OH) 2SO 4, was synthesized using hydrothermal techniques. The X-ray powder diffraction pattern indicates that the compound is isomorphous with the Th(IV) and U(IV) analogs. Cell constants for the three compounds clearly show the effects of the actinide contraction. Visible and near-ir spectra are consistent with the presence of Np(IV) and are compared to spectra of Np(IV) in acidic solution. The ir spectrum contains bands which are assigned to the hydroxy and sulfate groups.

  16. Slater-Pauling behavior within quaternary intermetallic borides of the Ti 3Co 5B 2 structure-type

    NASA Astrophysics Data System (ADS)

    Burghaus, Jens; Dronskowski, Richard; Miller, Gordon J.

    2009-10-01

    First-principles, density-functional studies of several intermetallic borides of the general type M2M'Ru 5-nRh nB 2 ( n=0-5; M=Sc, Ti, Nb; M'=Fe, Co) show that the variation in saturation magnetic moment with valence-electron count follows a Slater-Pauling curve, with a maximum moment occurring typically at 66 valence electrons. The magnetic moments in these compounds occur primarily from the 3 d electrons of the magnetically active M' sites, with some contribution from the Ru/Rh sites via magnetic polarization. Electronic DOS curves reveal that a rigid-band approach is a reasonable approximation for the estimation of saturation moments and the analysis of orbital interactions in this family of complex borides. COHP analyses of the M'- M' orbital interactions indicate optimized interactions in the minority spin states for Co-containing phases, but strong bonding interactions remaining in Fe-containing phases.

  17. The Wyckoff positional order and polyhedral intergrowth in the M3B2- and M5B3-type boride precipitated in the Ni-based superalloys.

    PubMed

    Hu, X B; Zhu, Y L; Sheng, N C; Ma, X L

    2014-01-01

    Ni-based single superalloys play a crucial role in the hottest parts of jet engines. However, due to the complex geometry and macro-segregation during the solidification process, the cast defect such as stray grains is inevitable. Therefore, the transient liquid phase (TLP) bonding which can join several small single crystalline castings together is gradually believed to be an effective method for improving the yields of production of the complex components. The melting point depressant element B is always added into the interlayer filler material. Consequently, borides including the M3B2 and M5B3 phase usually precipitate during the TLP bonding process. So a comprehensive knowledge of the fine structural characteristics of the borides is very critical for an accurate evaluation of the TLP bonding process. In this work, by means of the aberration-corrected transmission electron microscopy, we show, at an atomic scale, the Wyckoff positional order phenomenon of the metal atoms in the unit cell of M3B2- and M5B3-type boride. Meanwhile, the defect along the (001) plane of the above two types of boride are determined to be the polyhedral intergrowth with complex configurations. PMID:25482386

  18. Surface decoration through electrostatic interaction leading to enhanced reactivity: Low temperature synthesis of nanostructured chromium borides (CrB and CrB{sub 2})

    SciTech Connect

    Menaka,; Kumar, Bharat; Kumar, Sandeep; Ganguli, A.K.

    2013-04-15

    The present study describes a novel low temperature route at ambient pressure for the synthesis of nanocrystalline chromium borides (CrB and CrB{sub 2}) without using any flux or additives. The favorable and intimate mixing of nanoparticles of chromium acetate (Cr source) and boron forms an active chromium–boron precursor which decomposes at much lower temperature (400 °C) to form CrB (which is ∼1000 °C less than the known ambient pressure synthesis). The chromium acetate nanoparticles (∼5 nm) decorate the larger boron particles (150–200 nm) due to electrostatic interactions resulting from opposing surface charges of boron (zeta potential:+48.101 mV) and chromium acetate (zeta potential:−4.021 mV) in ethanolic medium and is evident in the TEM micrographs. The above method leads to the formation of pure CrB film like structure at 400 °C and nanospheres (40–60 nm) at 600 °C. Also, chromium diboride (CrB{sub 2}) nanoparticles (25 nm) could be obtained at 1000 °C. - Graphical abstract: Variation of surface charge of reactants, precursor and the products, chromium borides (CrB and CrB{sub 2}). Highlights: ► Novel borothermal reduction process for synthesis of chromium boride. ► Significant lowering of reaction temperature to obtain nanocrystalline chromium boride. ► Enhanced reactivity due to appropriate surface interactions.

  19. The Wyckoff positional order and polyhedral intergrowth in the M3B2- and M5B3-type boride precipitated in the Ni-based superalloys.

    PubMed

    Hu, X B; Zhu, Y L; Sheng, N C; Ma, X L

    2014-12-08

    Ni-based single superalloys play a crucial role in the hottest parts of jet engines. However, due to the complex geometry and macro-segregation during the solidification process, the cast defect such as stray grains is inevitable. Therefore, the transient liquid phase (TLP) bonding which can join several small single crystalline castings together is gradually believed to be an effective method for improving the yields of production of the complex components. The melting point depressant element B is always added into the interlayer filler material. Consequently, borides including the M3B2 and M5B3 phase usually precipitate during the TLP bonding process. So a comprehensive knowledge of the fine structural characteristics of the borides is very critical for an accurate evaluation of the TLP bonding process. In this work, by means of the aberration-corrected transmission electron microscopy, we show, at an atomic scale, the Wyckoff positional order phenomenon of the metal atoms in the unit cell of M3B2- and M5B3-type boride. Meanwhile, the defect along the (001) plane of the above two types of boride are determined to be the polyhedral intergrowth with complex configurations.

  20. The Wyckoff positional order and polyhedral intergrowth in the M3B2- and M5B3-type boride precipitated in the Ni-based superalloys

    NASA Astrophysics Data System (ADS)

    Hu, X. B.; Zhu, Y. L.; Sheng, N. C.; Ma, X. L.

    2014-12-01

    Ni-based single superalloys play a crucial role in the hottest parts of jet engines. However, due to the complex geometry and macro-segregation during the solidification process, the cast defect such as stray grains is inevitable. Therefore, the transient liquid phase (TLP) bonding which can join several small single crystalline castings together is gradually believed to be an effective method for improving the yields of production of the complex components. The melting point depressant element B is always added into the interlayer filler material. Consequently, borides including the M3B2 and M5B3 phase usually precipitate during the TLP bonding process. So a comprehensive knowledge of the fine structural characteristics of the borides is very critical for an accurate evaluation of the TLP bonding process. In this work, by means of the aberration-corrected transmission electron microscopy, we show, at an atomic scale, the Wyckoff positional order phenomenon of the metal atoms in the unit cell of M3B2- and M5B3-type boride. Meanwhile, the defect along the (001) plane of the above two types of boride are determined to be the polyhedral intergrowth with complex configurations.

  1. The Wyckoff positional order and polyhedral intergrowth in the M3B2- and M5B3-type boride precipitated in the Ni-based superalloys

    PubMed Central

    Hu, X. B.; Zhu, Y. L.; Sheng, N. C.; Ma, X. L.

    2014-01-01

    Ni-based single superalloys play a crucial role in the hottest parts of jet engines. However, due to the complex geometry and macro-segregation during the solidification process, the cast defect such as stray grains is inevitable. Therefore, the transient liquid phase (TLP) bonding which can join several small single crystalline castings together is gradually believed to be an effective method for improving the yields of production of the complex components. The melting point depressant element B is always added into the interlayer filler material. Consequently, borides including the M3B2 and M5B3 phase usually precipitate during the TLP bonding process. So a comprehensive knowledge of the fine structural characteristics of the borides is very critical for an accurate evaluation of the TLP bonding process. In this work, by means of the aberration-corrected transmission electron microscopy, we show, at an atomic scale, the Wyckoff positional order phenomenon of the metal atoms in the unit cell of M3B2- and M5B3-type boride. Meanwhile, the defect along the (001) plane of the above two types of boride are determined to be the polyhedral intergrowth with complex configurations. PMID:25482386

  2. High-temperature thermochemistry of transition metal borides, silicides and related compounds. Final report

    SciTech Connect

    Klemppa, Ole J.

    2000-10-01

    Earlier this year in collaboration with Dr. Susan V. Meschel we prepared a major review paper which gives a comprehensive summary of what our laboratory has accomplished with support from DOE. This paper is No.43 in the List of Publications provided. It was presented to TMS at its National Meeting in Nashville, TN last March. A copy of the manuscript of this paper was recently mailed to DOE. It has been submitted for publication in Journal of Alloys and Compounds. This review paper summarizes our observed trends in the enthalpies of formation of TR-X and RE-X compounds (where X is a IIIB or IVB element) in their dependence of the atomic number of the transition metal (TR) and the lanthanide metal (RE). In this paper our measured enthalpies of formation for each alloy family are compared for the 3d, 4d and 5d transition metal elements. We also compare our experimental results with predicted values based on Miedema's semi-empirical model. Data are presented for the carbides, silicides, germanides and stannides in Group IVB, and for the borides and aluminides in Group IIIB. During the past year (1999-2000) we have extended our work to compounds of the 3d, 4d and 5d elements with gallium (see papers No.40, No.41, and No.45 in the List of Publications). Fig. 1 (taken from No.45) presents a systematic picture of our experimental values for the most exothermic gallide compounds formed with the transition elements. This figure is characteristic of the other systematic pictures which we have found for the two other IIIB elements which we have studied and for the four IVB elements. These figures are all presented in Ref. No.43. This paper also illustrates how the enthalpy of formation of compounds of the IIIB and IVB elements with the lanthanide elements (with the exception of Pm, Eu and Yb) depend on the atomic number of RE. Finally our results for the RE-X compounds are compared with the predictions of Gschneidner (K.A. Gschneidner, Jr., J. Less Common Metals 17, 1

  3. Structural and Physical Properties Diversity of New CaCu5-Type Related Europium Platinum Borides

    PubMed Central

    2013-01-01

    Three novel europium platinum borides have been synthesized by arc melting of constituent elements and subsequent annealing. They were characterized by X-ray powder and single-crystal diffraction: EuPt4B, CeCo4B type, P6/mmm, a = 0.56167(2) nm, c = 0.74399(3) nm; Eu3Pt7B2, Ca3Al7Cu2 type as an ordered variant of PuNi3, R3̅m, a = 0.55477(2) nm, c = 2.2896(1) nm; and Eu5Pt18B6–x, a new unique structure type, Fmmm, a = 0.55813(3) nm, b = 0.95476(5) nm, c = 3.51578(2) nm. These compounds belong to the CaCu5 family of structures, revealing a stacking sequence of CaCu5-type slabs with different structural units: CaCu5 and CeCo3B2 type in EuPt4B; CeCo3B2 and Laves MgCu2 type in Eu3Pt7B2; and CaCu5-, CeCo3B2-, and site-exchange ThCr2Si2-type slabs in Eu5Pt18B6–x. The striking motif in the Eu5Pt18B6–x structure is the boron-centered Pt tetrahedron [BPt4], which build chains running along the a axis and plays a decisive role in the structure arrangement by linking the terminal fragments of repeating blocks of fused Eu polyhedra. Physical properties of two compounds, EuPt4B and Eu3Pt7B2, were studied. Both compounds were found to order magnetically at 36 and 57 K, respectively. For EuPt4B a mixed-valence state of the Eu atom was confirmed via magnetic and specific heat measurements. Moreover, the Sommerfeld value of the specific heat of Eu3Pt7B2 was found to be extraordinarily large, on the order of 0.2 J/mol K2. PMID:23540751

  4. Electronic structure of the Np MT 5 ( M = Fe, Co, Ni; T = Ga, In) series of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Lukoyanov, A. V.; Shorikov, A. O.; Anisimov, V. I.

    2016-03-01

    Evolution of the electronic structure of the Np MGa5 ( M = Fe, Co, Ni) series of neptunium compounds, whose crystal structure is similar to that of the known family of Pu115 superconductors, was studied by the LDA + U + SO method. The calculations took into account both the strong electron correlations and the spin‒orbit coupling in the 5 f shell of neptunium. For the first time, the electronic structure was calculated for a hypothetical series of compounds in which gallium is replaced with indium. Parameters of the crystal structure of the given series were obtained using the relationship between the parameters of the crystal structure of the earlier-studied compounds PuCoGa5 and PuCoIn5. The analysis of the electronic structure and characteristics of neptunium ions calculated in the framework of the LDA + U + SO method showed that the neptunium ions in Np MIn5 with M = Fe, Co, and Ni should have an electron configuration closer to f 4, but a spin and magnetic characteristics close to those in Np MGa5.

  5. PROCESS FOR EXTRACTING NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID SOLUTIONS OF SAME CONTAINING URANYL NITRATE WITH A TERTIARY AMINE

    DOEpatents

    Sheppard, J.C.

    1962-07-31

    A process of selectively extracting plutonium nitrate and neptunium nitrate with an organic solution of a tertiary amine, away from uranyl nitrate present in an aqueous solution in a maximum concentration of 1M is described. The nitric acid concentration is adjusted to about 4M and nitrous acid is added prior to extraction. (AEC)

  6. Peak Stripping Methodology for Plutonium Analysis in the Presence of Neptunium

    SciTech Connect

    Hodge, Christ

    2005-05-17

    Quantitative Plutonium analysis depends upon the accurate identification of the assay peak. The Np[Pa] equilibrium pair introduces interfering peaks in {sup 239}Pu, {sup 238}Pu, and {sup 235}U assay peak region. When an interfering peak is present, it negates the assay unless an appropriate technique can be developed to deal with the interference. Peak Stripping is one such technique. Peak stripping involves an algorithm to strip an entire peak from another, resulting in a spectrum that can then be analyzed for the isotope of interest. A simpler method is a ''pseudo-peak-stripping'' whereby the effects of the interfering peak are quantified and those effects are stripped from the assay data. In this case the integrated peak areas are analyzed and corrected. There are two methods presented in this paper. Both assimilate the integrated data for the assay peak regions (in this case {sup 238}Pu, {sup 239}Pu, and {sup 235}U) and for the Neptunium/Protactinium secular equilibrium pair (Np[Pa]). Using Np[Pa] assumes that the Protactinium has come to equilibrium with Neptunium. This requires only {approx}6 months from the time chemical purification. Therefore it is a valid assumption in most cases. A correction is then applied to the assay peak areas to ''strip'' the underlying effects of Np[Pa].

  7. The absorption of ingested neptunium, plutonium and americium in newborn hamsters.

    PubMed

    David, A J; Harrison, J D

    1984-09-01

    Hamsters aged 1, 4, 7, 22 and 30 days were given oral doses of either plutonium-239 citrate or americium-241 nitrate. The values of gastrointestinal absorption obtained were 3.5, 1.4, 0.04, 0.007 and 0.003 per cent, respectively, for plutonium and 4.5, 1.7, 0.5, 0.006 and 0.02 per cent, respectively, for americium, compared with values in adults of 0.01 per cent for plutonium and 0.05 per cent for americium. The absorption of neptunium was measured in hamsters aged 2 and 4 days and values of 2.3 and 1.7 per cent, respectively, were obtained for 239Np as the nitrate and 5.5 and 2.1 per cent, respectively, for 239Np as the bicarbonate compared with the values in adults of 0.02 per cent for both chemical forms. Thus, the absorption of plutonium, americium and neptunium at 1-2 days of age was about 100 times greater than in adults. The results for plutonium and americium show that absorption decreased rapidly with age over the suckling period. The values of absorption obtained at the time of weaning at 22 days were lower than in adults.

  8. X-ray absorption spectroscopy studies of reactions of technetium, uranium and neptunium with mackinawite.

    PubMed

    Livens, Francis R; Jones, Mark J; Hynes, Amanda J; Charnock, John M; Mosselmans, J Fred W; Hennig, Christoph; Steele, Helen; Collison, David; Vaughan, David J; Pattrick, Richard A D; Reed, Wendy A; Moyes, Lesley N

    2004-01-01

    Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.

  9. Identification of transferrin as the principal neptunium-binding protein in the blood serum of rats.

    PubMed

    Wirth, R; Taylor, D M; Duffield, J

    1985-01-01

    The binding of 239Np(V) to blood serum components of rats was examined in vivo and in vitro. After gel filtration of the serum using a Sephacryl S-300 column, 98% of the applied activity appeared with protein fractions representing coeluted albumins and transferrin. A separation of the albumin- and transferrin-proteins by ion-exchange chromatography using DEAE-cellulose showed the 239Np being entirely bound to the iron-carrier protein transferrin. The high elution yields from the ion-exchange columns, greater than 90%, suggest that the binding may be quite strong. The binding capacity of transferrin for neptunium in vivo was found to decline when the iron level in blood serum was increased. Precipitation experiments showed that 84 +/- 2% of the 239Np was precipitated with 10% (w/v) trichloracetic acid, 77 +/- 3% with 90% ethanol but only 6 +/- 1% with saturated ammonium sulphate at pH 7.4. The available data indicate that as for plutonium, thorium, americium and curium, the iron transport protein, transferrin, may be the main carrier protein for neptunium in mammalian blood serum.

  10. Microscale Characterization of Uranium(VI) Silicate Solids and Associated Neptunium(V)

    SciTech Connect

    Douglas, Matt; Clark, Sue B.; Friese, Judah I.; Arey, Bruce W.; Buck, Edgar C.; Hanson, Brady D.; Utsunomiya, Satoshi; Ewing, Rodney C.

    2005-06-01

    The uranium(VI) silicate phases uranophane, Ca[(UO2)(SiO3OH)]2•5H2O, and sodium boltwoodite, Na[(UO2)(SiO3OH)]•1.5H2O, were synthesized in the presence of small, variable quantities (0.5 – 2.0 mol% relative to U) of pentavalent neptunium (Np(V), as NpO2+), to investigate the nature of its association with these U(VI) solid phases. Solids were characterized by X-ray powder diffraction (XRD), gamma spectrometry (GS), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM) with electron energy-loss spectroscopy (EELS). Neptunium concentration was determined in the bulk solid phases by GS and was found to range from 780 – 15,800 μg/g. In some cases, Np distributions between the aqueous and solid phases were monitored, and 78-97% of the initial Np was associated with the isolated solid. Characterization of individual crystallites by TEM/EELS suggests the Np is associated with the U(VI) phase. No discrete Np phases, such as Np-oxides, were observed. Because the U(VI) silicates are believed to be important solubility-controlling solids on a geologic timescale, these results suggest that the partitioning of the minor actinides to these solids must be considered when assessing the performance of a waste repository for spent nuclear fuel.

  11. Loading Capacities for Uranium, Plutonium and Neptunium in High Caustic Nuclear Waste Storage Tanks Containing Selected Sorbents

    SciTech Connect

    OJI, LAWRENCE

    2004-11-16

    In this study the loading capacities of selected actinides onto some of the most common sorbent materials which are present in caustic nuclear waste storage tanks have been determined. Some of these transition metal oxides and activated carbons easily absorb or precipitate plutonium, neptunium and even uranium, which if care is not taken may lead to unwanted accumulation of some of these fissile materials in nuclear waste tanks during waste processing. Based on a caustic synthetic salt solution simulant bearing plutonium, uranium and neptunium and ''real'' nuclear waste supernate solution, the loading capacities of these actinides onto iron oxide (hematite), activated carbon and anhydrous sodium phosphate have been determined. The loading capacities for plutonium onto granular activated carbon and iron oxide (hematite) in a caustic synthetic salt solution were, respectively, 3.4 0.22 plus or minus and 5.5 plus or minus 0.38 microgram per gram of sorbent. The loading capacity for plutonium onto a typical nuclear waste storage tank sludge solids was 2.01 microgram per gram of sludge solids. The loading capacities for neptunium onto granular activated carbon and iron oxide (hematite) in a caustic synthetic salt solution were, respectively, 7.9 plus or minus 0.52 and greater than 10 microgram per gram of sorbent. The loading capacity for neptunium onto a typical nuclear waste storage tank sludge solids was 4.48 microgram per gram of sludge solids. A typical nuclear waste storage tank solid material did not show any significant affinity for uranium. Sodium phosphate showed significant affinity for both neptunium and uranium, with loading capacities of 6.8 and 184.6 plus or minus 18.5 microgram per gram of sorbent, respectively.

  12. LIBS Spectral Data for a Mixed Actinide Fuel Pellet Containing Uranium, Plutonium, Neptunium and Americium

    SciTech Connect

    Judge, Elizabeth J.; Berg, John M.; Le, Loan A.; Lopez, Leon N.; Barefield, James E.

    2012-06-18

    Laser-induced breakdown spectroscopy (LIBS) was used to analyze a mixed actinide fuel pellet containing 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2}. The preliminary data shown here is the first report of LIBS analysis of a mixed actinide fuel pellet, to the authors knowledge. The LIBS spectral data was acquired in a plutonium facility at Los Alamos National Laboratory where the sample was contained within a glove box. The initial installation of the glove box was not intended for complete ultraviolet (UV), visible (VIS) and near infrared (NIR) transmission, therefore the LIBS spectrum is truncated in the UV and NIR regions due to the optical transmission of the window port and filters that were installed. The optical collection of the emission from the LIBS plasma will be optimized in the future. However, the preliminary LIBS data acquired is worth reporting due to the uniqueness of the sample and spectral data. The analysis of several actinides in the presence of each other is an important feature of this analysis since traditional methods must chemically separate uranium, plutonium, neptunium, and americium prior to analysis. Due to the historic nature of the sample fuel pellet analyzed, the provided sample composition of 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2} cannot be confirm without further analytical processing. Uranium, plutonium, and americium emission lines were abundant and easily assigned while neptunium was more difficult to identify. There may be several reasons for this observation, other than knowing the exact sample composition of the fuel pellet. First, the atomic emission wavelength resources for neptunium are limited and such techniques as hollow cathode discharge lamp have different dynamics than the plasma used in LIBS which results in different emission spectra. Secondly, due to the complex sample of four actinide elements, which all have very dense electronic energy levels, there may be reactions and

  13. Structural variability in neptunium(V) oxalate compounds: synthesis and structural characterization of Na2NpO2(C2O4)OH.H2O.

    PubMed

    Bean, Amanda C; Garcia, Eduardo; Scott, Brian L; Runde, Wolfgang

    2004-10-01

    Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions.

  14. Neptunium(V) Adsorption to Bacteria at Low and High Ionic Strength

    NASA Astrophysics Data System (ADS)

    Ams, D.; Swanson, J. S.; Reed, D. T.

    2010-12-01

    Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO2+ aquo and associated complexed species, is readily soluble, interacts weakly with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface containment. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO2+) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacteria/Np mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria used were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. The observed adsorption behavior may be linked to similarities and differences in the characteristics of the moieties between the cell walls of common gram-negative soil and halophilic bacteria. Moreover, differences in adsorption behavior may also reflect ionic

  15. Neptunium(V) adsorption to bacteria at low and high ionic strength

    SciTech Connect

    Ams, David A; Swanson, Juliet S; Reed, Donald T; Fein, Jeremy B

    2010-12-08

    Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO{sub 2}{sup +} aquo and associated complexed species, is readily soluble, weakly interacting with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface contaminant. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO{sub 2}{sup +}) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacterialNp mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight the key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. Similarities in adsorption behavior may be linked to similarities in the characteristics of the moieties between all bacterial cell walls. Differences in adsorption behavior may reflect differences in ionic strength effects, rather than

  16. THERMODYNAMICS OF NEPTUNIUM(V) FLOURIDE AND SULFATE AT ELEVATED TEMPERATURES

    SciTech Connect

    L. Rao; G. Tian; Y. Xia; J.I. Friese

    2006-03-06

    Complexation of neptunium(V) with fluoride and sulfate at elevated, temperatures was studied by microcalorimetry. Thermodynamic parameters, including the equilibrium constants and enthalpy of protonation of fluoride and sulfate, and the enthalpy of complexation between Np(V) and fluoride and sulfate at 25-70 C were determined. Results show that the complexation of Np(V) with fluoride and sulfate is endothermic and that the complexation is enhanced by the increase in temperature--a threefold increase in the stability constants of NpO{sub 2}F(aq) and NpO{sub 2}SO{sub 4}{sup -} as the temperature is increased from 25 to 70 C.

  17. Experimental Measurements of Short-Lived Fission Products from Uranium, Neptunium, Plutonium and Americium

    SciTech Connect

    Metz, Lori A.; Payne, Rosara F.; Friese, Judah I.; Greenwood, Lawrence R.; Kephart, Jeremy D.; Pierson, Bruce D.

    2009-11-01

    Fission yields are especially well characterized for long-lived fission products. Modeling techniques incorporate numerous assumptions and can be used to deduce information about the distribution of short-lived fission products. This work is an attempt to gather experimental (model-independent) data on the short-lived fission products. Fissile isotopes of uranium, neptunium, plutonium and americium were irradiated under pulse conditions at the Washington State University 1 MW TRIGA reactor to achieve ~108 fissions. The samples were placed on a HPGe (high purity germanium) detector to begin counting in less than 3 minutes post irradiation. The samples were counted for various time intervals ranging from 5 minutes to 1 hour. The data was then analyzed to determine which radionuclides could be quantified and compared to the published fission yield data.

  18. Young geologist trades neptunium for newspapers as 2012 AGU Mass Media Fellow

    NASA Astrophysics Data System (ADS)

    Adams, Mary Catherine

    2012-05-01

    Though the lure of rocks, minerals, and radioactive elements took her away from her original studies, one geology Ph.D. candidate is returning to her journalism roots this summer as AGU's 2012 Mass Media Science and Engineering Fellow. Jessica Morrison is one of 12 young scientists nationwide who are trading in their lab coats for reporters' notebooks in mid-June as part of the program coordinated by the American Association for the Advancement of Science, which helps young scientists cultivate communication skills to help disseminate scientific information to general audiences. Morrison is a Ph.D. student in the Department of Civil Engineering and Geological Sciences at the University of Notre Dame. She spends her days in a laboratory investigating the geochemistry of actinides, the radioactive elements in the "no man's land" of the periodic table—the section that often gets left off or moved to the bottom. These are elements like uranium, neptunium, and plutonium.

  19. Straightforward reductive routes to air-stable uranium(III) and neptunium(III) materials.

    PubMed

    Cross, Justin N; Villa, Eric M; Darling, Victoria R; Polinski, Matthew J; Lin, Jian; Tan, Xiaoyan; Kikugawa, Naoki; Shatruk, Michael; Baumbach, Ryan; Albrecht-Schmitt, Thomas E

    2014-07-21

    Studies of trivalent uranium (U(3+)) and neptunium (Np(3+)) are restricted by the tendency of these ions to oxidize in the presence of air and water, requiring manipulations to be carried out in inert conditions to produce trivalent products. While the organometallic and high-temperature reduction chemistry of U(3+) and, to a much smaller extent, Np(3+) has been explored, the study of the oxoanion chemistry of these species has been limited despite their interesting optical and magnetic properties. We report the synthesis of U(3+) and Np(3+) sulfates by utilizing zinc amalgam as an in situ reductant with absolutely no regard to the exclusion of O2 or water. By employing this method we have developed a family of alkali metal U(3+) and Np(3+) sulfates that are air and water stable. The structures, electronic spectra, and magnetic behavior are reported.

  20. Redox reactions of neptunium and plutonium in alkaline aqueous solutions upon gamma radiolysis

    NASA Astrophysics Data System (ADS)

    Pikaev, A. K.; Gogolev, A. V.; Shilov, V. P.

    1999-10-01

    The paper is a brief review of data obtained by the authors from the study on redox reactions of neptunium and plutonium ions upon γ-radiolysis of their aerated alkaline aqueous solutions. It includes the information on radiolytic reduction of Np(V), Np(VI), and Pu(VI) ions under various experimental conditions. It was found that the values of Np(VI) and Pu(VI) reduction yields do not depend on alkali concentration. The values considerably increase in the presence of some organic compounds (EDTA and formate were investigated). The formation of the Np(V) peroxo complex was observed in the γ-radiolysis of alkaline aqueous solutions of Np(VI) and Np(V) in the presence of nitrate. The mechanism of radiolytic redox reactions of the ions is discussed in some detail.

  1. Mineralogical Charecteristics of Yucca Mountain Alluvium and Effects on Neptunium (V) Sorption

    SciTech Connect

    M. Ding; S.J. Chipera; P.W. Reimus

    2006-09-05

    Saturated alluvium is expected to serve as an important natural barrier to radionuclide transport at Yucca Mountain, the proposed geological repository for disposal of high-level nuclear wastes. {sup 237}Np(V) (half-life = 2.4 x 10{sup 5} years) has been identified as one of the radionuclides that could potentially contribute the greatest dose to humans because of its relatively high solubility and weak adsorption to volcanic tuffs under oxidizing conditions. The previous studies suggested that the mineralogical characteristics of the alluvium play an important role in the interaction between Np(V) and the alluvium. The purpose of this study is to further evaluate the mineralogical basis for Neptunium (V) sorption by saturated alluvium located down-gradient of Yucca Mountain.

  2. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium.

  3. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium. PMID:14637345

  4. Evaluation of the efficiency of DTPA and other new chelating agents for removing neptunium from target organs.

    PubMed

    Paquet, F; Metivier, H; Poncy, J L; Burgada, R; Bailly, T

    1997-05-01

    Diethylenetriamine pentaacetic acid (DTPA) has been tested with 8 other new chelators for neptunium decorporation after systemic contamination in the rat. The ligands were injected intravenously at a dosage of 30 mumol kg-1 and the animals killed 24 h later. The results show that none of the chelators tested was efficient in removing significant amounts of the radionuclide from the body. In order to understand why these chelators were ineffective, in vitro approaches have since been developed in which high concentrations of DTPA were added to Np-bearing ligands in the blood, liver and skeleton. The main conclusions were that under our experimental conditions neptunium was not chelatable after its organ deposition.

  5. Slater-Pauling behavior within quaternary intermetallic borides of the Ti{sub 3}Co{sub 5}B{sub 2} structure-type

    SciTech Connect

    Burghaus, Jens; Dronskowski, Richard; Miller, Gordon J.

    2009-10-15

    First-principles, density-functional studies of several intermetallic borides of the general type M{sub 2}M'Ru{sub 5-n}Rh{sub n}B{sub 2} (n=0-5; M=Sc, Ti, Nb; M'=Fe, Co) show that the variation in saturation magnetic moment with valence-electron count follows a Slater-Pauling curve, with a maximum moment occurring typically at 66 valence electrons. The magnetic moments in these compounds occur primarily from the 3d electrons of the magnetically active M' sites, with some contribution from the Ru/Rh sites via magnetic polarization. Electronic DOS curves reveal that a rigid-band approach is a reasonable approximation for the estimation of saturation moments and the analysis of orbital interactions in this family of complex borides. COHP analyses of the M'-M' orbital interactions indicate optimized interactions in the minority spin states for Co-containing phases, but strong bonding interactions remaining in Fe-containing phases. - Graphical abstract: Theoretically determined (spin-polarized LMTO-GGA) local magnetic moments as a function of the chemical valence Z for various intermetallic borides.

  6. Surface Characterization and Mechanical Properties' Evaluation of Boride-Dispersed Nickel-Based Coatings Deposited on Copper Through Thermal Spray Routes

    NASA Astrophysics Data System (ADS)

    Sharma, Prashant; Majumdar, Jyotsna Dutta

    2012-09-01

    The present study concerns understanding the microstructures and wear resistance of nickel-based alloy (Ni 68.4, Cr 17, B 3.9, Si 4.9, and Fe 5.8) coatings on copper developed by flame spraying and high-velocity oxy-fuel (HVOF) coating techniques. The microstructure of flame spray deposition consists of predominantly equiaxed γ-Ni grains, refined Ni3B precipitates, and Ni2.9Cr0.7Fe0.36 phase. On the other hand, HVOF spray deposition reduces the porosity content significantly in the presence of very fine (with average precipitate size varying from μm to nm range) borides (chromium boride, Cr2B; and nickel boride, Ni3B) in γ-Ni matrix. The microhardness of the HVOF-sprayed and flame-sprayed surfaces were improved to 935 VHN and 251 VHN, respectively as compared with 82 VHN of the as-received substrate. Wear resistance property against WC indenter was also improved in deposited layers with a maximum improvement in HVOF spray deposition. The mechanism of wear was investigated.

  7. The effect of the mass and initial chemical form of neptunium on its molecular associations in blood and liver.

    PubMed

    Paquet, F; Ramounet, B; Métivier, H; Taylor, D M

    1996-09-01

    The present investigation was aimed at establishing the distribution of neptunium in blood and liver cells as a function of the mass and chemical form of the radionuclide injected. Four groups of rats received intravenous injections of 237Np(V), 237Np(IV), 239Np(V) or 239Np(IV). Twenty-four hours after injection of the radionuclide, subcellular structures of the liver were separated by ultracentrifugation and serum and liver cytosol were subjected to gel permeation chromatography. The intracellular distribution of neptunium in liver depends on the mass of the radionuclide injected; the relative specific activity for 237Np compared to 239Np was 2 in nuclei and 0.5-0.9 in cytosol. By contrast, the initial chemical form of the radionuclide has no significant effect on its intracellular distribution. In cytosol, neptunium was bound mainly by two proteins of molecular weight 450 and 200 kDa, respectively. The former was identified as ferritin, but the latter remains unidentified. In this compartment, no effect of mass or chemical form was seen. In blood, the bulk of the radionuclide was bound to transferrin whatever the mass and initial chemical form injected.

  8. Processing development of 4 tantalum carbide-hafnium carbide and related carbides and borides for extreme environments

    NASA Astrophysics Data System (ADS)

    Gaballa, Osama Gaballa Bahig

    Carbides, nitrides, and borides ceramics are of interest for many applications because of their high melting temperatures and good mechanical properties. Wear-resistant coatings are among the most important applications for these materials. Materials with high wear resistance and high melting temperatures have the potential to produce coatings that resist degradation when subjected to high temperatures and high contact stresses. Among the carbides, Al4SiC4 is a low density (3.03 g/cm3), high melting temperature (>2000°C) compound, characterized by superior oxidation resistance, and high compressive strength. These desirable properties motivated this investigation to (1) obtain high-density Al4SiC4 at lower sintering temperatures by hot pressing, and (2) to enhance its mechanical properties by adding WC and TiC to the Al4SiC4. Also among the carbides, tantalum carbide and hafnium carbide have outstanding hardness; high melting points (3880°C and 3890°C respectively); good resistance to chemical attack, thermal shock, and oxidation; and excellent electronic conductivity. Tantalum hafnium carbide (Ta4HfC 5) is a 4-to-1 ratio of TaC to HfC with an extremely high melting point of 4215 K (3942°C), which is the highest melting point of all currently known compounds. Due to the properties of these carbides, they are considered candidates for extremely high-temperature applications such as rocket nozzles and scramjet components, where the operating temperatures can exceed 3000°C. Sintering bulk components comprised of these carbides is difficult, since sintering typically occurs above 50% of the melting point. Thus, Ta4 HfC5 is difficult to sinter in conventional furnaces or hot presses; furnaces designed for very high temperatures are expensive to purchase and operate. Our research attempted to sinter Ta4HfC5 in a hot press at relatively low temperature by reducing powder particle size and optimizing the powder-handling atmosphere, milling conditions, sintering

  9. 2-Page Summary for Neptunium solubility in the Near-field Environment of A Proposed Yucca Mountain Repository

    SciTech Connect

    D. Sassani; A. Van Luik; J. Summerson

    2005-03-29

    The total system performance assessment (TSPA) for the proposed repository at Yucca Mountain, NV, includes a wide variety of processes to evaluate the potential release of radionuclides from the Engineered Barrier System into the unsaturated zone of the geosphere. The principal processes controlling radionuclide release and mobilization from the waste forms are captured in the model to assess the dissolved concentrations of radionuclides in the source-term. The TSPA model of the source-term incorporates the far-from-equilibrium dissolution of, for example, spent nuclear fuel (SNF) to capture bounding rates of radionuclide availability as the SNF degrades. In addition, for individual radionuclides, the source-term model evaluates solubility constraints that are more indicative of longer-term, equilibrium processes that can limit the potential mass transport from the source term in those cases. These solubility limits represent phase saturation and precipitation processes that can occur either at the waste form as it alters, or at other locations in the near-field environment (e.g., within the invert) if chemical conditions are different. Identification and selection of applicable constraints for solubility-limited radionuclide concentrations is a primary focus in formulating the source-term model for the TSPA. Neptunium is a long-lived radionuclide that becomes a larger fraction of the potential dose as radioactive decay of other radionuclides proceeds. To delineate appropriate long-term source-term controls on dissolved neptunium concentrations, a number of alternative models have been defined. The models are based on data both collected within the Yucca Mountain Project and taken from published literature, and have been evaluated against independent data sets to assess their applicability. The alternative models encompass ones based on precipitation of neptunium within its own separate oxide phases (i.e., ''pure'' Np-phases), and those where neptunium is

  10. On the transferability of electron density in binary vanadium borides VB, V3B4 and VB2.

    PubMed

    Terlan, Bürgehan; Akselrud, Lev; Baranov, Alexey I; Borrmann, Horst; Grin, Yuri

    2015-12-01

    Binary vanadium borides are suitable model systems for a systematic analysis of the transferability concept in intermetallic compounds due to chemical intergrowth in their crystal structures. In order to underline this structural relationship, topological properties of the electron density in VB, V3B4 and VB2 reconstructed from high-resolution single-crystal X-ray diffraction data as well as derived from quantum chemical calculations, are analysed in terms of Bader's Quantum Theory of Atoms in Molecules [Bader (1990). Atoms in Molecules: A Quantum Theory, 1st ed. Oxford: Clarendon Press]. The compounds VB, V3B4 and VB2 are characterized by a charge transfer from the metal to boron together with two predominant atomic interactions, the shared covalent B-B interactions and the polar covalent B-M interactions. The resembling features of the crystal structures are well reflected by the respective B-B interatomic distances as well as by ρ(r) values at the B-B bond critical points. The latter decrease with an increase in the corresponding interatomic distances. The B-B bonds show transferable electron density properties at bond critical points depending on the respective bond distances. PMID:26634735

  11. Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

    DOEpatents

    Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

    2003-09-23

    Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

  12. Thermodynamic modeling of neptunium(V)-acetate complexation in concentrated NaCl media

    SciTech Connect

    Novak, C.F.; Borkowski, M.; Choppin, G.R.

    1995-09-01

    The complexation of neptunium(V), Np(V), with the acetate anion, Ac{sup -}, was measured in sodium chloride media to high concentration using an extraction technique. The data were interpreted using the thermodynamic formalism of Pitzer, which is valid to high electrolyte concentrations. A consistent model for the deprotonation constants of acetic acid in NaCl and NaClO{sub 4} media was developed. For the concentrations of acetate expected in a waste repository, only the neutral complex NpO{sub 2}Ac(aq) was important in describing the interactions between the neptunyl ion and acetate. The thermodynamic stability constant log {beta}{sup 0}{sub 101} for the reaction NpO{sub 2}{sup +} + Ac{sup -} {leftrightarrow} NpO{sub 2}Ac was calculated to be 1.46{plus_minus}0.11. This weak complexing behavior between the neptunyl ion and acetate indicates that acetate will not significantly enhance dissolved Np(V) concentrations in ground waters associated with nuclear waste repositories that may contain acetate.

  13. Gas Generation Testing of Neptunium Oxide Generated Using the HB-Line Phase IIFlowsheet

    SciTech Connect

    Duffey, J

    2003-08-29

    The hydrogen (H{sub 2}) gas generation rate for neptunium dioxide (NpO{sub 2}) samples produced on a laboratory scale using the HB-Line Phase II flowsheet has been measured following exposure to 75% relative humidity (RH). As expected, the observed H{sub 2} generation rates for these samples increase with increasing moisture content. A maximum H{sub 2} generation rate of 1.8 x 10{sup -6} moles per day per kilogram (mol {center_dot} day{sup -1} kg{sup -1}) was observed for NpO{sub 2} samples with approximately one and one-half times (1 1/2 X) the expected specific surface area (SSA) for the HB-Line Phase II product. The SSA of NpO{sub 2} samples calcined at 650 C is similar to plutonium dioxide (PuO{sub 2}) calcined at 950 C according to the Department of Energy (DOE) standard for packaging and storage of PuO{sub 2}. This low SSA of the HB-Line Phase II product limits moisture uptake to less than 0.2 weight percent (wt %) even with extended exposure to 75% RH.

  14. Dissolution of Neptunium and Plutonium Oxides Using a Catalyzed Electrolytic Process

    SciTech Connect

    Hylton, TD

    2004-10-25

    This report discusses the scoping study performed to evaluate the use of a catalyzed electrolytic process for dissolving {sup 237}Np oxide targets that had been irradiated to produce {sup 238}Pu oxide. Historically, these compounds have been difficult to dissolve, and complete dissolution was obtained only by adding hydrofluoric acid to the nitric acid solvent. The presence of fluoride in the mixture is undesired because the fluoride ions are corrosive to tank and piping systems and the fluoride ions cause interferences in the spectrophotometric analyses. The goal is to find a dissolution method that will eliminate these issues and that can be incorporated into a processing system to support the domestic production and purification of {sup 238}Pu. This study evaluated the potential of cerium(IV) ions, a strong oxidant, to attack and dissolve the oxide compounds. In the dissolution process, the cerium(IV) ions are reduced to cerium(III) ions, which are not oxidants. Therefore, an electrolytic process was incorporated to continuously convert cerium(III) ions back to cerium(IV) ions so that they can dissolve more of the oxide compounds. This study showed that the neptunium and plutonium oxides were successfully dissolved and that more development work should be performed to optimize the procedure.

  15. Application of the S=1 underscreened Anderson lattice model to Kondo uranium and neptunium compounds

    NASA Astrophysics Data System (ADS)

    Thomas, Christopher; da Rosa Simões, Acirete S.; Iglesias, J. R.; Lacroix, C.; Perkins, N. B.; Coqblin, B.

    2011-01-01

    Magnetic properties of uranium and neptunium compounds showing the coexistence of the Kondo screening effect and ferromagnetic order are investigated within the Anderson lattice Hamiltonian with a two-fold degenerate f level in each site, corresponding to 5f2 electronic configuration with S=1 spins. A derivation of the Schrieffer-Wolff transformation is presented and the resulting Hamiltonian has an effective f-band term, in addition to the regular exchange Kondo interaction between the S=1 f spins and the s=1/2 spins of the conduction electrons. The resulting effective Kondo lattice model can describe both the Kondo regime and a weak delocalization of the 5f electrons. Within this model we compute the Kondo and Curie temperatures as a function of model parameters, namely the Kondo exchange interaction constant JK, the magnetic intersite exchange interaction JH, and the effective f bandwidth. We deduce, therefore, a phase diagram of the model which yields the coexistence of the Kondo effect and ferromagnetic ordering and also accounts for the pressure dependence of the Curie temperature of uranium compounds such as UTe.

  16. Quantitative NDA measurements of advanced reprocessing product materials containing uranium, neptunium, plutonium, and americium

    NASA Astrophysics Data System (ADS)

    Goddard, Braden

    The ability of inspection agencies and facility operators to measure powders containing several actinides is increasingly necessary as new reprocessing techniques and fuel forms are being developed. These powders are difficult to measure with nondestructive assay (NDA) techniques because neutrons emitted from induced and spontaneous fission of different nuclides are very similar. A neutron multiplicity technique based on first principle methods was developed to measure these powders by exploiting isotope-specific nuclear properties, such as the energy-dependent fission cross sections and the neutron induced fission neutron multiplicity. This technique was tested through extensive simulations using the Monte Carlo N-Particle eXtended (MCNPX) code and by one measurement campaign using the Active Well Coincidence Counter (AWCC) and two measurement campaigns using the Epithermal Neutron Multiplicity Counter (ENMC) with various (alpha,n) sources and actinide materials. Four potential applications of this first principle technique have been identified: (1) quantitative measurement of uranium, neptunium, plutonium, and americium materials; (2) quantitative measurement of mixed oxide (MOX) materials; (3) quantitative measurement of uranium materials; and (4) weapons verification in arms control agreements. This technique still has several challenges which need to be overcome, the largest of these being the challenge of having high-precision active and passive measurements to produce results with acceptably small uncertainties.

  17. Creation of a simplified benchmark model for the neptunium sphere experiment

    SciTech Connect

    Mosteller, R. D.; Loaiza, D. J.; Sanchez, R. G.

    2004-01-01

    Although neptunium is produced in significant amounts by nuclear power reactors, its critical mass is not well known. In addition, sizeable uncertainties exist for its cross sections. As an important step toward resolution of these issues, a critical experiment was conducted in 2002 at the Los Alamos Critical Experiments Facility. In the experiment, a 6-kg sphere of {sup 237}Np was surrounded by nested hemispherical shells of highly enriched uranium. The shells were required in order to reach a critical condition. Subsequently, a detailed model of the experiment was developed. This model faithfully reproduces the components of the experiment, but it is geometrically complex. Furthermore, the isotopics analysis upon which that model is based omits nearly 1 % of the mass of the sphere. A simplified benchmark model has been constructed that retains all of the neutronically important aspects of the detailed model and substantially reduces the computer resources required for the calculation. The reactivity impact, of each of the simplifications is quantified, including the effect of the missing mass. A complete set of specifications for the benchmark is included in the full paper. Both the detailed and simplified benchmark models underpredict k{sub eff} by more than 1% {Delta}k. This discrepancy supports the suspicion that better cross sections are needed for {sup 237}Np.

  18. The effect of temperature on the sorption of technetium, uranium, neptunium and curium on bentonite, tuff and granodiorite

    SciTech Connect

    Baston, G.M.N.; Berry, J.A.; Brownsword, M.; Heath, T.G.; Ilett, D.J.; Tweed, C.J.; Yui, M.

    1997-12-31

    A study of the sorption of the radioelements technetium; uranium; neptunium; and curium onto geological materials has been carried out as part of the PNC program to increase confidence in the performance assessment for a high-level radioactive waste repository in Japan. Batch sorption experiments have been performed in order to study the sorption of the radioelements onto bentonite, tuff and granodiorite from equilibrated de-ionized water under strongly-reducing conditions at both room temperature and at 60 C. Mathematical modelling using the geochemical speciation program HARPHRQ in conjunction with the HATCHES database has been undertaken in order to interpret the experimental results.

  19. Anomalous effect of vanadium boride seeding on thermoelectric properties of YB{sub 22}C{sub 2}N

    SciTech Connect

    Prytuliak, A.; Maruyama, S.; Mori, T.

    2013-05-15

    Highlights: ► We doped YB{sub 22}C{sub 2}N; the long awaited n-type counterpart to p-type boron carbide. ► VB{sub 2} seeding of YB{sub 22}C{sub 2}N showed striking results. ► Thermal treatment effects led to VB{sub 2} being intrinsically doped. ► Large increase of both Seebeck coefficient and electrical conductivity was obtained. - Abstract: Vanadium boride seeded YB{sub 22}C{sub 2}N were synthesized and the thermoelectric properties investigated. YB{sub 22}C{sub 2}N is representative of the series of rare earth borocarbonitrides which is the potential long awaited n-type counterpart to p-type boron carbide. VB{sub 2} seeded samples of YB{sub 22}C{sub 2}N were prepared using VB{sub 2} directly as an initial additive and V{sub 2}O{sub 3} which also results in formation of vanadium diboride in the final product. The resistivity and Seebeck coefficient of samples were measured in the temperature range of 323 K to 1073 K. A dramatic effect of thermal treatment on the Seebeck coefficient of VB{sub 2} seeded samples was observed, and it is indicated that there is possible partial intrinsic doping of vanadium into YB{sub 22}C{sub 2}N. VB{sub 2} is revealed to be a promising additive to improve the thermoelectric properties of YB{sub 22}C{sub 2}N. An enhancement of more than 220% of the maximum absolute value of the Seebeck coefficient was obtained while the resistivity was also reduced considerably.

  20. Neptunium(V) sorption to goethite at attomolar to micromolar concentrations.

    PubMed

    Snow, Mathew S; Zhao, Pihong; Dai, Zurong; Kersting, Annie B; Zavarin, Mavrik

    2013-01-15

    Sorption of 10(-18)-10(-5)M neptunium (Np) to goethite was examined using liquid scintillation counting and gamma spectroscopy. A combination approach using (239)Np and long lived (237)Np was employed to span this wide concentration range. (239)Np detection limits were determined to be 2×10(-18)M and 3×10(-17)M for liquid scintillation counting and gamma spectroscopy, respectively. Sorption was found to be linear below 10(-11)M, in contrast to the non-linear behavior observed at higher concentrations both here and in the literature. 2-site and 3-site Langmuir models were used to simulate sorption behavior over the entire 10(-18)-10(-5)M range. The 3-site model fit yielded Type I and II site densities of 3.56 sites/nm(2) (99.6%) and 0.014±0.007 sites/nm(2) (0.4±0.1%), consistent with typical "high affinity" and "low affinity" sites reported in the literature [21]. Modeling results for both models suggest that sorption below ~10(-11)M is controlled by a third (Type III) site with a density on the order of ~7×10(-5)sites/nm(2) (~0.002%). While the nature of this "site" cannot be determined from isotherm data alone, the sorption data at ultra-low Np concentrations indicate that Np(V) sorption to goethite at environmentally relevant concentrations will be (1) linear and (2) higher than previous (high concentration) laboratory experiments suggest. PMID:23079039

  1. Atlas of Atomic Spectral Lines of Neptunium Emitted by Inductively Coupled Plasma

    SciTech Connect

    DeKalb, E.L. and Edelson, M. C.

    1987-08-01

    Optical emission spectra from high-purity Np-237 were generated with a glovebox-enclosed inductively coupled plasma (ICP) source. Spectra covering the 230-700 nm wavelength range are presented along with general commentary on the methodology used in collecting the data. The Ames Laboratory Nuclear Safeguards and Security Program has been charged with the task of developing optical spectroscopic methods to analyze the composition of spent nuclear fuels. Such materials are highly radioactive even after prolonged 'cooling' and are chemically complex. Neptunium (Np) is a highly toxic by-product of nuclear power generation and is found, in low abundance, in spent nuclear fuels. This atlas of the optical emission spectrum of Np, as produced by an inductively coupled plasma (ICP) spectroscopic source, is part of a general survey of the ICP emission spectra of the actinide elements. The ICP emission spectrum of the actinides originates almost exclusively from the electronic relaxation of excited, singly ionized species. Spectral data on the Np ion emission spectrum (i.e., the Np II spectrum) have been reported by Tomkins and Fred [1] and Haaland [2]. Tomkins and Fred excited the Np II spectrum with a Cu spark discharge and identified 114 Np lines in the 265.5 - 436.3 nm spectral range. Haaland, who corrected some spectral line misidentifications in the work of Tomkins and Fred, utilized an enclosed Au spark discharge to excite the Np II spectrum and reported 203 Np lines within the 265.4 - 461.0 nm wavelength range.

  2. Neptunium(V) sorption to goethite at attomolar to micromolar concentrations.

    PubMed

    Snow, Mathew S; Zhao, Pihong; Dai, Zurong; Kersting, Annie B; Zavarin, Mavrik

    2013-01-15

    Sorption of 10(-18)-10(-5)M neptunium (Np) to goethite was examined using liquid scintillation counting and gamma spectroscopy. A combination approach using (239)Np and long lived (237)Np was employed to span this wide concentration range. (239)Np detection limits were determined to be 2×10(-18)M and 3×10(-17)M for liquid scintillation counting and gamma spectroscopy, respectively. Sorption was found to be linear below 10(-11)M, in contrast to the non-linear behavior observed at higher concentrations both here and in the literature. 2-site and 3-site Langmuir models were used to simulate sorption behavior over the entire 10(-18)-10(-5)M range. The 3-site model fit yielded Type I and II site densities of 3.56 sites/nm(2) (99.6%) and 0.014±0.007 sites/nm(2) (0.4±0.1%), consistent with typical "high affinity" and "low affinity" sites reported in the literature [21]. Modeling results for both models suggest that sorption below ~10(-11)M is controlled by a third (Type III) site with a density on the order of ~7×10(-5)sites/nm(2) (~0.002%). While the nature of this "site" cannot be determined from isotherm data alone, the sorption data at ultra-low Np concentrations indicate that Np(V) sorption to goethite at environmentally relevant concentrations will be (1) linear and (2) higher than previous (high concentration) laboratory experiments suggest.

  3. ELECTRONICS UPGRADE TO THE SAVANNAH RIVER NATIONAL LABORATORY COULOMETER FOR PLUTONIUM AND NEPTUNIUM ASSAY

    SciTech Connect

    Cordaro, J.; Holland, M.; Reeves, G.; Nichols, S.; Kruzner, A.

    2011-07-08

    The Savannah River Site (SRS) has the analytical measurement capability to perform high-precision plutonium concentration measurements by controlled-potential coulometry. State-of-the-art controlled-potential coulometers were designed and fabricated by the Savannah River National Laboratory and installed in the Analytical Laboratories process control laboratory. The Analytical Laboratories uses coulometry for routine accountability measurements of and for verification of standard preparations used to calibrate other plutonium measurement systems routinely applied to process control, nuclear safety, and other accountability applications. The SRNL Coulometer has a demonstrated measurement reliability of {approx}0.05% for 10 mg samples. The system has also been applied to the characterization of neptunium standard solutions with a comparable reliability. The SRNL coulometer features: a patented current integration system; continuous electrical calibration versus Faraday's Constants and Ohm's Law; the control-potential adjustment technique for enhanced application of the Nernst Equation; a wide operating room temperature range; and a fully automated instrument control and data acquisition capability. Systems have been supplied to the International Atomic Energy Agency (IAEA), Russia, Japanese Atomic Energy Agency (JAEA) and the New Brunswick Laboratory (NBL). The most recent vintage of electronics was based on early 1990's integrated circuits. Many of the components are no longer available. At the request of the IAEA and the Department of State, SRNL has completed an electronics upgrade of their controlled-potential coulometer design. Three systems have built with the new design, one for the IAEA which was installed at SAL in May 2011, one system for Los Alamos National Laboratory, (LANL) and one for the SRS Analytical Laboratory. The LANL and SRS systems are undergoing startup testing with installation scheduled for this summer.

  4. Kinetics of neptunium(V) sorption and desorption on goethite: An experimental and modeling study

    NASA Astrophysics Data System (ADS)

    Tinnacher, Ruth M.; Zavarin, Mavrik; Powell, Brian A.; Kersting, Annie B.

    2011-11-01

    Various sorption phenomena, such as aging, hysteresis and irreversible sorption, can cause differences between contaminant (ad)sorption and desorption behavior and lead to apparent sorption 'asymmetry'. We evaluate the relevance of these characteristics for neptunium(V) (Np(V)) sorption/desorption on goethite using a 34-day flow-cell experiment and kinetic modeling. Based on experimental results, the Np(V) desorption rate is much slower than the (ad)sorption rate, and appears to decrease over the course of the experiment. The best model fit with a minimum number of fitting parameters was achieved with a multi-reaction model including (1) an equilibrium Freundlich site (site 1), (2) a kinetically-controlled, consecutive, first-order site (site 2), and (3) a parameter ψ, which characterizes the desorption rate on site 2 based on a concept related to transition state theory (TST). This approach allows us to link differences in adsorption and desorption kinetics to changes in overall reaction pathways, without assuming different adsorption and desorption affinities (hysteresis) or irreversible sorption behavior a priori. Using modeling as a heuristic tool, we determined that aging processes are relevant. However, hysteresis and irreversible sorption behavior can be neglected within the time-frame (desorption over 32 days) and chemical solution conditions evaluated in the flow-cell experiment. In this system, desorption reactions are very slow, but they are not irreversible. Hence, our data do not justify an assumption of irreversible Np(V) sorption to goethite in transport models, which effectively limits the relevance of colloid-facilitated Np(V) transport to near-field environments. However, slow Np(V) desorption behavior may also lead to a continuous contaminant source term when metals are sorbed to bulk mineral phases. Additional long-term experiments are recommended to definitely rule out irreversible Np(V) sorption behavior at very low surface loadings and

  5. A Simple Kinetic Model for the Growth of Fe2B Layers on AISI 1026 Steel During the Powder-pack Boriding

    NASA Astrophysics Data System (ADS)

    Flores-Rentería, M. A.; Ortiz-Domínguez, M.; Keddam, M.; Damián-Mejía, O.; Elias-Espinosa, M.; Flores-González, M. A.; Medina-Moreno, S. A.; Cruz-Avilés, A.; Villanueva-Ibañez, M.

    2015-02-01

    This work focused on the determination of boron diffusion coefficient through the Fe2B layers on AISI 1026 steel using a mathematical model. The suggested model solves the mass balance equation at the (Fe2B/substrate) interface. This thermochemical treatment was carried out in the temperature range of 1123-1273 K for a treatment time ranging from 2 to 8 h. The generated boride layers were characterized by different experimental techniques such as light optical microscopy, scanning electron microscopy, XRD analysis and the Daimler-Benz Rockwell-C indentation technique. As a result, the boron activation energy for AISI 1026 steel was estimated as 178.4 kJ/mol. Furthermore, this kinetic model was validated by comparing the experimental Fe2B layer thickness with the predicted one at a temperature of 1253 K for 5 h of treatment. A contour diagram relating the layer thickness to the boriding parameters was proposed to be used in practical applications.

  6. Electronic, structural and magnetic studies of niobium borides of group 8 transition metals, Nb2MB2 (M=Fe, Ru, Os) from first principles calculations

    NASA Astrophysics Data System (ADS)

    Touzani, Rachid St.; Fokwa, Boniface P. T.

    2014-03-01

    The Nb2FeB2 phase (U3Si2-type, space group P4/mbm, no. 127) is known for almost 50 years, but until now its magnetic properties have not been investigated. While the synthesis of Nb2OsB2 (space group P4/mnc, no. 128, a twofold superstructure of U3Si2-type) with distorted Nb-layers and Os2-dumbbells was recently achieved, "Nb2RuB2" is still not synthesized and its crystal structure is yet to be revealed. Our first principles density functional theory (DFT) calculations have confirmed not only the experimental structures of Nb2FeB2 and Nb2OsB2, but also predict "Nb2RuB2" to crystalize with the Nb2OsB2 structure type. According to chemical bonding analysis, the homoatomic B-B interactions are optimized and very strong, but relatively strong heteroatomic M-B, B-Nb and M-Nb bonds (M=Fe, Ru, Os) are also found. These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of these ternary borides. The density-of-states at the Fermi level predicts metallic behavior, as expected, from metal-rich borides. Analysis of possible magnetic structures concluded preferred antiferromagnetic ordering for Nb2FeB2, originating from ferromagnetic interactions within iron chains and antiferromagnetic exchange interactions between them.

  7. Kinetics of reduction of plutonium(VI) and neptunium(VI) by sulfide in neutral and alkaline solutions

    USGS Publications Warehouse

    Nash, K.L.; Cleveland, J.M.; Sullivan, J.C.; Woods, M.

    1986-01-01

    The rate of reduction of plutonium(VI) and neptunium(VI) by bisulfide ion in neutral and mildly alkaline solutions has been investigated by the stopped-flow technique. The reduction of both of these ions to the pentavalent oxidation state appears to occur in an intramolecular reaction involving an unusual actinide(VI)-hydroxide-bisulfide complex. For plutonium the rate of reduction is 27.4 (??4.1) s-1 at 25??C with ??H* = +33.2 (??1.0) kJ/mol and ??S* = -106 (??4) J/(mol K). The apparent stability constant for the transient complex is 4.66 (??0.94) ?? 103 M-1 at 25??C with associated thermodynamic parameters of ??Hc = +27.7 (??0.4) kJ/mol and ??Sc = +163 (??2) J/(mol K). The corresponding rate and stability constants are determined for the neptunium system at 25??C (k3 = 139 (??30) s-1, Kc. = 1.31 (??0.32) ?? 103 M-1), but equivalent parameters cannot be determined at reduced temperatures. The reaction rate is decreased by bicarbonate ion. At pH > 10.5, a second reaction mechanism, also involving a sulfide complex, is indicated. ?? 1986 American Chemical Society.

  8. New Synthetic Methods and Structure-Property Relationships in Neptunium, Plutonium, and Americium Borates. Final report

    SciTech Connect

    Albrecht-Schmitt, Thomas Edward

    2013-09-14

    The past three years of support by the Heavy Elements Chemistry Program have been highly productive in terms of advanced degrees awarded, currently supported graduate students, peer-reviewed publications, and presentations made at universities, national laboratories, and at international conferences. Ph.D. degrees were granted to Shuao Wang and Juan Diwu, who both went on to post-doctoral appointments at the Glenn T. Seaborg Center at Lawrence Berkeley National Laboratory with Jeff Long and Ken Raymond, respectively. Pius Adelani completed his Ph.D. with me and is now a post-doc with Peter C. Burns. Andrea Alsobrook finished her Ph.D. and is now a post-doc at Savannah River with Dave Hobbs. Anna Nelson completed her Ph.D. and is now a post-doc with Rod Ewing at the University of Michigan. As can be gleaned from this list, students supported by the Heavy Elements Chemistry grant have remained interested in actinide science after leaving my program. This follows in line with previous graduates in this program such as Richard E. Sykora, who did his post-doctoral work at Oak Ridge National Laboratory with R. G. Haire, and Amanda C. Bean, who is a staff scientist at Los Alamos National Laboratory, and Philip M. Almond and Thomas C. Shehee, who are both staff scientists at Savannah River National Laboratory, Gengbang Jin who is a staff scientist at Argonne National Lab, and Travis Bray who has been a post-doc at both LBNL and ANL. Clearly this program is serving as a pipe-line for students to enter into careers in the national laboratories. About half of my students depart the DOE complex for academia or industry. My undergraduate researchers also remain active in actinide chemistry after leaving my group. Dan Wells was a productive undergraduate of mine, and went on to pursue a Ph.D. on uranium and neptunium chalcogenides with Jim Ibers at Northwestern. After earning his Ph.D., he went directly into the nuclear industry.

  9. Sorption Modeling of Strontium, Plutonium, Uranium and Neptunium Adsorption on Monosodium Titanate

    SciTech Connect

    Fondeur, F.F.

    2003-10-30

    We examined the ability of various equilibrium isotherms to replicate the available data for the adsorption of strontium (Sr), plutonium (Pu), uranium (U) and neptunium (Np) on monosodium titanate (MST) during the treatment of simulated and actual Savannah River Site high-level waste. The analysis considered 29 isotherm models from the literature. As part of this study, we developed a general method for selecting the best isotherm models. The selection criteria for rating the isotherms considered the relative error in predicting the experimental data, the complexity of the mathematical expressions, the thermodynamic validity of the expressions, and statistical significance for the expressions. The Fowler Guggenheim-Jovanovic Freundlich (FG-JF), the Fowler Guggenheim-Langmuir Freundlich (FG-LF) and the Dubinin-Astashov (DA) models each reliably predicted the actinide and strontium adsorption on MST. The first two models describe the adsorption process by single layer formation and later al interactions between adsorbed sorbates while the Dubinin-Astashov model assumes volume filling of micropores (by osmotic pressure difference). These two mechanisms include mutually exclusive assumptions. However, we can not determine which model best represents the various adsorption mechanisms on MST. Based on our analysis, the DA model predicted the data well. The DA model assumes that an initial sorption layer forms after which networking begins in the pore spaces, filling the volume by a second mechanism. If this mechanism occurs in MST, as the experimental data suggests, then we expect all the empty and closed spaces of MST to contain actinides and strontium when saturated. Prior microstructure analyses determined that the MST surface is best described as heterogeneous (i.e., a semi-crystalline outer layer on an amorphous core) or composite material for adsorption. Therefore, we expect the empty spaces (of nanometer size) between the crystalline units in the fibrous material

  10. Surface complexation of neptunium (V) onto whole cells and cell componets of Shewanella alga

    SciTech Connect

    Reed, Donald Timothy; Deo, Randhir P; Rittmann, Bruce E; Songkasiri, Warinthorn

    2008-01-01

    We systematically quantified surface complexation of neptunium(V) onto whole cells of Shewanella alga strain BrY and onto cell wall and extracellular polymeric substances (EPS) of S. alga. We first performed acid and base titrations and used the mathematical model FITEQL with constant-capacitance surface-complexation to determine the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl site associated with amino acids (pK{sub a} {approx} 2.4), a carboxyl group not associated with amino acids (pK{sub a} {approx} 5), a phosphoryl site (pK{sub a} {approx} 7.2), and an amine site (pK{sub a} > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components at different pHs. Results show that solution pH influenced the speciation of Np(V) and each of the surface functional groups. We used the speciation sub-model of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, NpO{sub 2}{sup +} was the dominant form of Np(V), and its log K values for the low-pK{sub a} carboxyl, other carboxyl, and phosphoryl groups were 1.75, 1.75, and 2.5 to 3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH3+, which complexed with NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-}. The log K for NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-} complexed onto the amine groups was 3.1 to 3.6. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results point towards the important role of surface complexation in defining key actinide-microbiological interactions in the subsurface.

  11. Chemical speciation of neptunium(VI) under strongly alkaline conditions. Structure, composition, and oxo ligand exchange.

    PubMed

    Clark, David L; Conradson, Steven D; Donohoe, Robert J; Gordon, Pamela L; Keogh, D Webster; Palmer, Phillip D; Scott, Brian L; Tait, C Drew

    2013-04-01

    Hexavalent neptunium can be solubilized in 0.5-3.5 M aqueous MOH (M = Li(+), Na(+), NMe4(+) = TMA(+)) solutions. Single crystals were obtained from cooling of a dilute solution of Co(NH3)6Cl3 and NpO2(2+) in 3.5 M [N(Me)4]OH to 5 °C. A single-crystal X-ray diffraction study revealed the molecular formula of [Co(NH3)6]2[NpO2(OH)4]3·H2O, isostructural with the uranium analogue. The asymmetric unit contains three distinct NpO2(OH)4(2-) ions, each with pseudooctahedral coordination geometry with trans-oxo ligands. The average Np═O and Np-OH distances were determined to be 1.80(1) and 2.24(1) Å, respectively. EXAFS data and fits at the Np L(III)-edge on solid [Co(NH3)6]2[NpO2(OH)4]3·H2O and aqueous solutions of NpO2(2+) in 2.5 and 3.5 M (TMA)OH revealed bond lengths nearly identical with those determined by X-ray diffraction but with an increase in the number of equatorial ligands with increasing (TMA)OH concentration. Raman spectra of single crystals of [Co(NH3)6]2[NpO2(OH)4]3·H2O reveal a ν1(O═Np═O) symmetric stretch at 741 cm(-1). Raman spectra of NpO2(2+) recorded in a 0.6-2.2 M LiOH solution reveal a single ν1 frequency of 769 cm(-1). Facile exchange of the neptunyl oxo ligands with the water solvent was also observed with Raman spectroscopy performed with (16)O- and (18)O-enriched water solvent. The combination of EXAFS and Raman data suggests that NpO2(OH)4(2-) is the dominant solution species under the conditions of study and that a small amount of a second species, NpO2(OH)5(3-), may also be present at higher alkalinity. Crystal data for [Co(NH3)6]2[NpO2(OH)4]3·H2O: monoclinic, space group C2/c, a = 17.344(4) Å, b = 12.177(3) Å, c = 15.273 Å, β = 120.17(2)°, Z = 4, R1 = 0.0359, wR2 = 0.0729.

  12. Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange

    SciTech Connect

    Kyser, E

    2004-11-18

    A series of laboratory column runs has been performed that demonstrates the recovery of neptunium (Np) containing up to 0.05 M oxalate. Np losses were generally less than one percent to the raffinate for feed solutions that contained 2 to 10 g Np/L. Up to 16 percent Np losses were observed with lower Np feed concentrations, but those losses were attributed to the shortened residence times rather than the higher oxalate to Np ratios. Losses in the plant are expected to be significantly less due to the lower cross-section flowrate possible with existing plant pumps. Elimination of the permanganate treatment of filtrates appears to be reasonable since the amount of Np in those filtrates does not appear to be practical to recover. Combination of untreated filtrates with other actinide rich solutions is not advisable as precipitation problems are likely. If untreated filtrates are kept segregated from other actinide rich streams, the recovery of the remaining Np is probably still possible, but could be limited due to the excessively high oxalate to Np ratio. The persistence of hydrazine/hydrazoic acid in filtrate solutions dictates that the nitrite treatment be retained to eliminate those species from the filtrates prior to transfer to the canyon. Elimination of the permanganate treatment of precipitator flushes and recovery by anion exchange does not appear to be limited by the oxalate effect on anion exchange. Np from solutions with higher oxalate to Np molar ratios than expected in precipitator flushes was recovered with low to modest losses. Solubility problems appear to be unlikely when the moles of oxalate involved are less than the total number of moles of Np due to complexation effects. The presence of significant concentrations of iron (Fe) in the solutions will further decrease the probability of Np oxalate precipitation due the formation of Fe oxalate complexes. Np oxalate solubility data in 8 M HNO{sub 3} with from one to six times as much oxalate as Np have

  13. Computer modelling of the chemical speciation of caesium, uranium(VI) and neptunium(V) in human duodenal fluids under fasting conditions.

    PubMed

    Jones, Paul W; Taylor, David M; Webb, Louise M; Williams, David R

    2002-08-01

    A model simulating the human duodenal contents under physiologically realistic, fasting conditions was developed using the joint expert speciation system (JESS) computer program and database and used to investigate the chemical speciation of caesium, uranium(VI) and neptunium(V). Over the pH range 5.0-9.0, and the concentration range 5 x 10(-15) x 10(-5) mol dm(-3), caesium was predicted to occur predominantly as the absorbable free monovalent cation Cs+ (approximately 95%) with species such as CsHPO4- and CsCl representing the remainder. The presence or absence of sulphate at 2.1 x 10(-3) mol dm(-3) did not influence the predicted speciation. Uranium was predicted to be present entirely as a soluble, highly charged species, both in the absence and in the presence of sulphate. Between pH 5.0 and approximately 6.5 the UO2H2(PO4)2(2-) predominated, above this pH carbonate species, either UO2(CO3)4(6-) or, possibly, UO2(CO3)5(8-). At pH 8.0, and in the presence of sulphate, neptunium(V) was predicted to exist solely as the tetrasulphate species, whilst in the absence of sulphate, an array of negatively charged soluble carbonate species predominated. Studies over the pH range 5.0-9.0 predicted the formation of a spectrum of negatively charged carbonate and phosphate species, approximately 40% of the total neptunium was predicted to be present as the electrically net-neutral species NpO2HCO3 at pH6.0, approximately 20% at pH 7.0, approximately 10% at pH 7.5 and approximately 1% at pH 8.0. The observed speciation patterns of uranium and neptunium did not change over the concentration range 5 x 10(-15) - 5 x 10(-5) mol dm(-3) and no solid species were predicted to occur under the conditions simulated. Whether the predicted electrically net-neutral neptunium species or the uranium pentacarbonate species do actually occur under true physiological conditions remains to be established. The observed speciation patterns for caesium and uranium are consistent with the observed

  14. ESTIMATED NEPTUNIUM SEDIMENT SORPTION VALUES AS A FUNCTION OF PH AND MEASURED BARIUM AND RADIUM KD VALUES

    SciTech Connect

    Kaplan, D.

    2011-01-13

    The objective of this document is to provide traceability and justification for a select few new geochemical data used in the Special Analysis entitled 'Special Analysis for the Dose Assessment of the Final Inventories in Center Slit Trenches One through Five'. Most values used in the Special Analysis came from the traditional geochemical data package, however, some recent laboratory measurements have made it possible to estimate barium K{sub d} values. Additionally, some recent calculations were made to estimate neptunium K{sub d} values as a function of pH. The assumptions, justifications, and calculations needed to generate these new values are presented in this document, and the values are summarized.

  15. Subcellular localization of neptunium-237 in lung and kidney after intratracheal administration in the rat: An ultrastructural and microanalytical study

    SciTech Connect

    Boulahdour, H.; Berry, J.P.; Galle, P.; Poncy, J.L.

    1996-12-01

    Chronic intratacheal administration of {sup 237}Np to rats was performed during 6 weeks. The total dose administered was 45.8 kBq. Two methods, electron microscopy and electron probe X-ray microanalysis, were used to determined the intracellular sites of localization of {sup 237}Np. Clusters of dense granules were observed in nuclei of pneumocytes and proximal tubular cells of the kidneys. These clusters have been shown to contain neptunium associated with phosphorus, sulfur and calcium. Alternations of nuclei and ultrastructural cytoplasmic lesions were observed. The absorbed doses in lungs and kidneys were very low. These results suggest that the chemical toxicity of {sup 237}Np is more important than its radiological toxicity. 30 refs., 2 figs.

  16. A theoretical study of the structures and chemical bonds of neptunium (III) molecules by a density functional method

    NASA Astrophysics Data System (ADS)

    Yin, Yao-Peng; Dong, Chen-Zhong; Du, Lei-Qiang; Wu, Fang-Xian; Ding, Xiao-Bin

    2014-10-01

    In this paper, equilibrium structures and chemical bond characteristics of neptunium trihalide molecules NpX3 (X = F, Cl, Br and I) have been investigated by using density functional theory (DFT). The influences of the size of the relativistic effective core potential (RECP) have been examined on the molecular structures. The chemical bond characteristics have also been systematically studied by calculating the density of states (DOS), bond length differences and electronic charge distributions. We have determined that the chemical bonds are mainly ionic in those molecules, and the covalency is enhancing while ionicity decreases from NpF3 to NpI3. The calculated bond energies show that the interaction strength in NpX3 molecules becomes weaker as the halogen atoms becoming heavier.

  17. Subcellular localization of neptunium-237 in lung and kidney after intratracheal administration in the rat: an ultrastructural and microanalytical study.

    PubMed

    Boulahdour, H; Poncy, J L; Berry, J P; Galle, P

    1996-12-01

    Chronic intratracheal administration of 237Np to rate was performed during 6 weeks. The total dose administered was 45.8 kBq. Two methods, electron microscopy and electron probe X-ray microanalysis, were used to determine the intracellular sites of localization of 237Np. Clusters of dense granules were observed in nuclei of pneumocytes and proximal tubular cells of the kidneys. These clusters have been shown to contain neptunium associated with phosphorus, sulfur and calcium. Alterations of nuclei and ultrastructural cytoplasmic lesions were observed. The absorbed doses in lungs and kidneys were very low. These results suggest that the chemical toxicity of 237Np is more important than its radiological toxicity.

  18. Formation of neptunium(IV)-silica colloids at near-neutral and slightly alkaline pH.

    PubMed

    Husar, Richard; Weiss, Stephan; Hennig, Christoph; Hübner, René; Ikeda-Ohno, Atsushi; Zänker, Harald

    2015-01-01

    The reducing conditions in a nuclear waste repository render neptunium tetravalent. Thus, Np is often assumed to be immobile in the subsurface. However, tetravalent actinides can also become mobile if they occur as colloids. We show that Np(IV) is able to form silica-rich colloids in solutions containing silicic acid at concentrations of both the regions above and below the "mononuclear wall" of silicic acid at 2 × 10(-3) M (where silicic acid is expected to start polymerization). These Np(IV)-silica colloids have a size of only very few nanometers and can reach significantly higher concentrations than Np(IV) oxyhydroxide colloids. They can be stable in the waterborne form over longer spans of time. In the Np(IV)-silica colloids, the actinide--oxygen--actinide bonds are increasingly replaced by actinide--oxygen--silicon bonds due to structural incorporation of Si. Possible implications of the formation of such colloids for environmental scenarios are discussed.

  19. X-Ray photoelectron spectroscopy study of radiofrequency-sputtered titanium, carbide, molybdenum carbide, and titanium boride coatings and their friction properties

    NASA Technical Reports Server (NTRS)

    Brainard, W. A.; Wheeler, D. R.

    1977-01-01

    Radiofrequency sputtered coatings of titanium carbide, molybdenum carbide and titanium boride were tested as wear resistant coatings on stainless steel in a pin on disk apparatus. X-ray photoelectron spectroscopy (XPS) was used to analyze the sputtered films with regard to both bulk and interface composition in order to obtain maximum film performance. Significant improvements in friction behavior were obtained when properly biased films were deposited on deliberately preoxidized substrates. XPS depth profile data showed thick graded interfaces for bias deposited films even when adherence was poor. The addition of 10 percent hydrogen to the sputtering gas produced coatings with thin poorly adherent interfaces. Results suggest that some of the common practices in the field of sputtering may be detrimental to achieving maximum adherence and optimum composition for these refractory compounds.

  20. Low-cost industrially available molybdenum boride and carbide as "platinum-like" catalysts for the hydrogen evolution reaction in biphasic liquid systems.

    PubMed

    Scanlon, Micheál D; Bian, Xiaojun; Vrubel, Heron; Amstutz, Véronique; Schenk, Kurt; Hu, Xile; Liu, BaoHong; Girault, Hubert H

    2013-02-28

    Rarely reported low-cost molybdenum boride and carbide microparticles, both of which are available in abundant quantities due to their widespread use in industry, adsorb at aqueous acid-1,2-dichloroethane interfaces and efficiently catalyse the hydrogen evolution reaction in the presence of the organic electron donor - decamethylferrocene. Kinetic studies monitoring biphasic reactions by UV/vis spectroscopy, and further evidence provided by gas chromatography, highlight (a) their superior rates of catalysis relative to other industrially significant transition metal carbides and silicides, as well as a main group refractory compound, and (b) their highly comparable rates of catalysis to Pt microparticles of similar dimensions. Insight into the catalytic processes occurring for each adsorbed microparticle was obtained by voltammetry at the liquid-liquid interface.

  1. Titanium boride formation and its subsequent influence on morphology and crystallography of alpha precipitates in titanium alloys

    NASA Astrophysics Data System (ADS)

    Nandwana, Peeyush

    faults has been explained by calculating the interfacial energy of B27/Bf interfaces along with stacking fault formation energy. The boride precipitates have also been shown to modify the morphology of alpha phase from lath like to more equiaxed like. However, the influence of TiB on the crystallography of alpha precipitation has not been explored in great detail. The present study will clearly demonstrate, for the first time, the influence of various alloying elements present in the titanium alloy, on the resulting effect of B addition on alpha morphology and its crystallography in Ti alloys. Thus, the influence of B addition on alpha precipitation in two classes of commercial Ti alloys, i.e. beta alloys and alpha + beta alloys have been explored. It has been found that TiB nucleated alpha can either become equiaxed by a loss of Burgers orientation relationship (OR) with beta or can retain the lath morphology in case of alloys containing a combination of Ti, Al and Mo.

  2. Metallic Borides, La2Re3B7 and La3Re2B5, Featuring Extensive Boron-Boron Bonding.

    PubMed

    Bugaris, Daniel E; Malliakas, Christos D; Chung, Duck Young; Kanatzidis, Mercouri G

    2016-02-15

    La2Re3B7 and La3Re2B5 have been synthesized in single-crystalline form from a molten La/Ni eutectic at 1000 °C in the first example of the flux crystal growth of ternary rare-earth rhenium borides. Both compounds crystallize in their own orthorhombic structure types, with La2Re3B7 (space group Pcca) having lattice parameters a = 7.657(2) Å, b = 6.755(1) Å, and c = 11.617(2) Å, and La3Re2B5 (space group Pmma) having lattice parameters a = 10.809(2) Å, b = 5.287(1) Å, and c = 5.747(1) Å. The compounds possess three-dimensional framework structures that are built up from rhenium boride polyhedra and boron-boron bonding. La3Re2B5 features fairly common B2 dumbbells, whereas La2Re3B7 has unique one-dimensional subunits composed of alternating triangular B3 and trans-B4 zigzag chain fragments. Also observed in La3Re2B5 is an unusual coordination of B by an octahedron of La atoms. Electronic band structure calculations predict that La2Re3B7 is a semimetal, which is observed in the electrical resistivity data as measured on single crystals, with behavior obeying the Bloch-Grüneisen model and a room-temperature resistivity ρ300 K of ∼375 μΩ cm. The electronic band structure calculations also suggest that La3Re2B5 is a regular metal. PMID:26812202

  3. Pressed boride cathodes

    NASA Technical Reports Server (NTRS)

    Wolski, W.

    1985-01-01

    Results of experimental studies of emission cathodes made from lanthanum, yttrium, and gadolinium hexaborides are presented. Maximum thermal emission was obtained from lanthanum hexaboride electrodes. The hexaboride cathodes operated stably under conditions of large current density power draw, at high voltages and poor vacuum. A microtron electron gun with a lanthanum hexaboride cathode is described.

  4. Synthesis of bimetallic uranium and neptunium complexes of a binucleating macrocycle and determination of the solid-state structure by magnetic analysis.

    PubMed

    Arnold, Polly L; Potter, Natalie A; Magnani, Nicola; Apostolidis, Christos; Griveau, Jean-Christophe; Colineau, Eric; Morgenstern, Alfred; Caciuffo, Roberto; Love, Jason B

    2010-06-21

    Syntheses of the bimetallic uranium(III) and neptunium(III) complexes [(UI)(2)(L)], [(NpI)(2)(L)], and [{U(BH(4))}(2)(L)] of the Schiff-base pyrrole macrocycles L are described. In the absence of single-crystal structural data, fitting of the variable-temperature solid-state magnetic data allows the prediction of polymeric structures for these compounds in the solid state.

  5. Critical role of water content in the formation and reactivity of uranium, neptunium, and plutonium iodates under hydrothermal conditions: implications for the oxidative dissolution of spent nuclear fuel.

    PubMed

    Bray, Travis H; Ling, Jie; Choi, Eun Sang; Brooks, James S; Beitz, James V; Sykora, Richard E; Haire, Richard G; Stanbury, David M; Albrecht-Schmitt, Thomas E

    2007-04-30

    The reactions of 237NpO2 with excess iodate under acidic hydrothermal conditions result in the isolation of the neptunium(IV), neptunium(V), and neptunium(VI) iodates, Np(IO3)4, Np(IO3)4.nH2O.nHIO3, NpO2(IO3), NpO2(IO3)2(H2O), and NpO2(IO3)2.H2O, depending on both the pH and the amount of water present in the reactions. Reactions with less water and lower pH favor reduced products. Although the initial redox processes involved in the reactions between 237NpO2 or 242PuO2 and iodate are similar, the low solubility of Pu(IO3)4 dominates product formation in plutonium iodate reactions to a much greater extent than does Np(IO3)4 in the neptunium iodate system. UO2 reacts with iodate under these conditions to yield uranium(VI) iodates solely. The isotypic structures of the actinide(IV) iodates, An(IO3)4 (An=Np, Pu), are reported and consist of one-dimensional chains of dodecahedral An(IV) cations bridged by iodate anions. The structure of Np(IO3)4.nH2O.nHIO3 is constructed from NpO9 tricapped-trigonal prisms that are bridged by iodate into a polar three-dimensional framework structure. Second-harmonic-generation measurements on a polycrystalline sample of the Th analogue of Np(IO3)4.nH2O.nHIO3 reveal a response of approximately 12x that of alpha-SiO2. Single-crystal magnetic susceptibility measurements of Np(IO3)4 show magnetically isolated Np(IV) ions.

  6. Incorporation of neptunium(V) and iodate into a uranyl phosphate: implications for mitigating the release of 237Np and 129I in repositories.

    PubMed

    Wu, Shijun; Chen, Fanrong; Simonetti, Antonio; Albrecht-Schmitt, Thomas E

    2010-04-15

    The simultaneous incorporation of IO3(-) and NpO2+ into Ba3(UO2)2(HPO4)2(PO4)2 (BaUP), which serves as a model for uranyl alteration phases, was investigated. LA-ICP-MS data demonstrate that the incorporation of both of these species is significantly enhanced when they are present together. The most probable explanation is that charge balance is obtained by the coupled substitutions of NpO2+ <--> UO2(2+) and IO3(-) <--> HPO4(2-). According to the LA-ICP-MS results, in the absence of iodate as much as 2.91 +/- 0.14 to 3.44 +/- 0.25% of the uranium in BaUP can be replaced by neptunium. When iodate is present in the reaction, the amount of uranium substitution by neptunium increases to 6.05 +/- 0.65% to 7.93 +/- 0.83%. The net increase for neptunium is 116 +/- 0.30% to 225 +/- 0.25%. Similarly, in the absence of NpO2+, iodate incorporation into BaUP reaches an I/U level of 0.0021 +/- 0.0004 to 0.0038 +/- 0.0005; whereas in its presence there is an increase to as much as 100 +/- 0.11% to 0.0042 +/- 0.0008.

  7. High-throughput sequential injection method for simultaneous determination of plutonium and neptunium in environmental solids using macroporous anion-exchange chromatography, followed by inductively coupled plasma mass spectrometric detection.

    PubMed

    Qiao, Jixin; Hou, Xiaolin; Roos, Per; Miró, Manuel

    2011-01-01

    This paper reports an automated analytical method for rapid and simultaneous determination of plutonium and neptunium in soil, sediment, and seaweed, with detection via inductively coupled plasma mass spectrometry (ICP-MS). A chromatographic column packed with a macroporous anion exchanger (AG MP-1 M) was incorporated in a sequential injection (SI) system for the efficient retrieval of plutonium, along with neptunium, from matrix elements and potential interfering nuclides. The sorption and elution behavior of plutonium and neptunium onto AG MP-1 M resin was compared with a commonly utilized AG 1-gel-type anion exchanger. Experimental results reveal that the pore structure of the anion exchanger plays a pivotal role in ensuring similar separation behavior of plutonium and neptunium along the separation protocol. It is proven that plutonium-242 ((242)Pu) performs well as a tracer for monitoring the chemical yield of neptunium when using AG MP-1 M resin, whereby the difficulties in obtaining a reliable and practicable isotopic neptunium tracer are overcome. An important asset of the SI setup is the feasibility of processing up to 100 g of solid substrates using a small-sized (ca. 2 mL) column with chemical yields of neptunium and plutonium being ≥79%. Analytical results of three certified/standard reference materials and two solid samples from intercomparison exercises are in good agreement with the reference values at the 0.05 significance level. The overall on-column separation can be completed within 3.5 h for 10 g of soil samples. Most importantly, the anion-exchange mini-column suffices to be reused up to 10-fold with satisfactory chemical yields (>70%), as demanded in environmental monitoring and emergency scenarios, making the proposed automated assembly well-suited for unattended and high-throughput analysis.

  8. The electronic structure, mechanical and thermodynamic properties of Mo{sub 2}XB{sub 2} and MoX{sub 2}B{sub 4} (X = Fe, Co, Ni) ternary borides

    SciTech Connect

    He, TianWei; Jiang, YeHua E-mail: jfeng@seas.harvard.edu; Zhou, Rong; Feng, Jing E-mail: jfeng@seas.harvard.edu

    2015-08-21

    The mechanical properties, electronic structure and thermodynamic properties of the Mo{sub 2}XB{sub 2} and MoX{sub 2}B{sub 4} (X = Fe, Co, Ni) ternary borides were calculated by first-principles methods. The elastic constants show that these ternary borides are mechanically stable. Formation enthalpy of Mo{sub 2}XB{sub 2} and MoX{sub 2}B{sub 4} (X = Fe, Co, Ni) ternary borides are at the range of −118.09 kJ/mol to −40.14 kJ/mol. The electronic structures and chemical bonding characteristics are analyzed by the density of states. Mo{sub 2}FeB{sub 2} has the largest shear and Young's modulus because of its strong chemical bonding, and the values are 204.3 GPa and 500.3 GPa, respectively. MoCo{sub 2}B{sub 4} shows the lowest degree of anisotropy due to the lack of strong direction in the bonding. The Debye temperature of MoFe{sub 2}B{sub 4} is the largest among the six phases, which means that MoFe{sub 2}B{sub 4} possesses the best thermal conductivity. Enthalpy shows an approximately linear function of the temperature above 300 K. The entropy of these compounds increase rapidly when the temperature is below 450 K. The Gibbs free energy decreases with the increase in temperature. MoCo{sub 2}B{sub 4} has the lowest Gibbs free energy, which indicates the strongest formation ability in Mo{sub 2}XB{sub 2} and MoX{sub 2}B{sub 4} (X = Fe, Co, Ni) ternary borides.

  9. Laboratory And Lysimeter Experimentation And Transport Modeling Of Neptunium And Strontium In Savannah River Site Sediments

    SciTech Connect

    Kaplan, Daniel I.; Powell, B. A.; Miller, Todd J.

    2012-09-24

    The Savannah River Site (SRS) conducts performance assessment (PA) calculations to determine the appropriate amount of low-level radiological waste that can be safely disposed on site. Parameters are included in these calculations that account for the interaction between the immobile solid phase and the mobile aqueous phase. These parameters are either the distribution coefficient (K{sub d} value) or the apparent solubility value (K{sub sp}). These parameters are readily found in the literature and are used throughout the DOE complex. One shortcoming of K{sub d} values is that they are only applicable to a given set of solid and aqueous phase conditions. Therefore, a given radionuclide may have several K{sub d} values as it moves between formations and comes into contact with different solids and different aqueous phases. It is expected that the K{sub d} construct will be appropriate to use for a majority of the PA and for a majority of the radionuclides. However, semi-mechanistic models would be more representative in isolated cases where the chemistry is especially transitory or the radionuclide chemistry is especially complex, bringing to bear multiple species of varying sorption tendencies to the sediment. Semi-mechanistic models explicitly accommodate the dependency of K{sub d} values, or other sorption parameters, on contaminant concentration, competing ion concentrations, pH-dependent surface charge on the adsorbent, and solute species distribution. Incorporating semi-mechanistic concepts into geochemical models is desirable to make the models more robust and technically defensible. Furthermore, these alternative models could be used to augment or validate a Kd?based DOE Order 435.1 Performance Assessment. The objectives of this study were to: 1) develop a quantitative thermodynamically-based model for neptunium sorption to SRS sediments, and 2) determine a sorption constant from an SRS 11-year lysimeter study. The modeling studies were conducted with

  10. Verifying the Presence of Low Levels of Neptunium in a Uranium Matrix with Electron Energy-Loss Spectroscopy

    SciTech Connect

    Buck, Edgar C.; Douglas, Matthew; Wittman, Richard S.

    2010-01-01

    This paper examines the problems associated with the analysis of low levels of neptunium (Np) in a uranium (U) matrix with electron energy-loss spectroscopy (EELS) on the transmission electron microscope (TEM). The detection of Np in a matrix of uranium (U) can be impeded by the occurrence of a plural scattering event from U (U-M5 + U-O4,5) that results in severe overlap on the Np-M5 edge at 3665 eV. Low levels (1600 - 6300 ppm) of Np can be detected in U solids by confirming the energy gap between the Np-M5 and Np-M4 edges is at 184 eV and showing that the M4/M5 ratio for the Np is smaller than that for U. The Richardson-Lucy deconvolution method was applied to energy-loss spectral images and was shown to increase the signal to noise. This method also improves the limits of detection for Np in a U matrix.

  11. Potential for radionuclide immobilization in the EBS/NFE: solubility limiting phases for neptunium, plutonium, and uranium

    SciTech Connect

    Rard, J. A., LLNL

    1997-10-01

    Retardation and dispersion in the far field of radionuclides released from the engineered barrier system/near field environment (EBS/NFE) may not be sufficient to prevent regulatory limits being exceeded at the accessible environment. Hence, a greater emphasis must be placed on retardation and/or immobilization of radionuclides in the EBS/NFE. The present document represents a survey of radionuclide-bearing solid phases that could potentially form in the EBS/NFE and immobilize radionuclides released from the waste package and significantly reduce the source term. A detailed literature search was undertaken for experimental solubilities of the oxides, hydroxides, and various salts of neptunium, plutonium, and uranium in aqueous solutions as functions of pH, temperature, and the concentrations of added electrolytes. Numerous solubility studies and reviews were identified and copies of most of the articles were acquired. However, this project was only two months in duration, and copies of some the identified solubility studies could not be obtained at short notice. The results of this survey are intended to be used to assess whether a more detailed study of identified low- solubility phase(s) is warranted, and not as a data base suitable for predicting radionuclide solubility. The results of this survey may also prove useful in a preliminary evaluation of the efficacy of incorporating chemical additives to the EBS/NFE that will enhance radionuclide immobilization.

  12. Stability and crystal chemistry of the ternary borides M2(Ni21-xMx)B6 (M tbnd Ti, Zr, Hf)

    NASA Astrophysics Data System (ADS)

    Artini, C.; Provino, A.; Valenza, F.; Pani, M.; Cacciamani, G.

    2016-01-01

    A crystallochemical study was undertaken to investigate the structural stability and the compositional extent of the ternary borides M2(Ni21-xMx)B6 (M tbnd Ti, Zr, Hf). This phase often occurs during the production of MB2 joints by means of Ni-B brazing alloys. Samples with the nominal compositions M2Ni21B6 and M3Ni20B6 were synthesized by arc melting and characterized by optical and electron microscopy, and X-ray diffraction. Crystal structure refinements were performed by the Rietveld method. The compositional boundaries of the ternary phases were experimentally determined and found strictly related to the M/Ni size ratio. The stability of this structure is mainly determined by the capability of the structure to expand under the effect of the Ni substitution by the M atom. The CALPHAD modeling of the three M-Ni-B ternary systems in the Ni-rich corner of the phase diagram, performed on the basis of the obtained structural data, shows a good agreement with experimental results.

  13. Microstructural Characterization and Wear Behavior of Nano-Boride Dispersed Coating on AISI 304 Stainless Steel by Hybrid High Velocity Oxy-Fuel Spraying Laser Surface Melting

    NASA Astrophysics Data System (ADS)

    Sharma, Prashant; Majumdar, Jyotsna Dutta

    2015-07-01

    The current study concerns the detailed microstructural characterization and investigation of wear behavior of nano-boride dispersed coating developed on AISI 304 stainless steel by high velocity oxy-fuel spray deposition of nickel-based alloy and subsequent laser melting. There is a significant refinement and homogenization of microstructure with improvement in microhardness due to laser surface melting (1200 VHN as compared to 945 VHN of as-sprayed and 250 VHN of as-received substrate). The high temperature phase stability of the as-coated and laser melted surface has been studied by differential scanning calorimeter followed by detailed phase analysis at room and elevated temperature. There is a significant improvement in wear resistance of laser melted surface as compared to as-sprayed and the as-received one due to increased hardness and reduced coefficient of friction. The mechanism of wear has been investigated in details. Corrosion resistance of the coating in a 3.56 wt pct NaCl solution is significantly improved (4.43 E-2 mm/year as compared to 5 E-1 mm/year of as-sprayed and 1.66 mm/year of as-received substrate) due to laser surface melting as compared to as-sprayed surface.

  14. Critical Role of Water Content in the Formation and Reactivity of Uraniu, Neptunium, and Plutonium Iodates Under Hydrothermal Conditions: Implications for the Oxidative Dissolution of Spent Nuclear Fuel

    SciTech Connect

    Bray, T. H.; Ling, Jie; Choi, E- Sang; Brooks, James S.; Beitz, James V.; Sykora, Richard E.; Haire, Richard {Dick} G; Stanbury, David M.; Albrecht-Schmitt, Thomas E.

    2007-01-01

    The reactions of {sup 237}NpO{sub 2} with excess iodate under acidic hydrothermal conditions result in the isolation of the neptunium(IV), neptunium(V), and neptunium(VI) iodates, Np(IO{sub 3}){sub 4}, Np(IO{sub 3}){sub 4}{center_dot}nH{sub 2}O{center_dot}nHIO{sub 3}, NpO2(IO3), NpO2(IO3)2(H2O), and NpO{sub 2}(IO{sub 3}){sub 2}{center_dot}H{sub 2}O, depending on both the pH and the amount of water present in the reactions. Reactions with less water and lower pH favor reduced products. Although the initial redox processes involved in the reactions between {sup 237}NpO{sub 2} or {sup 242}PuO{sub 2} and iodate are similar, the low solubility of Pu(IO{sub 3}){sub 4} dominates product formation in plutonium iodate reactions to a much greater extent than does Np(IO{sub 3}){sub 4} in the neptunium iodate system. UO{sub 2} reacts with iodate under these conditions to yield uranium(VI) iodates solely. The isotypic structures of the actinide(IV) iodates, An(IO{sub 3}){sub 4} (An = Np, Pu), are reported and consist of one-dimensional chains of dodecahedral An(IV) cations bridged by iodate anions. The structure of Np(IO3)4{center_dot}nH2O{center_dot}nHIO3 is constructed from NpO9 tricapped-trigonal prisms that are bridged by iodate into a polar three-dimensional framework structure. Second-harmonic-generation measurements on a polycrystalline sample of the Th analogue of Np(IO{sub 3}){sub 4}{center_dot}nH{sub 2}O{center_dot}nHIO{sub 3} reveal a response of approximately 12x that of {alpha}-SiO{sub 2}. Single-crystal magnetic susceptibility measurements of Np(IO{sub 3}){sub 4} show magnetically isolated Np(IV) ions.

  15. Sequential injection approach for simultaneous determination of ultratrace plutonium and neptunium in urine with accelerator mass spectrometry.

    PubMed

    Qiao, Jixin; Hou, Xiaolin; Roos, Per; Lachner, Johannes; Christl, Marcus; Xu, Yihong

    2013-09-17

    An analytical method was developed for simultaneous determination of ultratrace level plutonium (Pu) and neptunium (Np) using iron hydroxide coprecipitation in combination with automated sequential injection extraction chromatography separation and accelerator mass spectrometry (AMS) measurement. Several experimental parameters affecting the analytical performance were investigated and compared including sample preboiling operation, aging time, amount of coprecipitating reagent, reagent for pH adjustment, sedimentation time, and organic matter decomposition approach. The overall analytical results show that preboiling and aging are important for obtaining high chemical yields for both Pu and Np, which is possibly related to the aggregation and adsorption behavior of organic substances contained in urine. Although the optimal condition for Np and Pu simultaneous determination requires 5-day aging time, an immediate coprecipitation without preboiling and aging could also provide fairly satisfactory chemical yields for both Np and Pu (50-60%) with high sample throughput (4 h/sample). Within the developed method, (242)Pu was exploited as chemical yield tracer for both Pu and Np isotopes. (242)Pu was also used as a spike in the AMS measurement for quantification of (239)Pu and (237)Np concentrations. The results show that, under the optimal experimental condition, the chemical yields of (237)Np and (242)Pu are nearly identical, indicating the high feasibility of (242)Pu as a nonisotopic tracer for (237)Np determination in real urine samples. The analytical method was validated by analysis of a number of urine samples spiked with different levels of (237)Np and (239)Pu. The measured values of (237)Np and (239)Pu by AMS exhibit good agreement (R(2) ≥ 0.955) with the spiked ones confirming the reliability of the proposed method.

  16. INCORPORATION OF PENTAVALENT NEPTUNIUM INTO URANYL PHASES THAT MAY FORM AS ALTERATION PRODUCTS OF SPENT NUCLEAR FUEL

    SciTech Connect

    NA

    2005-06-21

    Laboratory-scale simulations and studies of natural analogues have shown that alteration of spent nuclear fuel in a moist, oxidizing environment results in the formation of a variety of uranyl phases. Neptunium-237 has a half-life of 2.14 million years, and the pentavalent oxidation state is soluble in groundwater. Release of Np-237 from spent nuclear fuel in a geological repository may significantly impact the long-term performance of such a repository. Incorporation of Np, in the pentavalent oxidation state, into uranyl phases by substitution for hexavalent U is likely because of the similarity of the coordination environments of these two cations, but a charge-balance mechanism is required for substitution. A preliminary study has shown incorporation of pentavalent Np into powders of the uranyl silicate uranophane, and Na-compreignacite, a uranyl oxyhydrate [1]. Using synthesis experiments under mild hydrothermal conditions, we are examining the incorporation of pentavalent Np into selected uranyl oxyhydrates and silicates as a function of temperature and the pH of the mother solution. Analyses of powders of these uranyl phases has demonstrated both temperature and pH dependences for incorporation. Experiments are underway directed at the synthesis of single crystals of uranyl phases in the presence of 500-750 ppm pentavalent Np. The intent is to develop a basic understanding of the crystallographic and crystal chemical factors that impact incorporation of pentavalent Np into uranyl phases. Following synthesis, crystals are analyzed for Np using laser ablation ICP-MS. Preliminary results for Na-substituted metaschoepite indicate significant Np has been incorporated into the crystals. Additional phases under study include compreignacite, becquerelite, soddyite, zippeite, and (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4}.

  17. History of ``NANO''-Scale VERY EARLY Solid-State (and Liquid-State) Physics/Chemistry/Metallurgy/ Ceramics; Interstitial-Alloys Carbides/Nitrides/Borides/...Powders and Cermets, Rock Shocks, ...

    NASA Astrophysics Data System (ADS)

    Maiden, Colin; Siegel, Edward

    History of ``NANO'': Siegel-Matsubara-Vest-Gregson[Mtls. Sci. and Eng. 8, 6, 323(`71); Physica Status Solidi (a)11,45(`72)] VERY EARLY carbides/nitrides/borides powders/cermets solid-state physics/chemistry/metallurgy/ ceramics FIRST-EVER EXPERIMENTAL NANO-physics/chemistry[1968 ->Physica Status Solidi (a)11,45(`72); and EARLY NANO-``physics''/NANO-``chemistry'' THEORY(after: Kubo(`62)-Matsubara(`60s-`70s)-Fulde (`65) [ref.: Sugano[Microcluster-Physics, Springer('82 `98)

  18. Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

    SciTech Connect

    Bykova, E.; Gou, H.; Bykov, M.; Hanfland, M.; Dubrovinsky, L.; Dubrovinskaia, N.

    2015-10-15

    We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for high bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.

  19. New ternary tantalum borides containing boron dumbbells: Experimental and theoretical studies of Ta2OsB2 and TaRuB

    NASA Astrophysics Data System (ADS)

    Mbarki, Mohammed; Touzani, Rachid St.; Rehorn, Christian W. G.; Gladisch, Fabian C.; Fokwa, Boniface P. T.

    2016-10-01

    The new ternary transition metal-rich borides Ta2OsB2 and TaRuB have been successfully synthesized by arc-melting the elements in a water-cooled crucible under an argon atmosphere. The crystal structures of both compounds were solved by single-crystal X-ray diffraction and their metal compositions were confirmed by EDX analysis. It was found that Ta2OsB2 and TaRuB crystallize in the tetragonal Nb2OsB2 (space group P4/mnc, no. 128) and the orthorhombic NbRuB (space group Pmma, no. 51) structure types with lattice parameters a=5.878(2) Å, c=6.857(2) Å and a=10.806(2) Å, b=3.196(1) Å, c=6.312(2) Å, respectively. Furthermore, crystallographic, electronic and bonding characteristics have been studied by density functional theory (DFT). Electronic structure relaxation has confirmed the crystallographic parameters while COHP bonding analysis indicates that B2-dummbells are the strongest bonds in both compounds. Moreover, the formation of osmium dumbbells in Ta2OsB2 through a Peierls distortion along the c-axis, is found to be the origin of superstructure formation. Magnetic susceptibility measurements reveal that the two phases are Pauli paramagnets, thus confirming the theoretical DOS prediction of metallic character. Also hints of superconductivity are found in the two phases, however lack of single phase samples has prevented confirmation. Furthermore, the thermodynamic stability of the two modifications of AMB (A=Nb, Ta; M =Ru, Os) are studied using DFT, as new possible phases containing either B4- or B2-units are predicted, the former being the most thermodynamically stable modification.

  20. Ternary borides Nb7Fe3B8 and Ta7Fe3B8 with Kagome-type iron framework.

    PubMed

    Zheng, Qiang; Gumeniuk, Roman; Borrmann, Horst; Schnelle, Walter; Tsirlin, Alexander A; Rosner, Helge; Burkhardt, Ulrich; Reissner, Michael; Grin, Yuri; Leithe-Jasper, Andreas

    2016-06-21

    Two new ternary borides TM7Fe3B8 (TM = Nb, Ta) were synthesized by high-temperature thermal treatment of samples obtained by arc-melting. This new type of structure with space group P6/mmm, comprises TM slabs containing isolated planar hexagonal [B6] rings and iron centered TM columns in a Kagome type of arrangement. Chemical bonding analysis in Nb7Fe3B8 by means of the electron localizability approach reveals two-center interactions forming the Kagome net of Fe and embedded B, while weaker multicenter bonding present between this net and Nb atoms. Magnetic susceptibility measurements reveal antiferromagnetic order below TN = 240 K for Nb7Fe3B8 and TN = 265 K for Ta7Fe3B8. Small remnant magnetization below 0.01μB per f.u. is observed in the antiferromagnetic state. The bulk nature of the magnetic transistions was confirmed by the hyperfine splitting of the Mössbauer spectra, the sizable anomalies in the specific heat capacity, and the kinks in the resistivity curves. The high-field paramagnetic susceptibilities fitted by the Curie-Weiss law show effective paramagnetic moments μeff≈ 3.1μB/Fe in both compounds. The temperature dependence of the electrical resistivity also reveals metallic character of both compounds. Density functional calculations corroborate the metallic behaviour of both compounds and demonstrate the formation of a sizable local magnetic moment on the Fe-sites. They indicate the presence of both antiferro- and ferrromagnetic interactions.

  1. Comment on “Hydrolysis of neptunium(V) at variable temperatures (10 85 °C)” by L. Rao, T.G. Srinivasan, A.Yu. Garnov, P. Zanonato, P. Di Bernardo, and A. Bismondo

    NASA Astrophysics Data System (ADS)

    Neck, V.

    2006-09-01

    In a recent study [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830.] the hydrolysis of Np(V) was investigated at 10-85 °C by absorption spectroscopy, potentiometry, and microcalorimetry along the titration of Np(V) solutions with tetramethylammonium hydroxide up to pH 10. However, there is strong evidence that the precautions to avoid competing reactions with carbonate were not sufficient and that the measured effects are not caused by the formation of Np(V) hydroxide complexes but primarily by the formation of Np(V) carbonate complexes. The reported equilibrium constants, enthalpies, entropies, and heat capacities for the complexes NpO 2OH(aq) and NpO(OH)2- are severely in error and must not be used for the geochemical modeling of neptunium. If the hydrolysis constants reported by Rao et al. [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830] are used to calculate neptunium solubilities in alkaline solutions relevant for nuclear waste repositories, the Np(V) concentrations are overestimated by orders of magnitude.

  2. Complex formation of neptunium(V) with 4-hydroxy-3-methoxybenzoic acid studied by time-resolved laser-induced fluorescence spectroscopy with ultra-short laser pulses.

    PubMed

    Vulpius, D; Geipel, G; Baraniak, L; Bernhard, G

    2006-03-01

    The complex formation of neptunium(V) with 4-hydroxy-3-methoxybenzoic acid (vanillic acid) was studied by time-resolved laser-induced fluorescence spectroscopy with ultra-short laser pulses using the fluorescence properties of 4-hydroxy-3-methoxybenzoic acid. A 2:1 complex of neptunium(V) with 4-hydroxy-3-methoxybenzoic acid was found. The stability constant of this complex was determined to be logbeta(210) = 7.33 +/- 0.10 at an ionic strength of 0.1 mol/l (NaClO(4)) and at 21 degrees C. The determination of the stability constant required an investigation of the excited-state proton transfer of 4-hydroxy-3-methoxybenzoic acid over the whole pH range. It was realized that 4-hydroxy-3-methoxybenzoic acid undergoes excited-state reactions only at pH values below 5. At pH values above 5 stability constants can be determined without kinetic calculation of the proton transfer.

  3. Effects of fasting and/or oxidizing and reducing agents on absorption of neptunium from the gastrointestinal tract of mice and adult or neonatal rats.

    PubMed

    Sullivan, M F; Ruemmler, P S; Ryan, J L

    1984-12-01

    Neptunium-237(V) nitrate was administered by gavage to groups of fed or fasted adult and 5-day-old rats. Some groups also received the oxidants quinhydrone or ferric iron, and others received the reducing agent ferrous iron. Adult mice received ferric or ferrous iron and 235Np. When the adult rats were killed at 7 days after gavage, measurements showed that, compared with rats that were fed, a 24-hr fast caused a fivefold increase in 237Np absorption and retention. Both quinhydrone and ferric iron caused an even greater increase in absorption in both fed and fasted rats. Ferrous iron, on the other hand, decreased absorption in fasted rats to values lower than those obtained in fed rats. Similar results were obtained in mice treated with 235Np and either ferric or ferrous iron. The highest absorption obtained after gavage of ferric iron to fasted rats and mice was about two orders of magnitude higher than the value obtained in animals that were fed before gavage. The effects of ferric and ferrous iron on neptunium absorption by neonatal rats were similar to their effects on adult animals but of lesser magnitude. These results are consistent with the hypothesis that Np(V), when given in small mass quantities to fed animals, is reduced in the gastrointestinal tract to Np(IV), which is less well absorbed than Np(V).

  4. Atomic site preferences and its effect on magnetic structure in the intermetallic borides M2Fe(Ru0.8T0.2)5B2 (M=Sc, Ti, Zr; T=Ru, Rh, Ir)

    NASA Astrophysics Data System (ADS)

    Brgoch, Jakoah; Mahmoud, Yassir A.; Miller, Gordon J.

    2012-12-01

    The site preference for a class of intermetallic borides following the general formula M2Fe(Ru0.8T0.2)5B2 (M=Sc, Ti, Zr; T=Ru, Rh, Ir), has been explored using ab initio and semi-empirical electronic structure calculations. This intermetallic boride series contains two potential sites, the Wyckoff 2c and 8j sites, for Rh or Ir to replace Ru atoms. Since the 8j site is a nearest neighbor to the magnetically active Fe atom, whereas the 2c site is a next nearest neighbor, the substitution pattern should play an important role in the magnetic structure of these compounds. The substitution preference is analyzed based on the site energy and bond energy terms, both of which arise from a tight-binding evaluation of the electronic band energy, and are known to influence the locations of atoms in extended solids. According to these calculations, the valence electron-rich Rh and Ir atoms prefer to occupy the 8j site, a result also corroborated by experimental evidence. Additionally, substitution of Rh or Ir at the 8j site results in a modification of the magnetic structure that ultimately results in larger local magnetic moment on the Fe atoms.

  5. Sensitive redox speciation of iron, neptunium, and plutonium by capillary electrophoresis hyphenated to inductively coupled plasma sector field mass spectrometry.

    PubMed

    Graser, Carl-Heinrich; Banik, Nidhu Lal; Bender, Kerstin Anne; Lagos, Markus; Marquardt, Christian Michael; Marsac, Rémi; Montoya, Vanessa; Geckeis, Horst

    2015-10-01

    The long-term safety assessment for nuclear waste repositories requires a detailed understanding of actinide (geo)chemistry. Advanced analytical tools are required to gain insight into actinide speciation in a given system. The geochemical conditions in the vicinity of a nuclear repository control the redox state of radionuclides, which in turn has a strong impact on their mobility. Besides the long-lived radionuclides plutonium (Pu) and neptunium (Np), which are key elements in high level nuclear waste, iron (Fe) represents a main component in natural systems controlling redox-related geochemical processes. Measuring the oxidation state distribution for redox sensitive radionuclides and other metal ions is challenging at trace concentrations below the detection limit of most available spectroscopic methods (≥10(-6) M). Consequently, ultrasensitive new analytical techniques are required. Capillary electrophoresis (CE) is a suitable separation method for metal cations. CE hyphenated to inductively coupled plasma sector field mass spectrometry (CE-ICP-SF-MS) was used to measure the redox speciation of Pu (III, IV, V, VI), Np (IV, V, VI), and Fe (II, III) at concentrations lower than 10(-7) M. CE coupling and separation parameters such as sample gas pressure, make up flow rate, capillary position, auxiliary gas flow, as well as the electrolyte system were optimized to obtain the maximum sensitivity. We obtain detection limits of 10(-12) M for Np and Pu. The various oxidation state species of Pu and Np in different samples were separated by application of an acetate-based electrolyte system. The separation of Fe (II) and Fe (III) was investigated using different organic complexing ligands, EDTA, and o-phenanthroline. For the Fe redox system, a limit of detection of 10(-8) M was calculated. By applying this analytical system to sorption studies, we were able to underline previously published results for the sorption behavior of Np in highly diluted concentrations, and

  6. Investigation of the system ThO 2-NpO 2-P 2O 5. Solid solutions of thorium-neptunium (IV) phosphate-diphosphate

    NASA Astrophysics Data System (ADS)

    Dacheux, N.; Thomas, A. C.; Brandel, V.; Genet, M.

    1998-11-01

    Considering that phosphate matrices could be potential candidates for the immobilization of actinides or for the final disposal of the excess plutonium from dismantled nuclear weapons, the chemistry of thorium phosphates has been re-examined. In the ThO 2-P 2O 5 system, the thorium phosphate-diphosphate Th 4(PO 4) 4P 2O 7 (TPD) can be synthesized by wet and dry chemical processes. The substitution of thorium by other tetravalent actinides like uranium or plutonium can be obtained for 0 < x < 3.0 and 0 < x < 1.63, respectively. In this work, we report the chemical conditions of synthesis of thorium-neptunium (IV) phosphate-diphosphate solid solutions Th 4- xNp x(PO 4) 4P 2O 7 (TNPD) with 0 < x < 1.6 from a mixture of thorium and neptunium (IV) nitrates and concentrated phosphoric acid. From the variation of the cell parameters and volume, the maximum substitution of Th 4+ by Np 4+ in the TPD structure is evaluated to 2.08 (which corresponds to about 52 mol% of thorium replaced by neptunium (IV)). The field of existence of solid solutions Th 4- xU- xNp- xPuU xUNp xNpPu xPu(PO 4)4P 2O 7 has been calculated. These solid solutions should be synthesized for 5 xU+7 xNp+9 xPu⩽15. In the NpO 2-P 2O 5 system, the unit cell parameters of Np 2O(PO 4) 2 were refined by analogy with U 2O(PO 4) 2 which crystallographic data have been published recently. For Np 2O(PO 4) 2 the unit cell is orthorhombic with the following cell parameters: a=7.033(2) Å, b=9.024(3) Å, c=12.587(6) Å and V=799(1) Å 3. The unit cell parameter obtained for α-NpP 2O 7 ( a=8.586(1) Å) is in good agreement with those already reported in literature.

  7. Expansion of the rich structures and magnetic properties of neptunium selenites: soft ferromagnetism in Np(SeO3)2.

    PubMed

    Diefenbach, Kariem; Lin, Jian; Cross, Justin N; Dalal, Naresh S; Shatruk, Michael; Albrecht-Schmitt, Thomas E

    2014-07-21

    Two new neptunium selenites with different oxidation states of the metal centers, Np(IV)(SeO3)2 and Np(VI)O2(SeO3), have been synthesized under mild hydrothermal conditions at 200 °C from the reactions of NpO2 and SeO2. Np(SeO3)2 crystallizes as brown prisms (space group P21/n, a = 7.0089(5) Å, b = 10.5827(8) Å, c = 7.3316(5) Å, β = 106.953(1)°); whereas NpO2(SeO3) crystals are garnet-colored with an acicular habit (space group P21/m, a = 4.2501(3) Å, b = 9.2223(7) Å, c = 5.3840(4) Å, β = 90.043(2)°). Single-crystal X-ray diffraction studies reveal that the structure of Np(SeO3)2 features a three-dimensional (3D) framework consisting of edge-sharing NpO8 units that form chains that are linked via SeO3 units to create a 3D framework. NpO2(SeO3) possesses a lamellar structure in which each layer is composed of NpO8 hexagonal bipyramids bridged via SeO3(2-) anions. Bond-valence sum calculations and UV-vis-NIR absorption spectra support the assignment of tetravalent and hexavalent states of neptunium in Np(SeO3)2 and NpO2(SeO3), respectively. Magnetic susceptibility data for Np(SeO3)2 deviates substantially from typical Curie-Weiss behavior, which can be explained by large temperature-independent paramagnetic (TIP) effects. The Np(IV) selenite shows weak ferromagnetic ordering at 3.1(1) K with no detectable hysteresis, suggesting soft ferromagnetic behavior.

  8. Cd - Np (Cadmium - Neptunium)

    NASA Astrophysics Data System (ADS)

    Predel, B.

    This document is part of Volume 12 Phase Equilibria, Crystallographic and Thermodynamic Data of Binary Alloys', Subvolume B 'B - Ba … Cu - Zr, Supplement to Subvolumes IV/5B, IV/5C and IV/5D', of Landolt-Börnstein - Group IV 'Physical Chemistry'.

  9. B - Np (Boron - Neptunium)

    NASA Astrophysics Data System (ADS)

    Predel, B.

    This document is part of Volume 12 Phase Equilibria, Crystallographic and Thermodynamic Data of Binary Alloys', Subvolume B 'B - Ba … Cu - Zr, Supplement to Subvolumes IV/5B, IV/5C and IV/5D', of Landolt-Börnstein - Group IV 'Physical Chemistry'.

  10. Neptunium Monochalcogenides: Heat Capacity

    NASA Astrophysics Data System (ADS)

    Troć, R.

    This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

  11. Neptunium Monochalcogenides: Magnetic Susceptibility

    NASA Astrophysics Data System (ADS)

    Troć, R.

    This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

  12. Neptunium Monochalcogenides: Electrical Resistivity

    NASA Astrophysics Data System (ADS)

    Troć, R.

    This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

  13. Neptunium Monochalcogenides: Reflectivity

    NASA Astrophysics Data System (ADS)

    Troć, R.

    This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

  14. Ternary boride product and process

    NASA Technical Reports Server (NTRS)

    Clougherty, Edward V. (Inventor)

    1976-01-01

    A hard, tough, strong ceramic body is formed by hot pressing a mixture of a powdered metal and a powdered metal diboride. The metal employed is zirconium, titanium or hafnium and the diboride is the diboride of a different member of the same group of zirconium, titanium or hafnium to form a ternary composition. During hot pressing at temperatures above about 2,000.degree.F., a substantial proportion of acicular ternary monoboride is formed.

  15. Structural Properties and Charge Distribution of the Sodium Uranium, Neptunium, and Plutonium Ternary Oxides: A Combined X-ray Diffraction and XANES Study.

    PubMed

    Smith, Anna L; Martin, Philippe; Prieur, Damien; Scheinost, Andreas C; Raison, Philippe E; Cheetham, Anthony K; Konings, Rudy J M

    2016-02-15

    The charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated in this work using X-ray absorption near-edge structure (XANES) spectroscopy at the U-L3, Np-L3, and Pu-L3 edges. In addition, a Rietveld refinement of monoclinic Na2PuO3, in space group C2/c, is reported for the first time, and the existence of the isostructural Na2NpO3 phase is revealed. In contrast to measurements in solution, the number of published XANES data for neptunium and plutonium solid phases with a valence state higher than IV is very limited. The present results cover a wide range of oxidation states, namely, IV to VII, and can serve as reference for future investigations. The sodium actinide series show a variety of local coordination geometries, and correlations between the shape of the XANES spectra and the local structural environments are discussed herein. PMID:26835549

  16. Structural Properties and Charge Distribution of the Sodium Uranium, Neptunium, and Plutonium Ternary Oxides: A Combined X-ray Diffraction and XANES Study.

    PubMed

    Smith, Anna L; Martin, Philippe; Prieur, Damien; Scheinost, Andreas C; Raison, Philippe E; Cheetham, Anthony K; Konings, Rudy J M

    2016-02-15

    The charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated in this work using X-ray absorption near-edge structure (XANES) spectroscopy at the U-L3, Np-L3, and Pu-L3 edges. In addition, a Rietveld refinement of monoclinic Na2PuO3, in space group C2/c, is reported for the first time, and the existence of the isostructural Na2NpO3 phase is revealed. In contrast to measurements in solution, the number of published XANES data for neptunium and plutonium solid phases with a valence state higher than IV is very limited. The present results cover a wide range of oxidation states, namely, IV to VII, and can serve as reference for future investigations. The sodium actinide series show a variety of local coordination geometries, and correlations between the shape of the XANES spectra and the local structural environments are discussed herein.

  17. Experimental and theoretical study of anion-exchange preparative chromatography for neptunium: the first application to thorium(IV) and its equilibrium and kinetics.

    PubMed

    Yamamura, Tomoo; Miyakoshi, Takeshi; Shiokawa, Yoshinobu; Mitsugashira, Toshiaki

    2007-10-26

    In order to study equilibrium and kinetic parameters in anion-exchange chromatography for preparatory purpose, a quantitative model for nonlinear anion-exchange chromatography in porous media was constructed, by paying special attention to interstitial length along void structure (cm) distinguished from apparent length (cm*). Langmuir-type adsorption isotherm for thorium(IV), as a natural substitution for neptunium(IV), in 6 mol dm(-3) nitric acid to anion-exchanger MSA-1 (200-400 mesh) was investigated in batch-wise and chromatographic experiments. The equilibrium parameters determined by batch-wise experiments determined as k=2.4x10(2) mol(-1) dm3 s(-1) and s0=0.5 mol dm(-3) agrees very well with the values of k=222 mol(-1) dm3 s(-1) and s0=0.5 mol dm(-3) derived from fitting by the numerical calculation. Kinetic parameters of ks and D affect band profile similarly, thereby maximum value of each parameter was evaluated as ks=1.3 mol(-1) dm3 s(-1) and D=9x10(-4) cm2 s(-1) by the numerical calculations.

  18. Method for determination of neptunium in large-sized urine samples using manganese dioxide coprecipitation and 242Pu as yield tracer.

    PubMed

    Qiao, Jixin; Hou, Xiaolin; Roos, Per

    2013-02-01

    A novel method for bioassay of large volumes of human urine samples using manganese dioxide coprecipitation for preconcentration was developed for rapid determination of (237)Np. (242)Pu was utilized as a nonisotopic tracer to monitor the chemical yield of (237)Np. A sequential injection extraction chromatographic (SI-EC) system coupled with inductively coupled plasma mass spectrometry (ICPMS) was exploited to facilitate the rapid column separation and quantification. The analytical results demonstrated satisfactory performance of the MnO(2) coprecipitation as indicated by the high chemical yields close to 100% and high separation capacity of processing up to 5 L of human urine samples. The MnO(2) coprecipitation process is simple and straightforward in which a batch (8-12) of samples can be pretreated within 4 h (i.e., <0.5 h/sample). In connection with the automated column separation and ICPMS quantification, which takes less than 1.5 h in total, the overall analytical time was on average less than 2 h for each sample. The high effectiveness and sample throughput make the developed method well suited for urine bioassay of (237)Np in routine monitoring of occupationally internal radiation exposure and rapid analysis of neptunium contamination level for emergency preparedness.

  19. Phase relations in neptunium, americium and the binary alloy systems Np-Am and Np-Ln (Ln = La, Nd, Lu)

    NASA Astrophysics Data System (ADS)

    Gibson, John K.; Haire, Richard G.

    1992-10-01

    High-temperature differential thermal analysis has been used to characterize the phase relations in neptunium, americium and the binary alloy systems, Np-Am, Np-La, Np-Nd, Np-Lu, Sm-Ce and Ce-Gd. The temperatures previously reported for the two solid-solid transformations and the fusion of Np, and for the β(fcc) → γ(bcc?) and the fusion transitions of Am were confirmed. A small endothermic event ( ~ 0.4 kJ mol -1) evident at 758°C for americium was assigned to its dhcp → fcc transition; this temperature is ~ 100°C higher than previously derived from dilatometry. Although the Np-Am DTA studies were limited in the range of alloy compositions which could be investigated, the results were useful in deciphering the nature of the phase diagram. Measurements on a sample of aggregate composition Np 0.54-Am 0.46 suggested some degree of mutual solubility, although two (terminal) solid phases, one Np-rich and one Am-rich, were found to coexist. The supporting studies of Np-Ln and Ln-Ln' (Ln and Ln' = selected lanthanides) alloy systems established the efficacy of the DTA technique and augmented the results for the Np-Am system.

  20. Synthesis, phase structure and microstructure of monazite-type Ce1-xPrxPO4 solid solutions for immobilization of minor actinide neptunium

    NASA Astrophysics Data System (ADS)

    Zeng, Pan; Teng, Yuancheng; Huang, Yi; Wu, Lang; Wang, Xiaohuan

    2014-09-01

    Praseodymium was used as the surrogate for trivalent minor actinide neptunium, and a complete series of pure monazite-type Ce1-xPrxPO4 (x = 0-1) solid solutions were successfully prepared by the solid state reaction. The effects of calcining temperature, holding time and Pr content on the structure of Ce1-xPrxPO4 solid solutions were investigated. The results show that although Pr6O11 (Pr23+Pr44+O11) exists two stabilized oxidation states, there has been no tetravalent praseodymium phosphate during the synthesis process. The optimized temperature for the synthesis of Ce0.8Pr0.2PO4 solid solution is more than 1100 °C, and a hypothetical reaction mechanism is also proposed. Besides, the crystalline grains coarsen as the increasing of holding time. The linear variation of unit cell parameters and a gradual hypsochromic shift in the Raman spectra are observed with the increase of Pr content, indicating that cerium is progressively replaced by praseodymium and Ce1-xPrxPO4 solid solutions were prepared.

  1. Complete titanium substitution by boron in a tetragonal prism: exploring the complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) by experiment and theory.

    PubMed

    Fokwa, Boniface P T; Hermus, Martin

    2011-04-18

    Polycrystalline samples and single crystals of four members of the new complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The new silvery phases were structurally characterized by powder and single-crystal X-ray diffraction as well as energy- and wavelength-dispersive X-ray spectroscopy analyses. They crystallize with the tetragonal Ti(3)Co(5)B(2) structure type in space group P4/mbm (No. 127). Tetragonal prisms of Ru/Ir atoms are filled with titanium in the boron-poorest phase (Ti(3)Ru(2.9)Ir(2.1)B(2)). Gradual substitution of titanium by boron then results in the successive filling of this site by a Ti/B mixture en route to the complete boron occupation, leading to the boron-richest phase (Ti(2)Ru(2.8)Ir(2.2)B(3)). Furthermore, both ruthenium and iridium share two sites in these structures, but a clear Ru/Ir site preference is found. First-principles density functional theory calculations (Vienna ab initio simulation package) on appropriate structural models (using a supercell approach) have provided more evidence on the stability of the boron-richest and -poorest phases, and the calculated lattice parameters corroborate very well with the experimentally found ones. Linear muffin-tin orbital atomic sphere approximation calculations further supported these findings through crystal orbital Hamilton population bonding analyses, which also show that the Ru/Ir-B and Ru/Ir-Ti heteroatomic interactions are mainly responsible for the structural stability of these compounds. Furthermore, some stable and unstable phases of this complex series could be predicted using the rigid-band model. According to the density of states analyses, all phases should be metallic conductors, as was expected from these metal-rich borides. PMID:21428308

  2. Thermal conductivity of layered borides: The effect of building defects on the thermal conductivity of TmAlB{sub 4} and the anisotropic thermal conductivity of AlB{sub 2}

    SciTech Connect

    Wang, X. J. E-mail: xwang58@illinois.edu; Mori, T. E-mail: xwang58@illinois.edu; Kuzmych-Ianchuk, I.; Michiue, Y.; Yubuta, K.; Shishido, T.; Grin, Y.; Okada, S.; Cahill, D. G.

    2014-04-01

    Rare earth metal borides have attracted great interest due to their unusual properties, such as superconductivity and f-electron magnetism. A recent discovery attributes the tunability of magnetism in rare earth aluminoborides to the effect of so-called “building defects.” In this paper, we report data for the effect of building defects on the thermal conductivities of α-TmAlB{sub 4} single crystals. Building defects reduce the thermal conductivity of α-TmAlB{sub 4} by ≈30%. At room temperature, the thermal conductivity of AlB{sub 2} is nearly a factor of 5 higher than that of α-TmAlB{sub 4}. AlB{sub 2} single crystals are thermally anisotropic with the c-axis thermal conductivity nearly twice the thermal conductivity of the a-b plane. Temperature dependence of the thermal conductivity near and above room temperature reveals that both electrons and phonons contribute substantially to thermal transport in AlB{sub 2} with electrons being the dominant heat carriers.

  3. Quantum chemistry study of uranium(VI), neptunium(V), and plutonium(IV,VI) complexes with preorganized tetradentate phenanthrolineamide ligands.

    PubMed

    Xiao, Cheng-Liang; Wu, Qun-Yan; Wang, Cong-Zhi; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-10-20

    The preorganized tetradentate 2,9-diamido-1,10-phenanthroline ligand with hard-soft donors combined in the same molecule has been found to possess high selectivity toward actinides in an acidic aqueous solution. In this work, density functional theory (DFT) coupled with the quasi-relativistic small-core pseudopotential method was used to investigate the structures, bonding nature, and thermodynamic behavior of uranium(VI), neptunium(V), and plutonium(IV,VI) with phenanthrolineamides. Theoretical optimization shows that Et-Tol-DAPhen and Et-Et-DAPhen ligands are both coordinated with actinides in a tetradentate chelating mode through two N donors of the phenanthroline moiety and two O donors of the amide moieties. It is found that [AnO2L(NO3)](n+) (An = U(VI), Np(V), Pu(VI); n = 0, 1) and PuL(NO3)4 are the main 1:1 complexes. With respect to 1:2 complexes, the reaction [Pu(H2O)9](4+)(aq) + 2L(org) + 2NO3(-)(aq) → [PuL2(NO3)2](2+)(org) + 9H2O(aq) might be another probable extraction mechanism for Pu(IV). From the viewpoint of energy, the phenanthrolineamides extract actinides in the order of Pu(IV) > U(VI) > Pu(VI) > Np(V), which agrees well with the experimental results. Additionally, all of the thermodynamic reactions are more energetically favorable for the Et-Tol-DAPhen ligand than the Et-Et-DAPhen ligand, indicating that substitution of one ethyl group with one tolyl group can enhance the complexation abilities toward actinide cations (anomalous aryl strengthening).

  4. In{sub 3}Ir{sub 3}B, In{sub 3}Rh{sub 3}B and In{sub 5}Ir{sub 9}B{sub 4}, the first indium platinum metal borides

    SciTech Connect

    Kluenter, Wilhelm; Jung, Walter . E-mail: walter.jung@uni-koeln.de

    2006-09-15

    The first indium platinum metal borides have been synthesized and structurally characterized by single crystal X-ray diffraction data. In{sub 3}Ir{sub 3}B and In{sub 3}Rh{sub 3}B are isotypic. They crystallize with the hexagonal space group P6-bar 2m and Z=1. The lattice constants are a=685.78(1)pm, c=287.30(1)pm for In{sub 3}Ir{sub 3}B and a=678.47(3)pm, c=288.61(6)pm for In{sub 3}Rh{sub 3}B. The structure which is derived from the Fe{sub 2}P type is characterized by columns of boron centered triangular platinum metal prisms inserted in a three-dimensional indium matrix. The indium atoms are on split positions. In{sub 5}Ir{sub 9}B{sub 4} (hexagonal, space group P6-bar 2m, a=559.0(2)pm, c=1032.6(3)pm, Z=1) crystallizes with a structure derived from the CeCo{sub 3}B{sub 2} type. The structure can be interpreted as a layer as well as a channel structure. In part the indium atoms are arranged at the vertices of a honeycomb net (Schlaefli symbol 6{sup 3}) separating slabs consisting of double layers of triangular Ir{sub 6}B prisms, and in part they form a linear chain in a hexagonal channel formed by iridium prisms and indium atoms of the honeycomb lattice.

  5. Single crystal studies on boron-rich {tau}-borides Ni{sub 23-x}M{sub x}B{sub 6} (M=Zn, Ga, In, Sn, Ir)-The surprising occurrence of B{sub 4}-tetraheda as a normal case?

    SciTech Connect

    Kotzott, Dominik; Ade, Martin; Hillebrecht, Harald

    2010-10-15

    Single crystals of the cubic {tau}-borides Ni{sub 23-x}M{sub x}B{sub 6} (M=Zn, Ga, In, Sn, Ir) were synthesised from the elements at temperatures between 1200 and 1500 {sup o}C. The structure refinements show that the existence of boron-rich phases is quite common. Starting from the idealised composition Ni{sub 20}M'{sub 3}B{sub 6} a part of the metal atoms on site 8c is substituted by B{sub 4} tetrahedra. For M'=Ga a complete exchange seems to be possible leading to the composition Ni{sub 20}GaB{sub 14}. For M'=Zn and Sn the formation of solid solutions is less extended. For M'=In no exchange is observed but an unusual pattern of Ni/In distribution is observed. With M=Ir mixed occupations occur for all sites and the boron content varies, too. All compositions were confirmed by EDX measurements. - Graphical abstract: Crystal structure of {tau}-Borides M{sub 23}B{sub 6}; M1: M{sub 8}-cubes, M2: M{sub 12}-cuboctahedra centred by M3, isolated M-atoms: M4; grey circles: boron, black circles: metal atoms.

  6. Boron induced structure modifications in Pd-Cu-B system: new Ti2Ni-type derivative borides Pd3Cu3B and Pd5Cu5B2.

    PubMed

    Sologub, Oksana; Salamakha, Leonid P; Eguchi, Gaku; Stöger, Berthold; Rogl, Peter F; Bauer, Ernst

    2016-03-21

    The formation of two distinct derivative structures of Ti2Ni-type, interstitial Pd3Cu3B and substitutive Pd5Cu5B2, has been elucidated in Pd-Cu-B alloys from analysis of X-ray single crystal and powder diffraction data and supported by SEM. The metal atom arrangement in the new boride Pd3Cu3B (space group Fd3m, W3Fe3C-type structure, a = 1.1136(3) nm) follows the pattern of atom distribution in the CdNi-type structure. Pd5Cu5B2 (space group F(4)3m, a = 1.05273(5) nm) exhibits a non-centrosymmetric substitutive derivative of the Ti2Ni-type structure. The reduction of symmetry on passing from Ti2Ni-type structure to Pd5Cu5B2 corresponds to the loss of an inversion centre delivered by an ordered occupation of the Ni position (32e) by dissimilar atoms, Cu and B. In both structures, the boron atom centers Pd forming [BPd6] octahedra in Pd3Cu3B and [BPd6] trigonal prisms in Pd5Cu5B2. Neither a perceptible homogeneity range nor mutual solid solubility was observed for two compounds at 600 °C, while in as cast conditions Pd5Cu5B2 exhibits an extended homogeneity range formed by a partial substitution of Cu atoms (in 24f) by Pd (Pd5+xCu5-xB2, 0 ≤x≤ 1). Electrical resistivity measurements performed on Pd3Cu3B as well as on Pd-poor and Pd-rich termini of Pd5+xCu5-xB2 annealed at 600 °C and in as cast conditions respectively demonstrated the absence of any phase transitions for this compounds in the temperature region from 0.3 K to 300 K. PMID:26875687

  7. New examples of ternary rare-earth metal boride carbides containing finite boron carbon chains: The crystal and electronic structure of RE15B6C20 (RE=Pr, Nd)

    NASA Astrophysics Data System (ADS)

    Babizhetskyy, Volodymyr; Mattausch, Hansjürgen; Simon, Arndt; Hiebl, Kurt; Ben Yahia, Mouna; Gautier, Régis; Halet, Jean-François

    2008-08-01

    The ternary rare-earth metal boride carbides RE15B6C20 (RE=Pr, Nd) were synthesized by co-melting the elements. They exist above 1270 K. Their crystal structures were determined from single-crystal X-ray diffraction data. Both crystallize in the space group P1¯, Z=1, a=8.3431(8) Å, b=9.2492(9) Å, c=8.3581(8) Å, α=84.72(1)°, β=89.68(1)°, γ =84.23(1)° (R1=0.041 (wR2=0.10) for 3291 reflections with Io>2σ(Io)) for Pr15B6C20, and a=8.284(1) Å, b=9.228(1) Å, c=8.309(1) Å, α=84.74(1)°, β=89.68(1)°, γ=84.17(2)° (R1=0.033 (wR2=0.049) for 2970 reflections with Io>2σ(Io)) for Nd15B6C20. Their structure consists of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with unprecedented B2C4 finite chains, disordered C3 entities and isolated carbon atoms, respectively. Structural and theoretical analyses suggest the ionic formulation (RE3+)15([B2C4]6-)3([C3]4-)2(C4-)2·11ē. Accordingly, density functional theory calculations indicate that the compounds are metallic. Both structural arguments as well as energy calculations on different boron vs. carbon distributions in the B2C4 chains support the presence of a CBCCBC unit. Pr15B6C18 exhibits antiferromagnetic order at TN=7.9 K, followed by a meta-magnetic transition above a critical external field B>0.03 T. On the other hand, Nd15B6C18 is a ferromagnet below TC≈40 K.

  8. Neptunium Monochalcogenides: Magnetic Hyperfine Fields

    NASA Astrophysics Data System (ADS)

    Troć, R.

    This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

  9. Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) with Th{sub 7}Fe{sub 3}-type structure

    SciTech Connect

    Misse, Patrick R.N.; Mbarki, Mohammed; Fokwa, Boniface P.T.

    2012-08-15

    Powder samples and single crystals of the new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3}mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. - Graphical abstract: The new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) has been synthesized by arc melting the elements under purified argon atmosphere. Beside the 3d/4d site preference within the whole solid solution, an unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. Highlights: Black-Right-Pointing-Pointer Synthesis of a new boride series fulfilling Vegard Acute-Accent s rule. Black-Right-Pointing-Pointer 3d/4d site preference. Black-Right-Pointing-Pointer Unexpected Ru/Rh site preference. Black-Right-Pointing-Pointer Rh-rich region is Pauli paramagnetic. Black-Right-Pointing-Pointer Ru-rich region is Pauli and temperature-dependent paramagnetic.

  10. The complex metal-rich boride Ti{sub 1+x}Rh{sub 2-x+y}Ir{sub 3-y}B{sub 3} (x=0.68, y=1.06) with a new structure type containing B{sub 4} zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

    SciTech Connect

    Goerens, Christian; Fokwa, Boniface P.T.

    2012-08-15

    Polycrystalline samples and single crystals of the new complex boride Ti{sub 1+x}Rh{sub 2-x+y}Ir{sub 3-y}B{sub 3} (x=0.68; y=1.06) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-Ray diffraction as well as EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase, which represents a new structure type containing trans zigzag B{sub 4} fragments as well as isolated boron atoms crystallizes in the orthorhombic space group Pbam (Nr. 55) with the lattice parameters a=8.620(1) A, b=14.995(2) A and c=3.234(1) A. First-principles density functional theory calculations using the Vienna ab-initio simulation package (VASP) were performed on an appropriate structural model (using a supercell approach) and the experimental crystallographic data could be reproduced accurately. Based on this model, the density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron-boron interactions are observed in the trans zigzag B{sub 4} fragment, which induce a clear differentiation of two types of metal-boron contacts with different strength. The observed three-dimensional metal-metal interaction is in good agreement with the predicted metallic behavior. - graphical abstract: The structure of Ti{sub 1.68(2)}Rh{sub 2.38(6)}Ir{sub 1.94(4)} B{sub 3}, a new structure type containing planar trans zigzag B{sub 4} units, is another example which illustrates the tendency of metal-rich borides to form B-B bonds with increasing boron content. Beside the B{sub 4} fragment it exhibits one-dimensional chains of titanium atoms and hold one-dimensional strings of face-sharing empty tetrahedral and square pyramidal clusters (see figure). Highlights

  11. Combustion synthesis of boride and other composites

    DOEpatents

    Halverson, D.C.; Lum, B.Y.; Munir, Z.A.

    1988-07-28

    A self-sustaining combustion synthesis process for producing hard, tough, lightweight B/sub 4/C/TiB/sub 2/ composites is described. It is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B/sub 4/C and TiB/sub 2/ reactants. For lightweight products the composition must be relatively rich in the B/sub 4/C component. B/sub 4/C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component. 9 figs., 4 tabs.

  12. Combustion synthesis of boride and other composites

    DOEpatents

    Halverson, Danny C.; Lum, Beverly Y.; Munir, Zuhair A.

    1989-01-01

    A self-sustaining combustion synthesis process for producing hard, tough, lightweight B.sub.4 C/TiB.sub.2 composites is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B.sub.4 C and TiB.sub.2 reactants. For lightweight products the composition must be relatively rich in the B.sub.4 C component. B.sub.4 C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component.

  13. Measured solubilities and speciations of neptunium, plutonium, and americium in a typical groundwater (J-13) from the Yucca Mountain region; Milestone report 3010-WBS 1.2.3.4.1.3.1

    SciTech Connect

    Nitsche, H.; Gatti, R.C.; Standifer, E.M.

    1993-07-01

    Solubility and speciation data are important in understanding aqueous radionuclide transport through the geosphere. They define the source term for transport retardation processes such as sorption and colloid formation. Solubility and speciation data are useful in verifying the validity of geochemical codes that are part of predictive transport models. Results are presented from solubility and speciation experiments of {sup 237}NpO{sub 2}{sup +}, {sup 239}Pu{sup 4+}, {sup 241}Am{sup 3+}/Nd{sup 3+}, and {sup 243}Am{sup 3+} in J-13 groundwater (from the Yucca Mountain region, Nevada, which is being investigated as a potential high-level nuclear waste disposal site) at three different temperatures (25{degree}, 60{degree}, and 90{degree}C) and pH values (5.9, 7.0, and 8.5). The solubility-controlling steady-state solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined. The neptunium solubility decreased with increasing temperature and pH. Plutonium concentrations decreased with increasing temperature and showed no trend with pH. The americium solutions showed no clear solubility trend with increasing temperature and increasing pH.

  14. Measured solubilities and speciations from oversaturation experiments of neptunium, plutonium, and americium in UE-25p No. 1 well water from the Yucca Mountain region: Milestone report 3329-WBS1.2.3.4.1.3.1

    SciTech Connect

    Nitsche, H.; Roberts, K.; Prussin, T.; Mueller, A.; Becraft, K.; Keeney, D.; Carpenter, S.A.; Gatti, R.C.

    1994-04-01

    Solubility and speciation are important in understanding aqueous radionuclide transport through the geosphere. They define the source term for transport retardation processes such as sorption and colloid formation. Solubility and speciation data are useful in verifying the validity of geochemical codes that are a part of predictive transport models. Results are presented from solubility and speciation experiments of {sup 237}NpO{sub 2}{sup +}, {sup 239}Pu{sup 4+}, and {sup 241}Am{sup 3+}/Nd{sup 3+} in a modified UE-25p No. 1 groundwater (from the Yucca Mountain region, Nevada, which is being investigated as a potential high-level nuclear waste disposal site) at two different temperatures (25{degree} and 60{degree}C) and three pH values (6.0, 7.0, 8.5). The solubility-controlling steady-state solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined. The neptunium solubility decreased with increasing temperature and pH. Plutonium concentrations significantly decreased with increasing temperature at pH 6 and 7. The concentration at pH 8.5 hardly decreased at all with increasing temperature. At both temperatures the concentrations were highest at pH 8.5, lowest at pH 7, and in between at pH 6. For the americium/neodymium solutions, the solubility decreased significantly with increasing temperature and increased somewhat with increasing pH.

  15. Thermal analysis, phase equilibria, and superconducting properties in magnesium boride and carbon doped magnesium boride

    NASA Astrophysics Data System (ADS)

    Bohnenstiehl, Scot David

    In this work, the low temperature synthesis of MgB2 from Mg/B and MgH2/B powder mixtures was studied using Differential Scanning Calorimetry (DSC). For the Mg/B powder mixture, two exothermic reaction events were observed and the first reaction event was initiated by the decomposition of Mg(OH)2 on the surface of the magnesium powder. For the MgH 2/B powder mixture, there was an endothermic event at ˜375 °C (the decomposition of MgH2 into H2 and Mg) and an exothermic event ˜600 °C (the reaction of Mg and B). The Kissinger analysis method was used to estimate the apparent activation energy of the Mg and B reaction using DSC data with different furnace ramp rates. The limitations of MgB2 low temperature synthesis led to the development of a high pressure induction furnace that was constructed using a pressure vessel and an induction heating power supply. The purpose was to not only synthesize more homogeneous MgB2 samples, but also to determine whether MgB2 melts congruently or incongruently. A custom implementation of the Smith Thermal Analysis method was developed and tested on aluminum and AlB2, the closest analogue to MgB2. Measurements on MgB2 powder and a high purity Mg/B elemental mixture confirmed that MgB2 melts incongruently and decomposes into a liquid and MgB4 at ˜1445 °C at 10 MPa via peritectic decomposition. Another measurement using a Mg/B elemental mixture with impure boron suggested that ˜0.7 wt% carbon impurity in the boron raised the incongruent melting temperature to ˜1490-1500 °C. Lastly, the solubility limit for carbon in MgB2 was studied by making samples from B4C and Mg at 1530 °C, 1600 °C and 1700 °C in the high pressure furnace. All three samples had three phases: Mg, MgB2C2, and carbon doped MgB2. The MgB 2C2 and carbon doped MgB2 grain size increased with temperature and the 1700 °C sample had needle-like grains for both phases. The presence of the ternary phase, MgB2C2, suggested that the maximum doping limit for carbon in MgB2 had been reached. The 1530 °C sample was characterized by Electron Probe Microanalysis at the University of Oregon and the average carbon concentration was estimated to be ˜5.9 at%. Further investigation using TEM found MgO inclusions in the 1530 °C sample which were not detected with X-ray diffraction.

  16. Improving hardness and toughness of boride composites based on aluminum magnesium boride

    NASA Astrophysics Data System (ADS)

    Peters, Justin Steven

    The search for new super-hard materials has usually focused on strongly bonded, highly symmetric crystal structures similar to diamond. The two hardest single-phase materials, diamond and cubic boron nitride (cBN), are metastable, and both must be produced at high temperatures and pressures, which makes their production costly. In 2000, a superhard composite based on a low-symmetry, boron-rich compound was reported. Since then, many advances have been made in the study of this AlMgB14--TiB2 composite. The composite has been shown to exhibit hardness greater than either of its constituent phases, relying on its sub-micron microstructure to provide hardening and strengthening mechanisms. With possible hardness around 40 GPa, an AlMgB 14--60 vol% TiB2 approaches the hardness of cBN, yet is amenable to processing under ambient pressure conditions. There are interesting aspects of both the AlMgB14 and TiB 2 phases. AlMgB14 is comprised of a framework of boron, mostly in icosahedral arrangements. It is part of a family of 12 known compounds with the same boron lattice, with the metal atoms replaced by Li, Na, Y or a number of Lanthanides. Another peculiar trait of this family of compounds is that every one contains a certain amount of intrinsic vacancies on one or both of the metal sites. These vacancies are significant, ranging from 3 to 43% of sites depending on the composition. TiB2 is a popular specialty ceramic material due to its high hardness, moderate toughness, good corrosion resistance, and high thermal and electrical conductivity. The major drawback is the difficulty of densification of pure TiB2 ceramics. A combination of sintering aids, pressure, and temperatures of 1800°C are often required to achieve near full density articles. The AlMgB14--TiB2 composites can achieve 99% density from hotpressing at 1400°C. This is mostly due to the preparation of powders by a high-energy milling technique known as mechanical alloying. The resulting fine powders have high activity, and Fe from wear debris acts as a sintering aid. Mechanical alloying improves the sinterability of the composite material, it has the same effect on pure TiB2. TiB 2 processed by high-energy milling has been found to achieve 99% theoretical density at 1400°C with the addition of ˜1 wt% Fe. Both the AlMgB14--TiB2 composites and pure TiB2 produced from these methods have enhanced mechanical properties due to their fine microstructures. These materials show exceptional promise in the field of wear resistance. This includes cutting tools, erosion resistant coatings, and low-friction sliding contacts to name a few. Under certain wear conditions, the composite material can show performance on par with that of current high-end cBN and WC materials tailored for wear resistance. The composite material also exhibits low reactivity with Ti alloys, a pre-requisite for effective machining of these alloys, a trait that few hard materials possess.

  17. Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Crx(Rh1-yRuy)7-xB3 (x=0.88-1; y=0-1) with Th7Fe3-type structure

    NASA Astrophysics Data System (ADS)

    Misse, Patrick R. N.; Mbarki, Mohammed; Fokwa, Boniface P. T.

    2012-08-01

    Powder samples and single crystals of the new complex boride series Crx(Rh1-yRuy)7-xB3 (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th7Fe3 structure type (space group P63mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region.

  18. Scaffolds of magnetically active 3d metals in the valence electron controlled borides Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr–Ni; x=0.5–1): Structutral, electronic and magnetic properties

    SciTech Connect

    Goerens, Christian; Brgoch, Jakoah; Miller, Gordon J.; Fokwa, Boniface P.T.

    2013-08-15

    Polycrystalline samples of the boride series Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr, Co, Mn, Ni) including single crystals of Ti{sub 8}Co{sub 3}Ru{sub 18}B{sub 8} have been prepared by arc-melting the elements. The phases were characterized by powder X-ray diffraction (Rietveld refinement), single-crystal X-ray diffraction (for M=Co), and energy-dispersive X-ray (EDX) analysis. They are substitutional variants of the Zn{sub 11}Rh{sub 18}B{sub 8} structure type, space group P4/mbm (No. 127) and contain a “scaffold” structural unit (M-ladders interacting with M/Ti-chains) as well as isolated M/Ti-chains. According to DFT calculations, the Ru–X (X=B, Ti, Ti/M) bonding interactions are nearly constant throughout the series and responsible for the structural stability of these phases, whereas the M–M and Ru–M interactions vary significantly with varying valence electron count. Furthermore, density of states (DOS) analyses predict the phases with M=Mn and Ni to develop a total magnetic moment but not the M=Co phase. Susceptibility measurements confirm the Co phase to be paramagnetic and the Mn Phase orders ferrimagnetically below 120 K and thus develops a magnetic moment, as predicted. - Graphical abstract: The crystal structures of the new phases (M=Cr, Mn, Co, Ni) are confirmed by Rietveld refinement of powder diffraction data and single crystal X-ray diffraction (for M=Co) to contain beside the M-ladder also M/Ti-chains. Similar to the series Ti{sub 9}M{sub 2}Ru{sub 18}B{sub 8}, the crystal structure of the new phases are mainly stabilized by the heteroatomic Ru–B and Ru–Ti bonds that remain nearly constant throughout the series, whereas the M-containing bonds vary significantly with varying valence electron count. An experimental finding confirmed and even extended by COHP bonding analyses. In addition, the DOS analyses of the M-elements reveal the development of magnetic moments for the M=Mn, Ni cases but not for M=Co. Indeed, Ti{sub 8}Co

  19. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

    SciTech Connect

    Salamakha, Leonid P.; Sologub, Oksana; Stöger, Berthold; Michor, Herwig; Bauer, Ernst; Rogl, Peter F.

    2015-09-15

    New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B

  20. Solvent-extraction purification of neptunium

    SciTech Connect

    Kyser, E.A.; Hudlow, S.L.

    2008-07-01

    The Savannah River Site (SRS) has recovered {sup 237}Np from reactor fuel that is currently being processed into NpO{sub 2} for future production of {sup 238}Pu. Several purification flowsheets have been utilized. An oxidizing solvent-extraction (SX) flowsheet was used to remove Fe, sulfate ion, and Th while simultaneously {sup 237}Np, {sup 238}Pu, u, and nonradioactive Ce(IV) was extracted into the tributyl phosphate (TBP) based organic solvent. A reducing SX flowsheet (second pass) removed the Ce and Pu and recovered both Np and U. The oxidizing flowsheet was necessary for solutions that contained excessive amounts of sulfate ion. Anion exchange was used to perform final purification of Np from Pu, U, and various non-actinide impurities. The Np(IV) in the purified solution was then oxalate-precipitated and calcined to an oxide for shipment to other facilities for storage and future target fabrication. Performance details of the SX purification and process difficulties are discussed. (authors)

  1. Neptunium Valence Chemistry in Anion Exchange Processing

    SciTech Connect

    KYSER, EDWARD

    2003-02-01

    The current anion resin in use in HB-Line Phase II, Reillex{trademark} HPQ, was tested in the laboratory under expected plant conditions for Np processing and was found to load between 50 and 70 g Np per liter of resin. Losses varied from 0.2 to 15 percent depending on a number of parameters. Hydrazine in the feed at 0.02 to 0.05 M appeared to keep the Np from oxidizing and increasing the losses within four to seven days after the FS addition. Losses of up to three percent were observed five days after FS addition when hydrazine was not used in the feed, compared with 0.3 percent when the feed was loaded immediately after FS addition. Based on these test results the following processing conditions are recommended: (1) Feed conditions: 8 M HNO{sub 3}, 0.02 M hydrazine, 0.05 M excess FS, less than 5 days storage of solution after FS addition. (2) Wash conditions: 100 liters of 8 M HNO{sub 3}, no FS, no hydrazine. (3) Elution conditions: 0.17 M HNO{sub 3}, 0.05 M hydrazine, no FS. (4) Precipitation feed conditions: 0.03 M excess ascorbic acid, no additional hydrazine, no FS, precipitation within three days.

  2. Neptunium(V) adsorption to calcite

    NASA Astrophysics Data System (ADS)

    Heberling, Frank; Brendebach, Boris; Bosbach, Dirk

    2008-12-01

    The migration behavior of the actinyl ions U(VI)O 22+, Np(V)O 2+ and Pu(V,VI)O 2(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO 2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0-9.4) and concentration (0.4 μM-40 μM) conditions. pH is adjusted by variation of CO 2 partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased KD values after desorption compared to adsorption.

  3. Neptunium Monochalcogenides: Néel Temperature

    NASA Astrophysics Data System (ADS)

    Troć, R.

    This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

  4. The neptunium-iron phase diagram

    NASA Astrophysics Data System (ADS)

    Gibson, J. K.; Haire, R. G.; Beahm, E. C.; Gensini, M. M.; Maeda, A.; Ogawa, T.

    1994-08-01

    The phase relations in the Np-Fe alloy system have been elucidated using differential thermal analysis. A phase diagram for this system is postulated based upon the experimental results, regular-solution model calculations, and an expected correspondence to the U-Fe and Pu-Fe diagrams. The postulated Np-Fe diagram is characterized by limited terminal solid solubilities, two intermetallic solid phases, NpFe 2 and Np 6Fe, and two eutectics.

  5. Structure, bonding, and magnetic response in two complex borides: Zr{sub 2}Fe{sub 1-{delta}}Ru{sub 5+{delta}}B2 and Zr{sub 2}Fe{sub 1-{delta}}(Ru{sub 1-x}Rh{sub x}){sub 5+{delta}}B2

    SciTech Connect

    Brgoch, Jakoah; Yeninas, Steven; Prozorov, Ruslan; Miller, Gordon J.

    2010-12-15

    Polycrystalline samples of two complex intermetallic borides Zr{sub 2}Fe{sub 1-{delta}}Ru{sub 5+{delta}}B2 and Zr{sub 2}Fe{sub 1-{delta}}(Ru{sub 1-x}Rh{sub x}){sub 5+{delta}}B2 ({delta}=ca. 0.10; x=0.20) were synthesized by high-temperature methods and characterized by single-crystal X-ray diffraction, energy dispersive spectroscopy, and magnetization measurements. Both structures are variants of Sc{sub 2}Fe(Ru{sub 1-x}Rh{sub x}){sub 5}B{sub 2} and crystallize in the space group P4/mbm (no. 127) with the Ti{sub 3}Co{sub 5}B{sub 2}-type structure. These structures contain single-atom, Fe-rich Fe/Ru or Fe/Ru/Rh chains along the c-axis with an interatomic metal-metal distance of 3.078(1) A, a feature which makes them viable for possible low-dimensional temperature-dependent magnetic behavior. Magnetization measurements indicated weak ferrimagnetic ordering with ordering temperatures ca. 230 K for both specimens. Tight-binding electronic structure calculations on a model 'Zr{sub 2}FeRu{sub 5}B{sub 2}' using LDA yielded a narrow peak at the Fermi level assigned to Fe-Fe antibonding interactions along the c-axis, a result that indicates an electronic instability toward ferromagnetic coupling along these chains. Spin-polarized calculations of various magnetic models were examined to identify possible magnetic ordering within and between the single-atom, Fe-rich chains. -- Graphical abstract: Zr{sub 2}FeRu{sub 5-x}Rh{sub x}B{sub 2} (x=0, 1) crystallizes with magnetic atoms forming chains which have been shown to order magnetically depending on the total valence electron count. Magnetic measurements and tight-binding electronic structure calculations are employed to investigate the ordering. Display Omitted

  6. Investigation of magnetic properties and electronic structure of layered-structure borides AlT{sub 2}B{sub 2} (T=Fe, Mn, Cr) and AlFe{sub 2–x}Mn{sub x}B{sub 2}

    SciTech Connect

    Chai, Ping; Stoian, Sebastian A.; Tan, Xiaoyan; Dube, Paul A.; Shatruk, Michael

    2015-04-15

    magnetic properties of these materials. - Graphical abstract: We follow a gradual evolution of magnetic properties in a series of ternary borides AlT{sub 2}B{sub 2}, from non-magnetic AlCr{sub 2}B{sub 2} and AlMn{sub 2}B{sub 2} to ferromagnetic AlFe{sub 2}B{sub 2}. - Highlights: • AlT{sub 2}B{sub 2} (T=Fe, Mn, Cr) and AlFe{sub 2−x}Mn{sub x}B{sub 2} were prepared by arc‐melting. • Bulk ferromagnetism of AlFe{sub 2}B{sub 2} is gradually suppressed by the introduction of Mn. • AlMn{sub 2}B{sub 2} and AlCr{sub 2}B{sub 2} do not exhibit magnetic ordering. • Nonmagnetic (Mn‐rich) and ferromagnetic (Fe‐rich) clustering in AlFe{sub 2–x}Mn{sub x}B{sub 2}. • Ferromagnetism is suppressed due to weakening of antibonding T–T interactions.

  7. Femtosecond pulsed laser deposition of amorphous, ultrahard boride thin films

    NASA Astrophysics Data System (ADS)

    Stock, Michael; Molian, Pal

    2004-05-01

    Amorphous thin films (300-500 nm) of ultrahard AlMgB10 with oxygen and carbon impurities were grown on Si (100) substrates at 300 K using a solid target of AlMgB14 containing a spinel phase (MgAl2O4) and using a 120 fs pulsed, 800 nm wavelength Ti:sapphire laser. The films were subsequently annealed in argon gas up to 1373 K for 2 h. Scanning electron microscopy (SEM) was used to examine the particulate formation, atomic force microscopy was employed to characterize the film surface topography, x-ray diffraction and transmission electron microscopy were used to determine the microstructure, x-ray photoelectron spectroscopy was performed to examine the film composition, and nanoindentation was employed to study the hardness of thin films. The as-deposited and postannealed films (up to 1273 K) had a stochiometry of AlMgB10 with a significant amount of oxygen and carbon impurities and exhibited amorphous structures for a maximum hardness of 40+/-3 GPa. However, postannealing at higher temperatures led to crystallization and transformation of the film to SiB6 with a substantial loss in hardness. Results are also compared with our previous study on 23 ns, 248 nm wavelength (KrF excimer) pulsed laser deposition of AlMgB14 reported in this journal [Y. Tian, A. Constant, C. C. H. Lo, J. W. Anderegg, A. M. Russell, J. E. Snyder, and P. A. Molian, J. Vac. Sci. Technol. A 21, 1055 (2003)]. .

  8. Rare earth boride electron emitter materials fabrication and evaluation

    NASA Astrophysics Data System (ADS)

    Swanson, L. W.; Davis, P. R.; Gesley, M. A.

    1982-03-01

    Techniques were developed for routine preparation of single crystal rods of LaB6, CeB6 and PrB6 by arc float zone refining. Single crystal, oriented samples were prepared from these rods and mounted as cathodes for testing. Several mounting systems were used, and flat, pointed cone and truncated cone thermionic cathodes were studied. Pointed field emitters of LaB6(100) were also investigated. Variation of thermionic emitted current density and thermal stability of materials were studied as functions of rare earth element, bulk stoichiometry and crystal orientation. Life tests were performed on several different LaB6(100) cathodes. One such cathode operated for over 3000 hours at approximately 10 A/sq cm emitted current density with no serious physical degradation. Surface properties of the materials were investigated by various surface analysis techniques.

  9. Investigation of the fracture mechanics of boride composites

    NASA Technical Reports Server (NTRS)

    Clougherty, E. V.; Pober, R. L.; Kaufman, L.

    1972-01-01

    Significant results were obtained in fabrication studies of the role of metallic additives of Zr, Ti, Ni, Fe and Cr on the densification of ZrB2. All elemental additions lower the processing temperatures required to effect full densification of ZrB2. Each addition effects enhanced densification by a clearly distinguishable and different mechanism and the resulting fabricated materials are different. A significant improvement in strength and fracture toughness was obtained for the ZrB2/Ti composition. Mechanical characterization studies for the ZrB2/SiC/C composites and the new ZrB2/Metal materials produced data relevant to the effect of impacting load on measured impact energies, a specimen configuration for which controlled fracture could occur in a suitably hard testing apparatus, and fracture strength data. Controlled fracture--indicative of measurable fracture toughness--was obtained for the ZrB2-SiC-C composite, and a ZrB2/Ti composite fabricated from ZrB2 with an addition of 30 weight per cent Ti. The increased strength and toughness of the ZrB2/Ti composite is consistent with the presence of a significantly large amount of a fine grained acicular phase formed by reaction of Ti with ZrB2 during processing.

  10. Charge transfer and negative curvature energy in magnesium boride nanotubes

    NASA Astrophysics Data System (ADS)

    Tang, Hui; Ismail-Beigi, Sohrab

    2016-07-01

    Using first-principles calculations based on density functional theory, we study the energetics and charge transfer effects in MgBx nanotubes and two-dimensional (2D) sheets. The behavior of adsorbed Mg on 2D boron sheets is found to depend on the amount of electron transfer between the two subsystems. The amount is determined by both the density of adsorbed Mg as well as the atomic-scale structure of the boron subsystem. The degree of transfer can lead to repulsive or attractive Mg-Mg interactions. In both cases, model MgBx nanotubes built from 2D MgBx sheets can display negative curvature energy: a relatively unusual situation in nanosystems where the energy cost to curve the parent 2D sheet into a small-diameter nanotube is negative. Namely, the small-diameter nanotube is energetically preferred over the corresponding flat sheet. We also discuss how these findings may manifest themselves in experimentally synthesized MgBx nanotubes.

  11. Designing thin film materials — Ternary borides from first principles

    PubMed Central

    Euchner, H.; Mayrhofer, P.H.

    2015-01-01

    Exploiting the mechanisms responsible for the exceptional properties of aluminum based nitride coatings, we apply ab initio calculations to develop a recipe for designing functional thin film materials based on ternary diborides. The combination of binary diborides, preferring different structure types, results in supersaturated metastable ternary systems with potential for phase transformation induced effects. For the exemplary cases of MxW1 − xB2 (with M = Al, Ti, V) we show by detailed ab initio calculations that the respective ternary solid solutions are likely to be experimentally accessible by modern depositions techniques. PMID:26082562

  12. Water Sorption and Radiolysis Studies for Neptunium Oxides

    SciTech Connect

    Icenhour, A.S.

    2004-02-03

    Plans are to convert the {sup 237}Np that is currently stored as a nitrate solution at the Savannah River Site to NpO{sub 2} and then ship it to the Y-12 National Security Complex in Oak Ridge for interim storage. This material will serve as feedstock for the {sup 238}Pu production program, and some will be periodically shipped to the Oak Ridge National Laboratory (ORNL) for fabrication into targets. The safe storage of this material requires an understanding of the radiolysis of moisture that is sorbed on the oxides, which, in turn, provides a basis for storage criteria (namely, moisture content). A two-component experimental program has been undertaken at ORNL to evaluate the radiolytic effects on NpO{sub 2}: (1) moisture uptake experiments and (2) radiolysis experiments using both gamma and alpha radiation. These experiments have produced two key results. First, the water uptake experiments demonstrated that the 0.5 wt % moisture limit that has been typically established for similar materials (e.g., uranium and plutonium oxides) cannot be obtained in a practical environment. In fact, the uptake in a typical environment can be expected to be at least an order of magnitude lower than the limit. The second key result is the establishment of steady-state pressure plateaus as a result of the radiolysis of sorbed moisture. These plateaus are the result of back reactions that limit the overall pressure increase and H{sub 2} production. These results clearly demonstrate that 0.5 wt % H{sub 2}O on NpO{sub 2} is safe for long-term storage--if such a moisture content could even be practically reached.

  13. The influence of desulfovibrio desulfuricans on neptunium chemistry.

    SciTech Connect

    Soderholm, L.; Williams, C.; Antonio, M. R.; Tischler, M. L.; Markos, M.

    1999-12-20

    The role of biotic Np(V) reduction is studied in light of its potential role in the environmental immobilization of this hazardous radionuclide. The speciation of Np in Desulfovibrio desulfuricans cultures is compared with Np speciation in the spent medium and in the uninoculated medium. Precipitates formed in all three samples. Optical spectroscopy and X-ray absorption near edge structure (XANES) were used to determine that Np(V) is almost quantitatively reduced in all three samples and that the precipitate is an amorphous Np(IV) species. These results demonstrate that the reduction of Np is independent of Desulfovibrio desulfuricans. The underlying chemistry associated with these results is discussed.

  14. The transuranium elements: From neptunium and plutonium to element 112

    SciTech Connect

    Hoffman, D.C. |

    1996-07-26

    Beginning in the 1930`s, both chemists and physicists became interested in synthesizing new artificial elements. The first transuranium element, Np, was synthesized in 1940. Over the past six decades, 20 transuranium elements have been produced. A review of the synthesis is given. The procedure of naming the heavy elements is also discussed. It appears feasible to produce elements 113 and 114. With the Berkeley Gas-filled Separator, it should be possible to reach the superheavy elements in the region of the spherical Z=114 shell, but with fewer neutrons than the N=184 spherical shell. 57 refs, 6 figs.

  15. Symmetry, Optical Properties and Thermodynamics of Neptunium(V) Complexes

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2009-12-21

    Recent results on the optical absorption and symmetry of the Np(V) complexes with dicarboxylate and diamide ligands are reviewed. The importance of recognizing the 'silent' feature of centrosymmetric Np(V) species in analyzing the absorption spectra and calculating the thermodynamic constants of Np(V) complexes is emphasized.

  16. Removal of Pu238 from Neptunium Solution by Anion Exchange

    SciTech Connect

    KYSER, EDWARD

    2003-12-01

    A new anion flowsheet for use in HB-Line was tested in the lab with Reillex{trademark} HPQ for removal of Pu{sup 238} contamination from Np. Significant rejection of Pu{sup 238} was observed by washing with 6 to 12 bed volumes (BV) of reductive wash containing reduced nitric acid concentration along with both ferrous sulfamate (FS) and hydrazine. A shortened-height column was utilized in these tests to match changes in the plant equipment. Lab experiments scaled to plant batch sizes of 1500 to 2200 g Np were observed with modest losses for up-flow washing. Down-flow washing was observed to have high losses. The following are recommended conditions for removing Pu{sup 238} from Np solutions by anion exchange in HB-Line: (1) Feed conditions: Up-flow 6.4-8 M HNO{sub 3}, 0.02 M hydrazine, 0.05 M excess FS, less than 5 days storage of solution after FS addition. (2) Reductive Wash conditions: Up-flow 6-12 BV of 6.4 M HNO{sub 3}, 0.05 M FS, 0.05 M hydrazine. 1.8 mL/min/cm{sup 2} flowrate. (3) Decontamination Wash conditions: Up-flow 1-2 BV of 6.4-8 M HNO{sub 3}, no FS, no hydrazine. (4) Elution conditions: Down-flow 0.17 M HNO{sub 3}, 0.05 M hydrazine, no FS.

  17. First-principles theory of multipolar order in neptunium dioxide

    NASA Astrophysics Data System (ADS)

    Suzuki, M.-T.; Magnani, N.; Oppeneer, P. M.

    2010-12-01

    We provide a first-principles, materials-specific theory of multipolar order and superexchange in NpO2 by means of a noncollinear local-density approximation +U (LDA+U) method. Our calculations offer a precise microscopic description of the triple- q antiferro ordered phase in the absence of any dipolar moment. We find that, while the most common nondipolar degrees of freedom (e.g., electric quadrupoles and magnetic octupoles) are active in the ordered phase, both the usually neglected higher-order multipoles (electric hexadecapoles and magnetic triakontadipoles) have at least an equally significant effect.

  18. Neptunium estimation in dissolver and high-level-waste solutions

    SciTech Connect

    Pathak, P.N.; Prabhu, D.R.; Kanekar, A.S.; Manchanda, V.K.

    2008-07-01

    This papers deals with the optimization of the experimental conditions for the estimation of {sup 237}Np in spent-fuel dissolver/high-level waste solutions using thenoyltrifluoroacetone as the extractant. (authors)

  19. Thermodynamics of Neptunium (V) Complexes with Phosphate at Elevated Temperatures

    SciTech Connect

    Xia, Y.; Friese, Judah I.; Bachelor, Paula P.; Moore, Dean A.; Rao, Linfeng

    2009-06-01

    Abstract – The complexation of Np(V) with phosphate at elevated temperatures was studied by a synergistic extraction method. A mixed buffer solution of TRIS and MES was used to maintain an appropriate pH value during the distribution experiments. The distribution ratio of Np(V) between the organic and aqueous phases was found to decrease as the concentrations of phosphate were increased. Stability constants of the 1:1 and 1:2 Np(V)-HPO42- complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of [HPO42-] on the distribution ratio. The thermodynamic parameters including enthalpy and entropy of complexation between Np(V) and HPO42- at 25o C – 55o C were calculated by the temperature coefficient method.

  20. Gastrointestinal absorption of neptunium and curium in humans.

    PubMed

    Popplewell, D S; Harrison, J D; Ham, G J

    1991-06-01

    The gastrointestinal absorption of Np and Cm has been determined in five male adult volunteers. The Np and Cm, which were in citrate solution, were taken with food. An initial experiment with each individual determined the fraction of each element excreted in the urine following intravenous administration. Subsequently, the results for urinary excretion for the two routes of administration were used to calculate the fractional absorption (f1) of ingested Np and Cm. The mean f1 values were: Np (2.0 +/- 0.2) X 10(-4), range (1.2-2.9) X 10(-4), and Cm (1.7 +/- 0.3) X 10(-4), range (0.95-3.0) X 10(-4), the quoted uncertainties being the standard error of the means. Currently, the International Commission on Radiological Protection recommends a value of 10(-3) for both elements. Cumulative urinary excretion over 1 wk after intravenous injection accounted for about 20%-40% of administered Np and 7%-10% of Cm. At the conclusion of the experiment, the total committed effective dose equivalent for each volunteer was calculated to be in the range 130-250 microSv, based on the individual f1 values, and, in some cases, a knowledge of the rate of clearance of 239Np through the gut as measured by whole-body counting.

  1. Crystal dynamics and thermal properties of neptunium dioxide

    NASA Astrophysics Data System (ADS)

    Maldonado, P.; Paolasini, L.; Oppeneer, P. M.; Forrest, T. R.; Prodi, A.; Magnani, N.; Bosak, A.; Lander, G. H.; Caciuffo, R.

    2016-04-01

    We report an experimental and theoretical investigation of the lattice dynamics and thermal properties of the actinide dioxide NpO2. The energy-wave-vector dispersion relation for normal modes of vibration propagating along the [001 ] , [110 ] , and [111 ] high-symmetry lines in NpO2 at room temperature has been determined by measuring the coherent one-phonon scattering of x rays from an ˜1.2 -mg single-crystal specimen, the largest available single crystal for this compound. The results are compared against ab initio phonon dispersions computed within the first-principles density functional theory in the generalized gradient approximation plus Hubbard U correlation (GGA+U ) approach, taking into account third-order anharmonicity effects in the quasiharmonic approximation. Good agreement with the experiment is obtained for calculations with an on-site Coulomb parameter U =4 eV and Hund's exchange J =0.6 eV in line with previous electronic structure calculations. We further compute the thermal expansion, heat capacity, thermal conductivity, phonon linewidth, and thermal phonon softening, and compare with available experiments. The theoretical and measured heat capacities are in close agreement with another. About 27% of the calculated thermal conductivity is due to phonons with energy higher than 25 meV (˜6 THz ), suggesting an important role of high-energy optical phonons in the heat transport. The simulated thermal expansion reproduces well the experimental data up to about 1000 K, indicating a failure of the quasiharmonic approximation above this limit.

  2. The complexation behavior of neptunium and plutonium with nitrilotriacetic acid

    SciTech Connect

    Nitsche, H.; Becraft, K.

    1990-08-01

    The first stability constant of NpO{sub 2}{sup +} with nitrilotriacetic acid (NTA) was determined at four ionic strengths (0.5, 1.0, 2.0, 3.0 M) using spectrophotometry. Nonlinear least-squares data fitting identified the complex as NpO{sub 2}NTA{sup 2-}. The Specific Ion Interaction Theory (S.I.T) approximation method was used to determine the stability constants at infinite dilution. First results on Pu{sup 4+} and PuO{sub 2}{sup 2+} complexation with NTA are reported. The stability constant for the Pu(NTA){sup +} complex at I = 0.1 M strength is given. From results for PuO{sub 2}{sup 2+} complexation with NTA (I = 1 M) at pH < 3, the stability constant was derived for PuO{sub 2} NTA{sup {minus}}. At pH > 3, NTA partially reduced PuO{sub 2}{sup 2+} to PuO{sub 2}{sup +}. 3 refs., 5 figs., 4 tabs.

  3. Neptunium Thiophosphate Chemistry: Intermediate Behavior between Uranium and Plutonium

    SciTech Connect

    Jin, Geng Bang; Skanthakumar, S; Haire, Richard G.; Soderholm, L; Ibers, James A.

    2011-01-01

    Black crystals of Np(PS4), Np(P2S6)2, K11Np7(PS4)13, and Rb11Np7(PS4)13 have been synthesized by the reactions of Np, P2S5, and S at 1173 and 973 K; Np, K2S, P, and S at 773 K; and Np, Rb2S3, P, and S at 823 K, respectively. The structures of these compounds have been characterized by single-crystal X-ray diffraction methods. Np(PS4) adopts a three-dimensional structure with Np atoms coordinated to eight S atoms from four bidentate PS4 3 ligands in a distorted square antiprismatic arrangement. Np(PS4) is isostructural to Ln(PS4) (Ln = LaNd, Sm, GdEr). The structure of Np(P2S6)2 is constructed from three interpenetrating diamondtype frameworks with Np atoms coordinated to eight S atoms from four bidentate P2S6 2 ligands in a distorted square antiprismatic geometry. The centrosymmetric P2S6 2 anion comprises two PS2 groups connected by two bridging S centers. Np(P2S6)2 is isostructural to U(P2S6)2. A11Np7(PS4)13 (A = K, Rb) adopts a threedimensional channel structure built from interlocking [Np7(PS4)13]11-screw helices with A cations residing in the channels. The structure of A11Np7(PS4)13 includes four crystallographically independent Np atoms. Three are connected to eight S atoms in bicapped trigonal prisms. The other Np atom is connected to nine S atoms in a tricapped trigonal prism. A11Np7(PS4)13 is isostructural to A11U7(PS4)13. From NpS bond distances and charge-balance, we infer that Np is trivalent in Np(PS4) and tetravalent in Np(P2S6)2 and A11Np7(PS4)13.Np exhibits a behavior intermediate betweenUand Pu in its thiophosphate chemistry.

  4. The solubility and colloidal behaviour of neptunium (IV).

    PubMed

    Moriyama, H; Pratopo, M I; Higashi, K

    1989-07-15

    The solubility and colloidal particle formation of Np(IV) in 10(-1) M Na2S2O4 solution in the pH range 2-10 were studied by sequential filtration with decreasing filter pore size. With the help of spectrophotometry and an extraction technique, the species remaining in the final filtrate were found to be Np(V) at pH less than 6 and Np(IV) at pH greater than 8; particle species were attributed to Np(IV). The solubility data obtained at pH less than 6 were interpreted using the reaction: Np(OH)4(am)----NpO2+ + e- + 2H2O, log K = -6.7 +/- 0.4 At pH greater than 8, the solubility increased rapidly with increasing pH in the presence of air, and this was interpreted as being due to the formation of the negatively charged species Np(CO3)4x - 2x. The formation constants beta 3 and beta 4 were estimated to be similar to those reported for Pu(IV). The size distribution of colloidal Np(IV) was also obtained. Some simple models used to describe the observed size distributions and to estimate the equilibrium size distributions of colloidal Np(IV) were examined.

  5. Neptunium redox behavior and solubility in J-13 conditions

    SciTech Connect

    Efurd, D.W.; Runde, W.; Tait, C.D.

    1997-08-01

    In order to confirm that the redox reaction Np(V) to Np(IV) may occur, studies are being conducted including exposure of Np(V) to solutions of known E{sub h} vs pH, temperature. Analytic results from ongoing solubility experiments from undersaturation, using Np solids formed in previous oversaturation experiments, are reported.

  6. Thermal expansion of neptunium-uranium mixed oxides

    NASA Astrophysics Data System (ADS)

    Yamashita, Toshiyuki; Nitani, Noriko; Tsuji, Toshihide; Kato, Tetsuya

    1997-08-01

    Thermal expansions of Np yU{1-y}O 2 solid solutions were investigated between room temperature and 1273 K by a high temperature X-ray diffraction technique. The lattice parameters of Np yU 1-yO 2 solid solutions at high temperatures were given in polynomial expressions of temperature. High temperature heat capacities, Cp of Np yU 1-yO 2 solid solutions were estimated from the thermodynamic relation using the measured thermal expansions and literature data. The estimated errors in the calculated Cp of UO 2 were less than ±5%.

  7. Gas-phase combustion synthesis of titanium boride (TiB{sub 2}) nanocrystallites

    SciTech Connect

    Axelbaum, R.L.; DuFaux, D.P.; Frey, C.A.; Kelton, K.F.; Lawton, S.A.; Rosen, L.J.; Sastry, S.M.

    1996-04-01

    Two techniques are described for synthesizing nanometer-sized TiB{sub 2} particles by gas-phase combustion reactions of sodium vapor with TiCl{sub 4} and BCl{sub 3}: a low-pressure, low temperature burner and a high-temperature flow reactor. Both methods produce TiB{sub 2} particles that are less than 15 nm in diameter. The combustion by-product, NaCl, is efficiently removed from the TiB{sub 2} by water washing or vacuum sublimation. Material collected from the low-temperature burner and annealed at 1000{degree}C consists of loosely agglomerated particles 20 to 100 nm in size. Washed material from the high-temperature flow reactor consists of necked agglomerates of 3 to 15 nm particles. A thermodynamic analysis of the Ti/B/Cl/Na system indicates that near 100{percent} yields of TiB{sub 2} are possible with appropriate reactant concentrations, pressures, and temperatures. {copyright} {ital 1996 Materials Research Society.}

  8. Improving Hardness and Toughness of Boride Composites Based on AIMgB14

    SciTech Connect

    Peters, Justin Steven

    2007-01-01

    The search for new super-hard materials has usually focused on strongly bonded, highly symmetric crystal structures similar to diamond. The two hardest single-phase materials, diamond and cubic boron nitride (cBN), are metastable, and both must be produced at high temperatures and pressures, which makes their production costly. In 2000, a superhard composite based on a low-symmetry, boron-rich compound was reported. Since then, many advances have been made in the study of this AlMgB14-TiB2 composite. The composite has been shown to exhibit hardness greater than either of its constituent phases, relying on its sub-micron microstructure to provide hardening and strengthening mechanisms. With possible hardness around 40 GPa, an AlMgB14 - 60 vol% TiB2 approaches the hardness of cBN, yet is amenable to processing under ambient pressure conditions. There are interesting aspects of both the AlMgB14 and TiB2 phases. AlMgB14 is comprised of a framework of boron, mostly in icosahedral arrangements. It is part of a family of 12 known compounds with the same boron lattice, with the metal atoms replaced by Li, Na, Y or a number of Lanthanides. Another peculiar trait of this family of compounds is that every one contains a certain amount of intrinsic vacancies on one or both of the metal sites. These vacancies are significant, ranging from 3 to 43% of sites depending on the composition. TiB2 is a popular specialty ceramic material due to its high hardness, moderate toughness, good corrosion resistance, and high thermal and electrical conductivity. The major drawback is the difficulty of densification of pure TiB2 ceramics. A combination of sintering aids, pressure, and temperatures of 1800 C are often required to achieve near full density articles. The AlMgB14 - TiB2 composites can achieve 99% density from hot-pressing at 1400 C. This is mostly due to the preparation of powders by a high-energy milling technique known as mechanical alloying. The resulting fine powders have high activity, and Fe from wear debris acts as a sintering aid. Mechanical alloying improves the sinterability of the composite material, it has the same effect on pure TiB2. TiB2 processed by high-energy milling has been found to achieve 99% theoretical density at 1400 C with the addition of ~1 wt% Fe. Both the AlMgB14 - TiB2 composites and pure TiB2 produced from these methods have enhanced mechanical properties due to their fine microstructures. These materials show exceptional promise in the field of wear resistance. This includes cutting tools, erosion resistant coatings, and low-friction sliding contacts to name a few. Under certain wear conditions, the composite material can show performance on par with that of current high-end cBN and WC materials tailored for wear resistance. The composite material also exhibits low reactivity with Ti alloys, a pre-requisite for effective machining of these alloys, a trait that few hard materials possess.

  9. Al insertion and additive effects on the thermoelectric properties of yttrium boride

    SciTech Connect

    Maruyama, Satofumi; Prytuliak, Anastasiia; Miyazaki, Yuzuru; Hayashi, Kei; Kajitani, Tsuyoshi; Mori, Takao

    2014-03-28

    The aluminoboride Y{sub x}Al{sub y}B{sub 14} (x ∼ 0.57, 0.41 ≤ y ≤ 0.63) has been found to show striking p-n control of the thermoelectric properties through variations of the y occupancy of the Al site. The effect of Al was investigated in further extremes. Polycrystalline samples of Al-free Y{sub x}B{sub 14}(x ∼ 0.55; “YB{sub 25}”) were successfully synthesized in sufficient amounts for bulk spark plasma sintering (SPS) samples and their thermoelectric properties were investigated. Y{sub 0.56}Al{sub 0.57}B{sub 14} was also prepared in comparison, and further Al was added to the samples through SPS treatment. We observed that Y{sub 0.55}B{sub 14} exhibits large positive Seebeck coefficients, ∼1000 μV K{sup −1}, around room temperature and the absolute value of the Seebeck coefficient largely decreases with increase of temperature while that of Y{sub 0.56}Al{sub 0.57}B{sub 14} is proportional to T{sup −1/2}, indicating a strong effect of Al on the electronic structure around the Fermi level. Y{sub 0.55}B{sub 14} was found to be strongly disordered with a relatively low thermal conductivity and short localization length of 0.65 Å which is close to that previously determined for the disordered and thermally glass-like compound YB{sub 66}. Occupancy of Al could not be increased further for the Al-rich sample, although Al was discovered to act as a sintering aid to enhance density and ZT could be significantly improved by 50%.

  10. Epitaxial Growth of Icosahedral Boride Semiconductors for Novel Energy Conversion Devices

    SciTech Connect

    Edgar, J.H.

    2006-01-03

    The chemical vapor deposition and properties of the boron-rich semiconductors B12As2 and B12P2 on 6H-SiC(0001) and silicon substrates were investigated. Crystalline, stoichiometric films were deposited between 1200 C and 1500 C using two types of reactants, hydrides (B2H6 and AsH3) for B12As2 and halides (BBr3 and PBr3) for B12P2. 6H-SiC proved to be the better substrate for B12As2 heteroepitaxy, in terms of the residual impurity concentrations. Films on Si substrates suffered from high concentrations of Si (up to 4at.%); in contrast, the Si and C concentrations in the B12As2 films deposited on 6H-SiC at 1300 C were at or below the detection limits of secondary ion mass spectrometry (SIMS). The deposition temperature was significant as films deposited at 1450 C contained high residual C and Si concentrations (>1020 cm-3), probably due to the decomposition of the substrate. The hydrogen concentration in all B12As2 films was relatively high, with a minimum concentration of 3x1019 cm-3 in undoped B12As2. SIMS measurements showed that the hydrogen concentration was directly proportional to and tracked the Si concentration, reaching values as high as 3 x 1020 cm-3. The structural properties of the B12As2 films were characterized by x-ray diffraction and transmission electron microscopy. The FWHM of typical high resolution x-ray rocking curves for the (333) peaks of the B12As2 films were 800 arcsec. The films are under tensile strain due the higher coefficient of thermal expansion for B12As2 than SiC. Rotational twins were present in B12As2 films deposited on (0001) oriented 6H-SiC substrates, as revealed by cross-sectional TEM and x-ray diffraction pole figures. While the c-plane 6H-SiC has six-fold rotational symmetry, rhombohedral B12As2 has only 3-fold symmetry (along its (111) axis), thus it randomly nucleates with two different in-plane orientations. The electrical properties of undoped and silicon-doped B12As2 deposited on semi-insulating 6H-SiC substrates were characterized by Hall effect measurements. The resistivity of p-type B12As2 films on semi-insulating 6H-SiC(0001) substrates was controllably varied over nearly four orders of magnitude by changing the concentrations of silicon into the films, incorporated by adding silane during deposition. The electrical properties of the B12As2 suffered from low hole mobilities, typically less than 3 cm2/V's. This was possibly a consequence of structural defects in the films. The resistivity of as-deposited undoped and silicon-doped B12As2 films decreased by two or more orders of magnitude after annealing at temperatures above 600 C in argon. This unexpected but reproducible effect of annealing on the resistivity of the semiconductor warrants further investigation. The properties of palladium, platinum, and chromium/platinum electrical contacts to B12As2 were tested at Pennsylvania State University. The Pd and Pt contacts exhibited nonlinear I-V characteristics and severe agglomeration upon annealing, but the Cr/Pt contacts were ohmic and remained smooth even after they were annealed at 750 C. The specific contact resistance of the Cr/Pt contacts dropped four orders of magnitude after samples were annealed in Ar for 30 s at 750 C. This reduction in specific contact resistance was linked to a simultaneous drop in the resistivity of B12As2 upon annealing. In subsequent experiments, a low specific contact resistance was also achieved when Cr/Pt was deposited on B12As2 films that were annealed prior to metallization instead of afterwards.

  11. Microstructure and thermal stability of transition metal nitrides and borides on GaN

    SciTech Connect

    Jasinski, J.; Kaminska, E.; Piotrowska, A.; Barcz, A.; Zielinski, M.

    2000-06-28

    Microstructure and thermal stability of ZrN/ZrB2 bilayer deposited on GaN have been studied using transmission electron microscopy methods (TEM) and secondary ion mass spectrometry (SIMS). It has been demonstrated that annealing of the contact structure at 1100 C in N2 atmosphere does not lead to any observable metal/ semiconductor interaction. In contrast, a failure of the integrity of ZrN/ZrB2 metallization at 800 C, when the heat treatment is performed in O2 ambient has been observed.

  12. Microstructure and mechanical properties of titanium alloys reinforced with titanium boride

    NASA Astrophysics Data System (ADS)

    Hill, Davion M.

    Microstructure features in TiB-reinforced titanium alloys are correlated with mechanical properties. Both laser deposition and arc melting are used to fabricate test alloys where microstructure evolution with heat treatment is examined. SEM and TEM investigations of microstructure are coupled with 3D reconstruction to provide an adequate picture of phases in these alloys. Mechanical properties are then studied. Wear testing of several test alloys is presented, followed by hardness and modulus measurements of individual phases via micro- and nano-indentation as well as a novel micro-compression technique. Bulk mechanical properties are then tested in Ti-6Al-4V and Ti-555 (Ti-5Al-5V-5Mo-3Cr-1Fe) with varying amounts of boron. Image processing methods are then applied to high resolution back-scattered scanning electron microscope images to quantify microstructure features in the tensile test specimens, and these values are then correlated with mechanical properties.

  13. Distribution of neptunium and plutonium in New Mexico lichen samples (Usnea arizonica) contaminated by atmospheric fallout

    DOE PAGESBeta

    Oldham, Jr., Warren J.; Hanson, Susan K.; Lavelle, Kevin B.; Miller, Jeffrey L.

    2015-08-30

    In this study, the concentrations of 237Np, 239Pu and 240Pu were determined in lichen samples (Usnea arizonica) that were collected from ten locations in New Mexico between 2011 and 2013 using isotope dilution inductively-coupled plasma mass spectrometry (ID-ICP-MS). The observed isotopic ratios for 237Np/239Pu and 240Pu/239Pu indicate trace contamination from global and regional fallout (e.g. Trinity test and atmospheric testing at the Nevada Test Site). The fact that actinide contamination is detected in recent lichen collections suggests continuous re-suspension of fallout radionuclides even 50 years after ratification of the Limited Test Ban Treaty.

  14. Reactor Physics Assessment of the Inclusion of Unseparated Neptunium in MOX Reactor Fuel

    SciTech Connect

    Ellis, Ronald James

    2009-01-01

    Reducing the number of actinide separation streams in a spent fuel recovery process would reduce the cost and complexity of the process, and lower the quantity and numbers of solvents needed. It is more difficult and costly to separate Np and recombine it with Am-Cm prior to co-conversion than to simply co-strip it with the U-Pu-Np. Inclusion of the Np in mixed oxide (MOX) fuel for light water reactor (LWR) applications should not seriously affect the operating behavior of the reactor, nor should it pose insurmountable fuel design issues. In this work, the U, Pu, and Np from typical discharged and cooled PWR spent nuclear fuel are assumed to be used together in the preparation of MOX fuel for use in a pressurized water reactor (PWR). The reactor grade Pu isotopic vector is used in the model and the relative mass ratio of the Pu and Np content (Np/Pu mass is 0.061) from the cooled spent fuel is maintained but the overall Pu-Np MOX wt% is adjusted with respect to the U content (assumed to be at 0.25 wt% 235U enrichment) to offset reactivity and cycle length effects. The SCALE 5.1 scientific package (especially modules TRITON, NEWT, ORIGEN-S, ORIGEN-ARP) was used for the calculations presented in this paper. A typical Westinghouse 17x17 fuel assembly design was modeled at nominal PWR operating conditions. It was seen that U-Pu-Np MOX fuel with NpO2 and PuO2 representing 11.5wt% of the total MOX fuel would be similar to standard MOX fuel in which PuO2 is 9wt% of the fuel. The reactivity, isotopic composition, and neutron and ? sources, and the decay heat details for the discharged MOX fuel are presented and discussed in this paper.

  15. Prediction Models for Plutonium, Strontium, Uranium and Neptunium Loading onto Monosodium Titanate (MST)

    SciTech Connect

    Fondeur, F. F.; Hobbs, D. T.; Barnes, M. J.; Peters, T. B.; Fink, S. D.

    2005-07-11

    The DA isotherm parameters for U, Pu, Sr and Np have been updated to include additional data obtained since the original derivation. The DA isotherms were modified to include a kinetic function derived by Rahn to describe sorbate loading from the beginning of sorption up to equilibrium. The final functions describe both kinetic and thermodynamic sorption. We selected the Rahn function to describe radionuclide sorption because it originates from diffusion and absorption controlled sorption. An investigation of the thermal behavior of radionuclide sorption on MST as shown by this data revealed the sorption process is diffusion (or transport) controlled (in solution). Transport in solution can in theory be accelerated by vigorous mixing but the range of available mixing speed in the facility design will probably not be sufficient to markedly increase radionuclide sorption rate on MST from diffusion-controlled sorption. The laboratory studies included mixing energies hydraulically-scaled to match those of the Actinide Removal Process and these likely approximate the range of energies available in the Salt Waste Processing Facility.

  16. Assessment of Neptunium, Americium, and Curium in the Savannah River Site Environment

    SciTech Connect

    Carlton, W.H.

    1997-12-17

    A series of documents has been published in which the impact of various radionuclides released to the environment by Savannah River Site (SRS) operations has been assessed. The quantity released, the disposition of the radionuclides in the environment, and the dose to offsite individuals has been presented for activation products, carbon cesium, iodine, plutonium, selected fission products, strontium, technetium, tritium, uranium, and the noble gases. An assessment of the impact of nonradioactive mercury also has been published.This document assesses the impact of radioactive transuranics released from SRS facilities since the first reactor became operational late in 1953. The isotopes reported here are 239Np, 241Am, and 244Cm.

  17. TOWARD AN IMPROVED UNDERSTANDING OF STRUCTURE AND MAGNETISM IN NEPTUNIUM AND PLUTONIUM PHOSPHONATES AND SULFONATES

    SciTech Connect

    Albrecht-Schmitt, Thomas

    2012-03-01

    This grant supported the exploratory synthesis of new actinide materials with all of the actinides from thorium to californium with the exceptions of protactinium and berkelium. We developed detailed structure-property relationships that allowed for the identification of novel materials with selective ion-exchange, selective oxidation, and long-range magnetic ordering. We found novel bonding motifs and identified periodic trends across the actinide series. We identified structural building units that would lead to desired structural features and novel topologies. We also characterized many different spectroscopic trends across the actinide series. The grant support the preparation of approximately 1200 new compounds all of which were structurally characterized.

  18. Spectrophotometric and electrochemical study of neptunium ions in molten NaCl-CsCl eutectic

    NASA Astrophysics Data System (ADS)

    Uehara, Akihiro; Nagai, Takayuki; Fujii, Toshiyuki; Shirai, Osamu; Yamana, Hajimu

    2013-06-01

    The chemical oxidation states of NpO2+, Np4+ and Np3+ in NaCl-CsCl eutectic were controlled by using Cl2, O2, H2 and Ar gas mixtures, the redox behavior and electronic absorption properties of their Np ions were studied. The Np4+ was prepared from NpO2Cl by bubbling Cl2 gas into the melt in the presence of carbon rod. Np3+ was quantitatively prepared by bubbling H2-Ar gas mixture. The molar absorptivities of NpO2+, Np4+ and Np3+ were determined in molten NaCl-CsCl eutectic at 923 K and hypersensitive transitions of Np4+ and Np3+ ions were assigned. Since the polarizing ability of the cations in the NaCl-CsCl eutectic is lower than that in some other melts, it has been shown that the coordination symmetry of the Np-Cl complex is higher. In the electrochemical measurement of Np4+, the cathodic current for the reduction of Np4+ was found to be controlled by the diffusion of Np4+. The temperature dependence of the diffusion coefficient between 823 and 923 K was formulated to be lnD=-4304/T-6.172. The formal redox potential of the Np4+|Np3+ couple depended on the temperature, this dependence was formulated as ENp|Np∘'=-1.313+6.210×10-4T V (vs. Cl2|Cl-).

  19. Criticality experiments and benchmarks for cross section evaluation: the neptunium case

    NASA Astrophysics Data System (ADS)

    Leong, L. S.; Tassan-Got, L.; Audouin, L.; Paradela, C.; Wilson, J. N.; Tarrio, D.; Berthier, B.; Duran, I.; Le Naour, C.; Stéphan, C.

    2013-03-01

    The 237Np neutron-induced fission cross section has been recently measured in a large energy range (from eV to GeV) at the n_TOF facility at CERN. When compared to previous measurement the n_TOF fission cross section appears to be higher by 5-7% beyond the fission threshold. To check the relevance of n_TOF data, we apply a criticality experiment performed at Los Alamos with a 6 kg sphere of 237Np, surrounded by enriched uranium 235U so as to approach criticality with fast neutrons. The multiplication factor ke f f of the calculation is in better agreement with the experiment (the deviation of 750 pcm is reduced to 250 pcm) when we replace the ENDF/B-VII.0 evaluation of the 237Np fission cross section by the n_TOF data. We also explore the hypothesis of deficiencies of the inelastic cross section in 235U which has been invoked by some authors to explain the deviation of 750 pcm. With compare to inelastic large distortion calculation, it is incompatible with existing measurements. Also we show that the v of 237Np can hardly be incriminated because of the high accuracy of the existing data. Fission rate ratios or averaged fission cross sections measured in several fast neutron fields seem to give contradictory results on the validation of the 237Np cross section but at least one of the benchmark experiments, where the active deposits have been well calibrated for the number of atoms, favors the n_TOF data set. These outcomes support the hypothesis of a higher fission cross section of 237Np.

  20. Validation of Cross Sections with Criticality Experiment and Reaction Rates: the Neptunium Case

    NASA Astrophysics Data System (ADS)

    Leong, L. S.; Tassan-Got, L.; Audouin, L.; Berthier, B.; Le Naour, C.; Stéphan, C.; Paradela, C.; Tarrío, D.; Duran, I.

    2014-04-01

    The 237Np neutron-induced fission cross section has been recently measured in a large energy range (from eV to GeV) at the n_TOF facility at CERN. When compared to previous measurements the n_TOF fission cross section appears to be higher by 5-7% beyond the fission threshold. To check the relevance of the n_TOF data, we considered a criticality experiment performed at Los Alamos with a 6 kg sphere of 237Np, surrounded by uranium highly enriched in 235U so as to approach criticality with fast neutrons. The multiplication factor keff of the calculation is in better agreement with the experiment when we replace the ENDF/B-VII.0 evaluation of the 237Np fission cross section by the n_TOF data. We also explored the hypothesis of deficiencies of the inelastic cross section in 235U which has been invoked by some authors to explain the deviation of 750 pcm. The large modification needed to reduce the deviation seems to be incompatible with existing inelastic cross section measurements. Also we show that the νbar of 237Np can hardly be incriminated because of the high accuracy of the existing data. Fission rate ratios or averaged fission cross sections measured in several fast neutron fields seem to give contradictory results on the validation of the 237Np cross section but at least one of the benchmark experiments, where the active deposits have been well calibrated for the number of atoms, favors the n_TOF data set. These outcomes support the hypothesis of a higher fission cross section of 237Np.

  1. Site-selective magnetic order of neptunium in Np2Ni17

    NASA Astrophysics Data System (ADS)

    Hen, A.; Magnani, N.; Griveau, J.-C.; Eloirdi, R.; Colineau, E.; Sanchez, J.-P.; Halevy, I.; Kozub, A. L.; Shick, A. B.; Orion, I.; Caciuffo, R.

    2015-07-01

    We present the results obtained by superconducting quantum interference device (SQUID) magnetometry, specific heat, and Mössbauer spectroscopy measurements carried out on Np2Ni17 polycrystalline samples. We show that long-range magnetic order, with a moment μ(2 b )˜2.25 μB, occurs below TN=17.5 K on the Np (2 b ) sites. A nontrivial situation is observed in that the other Np sites (2 d ) do not take part to the order transition and carry only an induced moment of about 0.2 μB below TN. A combined analysis of the different experimental data sets allowed us to determine key parameters associated with the electronic structure of the system. The experimental results are discussed against first-principles electronic structure calculations based on the spin-polarized local spin density approximation plus Hubbard interaction.

  2. Absence of superconductivity in fluorine-doped neptunium pnictide NpFeAsO

    NASA Astrophysics Data System (ADS)

    Walters, A. C.; Walker, H. C.; Springell, R.; Krisch, M.; Bosak, A.; Hill, A. H.; Zvorişte-Walters, C. E.; Colineau, E.; Griveau, J.-C.; Bouëxière, D.; Eloirdi, R.; Caciuffo, R.; Klimczuk, T.

    2015-08-01

    X-ray diffraction, specific heat, magnetic susceptibility and inelastic x-ray scattering measurements on the transurarium oxypnictides NpFeAsO and NpFeAsO0.85F0.15 are presented. No superconductivity down to 2 K was observed upon fluorine doping, contrary to the structurally analogous rare-earth pnictides. No modification of the phonon density of states was observed upon doping with fluorine. We discuss our results in light of the latest experimental and theoretical studies on the role of phonons in the superconducting pnictide compounds.

  3. Understanding the interactions of neptunium and plutonium ions with graphene oxide: scalar-relativistic DFT investigations.

    PubMed

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-11-01

    Due to the vast application potential of graphene oxide (GO)-based materials in nuclear waste processing, it is of pivotal importance to investigate the interaction mechanisms between actinide cations such as Np(V) and Pu(IV, VI) ions and GO. In this work, we have considered four types of GOs modified by hydroxyl, carboxyl, and carbonyl groups at the edge and epoxy group on the surface, respectively. The structures, bonding nature, and binding energies of Np(V) and Pu(IV, VI) complexes with GOs have been investigated systematically using scalar-relativistic density functional theory (DFT). Geometries and harmonic frequencies suggest that Pu(IV) ions coordinate more easily with GOs compared to Np(V) and Pu(VI) ions. NBO and electron density analyses reveal that the coordination bond between Pu(IV) ions and GO possesses more covalency, whereas for Np(V) and Pu(VI) ions electrostatic interaction dominates the An-OG bond. The binding energies in aqueous solution reveal that the adsorption abilities of all GOs for actinide ions follow the order of Pu(IV) > Pu(VI) > Np(V), which is in excellent agreement with experimental observations. It is expected that this study can provide useful information for developing more efficient GO-based materials for radioactive wastewater treatment.

  4. The gastrointestinal absorption of neptunium, plutonium and americium in a primate (C. jacchus).

    PubMed

    Ham, G J; Harrison, J D; Popplewell, D S; Garrod, I; Wilson, J; Dayan, A D

    1994-05-01

    Mixtures of Np, Pu and Am were administered to primates (C. jacchus) by gastric intubation to measure their fractional gastrointestinal absorption (f1 values). The values obtained were about 2 x 10(-3) and 1 x 10(-3), respectively, for Np and Pu administered as the citrate, and 2 x 10(-3) and 6 x 10(-4), respectively, for Pu and Am in potato. The significance of these values in terms of absorption in humans is discussed.

  5. Absence of superconductivity in fluorine-doped neptunium pnictide NpFeAsO.

    PubMed

    Walters, A C; Walker, H C; Springell, R; Krisch, M; Bosak, A; Hill, A H; Zvorişte-Walters, C E; Colineau, E; Griveau, J-C; Bouëxière, D; Eloirdi, R; Caciuffo, R; Klimczuk, T

    2015-08-19

    X-ray diffraction, specific heat, magnetic susceptibility and inelastic x-ray scattering measurements on the transurarium oxypnictides NpFeAsO and NpFeAsO0.85F0.15 are presented. No superconductivity down to 2 K was observed upon fluorine doping, contrary to the structurally analogous rare-earth pnictides. No modification of the phonon density of states was observed upon doping with fluorine. We discuss our results in light of the latest experimental and theoretical studies on the role of phonons in the superconducting pnictide compounds.

  6. Kinetics and Equilibrium Sorption Models: Fitting Plutonium, Strontium, Uranium and Neptunium Loading on Monosodium Titanate (MST)

    SciTech Connect

    Fondeur, F

    2006-03-08

    The Dubinin-Astashov (DA) isotherm parameters for U, Pu, Sr and Np have been updated to include additional data obtained since the original derivation. The DA isotherms were modified to include a kinetic function derived by Rahn to describe sorbate loading from the beginning of sorption up to steady state. The final functions describe both kinetic and thermodynamic sorption.

  7. Microcalorimetric measurement of reaction enthalpies in solutions of uranium and neptunium compounds

    SciTech Connect

    Schreiner, F.; Friedman, A.M.; Richards, R.R.; Sullivan, J.C.

    1984-01-01

    The formation of complexes of uranyl and neptunyl(VI) ions with carbonate and hydrogen carbonate has been studied by titration microcalorimetry. The measurements were carried out with a computer-controlled microcalorimeter which is described in detail. Sample volumes are typically in the range of 1.5 to 2.5 ccm, containing about 0.05 millimole of the ionic species to be studied. The small volume renders the calorimeter useful for the measurement of uncommon and strongly radioactive substances. Enthalpies of reaction were obtained for the formation of the dicarbonato and the tricarbonato uranyl ions in a sulfate medium of ionic strength 1.6. The enthalpies are ..delta..H/sub 2/ = -39.6 +- 1 kJ/mol and -57.5 +- 1.5 kJ/mol, respectively. The titration data for the neptunyl(VI) - carbonate system yield a value of -50 +- 2 kJ/mol for the tricarbonato-neptunyl ion when interpreted in analogy to the uranyl system.

  8. NEPTUNIUM IV AND V SORPTIN TO END-MEMBER SUBSURFACE SEDIMENTS TO THE SAVANNAH RIVER SITE

    SciTech Connect

    Kaplan, D.

    2009-11-13

    Migration of Np through the subsurface is expected to be primarily controlled by sorption to sediments. Therefore, understanding and quantifying Np sorption to sediments and sediments from the Savannah River Site (SRS) is vital to ensure safe disposal of Np bearing wastes. In this work, Np sorption to two sediments representing the geological extremes with respect to sorption properties expected in the SRS subsurface environment (named 'subsurface sandy sediment' and 'subsurface clayey sediment') was examined under a variety of conditions. First a series of baseline sorption tests at pH 5.5 under an oxic atmosphere was performed to understand Np sorption under typical subsurface conditions. These experiments indicated that the baseline K{sub d} values for the subsurface sandy and subsurface clayey sediments are 4.26 {+-} 0.24 L kg{sup -1} and 9.05 {+-} 0.61 L kg{sup -1}, respectively. These Np K{sub d} values of SRS sediments are the first to be reported since Sheppard et al. (1979). The previous values were 0.25 and 0.16 L kg{sup -1} for a low pH sandy sediment. To examine a possible range of K{sub d} values under various environmental scenarios, the effects of natural organic matter (NOM, also a surrogate for cellulose degradation products), the presence of various chemical reductants, and an anaerobic atmosphere on Np sorption were examined. The presence of NOM resulted in an increase in the Np K{sub d} values for both sediments. This behavior is hypothesized to be the result of formation of a ternary Np-NOM-sediment complex. Slight increases in the Np sorption (K{sub d} 13-24 L kg{sup -1}) were observed when performing experiments in the presence of chemical reductants (dithionite, ascorbic acid, zero-valent iron) or under anaerobic conditions. Presumably, the increased sorption can be attributed to a slight reduction of Np(V) to Np(IV), the stronger sorbing form of Np. The most significant result of this study is the finding that Np weakly sorbs to both end member sediments and that Np only has a slight tendency to reduce to its stronger sorbing form, even under the most strongly reducing conditions expected under natural SRS conditions. Also, it appears that pH has a profound effect on Np sorption. Based on the these new measurements and the revelations about Np redox chemistry, the following changes to 'Best K{sub d}' values, as defined in Kaplan (2006), for SRS performance assessment calculations are recommended.

  9. Neptunium Transport Behavior in the Vicinity of Underground Nuclear Tests at the Nevada Test Site

    SciTech Connect

    Zhao, P; Tinnacher, R M; Zavarin, M; Williams, R W; Kersting, A B

    2010-12-03

    We used short lived {sup 239}Np as a yield tracer and state of the art magnetic sector ICP-MS to measure ultra low levels of {sup 237}Np in a number of 'hot wells' at the Nevada National Security Site (NNSS), formerly known as the Nevada Test Site (NTS). The results indicate that {sup 237}Np concentrations at the Almendro, Cambric, Dalhart, Cheshire and Chancellor sites, are in the range of 3 x 10{sup -5} to 7 x 10{sup -2} pCi/L and well below the MCL for alpha emitting radionuclides (15 pCi/L) (EPA, 2009). Thus, while Np transport is believed to occur at the NNSS, activities are expected to be well below the regulatory limits for alpha-emitting radionuclides. We also compared {sup 237}Np concentration data to other radionuclides, including tritium, {sup 14}C, {sup 36}Cl, {sup 99}Tc, {sup 129}I, and plutonium, to evaluate the relative {sup 237}Np transport behavior. Based on isotope ratios relative to published unclassified Radiologic Source Terms (Bowen et al., 1999) and taking into consideration radionuclide distribution between melt glass, rubble and groundwater (IAEA, 1998), {sup 237}Np appears to be substantially less mobile than tritium and other non-sorbing radionuclides, as expected. However, this analysis also suggests that {sup 237}Np mobility is surprisingly similar to that of plutonium. The similar transport behavior of Np and Pu can be explained by one of two possibilities: (1) Np(IV) and Pu(IV) oxidation states dominate under mildly reducing NNSS groundwater conditions resulting in similar transport behavior or (2) apparent Np transport is the result of transport of its parent {sup 241}Pu and {sup 241}Am isotopes and subsequent decay to {sup 237}Np. Finally, measured {sup 237}Np concentrations were compared to recent Hydrologic Source Term (HST) models. The 237Np data collected from three wells in Frenchman Flat (RNM-1, RNM-2S, and UE-5n) are in good agreement with recent HST transport model predictions (Carle et al., 2005). The agreement provides confidence in the results of the predictive model. The comparison to Cheshire HST model predictions (Pawloski et al, 2001) is somewhat ambiguous due to the low concentration resolution of the particle transport model.

  10. Redox and complexation interactions of neptunium(V) with quinonoid-enriched humic derivatives

    SciTech Connect

    Shcherbina, Natalia S.; Perminova, Irina V.; Kalmykov, Stephan N.; Kovalenko, Anton N.; Novikov, Alexander P.; Haire, Richard {Dick} G

    2007-01-01

    Actinides in their higher valence states (e.g., MO{sub 2}{sup +} and MO{sub 2}{sup 2+}, where M can be Np, Pu, etc) possess a higher potential for migration and in turn pose a substantial environmental threat. To minimize this potential for migration, reducing them to lower oxidation states (e.g., their tetravalent state) can be an attractive and efficient remedial process. These lower oxidation states are often much less soluble in natural aqueous media and are, therefore, less mobile in the environment. The research presented here focuses on assessing the performance of quinonoid-enriched humic derivatives with regards to complexing and/or reducing Np(V) present in solution. These 'designer' humics are essentially derived reducing agents that can serve as reactive components of a novel humic-based remediation technology. The derivatives are obtained by incorporating different quinonoid-moieties into leonardite humic acids. Five quinonoid-derivatives are tested in this work and all five prove more effective as reducing agents for selected actinides than the parent leonardite humic acid, and the hydroquinone derivatives are better than the catechol derivatives. The reduction kinetics and the Np(V) species formed with the different derivatives are studied via a batch mode using near-infrared (NIR)-spectroscopy. Np(V) reduction by the humic derivatives under anoxic conditions at 293 K and at pH 4.7 obeys first-order kinetics. Rate constants range from 1.70 x 10{sup -6} (parent humic acid) to 1.06 x 10{sup -5} sec{sup -1} (derivative with maximum hydroquinone content). Stability constants for Np(V)-humic complexes calculated from spectroscopic data produce corresponding Log{beta} values of 2.3 for parent humic acid and values ranging from 2.5 to 3.2 at pH 4.7 and from 3.3 to 3.7 at pH 7.4 for humic derivatives. Maximum constants are observed for hydroquinone-enriched derivatives. It is concluded that among the humic derivatives tested, the hydroquinone-enriched ones are the most useful for addressing remedial needs of actinide-contaminated aquifers.

  11. An intercomparison study of neptunium-237 determination in artificial urine samples

    SciTech Connect

    Lee, S.C.; Hutchinson, J.M.R.; Inn, K.G.W.

    1995-12-31

    An intercomparison study of low-level {sup 237}Np determination in artificial urine samples has been carried out. The purpose of this study was to find the present {open_quotes}optimal{close_quotes} method available for use in a routine in vitro radiobioassay program for occupationally exposed workers. Four synthetic urine samples with differing {sup 237}np concentrations were prepared: (1) mBq kg{sup -1} of {sup 237}Np; (2) 3 mBq kg{sup -1} of {sup 237}Np with natural uranium, {sup 239}Pu and {sup 241}Am as interferences; (3) 50 mBq kg{sup -1} of {sup 237}Np; and (4) a matrix blank. The solutions were submitted to 10 alpha-particle and 10 inductively-coupled plasma-mass spectrometry (ICP-MS) laboratories of which six and four laboratories, respectively, returned results. Two laboratories performed assays using both techniques. The radiochemical method of choice used {sup 239}Np as the tracer which utilized a combination of coprecipitation and anion-exchange separation. The best results obtained by ICP-MS were comparable with the most accurate results obtained by alpha-particle spectrometry but not any better. Alpha-particle spectrometry measurements overall gave consistently better agreement with the known values.

  12. Fission cross sections of some thorium, uranium, neptunium and plutonium isotopes relative to /sup 235/U

    SciTech Connect

    Meadows, J W

    1983-10-01

    Earlier results from the measurements, at this Laboratory, of the fission cross sections of /sup 230/Th, /sup 232/Th, /sup 233/U, /sup 234/U, /sup 236/U, /sup 238/U, /sup 237/Np, /sup 239/Pu, /sup 240/Pu, and /sup 242/Pu relative to /sup 235/U are reviewed with revisions to include changes in data processing procedures, alpha half lives and thermal fission cross sections. Some new data have also been included. The current experimental methods and procedures and the sample assay methods are described in detail and the sources of error are presented in a systematic manner. 38 references.

  13. Sources of the transuranic elements plutonium and neptunium in arctic marine sediments.

    SciTech Connect

    Cooper, L. W.; Kelley, J. M.; Bond, L. A.; Orlandini, K. A.; Grebmeier, J. M.; Environmental Research; ORNL; PNNL; Univ. of Tennessee

    2000-01-01

    We report here thermal ionization mass spectrometry measurements of {sup 239}Pu, {sup 240}Pu, {sup 241}Pu, {sup 242}Pu, and {sup 237}Np isolated from oceanic, estuarine, and riverine sediments from the Arctic Ocean Basin. {sup 238}Pu/{sup 239+240}Pu activity ratios are also reported for alpha spectrometric analyses undertaken on a subset of these samples. Our results indicate that the Pu in sediments on the Alaskan shelf and slope, as well as that in the deep basins (Amerasian and Eurasian) of the Arctic Ocean, has its origin in stratospheric and tropospheric fallout. Sediments from the Ob and Yenisei Rivers show isotopic Pu signatures that are distinctly different from those of northern-hemisphere stratospheric fallout and indicate the presence of weapons-grade Pu originating from nuclear fuel reprocessing wastes generated at Russian facilities within these river catchments. Consequently, sediments of the Eurasian Arctic Ocean, particularly those in the Barents and Kara Seas, probably contain a mixture of Pu from stratospheric fallout, tropospheric fallout, and fuel-reprocessing wastes of riverine origin. In particular, the {sup 241}Pu/{sup 239}Pu ratios observed in these sediments are inconsistent with significant contributions of Pu to the arctic sediments studied from western European reprocessing facilities, principally Sellafield in the UK. Several other potential sources of Pu to arctic sediments can also be excluded as significant based upon the transuranic isotope ratios presented.

  14. Fabrication and characterization of americium, neptunium and curium bearing MOX fuels obtained by powder metallurgy process

    NASA Astrophysics Data System (ADS)

    Lebreton, Florent; Prieur, Damien; Jankowiak, Aurélien; Tribet, Magaly; Leorier, Caroline; Delahaye, Thibaud; Donnet, Louis; Dehaudt, Philippe

    2012-01-01

    MOX fuel pellets containing up to 1.4 wt% of Minor Actinides (MA), i.e. Am, Np and Cm, were fabricated to demonstrate the technical feasibility of powder metallurgy process involving, pelletizing and sintering in controlled atmosphere. The compounds were then characterized using XRD, SEM and EDX/EPMA. Dense pellets were obtained which closed porosity mean size is equal to 7 μm. The results indicate the formation of (U, Pu)O 2 solid solution. However, microstructure contains some isolated UO 2 grains. The distribution of Am and Cm appears to be homogeneous whereas Np was found to be clustered at some locations.

  15. Plutonium and Neptunium Speciation and Mobility in Soils and the Subsurface

    SciTech Connect

    Stout, Stephen A.; Reilly, Sean D.; Neu, Mary P.

    2006-06-01

    The DOE is conducting cleanup and stabilization activities at its nuclear weapons development sites, many of which have accumulated plutonium in soils for 60 years. To properly control Pu migration in soils and groundwaters within Federal sites and onto public lands, better evaluate the public risk, and design effective remediation strategies, a fundamental understanding of Pu speciation and environmental transport is needed. The DOE is increasingly relying on monitored natural attenuation (MNA) for site stewardship. While this is practical, and defensible based on fundamental actinide chemistry and most environmental data, there are significant gaps in the foundation of the approach. Key among them is the inability to project migration rates and redistribution of actinide contaminants, particularly given the diversity and heterogeneity of sites. Matrix sorption/desorption processes are the main factors that determine contaminant transport, but little data of this type are available for Pu or Np with minerals and sediments. To support MNA and predictive geochemical models we conducted the following research: (1) Studied environmentally relevant Pu and Np species. (2) Determined the mechanisms and thermodynamics of interactions of Pu and Np species with Mn and Fe (oxy)hydroxides and with sediments, including actinide sorption/desorption during mineral formation and redox cycling.

  16. Phase equilibria and thermal expansion of CaTiO 3 doped with neptunium

    NASA Astrophysics Data System (ADS)

    Sato, Tsuyoshi; Yamashita, Toshiyuki; Matsui, Tsuneo

    2005-09-01

    Phase relationships between NpO 2 and CaTiO 3 or Ca(Ti,Al)O 3 were investigated by X-ray diffraction (XRD) analysis at room temperature, using specimens prepared at 1773 K in Ar-8%H 2 atmosphere. Single phase solid solutions were formed for 0-7.5 mol% Np doped CaTiO 3 and 1-10 mol% Np doped Ca(Ti,Al)O 3. By substituting Al for Ti in CaTiO 3, Np solubility in Ca(Ti,Al)O 3 increased. Thermal expansions of (Ca 1- xNp x)TiO 3 ( x = 0.03, 0.05 and 0.075) were measured for temperatures between room temperature and 1273 K in Ar-8%H 2 atmosphere using high-temperature XRD technique. Volumetric thermal expansion coefficients of these three specimens were nearly the same value, suggesting that the incorporation of tetravalent Np into CaTiO 3 had practically no effect on stabilization of the crystal lattice.

  17. Microcalorimetric measurement of reaction enthalpies in solutions of uranium and neptunium compounds

    NASA Astrophysics Data System (ADS)

    Schreiner, Felix; Friedman, Arnold M.; Richards, R. Ronald; Sullivan, James C.

    1985-02-01

    The formation of complexes of uranyl and neptunyl (VI) ions with carbonate and hydrogen carbonate has been studied by titration microcalorimetry. The measurements were carried out with a computer-controlled microcalorimeter which is described in detail. Sample volumes are typically in the range of 1.5 to 2.5 ccm, containing about 0.05 millimole of the ionic species to be studied. The small volume renders the calorimeter useful for the measurement of uncommon and strongly radioactive substances. Enthalpies of reaction were obtained for the formation of the dicarbonato and the tricarbonato uranyl ions in a sulfate medium of ionic strength 1.6. The enthalpies are ΔH 2 = -39.6 ± 1 kJ/mol and ΔH 3 = -57.5 ± 1.5 kJ/mol , for the dicarbonato- and the tricarbonato-uranyl ions, respectively. The titration data for the neptunyl (VI) — carbonate system yield a value of ΔH Np -50 ± 2 kJ/mol for the tricarbonato-neptunyl ion when interpreted in analogy to the uranyl system.

  18. Investigation of the neptunium-zirconium system by X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Gensini, Michel M.; Haire, Richard G.; Gibson, John K.

    1994-10-01

    X-ray powder diffraction analysis at 25 C has been used to further characterize the Np-Zr phase diagram. We have studied a variety of Np-Zr aggregate compositions obtained by different preparative methods, including arc melting of the components. For the materials at ambient temperature, obtained by either slow cooling or quenching from elevated temperatures, we observed one or more of the following product phases: alpha-Np, alpha-Zr, NpZr2 and one new phase. The last was interpreted tentatively to be either Np4Zr or Np6Zr. Calculations based on the X-ray data suggested a limited solubility of Np in alpha-Zr and an even lower solubility of Zr in alpha-Np. The X-ray data for the NpZr2 phase showed that it possesses hexagonal symmetry and is isostructural with UZr2 and PuZr2. Annealing of Np-Zr composites at selected temperatures did not enhance the formation of NpZr2.

  19. Identification of hexanuclear Actinide(IV) carboxylates with Thorium, Uranium and Neptunium by EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Hennig, Christoph; Takao, Shinobu; Takao, Koichiro; Weiss, Stephan; Kraus, Werner; Emmerling, Franziska; Meyer, Michel; Scheinost, Andreas C.

    2013-04-01

    Hydrated actinide(IV) ions undergo hydrolysis and further polymerization and precipitation with increasing pH. The resulting amorphous and partly crystalline oxydydroxides AnOn(OH)4-2n·xH2O can usually be observed as colloids above the An(IV) solubility limit. The aging process of such colloids results in crystalline AnO2. The presence of carboxylates in the solution prevents the occurrence of such colloids by formation of polynuclear complexes through a competing reaction between hydrolysis and ligation. The majority of recently described carboxylates reveals a hexanuclear core of [An6(μ3-O)4(μ3-OH)4]12+ terminated by 12 carboxylate ligands. We found that the An(IV) carboxylate solution species remain often preserved in crystalline state. The An(IV) carboxylates show An-An distances which are ~ 0.03 Å shorter than the An-An distances in AnO2 like colloids. The difference in the distances could be used to identify such species in solution.

  20. Investigation of the neptunium-zirconium phase diagram by differential thermal analysis

    NASA Astrophysics Data System (ADS)

    Gibson, John K.; Haire, Richard G.

    Differential thermal analysis (DTA) of Np-Zr alloy specimens has been used to characterize the essential features of the Np-Zr phase diagram. DTA results for seven samples with approximate aggregate compositions of 25, 50 or 75 at% Zr led to the conclusion that there were limited mutual solubilities at the terminal portions of the diagram. The apparent immiscibility of the high-temperature bcc allotropes of Np and Zr contrasts with the behavior reported for the U-Zr and Pu-Zr systems. X-ray diffraction data have indicated the existence of an intermediate phase at lower temperatures, believed to have a nominal composition of NpZr 2, analogous to the δ- UZr2 phase.

  1. Effects of humic acid on the sorption of neptunium(V) on kaolinite

    NASA Astrophysics Data System (ADS)

    Niitsu, Yoshinobu; Sato, Seichi; Ohashi, Hiroshi; Sakamoto, Yoshiaki; Nagao, Seiya; Ohnuki, Toshihiko; Muraoka, Susumu

    1997-09-01

    The sorption coefficient of Np(V), Kd, on kaolinite was measured at pH 6 to 11 and in humic acid concentrations of 0 to 40 mg dm -3 at the ionic strength of 0.1 M. The Kd value increased with pH both with and without humic acid. The Kd value increased slightly with increasing concentration of humic acid in the pH range below 8 and decreased not more than an order of magnitude with increasing concentrations of humic acid in the pH region above 8. Below pH 8, Np(V) sorption is considered to be enhanced by the sorption of humic acid on the kaolinite to form Np(V)-humate complexes. Above 8, it is probable that the desorption of humic acid and formation of Np(V)-humate in solution result in the decrease of Kd. The behavior of Np(V) sorption on kaolinite with humic acid is described by a simple model.

  2. Neptunium(V) partitioning to uranium(VI) oxide and peroxide solids.

    PubMed

    Douglas, Matthew; Clark, Sue B; Friese, Judah I; Arey, Bruce W; Buck, Edgar C; Hanson, Brady D

    2005-06-01

    Metaschoepite, [(UO2)8O2(OH)12] x 10H2O, and metastudtite, UO4 x 4H2O, are alteration phases anticipated in a spent nuclear fuel repository following the moist oxidation of UO2 on a geologic time scale. Dissolved concentrations and hence potential mobility of other radionuclides in the fuel, such as the neptunyl cation (NpO2+), will likely be determined by the extent of their partitioning into these U(VI) solids. 237Np is of particular interest due to its potential high mobility and long half-life (2.1 x 10(6) years.) In this study, metaschoepite has been precipitated and subsequently transformed to studtite in the presence of dissolved Np. The metaschoepite and studtite solids that formed initially contained <10 and 6500 ppm Np, respectively. Batch dissolution studies of these solids at pH 6 demonstrate release of Np that exceeds congruent dissolution of U from metastudtite; furthermore, the released Np cation remains in solution. Thus, although the Np partitions into the metastudtite solid initially, it is released to solution over time, indicating that metastudtite is not likely to serve as a host solid for Np incorporation or sorption of the neptunyl cation on long time scales.

  3. Enhanced Erosion Protection of TWAS Coated Ti6Al4V Alloy Using Boride Bond Coat and Subsequent Laser Treatment

    NASA Astrophysics Data System (ADS)

    Mann, B. S.; Arya, Vivek; Pant, B. K.

    2011-08-01

    The material commonly used in low-pressure high-rating super critical/ultra super critical steam turbines as well as guide and moving blades of high speed aero compressors is Ti6Al4V alloy. These blades are severely affected owing to erosion which leads to drop in efficiency and increase in maintenance cost. This article deals with SHS 7170 coating on Ti6Al4V alloy using twin wire arc spraying (TWAS), enhancing its bonding by providing a thin bond coat and then treating with high-power diode laser (HPDL). Significant improvement in erosion resistance of this multilayer coating has been achieved because of the formation of fine-grained micro structure due to rapid heating and cooling rates associated with the laser surface treatment. After laser surface treatment, the fracture toughness of this multilayer has improved manifold. The water droplet and particulate erosion test results along with the damage mechanism are reported and discussed in this article.

  4. UNDERSTANDING VARIATION IN PARTITION COEFFICIENT KD, VALUES, VOLUME III: AMERICIUM, ARSENIC, CURIUM, IODINE, NEPTUNIUM, RADIUM, AND TECHNETIUM

    EPA Science Inventory

    This report describes the conceptualization, measurement, and use of the partition (or distribution) coefficient, Kd, parameter, and the geochemical aqueous solution and sorbent properties that are most important in controlling adsorption/retardation behavior of selected contamin...

  5. Analysis of trace neptunium in the vicinity of underground nuclear tests at the Nevada National Security Site.

    PubMed

    Zhao, P; Tinnacher, R M; Zavarin, M; Kersting, A B

    2014-11-01

    A high sensitivity analytical method for (237)Np analysis was developed and applied to groundwater samples from the Nevada National Security Site (NNSS) using short-lived (239)Np as a yield tracer and HR magnetic sector ICP-MS. The (237)Np concentrations in the vicinity of the Almendro, Cambric, Dalhart, Cheshire, and Chancellor underground nuclear test locations range from <4 × 10(-4) to 2.6 mBq/L (6 × 10(-17)-4.2 × 10(-13) mol/L). All measured (237)Np concentrations are well below the drinking water maximum contaminant level for alpha emitters identified by the U.S. EPA (560 mBq/L). Nevertheless, (237)Np remains an important indicator for radionuclide transport rates at the NNSS. Retardation factor ratios were used to compare the mobility of (237)Np to that of other radionuclides. The results suggest that (237)Np is less mobile than tritium and other non-sorbing radionuclides ((14)C, (36)Cl, (99)Tc and (129)I) as expected. Surprisingly, (237)Np and plutonium ((239,240)Pu) retardation factors are very similar. It is possible that Np(IV) exists under mildly reducing groundwater conditions and exhibits a retardation behavior that is comparable to Pu(IV). Independent of the underlying process, (237)Np is migrating downgradient from NNSS underground nuclear tests at very low but measureable concentrations. PMID:25078472

  6. Distribution of neptunium and plutonium in New Mexico lichen samples (Usnea arizonica) contaminated by atmospheric fallout

    SciTech Connect

    Oldham, Jr., Warren J.; Hanson, Susan K.; Lavelle, Kevin B.; Miller, Jeffrey L.

    2015-08-30

    In this study, the concentrations of 237Np, 239Pu and 240Pu were determined in lichen samples (Usnea arizonica) that were collected from ten locations in New Mexico between 2011 and 2013 using isotope dilution inductively-coupled plasma mass spectrometry (ID-ICP-MS). The observed isotopic ratios for 237Np/239Pu and 240Pu/239Pu indicate trace contamination from global and regional fallout (e.g. Trinity test and atmospheric testing at the Nevada Test Site). The fact that actinide contamination is detected in recent lichen collections suggests continuous re-suspension of fallout radionuclides even 50 years after ratification of the Limited Test Ban Treaty.

  7. Surface Complexation of Neptunium(V) onto Whole Cells and Cell Components of Shewanella alga: Modeling and Experimental Study

    SciTech Connect

    Deo, Randhir P.; Songkasiri, Warinthorn; Rittmann, Bruce E.; Reed, Donald T.

    2012-04-30

    We systematically quantified surface complexation of Np(V) onto whole cells, cell wall, and extracellular polymeric substances (EPS) of Shewanella alga strain BrY. We first performed acid and base titrations and used the mathematical model FITEQL to estimate the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl group not associated with amino acids (pK{sub a} {approx} 5), a phosphoryl site (pK{sub a} {approx} 7.2), and an amine site (pK{sub a} > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components as a function of pH. Since significant Np(V) sorption was observed on S. alga whole cells and its components in the pH range 2-5, we assumed the existence of a fourth site: a low-pK{sub a} carboxyl site (pK{sub a} {approx} 2.4) that is associated with amino acids. We used the SPECIATE submodel of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, the aquo NpO{sub 2}{sup +} species was the dominant form of Np(V), and its log K values for the low-pK{sub a} carboxyl, mid-pK{sub a} carboxyl, and phosphoryl groups were 1.8, 1.8, and 2.5-3.1, respectively. For pH greater than 8, the key surface ligand was amine > XNH{sub 3}{sup +}, which complexed with NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-}. The log K for NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-} complexed onto the amine groups was 3.1-3.9. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results help quantify the role of surface complexation in defining actinide-microbiological interactions in the subsurface.

  8. LITERATURE REVIEW ON THE SORPTION OF PLUTONIUM, URANIUM, NEPTUNIUM, AMERICIUM AND TECHNETIUM TO CORROSION PRODUCTS ON WASTE TANK LINERS

    SciTech Connect

    Li, D.; Kaplan, D.

    2012-02-29

    The Savannah River Site (SRS) has conducted performance assessment (PA) calculations to determine the risk associated with closing liquid waste tanks. The PA estimates the risk associated with a number of scenarios, making various assumptions. Throughout all of these scenarios, it is assumed that the carbon-steel tank liners holding the liquid waste do not sorb the radionuclides. Tank liners have been shown to form corrosion products, such as Fe-oxyhydroxides (Wiersma and Subramanian 2002). Many corrosion products, including Fe-oxyhydroxides, at the high pH values of tank effluent, take on a very strong negative charge. Given that many radionuclides may have net positive charges, either as free ions or complexed species, it is expected that many radionuclides will sorb to corrosion products associated with tank liners. The objective of this report was to conduct a literature review to investigate whether Pu, U, Np, Am and Tc would sorb to corrosion products on tank liners after they were filled with reducing grout (cementitious material containing slag to promote reducing conditions). The approach was to evaluate radionuclides sorption literature with iron oxyhydroxide phases, such as hematite ({alpha}-Fe{sub 2}O{sub 3}), magnetite (Fe{sub 3}O{sub 4}), goethite ({alpha}-FeOOH) and ferrihydrite (Fe{sub 2}O{sub 3} {center_dot} 0.5H{sub 2}O). The primary interest was the sorption behavior under tank closure conditions where the tanks will be filled with reducing cementitious materials. Because there were no laboratory studies conducted using site specific experimental conditions, (e.g., high pH and HLW tank aqueous and solid phase chemical conditions), it was necessary to extend the literature review to lower pH studies and noncementitious conditions. Consequently, this report relied on existing lower pH trends, existing geochemical modeling, and experimental spectroscopic evidence conducted at lower pH levels. The scope did not include evaluating the appropriateness of K{sub d} values for the Fe-oxyhydroxides, but instead to evaluate whether it is a conservative assumption to exclude this sorption process of radionuclides onto tank liner corrosion products in the PA model. This may identify another source for PA conservatism since the modeling did not consider any sorption by the tank liner.

  9. DEMONSTRATION OF THE DWPF FLOWSHEET IN THE SRNL SHIELDED CELLS WITH TANK 40 AND H CANYON NEPTUNIUM

    SciTech Connect

    Pareizs, J; Bradley Pickenheim, B; Cj Bannochie, C; Michael Stone, M

    2009-04-28

    The Defense Waste Processing Facility (DWPF) is currently processing Sludge Batch 5 (SB5) from Tank 40. SB5 contains the contents of Tank 51 from November 2008, qualified by the Savannah River National Laboratory (SRNL) and the heel in Tank 40 remaining from Sludge Batch 4. Current Liquid Waste Operations (LWO) plans are to (1) decant supernatant from Tank 40 to remove excess liquid caused by a leaking slurry pump and (2) receive a Np stream from H Canyon It should be noted that the Np stream contains significant nitrate requiring addition of nitrite to Tank 40 to maintain a high nitrite to nitrate ratio for corrosion control. SRNL has been requested to qualify the proposed changes; determine the impact on DWPF processability in terms of hydrogen generation, rheology, etc.; evaluate antifoam addition strategy; and evaluate mercury stripping. Therefore, SRNL received a 3 L sample of Tank 40 following the transfer of Tank 51 to Tank 40 (Tank Farm Sample HTF-40-08-157 to be used in testing and to perform the required Waste Acceptance Product Specifications radionuclide analyses). Based on Tank Farm projections, SRNL decanted a portion* of the sample, added sodium nitrite, and added a Np solution from H Canyon representative of the Np to be dispositioned to Tank 40 (neutralized to 0.6 M excess hydroxide). The resulting material was used in a DWPF Chemical Process Cell (CPC) demonstration -- a Sludge Receipt and Adjustment Tank (SRAT) cycle and a Slurry Mix Evaporator (SME) cycle. Preliminary data from the demonstration has been reported previously. This report includes discussion of these results and additional results, including comparisons to Tank Farm projections and the SB5 demonstration.

  10. Effect of Fe2+ Oxidation on the Removal of 238Pu from Neptunium Solution by Anion Exchange

    SciTech Connect

    KYSER, EDWARD

    2004-06-01

    The effect of ferrous sulfamate (FS) oxidation and variation in nitric acid concentration on the removal of {sup 238}Pu contamination from Np by the HB-Line anion exchange flowsheet has been tested. Significant rejection of {sup 238}Pu was observed by washing with a reductive wash solution containing 6.0 to 6.8 M nitric acid (HNO{sub 3}) with as little as 30% of the Fe{sup 2+} from the FS remaining in its reduced form. To achieve the desired 30% removal of {sup 238}Pu from the process, conditions should be controlled to maintain the Fe{sup 2+}/Fe{sup 3+} ratio in the reductive wash to be greater than 60%/40% (or 1.5). Since Fe{sup 2+} oxidation is strongly affected by temperature and nitric acid concentration, these parameters (as well as time after FS addition) need to be controlled to ensure predictable results. A shortened-height column was utilized in these tests to match changes in the plant equipment. Lab experiments scaled to plant batch sizes of 2000 g Np were observed with modest losses for ''up-flow'' washing. The following are recommended conditions for removing {sup 238}Pu from Np solutions by anion exchange in HB-Line: (1) Feed conditions: ''Up-flow'' 6.4-8.0 M HNO{sub 3}, 0.02 M hydrazine (N{sub 2}H{sub 4}), 0.05 M excess FS. (2) Reductive Wash conditions: ''Up-flow'' 6 Bed volumes (BV) of 6.4 M HNO{sub 3}, 0.05 M FS (minimum 0.03M Fe{sup 2+} during wash cycle), 0.05 M hydrazine, less than 1.8 mL/min/cm{sup 2} flowrate. (3) Decontamination Wash conditions: ''Up-flow'' 1-2 BV of 6.4-8.0 M HNO{sub 3}, no FS, no hydrazine, less than 1.8 mL/min/cm{sup 2} flowrate. (4) Elution conditions: ''Down-flow'' 0.17 M HNO{sub 3}, 0.05 M hydrazine, no FS.

  11. Neptunium (V) Adsorption to a Halophilic Bacterium Under High Ionic Strength Conditions: A Surface Complexation Modeling Approach

    SciTech Connect

    Ams, David A

    2012-06-11

    Rationale for experimental design: Np(V) -- important as analog for Pu(V) and for HLW scenarios; High ionic strength -- relevant to salt-based repositories such as the WIPP; Halophilic microorganisms -- representative of high ionic strength environments. For the first time showed: Significant adsorbant to halophilic microorganisms over entire pH range under high ionic strength conditions; Strong influence of ionic strength with increasing adsorption with increasing ionic strength (in contrast to trends of previous low ionic strength studies); Effect of aqueous Np(V) and bacterial surface site speciation on adsorption; and Developed thermodynamic models that can be incorporated into geochemical speciation models to aid in the prediction of the fate and transport of Np(V) in more complex systems.

  12. Surface complexation of Neptunium(V) onto whole cells and cell components of Shewanella alga: modeling and experimental study.

    PubMed

    Deo, Randhir P; Songkasiri, Warinthorn; Rittmann, Bruce E; Reed, Donald T

    2010-07-01

    We systematically quantified surface complexation of Np(V) onto whole cells, cell wall, and extracellular polymeric substances (EPS) of Shewanella alga strain BrY. We first performed acid and base titrations and used the mathematical model FITEQL to estimate the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl group not associated with amino acids (pK(a) approximately 5), a phosphoryl site (pK(a) approximately 7.2), and an amine site (pK(a) > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components as a function of pH. Since significant Np(V) sorption was observed on S. alga whole cells and its components in the pH range 2-5, we assumed the existence of a fourth site: a low-pK(a) carboxyl site (pK(a) approximately 2.4) that is associated with amino acids. We used the SPECIATE submodel of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, the aquo NpO(2)(+) species was the dominant form of Np(V), and its log K values for the low-pK(a) carboxyl, mid-pK(a) carboxyl, and phosphoryl groups were 1.8, 1.8, and 2.5-3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH(3)(+), which complexed with NpO(2)(CO(3))(3)(5-). The log K for NpO(2)(CO(3))(3)(5-) complexed onto the amine groups was 3.1-3.9. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results help quantify the role of surface complexation in defining actinide-microbiological interactions in the subsurface.

  13. Theoretical study on K, L, and M X-ray transition energies and rates of neptunium and its ions

    NASA Astrophysics Data System (ADS)

    Ismail Abdalla, Saber; Dong, Chen-Zhong; Wang, Xiang-Li; Zhou, Wei-Dong; Wu, Zhong-Wen

    2014-02-01

    The transition energies and electric dipole (E1) transition rates of the K, L, and M lines in neutral Np have been theoretically determined from the MultiConfiguration Dirac—Fock (MCDF) method. In the calculations, the contributions from Breit interaction and quantum electrodynamics (QED) effects (vacuum polarization and self-energy), as well as nuclear finite mass and volume effects, are taken into account. The calculated transition energies and rates are found to be in good agreement with other experimental and theoretical results. The accuracy of the results is estimated and discussed. Furthermore, we calculated the transition energies of the same lines radiating from the decaying transitions of the K-, L-, and M-shell hole states of Np ions with the charge states Np1+ to Np6+ for the first time. We found that for a specific line, the corresponding transition energies relating to all the Np ions are almost the same; it means the outermost electrons have a very small influence on the inner-shell transition processes.

  14. First-principles investigation of higher oxides of uranium and neptunium: U3O8 and Np2O5

    NASA Astrophysics Data System (ADS)

    Yun, Y.; Rusz, J.; Suzuki, M.-T.; Oppeneer, P. M.

    2011-02-01

    A computational study is presented of the structural, electronic, and magnetic properties of U3O8 and Np2O5, which are actinide oxides in a higher oxidation state than the tetravalent state of the common dioxide phases, UO2 and NpO2. The calculations are based on the density functional theory+U approach, in which additional Coulomb correlations on the actinide atom are taken into account. The calculated properties of these two higher oxidized actinide oxides are analyzed and compared to those of their tetravalent analogs. The optimized structural parameters of these noncubic oxides are found to be in reasonable agreement with available experimental data. U3O8 is predicted to be a magnetic insulator, having one U atom in a hexavalent oxidation state and two U atoms in a pentavalent oxidation state. For Np2O5, which is also predicted to be an insulator, a complicated noncollinear magnetic structure is computed, leading to a nonzero overall magnetization with a slight antiferromagnetic canting. The calculated electronic structures are presented and the variation of the U 5f or Np 5f-O 2p hybridization with the oxidation state is analyzed. With increasing oxygen content, the nearly localized 5f electrons of the actinide elements are more positioned near the Fermi level and the hybridization between 5f and 2p states is markedly increased.

  15. Complexation of Neptunium(V) with Glutaroimide Dioxime: A Study by Absorption Spectroscopy, Microcalorimetry, and Density Functional Theory Calculations.

    PubMed

    Ansari, Seraj A; Bhattacharyya, Arunasis; Zhang, Zhicheng; Rao, Linfeng

    2015-09-01

    Complexation of NpO2(+) ions with glutaroimide dioxime (H2L), a cyclic imide dioxime ligand that has been shown to form strong complexes with UO2(2+) in aqueous solutions, was studied by absorption spectroscopy and microcalorimetry in 1.0 M NaClO4 aqueous solutions. NpO2(+) forms two successive complexes, NpO2(HL)(aq) and NpO2(HL)2(-) (where HL(-) stands for the partially deprotonated glutaroimide dioxime ligand), with stability constants of log β111 = 17.8 ± 0.1 and log β122 = 33.0 ± 0.2, respectively. The complexation is both enthalpy- and entropy-driven, with negative enthalpies (ΔH111 = -52.3 ± 1.0 kJ/mol and ΔH122 = -96.1 ± 1.4 kJ/mol) and positive entropies (ΔS111 = 164 ± 3 J/mol/K and ΔS122 = 310 ± 4 J/mol/K). The thermodynamic parameters suggest that, similar to complexation of UO2(2+), the ligand coordinates with NpO2(+) in a tridentate mode, via the two oxygen atoms of the oxime groups and the nitrogen atom of the imide group. Density functional theory calculations have helped to interpret the optical absorption properties of the NpO2(HL)2(-) complex, by showing that the cis and trans configurations of the complex have very similar energies so that both configurations could be present in the aqueous solutions. It is the noncentrosymmetric cis configuration that makes the 5f → 5f transition allowable so that the NpO2(HL)2(-) complex absorbs in the near-IR region.

  16. Analysis of trace neptunium in the vicinity of underground nuclear tests at the Nevada National Security Site.

    PubMed

    Zhao, P; Tinnacher, R M; Zavarin, M; Kersting, A B

    2014-11-01

    A high sensitivity analytical method for (237)Np analysis was developed and applied to groundwater samples from the Nevada National Security Site (NNSS) using short-lived (239)Np as a yield tracer and HR magnetic sector ICP-MS. The (237)Np concentrations in the vicinity of the Almendro, Cambric, Dalhart, Cheshire, and Chancellor underground nuclear test locations range from <4 × 10(-4) to 2.6 mBq/L (6 × 10(-17)-4.2 × 10(-13) mol/L). All measured (237)Np concentrations are well below the drinking water maximum contaminant level for alpha emitters identified by the U.S. EPA (560 mBq/L). Nevertheless, (237)Np remains an important indicator for radionuclide transport rates at the NNSS. Retardation factor ratios were used to compare the mobility of (237)Np to that of other radionuclides. The results suggest that (237)Np is less mobile than tritium and other non-sorbing radionuclides ((14)C, (36)Cl, (99)Tc and (129)I) as expected. Surprisingly, (237)Np and plutonium ((239,240)Pu) retardation factors are very similar. It is possible that Np(IV) exists under mildly reducing groundwater conditions and exhibits a retardation behavior that is comparable to Pu(IV). Independent of the underlying process, (237)Np is migrating downgradient from NNSS underground nuclear tests at very low but measureable concentrations.

  17. In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

    PubMed

    Müller, Katharina; Gröschel, Annett; Rossberg, André; Bok, Frank; Franzen, Carola; Brendler, Vinzenz; Foerstendorf, Harald

    2015-02-17

    Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

  18. Tetrapositive plutonium, neptunium, uranium, and thorium coordination complexes: chemistry revealed by electron transfer and collision induced dissociation.

    PubMed

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K

    2014-04-17

    The Pu(4+), Np(4+), and U(4+) ions, which have large electron affinities of ∼34.6, ∼33.6, and ∼32.6 eV, respectively, were stabilized from solution to the gas phase upon coordination by three neutral tetramethyl-3-oxa-glutaramide ligands (TMOGA). Both collision induced dissociation (CID) and electron transfer dissociation (ETD) of Pu(TMOGA)3(4+) reveal the propensity for reduction of Pu(IV) to Pu(III), by loss of TMOGA(+) in CID and by simple electron transfer in ETD. The reduction of Pu(IV) is in distinct contrast to retention of Th(IV) in both CID and ETD of Th(TMOGA)3(4+), where only the C-Oether bond cleavage product was observed. U(TMOGA)3(4+) behaves similarly to Th(TMOGA)3(4+) upon CID and ETD, while the fragmentation patterns of Np(TMOGA)3(4+) lie between those of Pu(TMOGA)3(4+) and U(TMOGA)3(4+). It is notable that the gas-phase fragmentation behaviors of these exceptional tetrapositive complexes parallel fundamental differences in condensed phase chemistry within the actinide series, specifically the tendency for reduction from the IV to III oxidation states.

  19. Determining Sources and Transport of Nuclear Contamination in Hudson River Sediments with Plutonium, Neptunium, and Cesium isotope ratios

    NASA Astrophysics Data System (ADS)

    Kenna, T. C.; Chillrud, S. N.; Chaky, D. A.; Simpson, H. J.; McHugh, C. M.; Shuster, E. L.; Bopp, R. F.

    2004-12-01

    Different sources of radioactive contamination contain characteristic and identifiable isotopic signatures, which can be used to study sediment transport. We focus on Pu-239, Pu-240, Np-237 and Cs-137, which are strongly bound to fine grained sediments. The Hudson River drainage basin has received contamination from at least three separate sources: 1) global fallout from atmospheric testing of nuclear weapons, which contributed Pu, Np and Cs; 2) contamination resulting from reactor releases at the Indian Point Nuclear Power Plant (IPNPP) located on the Hudson River Estuary ˜70km north of New York Harbor, where records document releases of Cs-137; 3) contamination resulting from activities at the Knolls Atomic Power Laboratory (KAPL) located on the Mohawk River, where incomplete records document releases of Cs-137 but no mention is made of Pu or Np. Here we report measurements of Pu isotopes, Np-237 and Cs-137 for a series of sediment cores collected from various locations within the drainage basin: 1) Mohawk River downstream of KAPL, 2) Hudson River upstream of its confluence with the Mohawk River, and 3) lower Hudson River at a location in close proximity to IPNPP. In addition, we present data from selected samples from two other lower Hudson River locations: One site located ˜30km downstream of IPNPP and another ˜30km upstream of IPNPP. By comparing the isotopic ratios Pu-240/Pu-239, Np-237/Pu-239, and Cs-137/Pu-239, measured in fluvial sediments to mean global fallout values, it is possible to identify and resolve different sources of non-fallout contamination. To date, isotopic data for sediments indicate non-fallout sources of Pu-239, Pu-240, and Cs-137; Np-237, however, appears to originate from global fallout only. Mohawk River sediments downstream of KAPL exhibit enrichments in Pu-239, Pu-240, and Cs-137 that are 7 to 20 times higher than levels expected from global fallout as indicated from Np-237. The elevated levels, non-fallout isotopic signatures, and core location are all consistent with KAPL being a source of Pu and Cs isotopes. Sediments from upper Hudson River and a section of the lower Hudson Estuary both contain Cs-137 levels that are more than twice that expected from global fallout. While elevated Cs-137 in selected lower Hudson samples is consistent with reported reactor releases from IPNPP, there is no known source of non-fallout Cs in the upper Hudson. We have been able to estimate end-member isotopic compositions of radionuclides originating from KAPL as well as detect its presence and estimate its contribution to contaminant inventories far downstream in tidal Hudson sediments. By comparing KAPL-derived Pu-239 inventories measured in the Mohawk and Lower Hudson Rivers, we estimate a dilution factor of ˜140. While there is isotopic evidence of KAPL derived radionuclides in all the lower Hudson sediments that we have analyzed, elevated levels of Cs-137 (not attributable to KAPL)were only observed in sediments collected in the vicinity of IPNPP and those collected 30km downstream of the plant's location. We attribute the elevated Cs-137 levels in these Lower Hudson sediments to contamination originating from IPNPP. The lack of elevated levels of Cs-137 in sediments collected 30km upstream of the plant's location plus a dilution factor for Upper Hudson sediments that is larger than that estimated for Mohawk River sediments alone, allows us to conclude that Cs-137 enrichment observed in the Upper Hudson is not likely to be a significant source of Cs-137 contamination to lower Hudson River sediments.

  20. Effects of the chemical forms and valency states of neptunium on its jejunal transfer in the rat.

    PubMed

    Fritsch, P; Beauvallet, M; Jouniaux, B; Moutairou, K; Metivier, H; Masse, R

    1987-10-01

    The transfer of various Np(IV) and Np(V) chemical forms across the small intestine of rats was measured in instilled and perfused jejunum. Instillation of Np(V) nitrate together with citrate or DTPA resulted in the same absorption of Np as after instillation of Np(V) nitrate alone (3 per cent per hour). Perfusion of Np(V) nitrate with bicarbonate or DTPA resulted in a similar transfer (2 per cent) but added citrate or ascorbate resulted in reduced transfer (0.8 per cent). Addition of phytate reduced Np transfer in both instilled and perfused jejunum (0.4 per cent). Np(IV) transfer was usually the same as, or less than that of, the corresponding Np(V) forms. Np(IV) transfer was similar in perfused and instilled jejunum, increasing from 0.2 per cent in the presence of citrate and phytate, to 1 per cent with EDTA and DTPA. Except for phytate, all the forms of Np(V) tested behaved like Np(V) nitrate after transfer from the intestine or after intravenous injection. By contrast, the behaviour of Np(IV) varied for all the forms tested and, for a given form, varied as a function of the experimental procedure used, i.e. jejunal instillation, perfusion, or intravenous injection. These findings suggest that the intestinal transfer of Np might occur via the intercellular pathway, and that it is controlled by both the molecular weight of the Np compound and its stability constant.

  1. Leaching and migration of neptunium in a simulated engineered barrier system consisting of HLW glass and compacted bentonite

    NASA Astrophysics Data System (ADS)

    Inagaki, Y.; Furuya, H.; Idemitsu, K.; Arima, T.; Osako, H.; Banba, T.; Maeda, T.; Matsumoto, S.; Nomura, I.; Kikkawa, S.; Saito, M.; Okamoto, H.

    2001-09-01

    In a simulated engineered barrier system consisting of a simulated HLW glass doped with 237Np, a compacted bentonite and water under reducing conditions, leaching of Np from the glass and diffusion of the leached Np through the bentonite were measured systematically. The following results were obtained: (1) The concentration of dissolved species of Np in the leachate is 10 -7-10 -8 M, which indicates that Np(IV) is the dominant oxidation state in the system and the concentration may be controlled by solubility of NpO2xH2O ( am) . (2) The presence of compacted bentonite facilitates reduction of Np(V) to Np(IV) in the system. (3) The apparent diffusion coefficient of the leached Np through the bentonite is evaluated to be lower than 1.5×10 -13 m2/ s, showing that the diffusivity of Np(IV) is more than one order of magnitude lower than that of Np(V).

  2. Single-crystal structures of uranium and neptunium oxychalcogenides (An=U,Np; Q=S,Se).

    SciTech Connect

    Jin, Geng Bang; Raw, Adam D.; Skanthakumar, S; Haire, Richard G.; Soderholm, L; Ibers, James A.

    2010-01-01

    The compoundsUOS,UOSe,NpOS,andNpOSehavebeensynthesizedandtheirstructuresdetermined by meansofsingle-crystalX-raydiffractionmethods.Theresultsprovidemoredetailedcrystallographic information,includingmorepreciseinteratomicdistances,thanearlierdeterminationsfrompowder diffractiondata.TheseisostructuralcompoundsadoptthePbFClstructuretype.Each An atom is surroundedbyfourOandfive Q atomsinadistortedmonocappedsquare-antiprismaticarrangement

  3. Single-crystal structures of uranium and neptunium oxychalcogenides AnOQ (An=U, Np; Q=S, Se)

    SciTech Connect

    Jin, Geng Bang; Raw, Adam D.; Skanthakumar, S.; Haire, Richard G.; Soderholm, L.; Ibers, James A.

    2010-03-15

    The compounds UOS, UOSe, NpOS, and NpOSe have been synthesized and their structures determined by means of single-crystal X-ray diffraction methods. The results provide more detailed crystallographic information, including more precise interatomic distances, than earlier determinations from powder diffraction data. These isostructural compounds adopt the PbFCl structure type. Each An atom is surrounded by four O and five Q atoms in a distorted monocapped square-antiprismatic arrangement. - Graphical abstract: View down [010] of the structure of AnOQ.

  4. Thermionic emission and vaporization behavior of the ternary systems of lanthanum hexaboride containing molybdenum boride, molybdenum diboride, zirconium diboride, gadolinium hexaboride, and neodymium hexaboride

    NASA Astrophysics Data System (ADS)

    Storms, E. K.

    1983-02-01

    The addition of various compounds to LaB6 did not improve the thermionic emission over that of pure LaB6. This experience and general conclusions, which result by considering the vaporization properties of these and other materials, greatly limit the options available to improve the properties of LaB6 by forming a ternary system. The principles which must be considered, in order to simplify future work, are described.

  5. Disorder-induced localization and itinerant magnetism in the Half-Heusler alloys and dilution studies of the beta-titanium tin and barium boride compounds

    NASA Astrophysics Data System (ADS)

    Drymiotis, Fivos

    We present experimental results of magnetization, resistance and specific heat, on single crystals of several Half Heusler alloys. In particular we focus on the 18 valence electrons TiCoSb and TiNiSn and their evolution from their non magnetic ground state to the metallic TiFeSb, VCoSb and TiCoSn. Contrary to previous experimental results we find the ground state of TiCoSb to be metallic but driven to semiconducting through disorder induced localization. In all samples studied we find that the semiconductor to metal transition occurs concurrently with a lattice parameter change. Ferromagnetic ordering appears to occur only if the Stoner criterion is satisfied and long range ordering occurs even in the presence of localizes states. The transport behavior of all samples depends on the dimensional ratio WB corresponding to the ratio of the extent of localization to the bandwidth. Experimental results are also presented on the beta-Ti 6Sn5 compound which according to magnetization and specific heat measurements is very close to ferromagnetic instability. Ferromagnetic ordering occurs after minute amounts of doping with certain elements (La, Ce, Pr, Sm, Co) on the Ti site. Large values of the critical temperatures are observed which do not scale with the dopant dilution concentration. Experimental evidence is also presented on the existence of a ferromagnetic ground state for BaB6 and La doped BaB6.

  6. CaB(2)C(2): Reinvestigation of a Semiconducting Boride Carbide with a Layered Structure and an Interesting Boron/Carbon Ordering Scheme.

    PubMed

    Albert, Barbara; Schmitt, Konny

    1999-12-27

    Calcium diboride dicarbide, CaB(2)C(2), was synthesized as a crystalline powder and investigated by electron energy loss spectroscopy, X-ray powder diffractometry, conductivity measurements, and LMTO band structure calculations. A new structure model was derived, and the crystal structure was refined by Rietveld methods in the tetragonal space group I4/mcm (No. 140, a = 537.33(1) pm and c = 741.55(2) pm, Z = 4). The boron and carbon atoms are well ordered within layers consisting of four- and eight-membered rings. A convincing coloring scheme is proven by the detection of a superstructure reflection. An earlier assignment of the compound into the LaB(2)C(2) structure family (space group P&fourmacr;2c or P4(2)/mmc, respectively) has been shown to be incorrect. LMTO band structure calculations suggest semiconducting behavior for CaB(2)C(2), which has been confirmed by conductivity measurements.

  7. Identification of specific phonon contributions in BCS-type superconductivity of boride-carbide crystals with a layer-like structure

    NASA Astrophysics Data System (ADS)

    Uzunok, H. Y.; Tütüncü, H. M.; Özer, S.; Ugˇur, Ş.; Srivastava, G. P.

    2015-03-01

    We report on an ab initio study of the BCS-type superconductivity in the intermetallic borocarbides YPd2B2C, YPt2B2C and LaPt2B2C with a layer-like structure. The largest contribution to the electron-phonon coupling constant λ is identified to come from transverse acoustic phonons at a zone-edge, arising from the atomic vibrations in the boron-transition metal layer. A detailed examination of the atomic geometry in the boron-transition metal layer, the electron-phonon coupling constant λ, and the logarithmically averaged phonon frequency ωln helps explain the relatively higher superconducting temperature Tc of YPd2B2C (20.6 K) compared to that of YPt2B2C (11.3 K) and LaPt2B2C (10.40 K).

  8. Plutonium-238 processing at Savannah River Plant

    SciTech Connect

    Burney, G.A.

    1983-01-01

    Plutonium-238 is produced by irradiating NpO/sub 2/-Al cermet slugs or tubes with neutrons. The neptunium-237 is produced as a by-product when natural or enriched uranium is irradiated with neutrons. The neptunium is separated by solvent extraction and ion exchange and precipitated as neptunium oxalate. Neptunium oxalate is calcined to neptunium oxide and fabricated into targets for irradiation. The irradiation conditions are controlled to produce plutonium with 80 to 90 wt % /sup 238/Pu.

  9. Further examples of the failure of surrogates to properly model the structural and hydrothermal chemistry of transuranium elements: Insights provided by uranium and neptunium diphosphonates

    SciTech Connect

    Nelson, Anna-Gay D; Bray, Travis H; Zhang, Wei; Haire, Richard G.; Sayler, Todd S.; Albrecht-Schmitt, Thomas E

    2008-01-01

    In situ hydrothermal reduction of Np(VI) to Np(IV) in the presence of methylenediphosphonic acid (C1P2) results in the crystallization of Np[CH2(PO3)2](H2O)2 (NpC1P2-1). Similar reactions have been explored with U(VI) resulting in the isolation of the U(IV) diphosphonate U[CH2(PO3)2](H2O) (UC1P2-1), and the two U(VI) diphosphonates (UO2)2[CH2(PO3)2](H2O)3 H2O (UC1P2-2) and UO2[CH2(PO3H)2](H2O) (UC1P2-3). Single crystal diffraction studies of NpC1P2-1 reveal that it consists of eight-coordinate Np(IV) bound by diphosphonate anions and two coordinating water molecules to create a polar three-dimensional framework structure wherein the water molecules reside in channels. The structure of UC1P2-1 is similar to that of NpC1P2-1 in that it also adopts a three-dimensional structure. However, the U(IV) centers are seven-coordinate with only a single bound water molecule. UC1P2-2 and UC1P2-3 both contain U(VI). Nevertheless, their structures are quite distinct with UC1P2-2 being composed of corrugated layers containing UO6 and UO7 units bridged by C1P2; whereas, UC1P2-3 is found as a polar three-dimensional network structure containing only pentagonal bipyramidal U(VI). Fluorescence measurements on UC1P2-2 and UC1P2-3 exhibit emission from the uranyl moieties with classical vibronic fine-structure.

  10. Metabolic studies of neptunium in the adult baboon: retention, distribution, kinetics, and enhanced excretion by chelation therapy. Technical progress report summary

    SciTech Connect

    Not Available

    1984-01-01

    These investigations provided additional data on the uptake, distribution, retention and excretion of Np-237, Np-239 and Pa-233 in baboons following single intravenous or gavage administration. The influence of oxidation state, chemical medium, pH, mass, etc. on the metabolism of these radionuclides is related.

  11. Cerium(IV), neptunium(IV), and plutonium(IV) 1,2-phenylenediphosphonates: correlations and differences between early transuranium elements and their proposed surrogates.

    PubMed

    Diwu, Juan; Wang, Shuao; Liao, Zuolei; Burns, Peter C; Albrecht-Schmitt, Thomas E

    2010-11-01

    The in situ hydrothermal reduction of Np(VI) to Np(IV) and Pu(VI) to Pu(IV) in the presence of 1,2-phenylenediphosphonic acid (PhP2) results in the crystallization of Np[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (NpPhP2) and Pu[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (PuPhP2), respectively. Similar reactions have been explored with Ce(IV) resulting in the isolation of the Ce(IV) phenylenediphosphonate Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (CePhP2). Single crystal diffraction studies reveal that although all these three compounds all crystallize in the triclinic space group P1̅, only PuPhP2 and CePhP2 are isotypic, whereas NpPhP2 adopts a distinct structure. In the cerium and plutonium compounds edge-sharing dimers of MO(8) polyhedra are bridged by the diphosphonate ligand to create one-dimensional chains. NpPhP2 also forms chains. However, the NpO(8) units are monomeric. The protonation of the ligands is also different in the two structure types. Furthermore, the NpO(8) polyhedra are best described as square antiprisms (D(4d)), whereas the CeO(8) and PuO(8) units are trigonal dodecahedra (D(2d)). Bond-valence parameters of R(o) = 1.972 and b = 0.538 have been derived for Np(4+) using a combination of the data reported in this work with that available in crystallographic databases. The UV-vis-NIR absorption spectra of NpPhP2 and PuPhP2 are also reported and used to confirm the tetravalent oxidation states.

  12. Using sequential extraction techniques to assess the partitioning of plutonium and neptunium-237 from multiple sources in sediments from the Ob River (Siberia).

    PubMed

    Kenna, Timothy C

    2009-07-01

    Sequential extraction techniques have been developed to assess partitioning of anthropogenic radionuclides ((240)Pu, (239)Pu, and (237)Np), originating from a variety of sources, as identified by using bulk sediment isotopic composition. Sediments were leached sequentially with a series of six chemical treatments designed to approximate different environmental processes that may occur or to selectively extract trace metals contained in different solid phases of the sediments (i.e., exchangeable, reducible, carbonate, organic, acid leachable, and refractory). Results indicate the majority of Pu and Np is similarly distributed within many of the extracted fractions, with the largest percentage (66-97%) of both elements being observed in sediments treated with buffered citrate dithionite (CDB), which targets easily reduced constituents such as Mn and Fe hydrous oxides. While these results do indicate an association of Pu and Np with redox sensitive elements, the environmental implications are unclear given that the CDB treatment is more extreme than naturally occurring conditions. Minor amounts of Np partition differently from Pu in sediments. The NH(4)-acetate treatment, which is designed to liberate trace metals that are loosely adsorbed onto the surfaces of sedimentary materials such as hydrated iron oxides and humic substances, or present at exchangeable sites in clay minerals, mobilized approximately 12% of the total Np while Pu levels were below detection. The H(2)O(2) treatment, which is designed to liberate trace metals bound to organic matter, mobilized approximately 8 and approximately 1% of Np and Pu, respectively. These results indicate that a minor portion of the total Np may be affected by environmental conditions that have little or no effect on Pu. Between 7 and 24% of the Pu was observed in treatments designed to liberate Pu and Np that are tightly bound to lithogenic phases or refractory silicates. The (240)Pu/(239)Pu observed in accessible and refractory fractions ranged between 0.11 and 0.18. With the exception of one sample, the (240)Pu/(239)Pu isotope ratios measured in the refractory fractions are essentially identical having a mean ratio value of 0.123+/-0.001 (1sigma). The (240)Pu/(239)Pu ratios provide isotopic evidence that suggests a portion of non-fallout contamination has a refractory nature. The presence of similarly low (240)Pu/(239)Pu ratios in refractory fractions of sediments from the Ob and Irtysh Rivers suggests the existence of a source of refractory Pu which is consistent with refractory "hot particles" derived from surface tests at the Semipalitinsk test site.

  13. Aqueous complexation of thorium(IV), uranium(IV), neptunium(IV), plutonium(III/IV), and cerium(III/IV) with DTPA.

    PubMed

    Brown, M Alex; Paulenova, Alena; Gelis, Artem V

    2012-07-16

    Aqueous complexation of Th(IV), U(IV), Np(IV), Pu(III/IV), and Ce(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce(III)DTPA, Ce(III)HDTPA, and Th(IV)DTPA of log β(101) = 20.01 ± 0.02, log β(111) = 22.0 ± 0.2, and log β(101) = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U(IV)DTPA, Np(IV)DTPA, and Pu(IV)DTPA of log β(101) = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce(IV) and Pu(III) of log β(101) = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal.

  14. Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates.

    PubMed

    Wang, Shuao; Villa, Eric M; Diwu, Juan; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-03-21

    U(VI), Np(VI), and Pu(VI) borates with the formula AnO(2)[B(8)O(11)(OH)(4)] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO(2)(2+), surrounded by BO(3) triangles and BO(4) tetrahedra to create an AnO(8) hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO(3) triangles and BO(4) tetrahedra extend from the polyborate layers and connect these sheets together to form a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

  15. Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates

    SciTech Connect

    none,

    2011-02-03

    U(VI), Np(VI), and Pu(VI) borates with the formula AnO2[B8O11(OH)4] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO22+, surrounded by BO3 triangles and BO4 tetrahedra to create an AnO8 hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO3 triangles and BO4 tetrahedra extend from the polyborate layers and connect these sheets together to form a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

  16. Uptake and translocation of neptunium-237, plutonium-238, plutonium-239,240, americium-241, and curium-244 by a wheat crop

    SciTech Connect

    Schulz, R.K.; Ruggieri, M.R.

    1981-07-01

    We carried out a plant uptake and translocation experiment in which a wheat crop was grown on Yolo soil contaminated with /sup 237/Np, /sup 238/Pu, /sup 239/ /sup 240/Pu, /sup 241/Am, and /sup 244/Cm. Studying pot-to-pot variability, we found the data a coefficient of variation of 21 percent. About 9 percent of this variability we ascribe to that of radioanalyses of the plant material. Both uptake and translocation of /sup 238/Pu and /sup 239/ /sup 240/Pu were found to be identical. Likewise, both uptake and translocation of /sup 241/Am and /sup 244/Cm were identical. The Pu concentration was about 10/sup 3/ lower in the grain than in the bottom one-half of the stem plus leaves.

  17. Neptunium(V) hydrolysis and carbonate complexation: Experimental and predicted neptunyl solubility in concentrated NaCl using the Pitzer approach

    NASA Astrophysics Data System (ADS)

    Runde, W.; Neu, M. P.; Clark, D. L.

    1996-06-01

    The solid-liquid equilibrium of Np (V) has been studied in NaCl at 25°C and 0.01 atm CO 2. The equilibrium solids were characterized using X-ray powder diffraction, and the Np (V) solution species were characterized using NIR absorption spectroscopy. The solid phases NaNPO 2CO 3 · nH 2O at [CO 3] < 10 -3 M and Na 3NPO 2(CO 3) 2 · nH 2O at [CO 3] > 10 -3 M were found as solubility-limiting solid equilibrium phases. Pure Np (V) carbonato complexes were formed in solution; hydroxo, bicarbonato, or mixed hydroxocarbonato Np (V) complexes were determined not to be significant. The comparison of Np (V) solubility data in NaCl and NaClO 4 solutions indicated a stabilization of Np (V) in solution due to the interaction with chloride ions. Absorption spectra of NpO 2+ and NpO 2CO 3 in 5 M NaCl were shifted slightly towards higher wavelengths, also suggesting an interaction with chloride ions. The Pitzer approach was applied to parameterize experimental data and to predict Np (V) solubility in brine solutions. The activity of water changes with electrolyte concentration; thus incorporation of the reported molecules of hydration water in NaNPO 2CO 3 · nH 2O ( n = 3.5) to determine the chemical potential of this solid improved the agreement between predicted solubility and experimental data. NaNPO 2CO 3 · nH 2O and NaAmO 2CO 3 · nH 2O showed the same solubility in 3 and 5 M NaCl.

  18. Neptunium, plutonium, and americium solubility and speciation studies in a neutral electrolyte with a total carbonate concentration simulating UE-25P No. 1 well water

    SciTech Connect

    Becraft, K.A.; Torretto, P.C.; Nitsche, H.

    1995-12-01

    In these experiments we have approached the solubility equilibrium from oversaturation. Results are given for solubility and speciation experiments of {sup 237}NpO{sub 2}+, {sup 239}Pu{sup 4+}, and {sup 241}Am{sup 3+} in a neutral electrolyte (0.1 M NaC1O{sub 4}) containing a total carbonate concentration similar to UE-25p No. 1 groundwater (0.015 M) at 25{degrees} C and at three pH values (6, 7, and 8.5). In these experiments, the solubility-controlling solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined. Trivalent neodymium was used as an oxidation state analog for {sup 241}Am(III) in order to reduce the radiolysis effects in the solutions. The {sup 241}Am(III) was included as a tracer for radioanalytical counting of samples.

  19. Synthesis and characterization of titanium carbide, titanium boron carbonitride, titanium boride/titanium carbide and titanium carbide/chromium carbide multilayer coatings by reactive and ion beam assisted, electron beam-physical vapor deposition (EB-PVD)

    NASA Astrophysics Data System (ADS)

    Wolfe, Douglas Edward

    The purpose of the present work was to investigate the synthesis of titanium carbide, TiBCN, TiB2/TiC and TiC/Cr23C6 multilayer coatings by several methods of electron beam-physical vapor deposition (EB-PVD) and examine the affects of various processing parameters on the properties and microstructures of the coatings. TiC was successfully deposited by reactive ion beam assisted (RIBA), EB-PVD and the results were compared to various titanium carbide coatings deposited by a variety of techniques. The affects of substrate temperature and ion beam current density were correlated with composition, hardness, changes in the lattice parameter, degree of crystallographic texture, residual stress, surface morphology, and microstructure. The average Vicker's hardness number was found to increase with increasing ion beam current density and increase over the substrate temperature range of 250°C to 650°C. The average Vicker's hardness number decreased at a substrate temperature of 750°C as a result of texturing and microstructure. The present investigation shows that the average Vicker's hardness number is not only a function of the composition, but also the microstructure including the degree of crystallographic texture. TiB2/TiC multilayer coatings were deposited by argon ion beam assisted, EB-PVD with varying number of total layers to two different film thicknesses under slightly different deposition conditions. In both cases, the hardness of the coatings increased with increasing number of total layers. The adhesion of the coatings ranged from 30 N to 50 N, with the better adhesion values obtained with the thinner coatings. The crystallographic texture coefficients of both the TiC and TiB2 layers were found to change with increasing number of total layers. The multilayer design was found to significantly affect the microstructure and grain size of the deposited coatings. The fracture toughness was found to decrease with increasing number of total layers and was attributed to the increase in hardness and reduction in the total amount of compressive stress. TiBCN coatings were synthesized by the co-evaporation of titanium, titanium diboride, and carbon (through tungsten) while simultaneously bombarding the substrate surface with a mixture of argon and nitrogen ionized gas which has not been performed to the author's knowledge. The bulk composition was determined by EPMA and suggests that TiBCN has a wide compositional range similar to TiN and TiC. The TiBCN coatings were determined to be nano-crystalline with a cubic crystallographic structure. The average Vicker's hardness number of the TiBCN coatings ranged from 2777 VHN0.050 to 3343 VHN0.050 with the highest value reported for the higher concentrations of boron. The adhesion of the coatings to WC-6wt.Co-0.3wt.%TaC was found to increase from 20 N to 52 N with decreasing compressive stress. Lastly, multilayer titanium carbide and chromium carbide coatings with varying individual layer thickness were synthesized by the co-evaporation of Ti, Cr and C through tungsten at elevated temperatures. The average Vicker's hardness number was found to increase from 1302 VHN0.050 to 2052 VHN0.050 by changing the individual layer thickness of the multilayers. In addition, the grain size, measured compressive stress, and fracture toughness values all decreased with decreasing individual layer thickness.

  20. Nickel and titanium nanoboride composite coating

    NASA Astrophysics Data System (ADS)

    Efimova, K. A.; Galevsky, G. V.; Rudneva, V. V.; Kozyrev, N. A.; Orshanskaya, E. G.

    2015-09-01

    Electrodeposition conditions, structural-physical and mechanical properties (microhardness, cohesion with a base, wear resistance, corrosion currents) of electroplated composite coatings on the base of nickel with nano and micro-powders of titanium boride are investigated. It has been found out that electro-crystallization of nickel with boride nanoparticles is the cause of coating formation with structural fragments of small sizes, low porosity and improved physical and mechanical properties. Titanium nano-boride is a component of composite coating, as well as an effective modifier of nickel matrix. Nano-boride of the electrolyte improves efficiency of the latter due to increased permissible upper limit of the cathodic current density.

  1. Methods of repairing a substrate

    NASA Technical Reports Server (NTRS)

    Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

    2011-01-01

    A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

  2. SEPARATION PROCESS FOR TRANSURANIC ELEMENT AND COMPOUNDS THEREOF

    DOEpatents

    Magnusson, L.B.

    1958-04-01

    A process is described for the separation of neptunium, from aqueous solutions of neptunium, plutonium, uraniunn, and fission prcducts. This separation from an acidic aqueous solution of a tetravalent neptuniunn can be made by contacting the solution with a certain type of chelating,; agent, preferably dissolved in an organic solvent, to form a neptunium chelate compound. When the organic solvent is present, the neptunium chelate compound is extracted; otherwise, it precipitates from the aqueous solution and is separated by any suitable means. The chelating agent is a fluorinated BETA -diketone. such as trifluoroacetyl acetone.

  3. A Linear trans -Bis(imido) Neptunium(V) Actinyl Analog: NpV (NDipp)2 ( tBu2 bipy)2Cl (Dipp = 2,6- i Pr2C6H3)

    DOE PAGESBeta

    Brown, Jessie L.; Batista, Enrique R.; Boncella, James M.; Gaunt, Andrew J.; Reilly, Sean D.; Scott, Brian L.; Tomson, Neil C.

    2015-07-22

    We present the discovery that imido analogs of actinyl dioxo cations can be extended beyond uranium into the transuranic elements. Synthesis of the Np(V) complex, Np(NDipp)2(tBu2bipy)2Cl (1), is achieved through treatment of a Np(IV) precursor with a bipyridine co-ligand and lithium-amide reagent. Complex 1 has been structurally characterized, analyzed by 1H NMR and UV/vis/NIR spectroscopies, and the electronic structure evaluated by DFT calculations.

  4. A Linear trans-Bis(imido) Neptunium(V) Actinyl Analog: Np(V)(NDipp)2((t)Bu2bipy)2Cl (Dipp = 2,6-(i)Pr2C6H3).

    PubMed

    Brown, Jessie L; Batista, Enrique R; Boncella, James M; Gaunt, Andrew J; Reilly, Sean D; Scott, Brian L; Tomson, Neil C

    2015-08-01

    The discovery that imido analogs of actinyl dioxo cations can be extended beyond uranium into the transuranic elements is presented. Synthesis of the Np(V) complex, Np(NDipp)2((t)Bu2bipy)2Cl (1), is achieved through treatment of a Np(IV) precursor with a bipyridine coligand and lithium-amide reagent. Complex 1 has been structurally characterized, analyzed by (1)H NMR and UV-vis-NIR spectroscopies, and the electronic structure evaluated by DFT calculations.

  5. Further Insights into Intermediate- and Mixed-Valency in Neptunium Oxoanion Compounds: Structure and Absorption Spectroscopy of K2[(NpO2)3B10O16(OH)2(NO3)2

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2010-01-01

    The reaction of Np(V) chloride with molten boric acid results in the disproportionation of Np(V) into Np(IV) and Np(VI), and the crystallization of K{sub 2}[(NpO{sub 2}){sub 3}B{sub 10}O{sub 16}(OH){sub 2}(NO{sub 3}){sub 2}]. UV-vis-NIR spectroscopy demonstrates that in addition to the Np(VI) and Np(V) found in the crystal structure, Np(IV) is also present.

  6. Calculated Thermodynamic Functions for Gas Phase Uranium, Neptunium, Plutonium, and Americium Oxides (AnO3), Oxyhydroxides (AnO2(OH)2), Oxychlorides (AnO2Cl2), and Oxyfluorides (AnO2F2)

    SciTech Connect

    Ebbinghaus, B B

    2002-10-31

    Based on known and estimated molecular constants, the thermodynamic functions, C{sub p}, S{sup o}, H{sup o}-H{sup o}(298), and -(G{sup o} - H{sup o}(298))/T, have been calculated and tabulated for actinide vapors species of the formulas AnO{sub 3}(g), AnO{sub 2}(OH){sub 2}(g), AnO{sub 2}Cl{sub 2}(g), and AnO{sub 2}F{sub 2}(g) where An = U, Np, Pu, and Am. A method to calculate the thermodynamic functions for the mixed species, AnO{sub 2}ClOH(g), AnO{sub 2}FOH(g), and AnO{sub 2}FCl(g), is also given.

  7. Solubility and speciation results from oversaturation experiments on neptunium, plutonium and americium in a neutral electrolyte with a total carbonate similar to water from Yucca Mountain Region Well UE- 25p No. 1

    SciTech Connect

    Torretto, P.; Becraft, K.; Prussin, T.; Roberts, K.; Carpenter, S.; Hobart, D.; Nitsche, H.

    1995-12-01

    Solubility and speciation are important in understanding aqueous radionuclide transport through the geosphere. They define the source term for transport retardation processes such as sorption and colloid formation. Solubility and speciation data are useful in verifying the validity of geochemical codes that are a part of predictive transport models. Solubility experiments will approach solution equilibrium from both oversaturation and undersaturation. In these experiments, we have approached the solubility equilibrium from oversaturation, Results are given for solubility and speciation experiments from oversaturation of {sup 237} NpO{sub 2}{sup +} {sup 239}Pu{sup 4+}, and {sup 241}Am{sup 3+}/Nd{sup 3+} in a neutral electrolyte containing a total carbonate concentration similar to groundwater from the Yucca Mountain region, Nevada, which is being investigated as a potential high-level nuclear waste disposal site, at 25{degrees}C and three pH values. In these experiments, the solubilitycontrolling steady-state solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined.

  8. Final Report on Phase III Testing of Monosodium Titanate Adsorption Kinetics

    SciTech Connect

    Hobbs, D.T.

    1999-09-29

    This study consisted of a statistically designed set of tests to determine the extent and rate of adsorption of strontium, plutonium, uranium, and neptunium as a function of temperature, monosodium titanate (MST) concentration, and concentrations of sodium, strontium, plutonium, uranium, and neptunium.

  9. Thermal expansion and lattice dynamics of RB66 compounds at low temperatures

    SciTech Connect

    Novikov, V V; Avdashchenko, D V; Mitroshenkov, N V; Matovnikov, A V; Budko, Serguei L

    2014-10-01

    Thermal characteristics of the phonon and magnon subsystems of icosahedral borides RB66 (R = Gd, Tb, Dy, Ho, Eu, or Lu) have been studied based on the obtained experimental data on the thermal expansion of the borides and the earlier results on their heat capacity in the range of 2–300 K. The contribution to the expansion of borides containing paramagnetic R 3+ ions, which is characteristic of transition to the spin-glass state, has been revealed. The phonon spectrum moments of RB66 compounds and the Grüneisen parameters have been calculated.

  10. Evolution of dispersion of high temperature chromium compounds

    NASA Astrophysics Data System (ADS)

    Shiryaeva, L. S.; Nozdrin, I. V.; Rudneva, V. V.; Galevsky, G. V.

    2016-09-01

    Chromium compound - boride Cr3B2 and carbide Cr3C2 are hard, wear-resistant, chemically inert materials, demanded for production of protective coatings of metals and cermets as components and alloying additives of tungsten free solid alloys. Future prospects for expansion of boride and chromium carbide usage are related to their production in the form of nanopowders. The researches into change of the particles shape and size of high-temperature chromium compounds in the conditions of plasma flow were carried out. There is coarsening of boride and carbonitride particles of nanoscale level at the reduction in the linear velocity of their growth.

  11. Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

    NASA Technical Reports Server (NTRS)

    Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

    2009-01-01

    A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

  12. NEUTRONIC REACTOR FUEL COMPOSITION

    DOEpatents

    Thurber, W.C.

    1961-01-10

    Uranium-aluminum alloys in which boron is homogeneously dispersed by adding it as a nickel boride are described. These compositions have particular utility as fuels for neutronic reactors, boron being present as a burnable poison.

  13. Interfacial reactions between titanium and borate glass

    SciTech Connect

    Brow, R.K.; Saha, S.K.; Goldstein, J.I.

    1992-12-31

    Interfacial reactions between melts of several borate glasses and titanium have been investigated by analytical scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). A thin titanium boride interfacial layer is detected by XPS after short (30 minutes) thermal treatments. ASEM analyses after longer thermal treatments (8--120 hours) reveal boron-rich interfacial layers and boride precipitates in the Ti side of the interface.

  14. Radioactivity studies: Final report, June 1985-August 1986

    SciTech Connect

    Ralston, L.; Cohen, N.

    1987-11-01

    We instigated studies of neptunium metabolism in two nonhuman primate species to derive dosimetric parameters necessary for accurate human radiation risk assessments. The metabolism of neptunium was studied in adult female baboons and tamarins following intravenous injection and intragastric intubation. Neptunium-237 and /sup 239/Np isotopes were prepared as citrate, nitrate, and bicarbonate complexs with valence states of +4, +5 and +6. Samples of blood, urine, feces and autopsy tissues were measured by both gamma-ray and alpha spectrometry techniques. Retention of injected neptunium was determined in vivo using whole and partial body gamma-scintillation spectroscopy. Immediately following intravenous injection, neptunium (+5 and +6) cleared rapidly from blood, deposited primarily in the skeleton (54 +- 5%) and liver (3 +- 1%), and was excreted predominately via urine (40 +- 3%). For the first year post injection, neptunium was retained with a composite biological half-time of 100 yrs in liver and 1.5 yrs in bone. In comparison, injected Np(+4) was retained in blood in higher concentrations and was eliminated initially via urine to a lesser extent (12%). Np(+4) was deposited primarily in the carcass (38 +- 4%) and liver (43 +- 4%). Differences in the chemical forms and radionuclide concentrations injected did not alter neptunium metabolic patterns. 78 refs., 20 figs., 30 tabs.

  15. Alpha self-irradiation effects in ternary oxides of actinides elements: The zircon-like phases Am{sup III}VO{sub 4} and A{sup II}Np{sup IV}(VO{sub 4}){sub 2} (A=Sr, Pb)

    SciTech Connect

    Goubard, F. . E-mail: fabrice.goubard@chim.u-cergy.fr; Griesmar, P.; Tabuteau, A.

    2005-06-15

    We report the experimental studies of irradiation damage from alpha decay in neptunium and americium vanadates versus cumulative dose. The isotopes used were the transuranium {alpha}-emitter {sup 237}Np and the {alpha},{gamma}-emitter {sup 241}Am. Neptunium and americium vanadates self-irradiation was studied by X-ray diffraction method (XRD). The comparison of the powder diffraction patterns reveal that the irradiation has no apparent effect on the neptunium phases while the americium vanadate swells and becomes metamict as a function of cumulative dose.

  16. Influence of laser alloying with boron and niobium on microstructure and properties of Nimonic 80A-alloy

    NASA Astrophysics Data System (ADS)

    Makuch, N.; Piasecki, A.; Dziarski, P.; Kulka, M.

    2015-12-01

    Ni-base superalloys were widely used in aeronautics, chemical and petrochemical industries due to their high corrosion resistance, high creep and rupture strength at high temperature. However, these alloys were not considered for applications in which conditions of appreciable mechanical wear were predominant. The diffusion boriding provided suitable protection against wear. Unfortunately, this process required long duration and high temperature. In this study, instead of the diffusion process, the laser alloying with boron and niobium was used in order to produce the hard and wear resistant layer on Nimonic 80A-alloy. The laser-alloying was carried out as a two-step process. First, the external cylindrical surface of specimens was pre-placed with a paste containing boron and niobium. Then, the pre-placed coating and the thin surface layer of the substrate were re-melted by a laser beam. The high laser beam power (P=1.56 kW) and high averaging irradiance (E=49.66 kW/cm2) provided the thick laser re-melted zone. The laser-borided layers were significantly thicker (470 μm) in comparison with the layers obtained as a consequence of the diffusion boriding. Simultaneously, the high overlapping of multiple laser tracks (86%) caused that the laser-alloyed layer was uniform in respect of the thickness. The produced layer consisted of nickel borides (Ni3B, Ni2B, Ni4B3, NiB), chromium borides (CrB, Cr2B), niobium borides (NbB2, NbB) and Ni-phase. The presence of hard borides caused the increase in microhardness up to 1000 HV in the re-melted zone. However, the measured values were lower than those-characteristic of niobium borides, chromium borides and nickel borides. The presence of the soft Ni-phase in re-melted zone was the reason for such a situation. After laser alloying, the significant increase in abrasive wear resistance was also observed. The mass wear intensity factor, as well as the relative mass loss of the laser-alloyed specimens, was over 10 times smaller in

  17. 10 CFR 110.23 - General license for the export of byproduct material.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... Einsteinium-255 Fermium-257 Gadolinium-148 Mendelevium-258 Neptunium-235 Polonium-208 Polonium-209 Polonium... § 110.54(b). (7) For polonium-210, exports under the general license, when contained in...

  18. 10 CFR 110.23 - General license for the export of byproduct material.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... Einsteinium-255 Fermium-257 Gadolinium-148 Mendelevium-258 Neptunium-235 Polonium-208 Polonium-209 Polonium... § 110.54(b). (7) For polonium-210, exports under the general license, when contained in...

  19. 10 CFR 110.23 - General license for the export of byproduct material.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... Einsteinium-255 Fermium-257 Gadolinium-148 Mendelevium-258 Neptunium-235 Polonium-208 Polonium-209 Polonium... § 110.54(b). (7) For polonium-210, exports under the general license, when contained in...

  20. 10 CFR 110.23 - General license for the export of byproduct material.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... Einsteinium-255 Fermium-257 Gadolinium-148 Mendelevium-258 Neptunium-235 Polonium-208 Polonium-209 Polonium... § 110.54(b). (7) For polonium-210, exports under the general license, when contained in...

  1. 10 CFR 110.23 - General license for the export of byproduct material.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...-257, gadolinium-148, mendelevium-258, neptunium-235 and -237, polonium-210, and radium-223 must be... country. (5) For polonium-210, the material must be contained in static eliminators and may not exceed...

  2. Integrated study of the behavior of transuranic elements in the marine environment

    SciTech Connect

    Choppin, G. R.; Morse, J. W.

    1981-01-01

    In order to construct a model of radionuclide kinetics in an aquatic ecosystem, americium ions were chosen for study. Results will be applied to thorium, plutonium, neptunium and uranium for comparison of environmental behavior. (PSB)

  3. PRODUCING ENERGY AND RADIOACTIVE FISSION PRODUCTS

    DOEpatents

    Segre, E.; Kennedy, J.W.; Seaborg, G.T.

    1959-10-13

    This patent broadly discloses the production of plutonium by the neutron bombardment of uranium to produce neptunium which decays to plutonium, and the fissionability of plutonium by neutrons, both fast and thermal, to produce energy and fission products.

  4. Lab Scale Production of NpO2

    SciTech Connect

    Duffey, J

    2003-08-29

    The Savannah River Site (SRS) plans to disposition its legacy H-Canyon neptunium to Oak Ridge National Laboratory after converting it to oxide in HB-Line. Neptunium oxide, (NpO{sub 2}) was produced at the Savannah River Technology Center using the anticipated HB-Line flowsheet conditions. The oxide was produced from a neptunium nitrate solution via anion exchange, oxalate precipitation, and calcination at either 600 C or 650 C. The 98 grams of NpO{sub 2} produced in the laboratory should be representative of material produced in HB-Line and is to be used for gas generation testing to support radioactive material transportation safety analysis as part of the neptunium stabilization and disposition program at SRS. Results of each step of the oxide production will be presented.

  5. A survey of metallurgical research on several actinides

    SciTech Connect

    Olivas, J.D.; Schonfeld, F.W.

    1993-11-01

    A Los Alamos perspective on metallurgical research on neptunium, plutonium, americium, curium, and californium is presented. Alloying behaviors of these metals are discussed. Metal fabrication technologies, principally for plutonium, are emphasized.

  6. METHOD OF SEPARATING Pu FROM METATHESIZED BiPO$sub 4$ CARRIER

    DOEpatents

    Knox, W.J.; Thompson, S.G.

    1960-05-31

    A process is given for separating uranium, neptunium, and/or plutonium from a bismuth hydroxide carrier by selective dissolution of these actinides with nitric acid of a concentration of from 0.05 to 0.5N.

  7. Np Behavior in Synthesized Uranyl Phases: Results of Initial Tests

    SciTech Connect

    Friese, Judah I.; Douglas, Matthew; McNamara, Bruce K.; Clark, Sue B.; Hanson, Brady D.

    2004-09-28

    Initial tests were completed at Pacific Northwest National Laboratory for developing a potential mechanism to retard the mobility of neptunium at the Yucca Mountain repository. Neptunium is of concern because of its mobility in the environment and long half life, contributing a large percentage of the potential dose over extended times at the perimeter of the site. The mobility of neptunium could be retarded by associating with uranium mineral phases. The following four uranium mineral phases were examined and are potential secondary phases expected to form as a result of interactions of spent nuclear fuel with the local environment: meta-schoepite, studtite, uranophane, and sodium boltwoodite. The fate of the neptunium was examined in these synthetic experiments.

  8. Redox reactions of actinides in carbonate and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Shilov, Vladimir P.; Yusov, Aleksander B.

    2002-06-01

    Data on redox reactions involving uranium, neptunium, plutonium and americium ions in carbonate and alkaline solutions are generalised. The results of kinetic studies of these reactions are analysed and their mechanisms are discussed. The bibliography includes 169 references.

  9. Relativistic effects on the thermal expansion of the actinide elements

    SciTech Connect

    Soederlind, P.; Nordstroem, L.; Lou Yongming; Johansson, B. )

    1990-09-01

    The room-temperature linear thermal-expansion coefficient is calculated for the light actinides thorium, protactinium, uranium, neptunium, and plutonium for the fcc crystal structure. The relativistic spin-orbit interaction is included in these calculations. We show that the spin-orbit splitting of the 5{ital f} band gives rise to a considerable increase of the thermal expansion and to a large extent explains the observed anomalously large thermal expansion for the neptunium and plutonium metals.

  10. A study on the formation of solid state nanoscale materials using polyhedral borane compounds

    NASA Astrophysics Data System (ADS)

    Romero, Jennifer V.

    The formation of boron containing materials using a variety of methods was explored. The pyrolysis of a metal boride precursor solution can be accomplished using a one-source method by combining TiCl4, B10H 14 and CH3CN in one reaction vessel and pyrolyzing it at temperatures above 900 °C. Amorphous dark blue colored films were obtained after the pyrolysis reactions. Well-defined spherical shaped grains or particles were observed by SEM. The amorphous films generated contained titanium, however, the determination of the boron content of the films was inconclusive. This one pot method making metal boride thin films has the advantage of being able to dictate the stoichiometry of the reactants. Another part of this work represents the first report of both the use of metal boride materials and the use of a titanium-based compound for the formation of nanotubes. This method provides a facile method for generating well-formed boron-containing carbon nanotubes in a "one-pot" process through an efficient aerosol process. The formation of metal boride corrosion resistant layers was also explored. It was shown that metallic substrates can be effectively boronized using paste mixtures containing boron carbide and borax. The formation of a Fe4B 2 iron boride phase was achieved, however, this iron boride phase does not give enough corrosion protection. The formation of a corrosion resistant metal boride coating with strong adhesion was accomplished by boronization of a thermal sprayed nickel layer on the surface of steel. Surfactants were explored as possible nanoreactors in which metal boride nanoparticles could be formed to use as nanotube growth catalyst via room temperature reaction. Different surfactants were used, but none of them successfully generated very well dispersed metal boride nanoparticles. Nanoparticles with varying shapes and sizes were generated which were highly amorphous. The carboxylic acid derivative of closo-C2B 10 cages was explored as a ligand in the

  11. Method of boronizing transition metal surfaces

    DOEpatents

    Koyama, Koichiro; Shimotake, Hiroshi

    1983-01-01

    A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB.sub.2, or CrB.sub.2. A transition metal to be coated is immersed in the melt at a temperature of no more than 700.degree. C. and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

  12. Method of boronizing transition metal surfaces

    DOEpatents

    Koyama, Koichiro; Shimotake, Hiroshi.

    1983-08-16

    A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB[sub 2], or CrB[sub 2]. A transition metal to be coated is immersed in the melt at a temperature of no more than 700 C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface. 4 figs.

  13. Investigation of the structure and properties of boron-containing coatings obtained by electron-beam treatment

    SciTech Connect

    Krivezhenko, Dina S. Drobyaz, Ekaterina A. Bataev, Ivan A. Chuchkova, Lyubov V.

    2015-10-27

    An investigation of surface-hardened materials obtained by cladding with an electron beam injected into the air atmosphere was carried out. Structural investigations of coatings revealed that an increase in boron carbide concentration in a saturating mixture contributed to a rise of a volume fraction of iron borides in coatings. The maximum hardened depth reached 2 mm. Hardened layers were characterized by the formation of heterogeneous structure which consisted of iron borides and titanium carbides distributed uniformly in the eutectic matrix. Areas of titanium boride conglomerations were detected. It was found that an increase in the boron carbide content led to an enhancement in hardness of the investigated materials. Friction testing against loosely fixed abrasive particles showed that electron-beam cladding of powder mixtures containing boron carbides, titanium, and iron in air atmosphere allowed enhancing a resistance of materials hardened in two times.

  14. M3B2 and M5B3 Formation in Diffusion-Affected Zone During Transient Liquid Phase Bonding Single-Crystal Superalloys

    NASA Astrophysics Data System (ADS)

    Sheng, Naicheng; Hu, Xiaobing; Liu, Jide; Jin, Tao; Sun, Xiaofeng; Hu, Zhuangqi

    2015-04-01

    Precipitates in the diffusion-affected zone (DAZ) during transient liquid phase bonding (TLP) single-crystal superalloys were observed and investigated. Small size and dendritic-shaped precipitates were identified to be M3B2 borides and intergrowth of M3B2/M5B3 borides. The orientation relationships among M3B2, M5B3, and matrix were determined using transmission electron microscope (TEM). Composition characteristics of these borides were also analyzed by TEM energy-dispersive spectrometer. Because this precipitating phenomenon deviates from the traditional parabolic transient liquid phase bonding model which assumed a precipitates free DAZ during TLP bonding, some correlations between the deviation of the isothermal solidification kinetics and these newly observed precipitating behaviors were discussed and rationalized when bonding the interlayer containing the high diffusivity melting point depressant elements and substrates of low solubility.

  15. Investigation of the structure and properties of boron-containing coatings obtained by electron-beam treatment

    NASA Astrophysics Data System (ADS)

    Krivezhenko, Dina S.; Drobyaz, Ekaterina A.; Bataev, Ivan A.; Chuchkova, Lyubov V.

    2015-10-01

    An investigation of surface-hardened materials obtained by cladding with an electron beam injected into the air atmosphere was carried out. Structural investigations of coatings revealed that an increase in boron carbide concentration in a saturating mixture contributed to a rise of a volume fraction of iron borides in coatings. The maximum hardened depth reached 2 mm. Hardened layers were characterized by the formation of heterogeneous structure which consisted of iron borides and titanium carbides distributed uniformly in the eutectic matrix. Areas of titanium boride conglomerations were detected. It was found that an increase in the boron carbide content led to an enhancement in hardness of the investigated materials. Friction testing against loosely fixed abrasive particles showed that electron-beam cladding of powder mixtures containing boron carbides, titanium, and iron in air atmosphere allowed enhancing a resistance of materials hardened in two times.

  16. Silicon carbide sintered body manufactured from silicon carbide powder containing boron, silicon and carbonaceous additive

    NASA Technical Reports Server (NTRS)

    Tanaka, Hidehiko

    1987-01-01

    A silicon carbide powder of a 5-micron grain size is mixed with 0.15 to 0.60 wt% mixture of a boron compound, i.e., boric acid, boron carbide (B4C), silicon boride (SiB4 or SiB6), aluminum boride, etc., and an aluminum compound, i.e., aluminum, aluminum oxide, aluminum hydroxide, aluminum carbide, etc., or aluminum boride (AlB2) alone, in such a proportion that the boron/aluminum atomic ratio in the sintered body becomes 0.05 to 0.25 wt% and 0.05 to 0.40 wt%, respectively, together with a carbonaceous additive to supply enough carbon to convert oxygen accompanying raw materials and additives into carbon monoxide.

  17. Synthesis and Characterization of TiB2 Reinforced Aluminium Matrix Composites: A Review

    NASA Astrophysics Data System (ADS)

    Kumar, Narendra; Gautam, Gaurav; Gautam, Rakesh Kumar; Mohan, Anita; Mohan, Sunil

    2015-09-01

    Aluminium-matrix composites (AMCs) are developed to meet the demands of light weight high performance materials in aerospace, automotive, marine and other applications. The properties of AMCs can be tailored suitably by combinations of matrix, reinforcement and processing route. AMCs are one of the most attractive alternatives for the manufacturing of light weight and high strength parts due to their low density and high specific strength. There are various techniques for preparing the AMCs with different reinforcement particles. In AMCs, the reinforcements are usually in the form of metal oxides, carbides, borides, nitrides and their combination. Among the various reinforcements titanium di-boride (TiB2) is of much interest due to its excellent stiffness, hardness, and wear resistance. This paper attempts to provide an overview to explore the possibilities of synthesizing titanium di-boride reinforced AMCs with different techniques. The mechanical and tribological properties of these composites have been emphasized to project these as tribo-materials.

  18. New Process for Grain Refinement of Aluminum. Final Report

    SciTech Connect

    Dr. Joseph A. Megy

    2000-09-22

    A new method of grain refining aluminum involving in-situ formation of boride nuclei in molten aluminum just prior to casting has been developed in the subject DOE program over the last thirty months by a team consisting of JDC, Inc., Alcoa Technical Center, GRAS, Inc., Touchstone Labs, and GKS Engineering Services. The Manufacturing process to make boron trichloride for grain refining is much simpler than preparing conventional grain refiners, with attendant environmental, capital, and energy savings. The manufacture of boride grain refining nuclei using the fy-Gem process avoids clusters, salt and oxide inclusions that cause quality problems in aluminum today.

  19. Electrically conductive containment vessel for molten aluminum

    DOEpatents

    Holcombe, C.E.; Scott, D.G.

    1984-06-25

    The present invention is directed to a containment vessel which is particularly useful in melting aluminum. The vessel of the present invention is a multilayered vessel characterized by being electrically conductive, essentially nonwettable by and nonreactive with molten aluminum. The vessel is formed by coating a tantalum substrate of a suitable configuration with a mixture of yttria and particulate metal 10 borides. The yttria in the coating inhibits the wetting of the coating while the boride particulate material provides the electrical conductivity through the vessel. The vessel of the present invention is particularly suitable for use in melting aluminum by ion bombardment.

  20. Electrically conductive containment vessel for molten aluminum

    DOEpatents

    Holcombe, Cressie E.; Scott, Donald G.

    1985-01-01

    The present invention is directed to a containment vessel which is particularly useful in melting aluminum. The vessel of the present invention is a multilayered vessel characterized by being electrically conductive, essentially nonwettable by and nonreactive with molten aluminum. The vessel is formed by coating a tantalum substrate of a suitable configuration with a mixture of yttria and particulate metal borides. The yttria in the coating inhibits the wetting of the coating while the boride particulate material provides the electrical conductivity through the vessel. The vessel of the present invention is particularly suitable for use in melting aluminum by ion bombardment.