WorldWideScience

Sample records for americium halides

  1. Preparation of americium amalgam

    International Nuclear Information System (INIS)

    The authors describe a method for the electrochemical preparation of an americium amalgam from americium dioxide and americium 241 and 243 for use in determining the physicochemical properties of the alloy. Moessbauer spectra were made using neptunium dioxide, in the neptunium 237 form, as an absorber. Results show that electrolysis produces a homogeneous amalgam that gives an unoxidized product on vacuum distillation at 200 degrees C

  2. Americium recovery from reduction residues

    Science.gov (United States)

    Conner, W.V.; Proctor, S.G.

    1973-12-25

    A process for separation and recovery of americium values from container or bomb'' reduction residues comprising dissolving the residues in a suitable acid, adjusting the hydrogen ion concentration to a desired level by adding a base, precipitating the americium as americium oxalate by adding oxalic acid, digesting the solution, separating the precipitate, and thereafter calcining the americium oxalate precipitate to form americium oxide. (Official Gazette)

  3. Preparation of americium amalgam

    International Nuclear Information System (INIS)

    Using the method of NGR-spectroscopy with the aid of 241Am isotope chemical state of transuranium elements in the volume and on the surface of amalgams is studied. Amalgam preparation was realized in a simplified electrolytic cell. It is shown that in the process of amalgam preparation the first order of reaction as to actinide is observed; americium is distributed gradually over the volume and it is partially sorbed by the surface of glass capillary. NGR spectrum of dry residue after mercury distillation at 200 deg C points to the presence of americium-mercury intermetal compounds

  4. Chemistry of americium

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1976-01-01

    Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

  5. Americium-241 - ED 4308

    International Nuclear Information System (INIS)

    This sheet presents the characteristics of Americium-241, its origin, and its radio-physical and biological properties. It briefly describes its use in nuclear medicine. It indicates its dosimetric parameters for external exposure, cutaneous contamination, and internal exposure due to acute contamination or to chronic contamination. It indicates and comments the various exposure control techniques: ambient dose rate measurement, surface contamination measurement, atmosphere contamination. It addresses the means of protection: premise design, protection against external exposure and against internal exposure. It describes how areas are delimited and controlled within the premises: regulatory areas, controls to be performed. It addresses the personnel classification, training and medical survey. It addresses the issue of wastes and effluents. It briefly recalls the administrative procedures related to the authorization and declaration of possession and use of sealed and unsealed sources. It indicates regulatory aspects related to the road transport of Americium-241, describes what is to be done in case of incident or accident (for the different types of contamination or exposure)

  6. The Biokinetic Model of Americium

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    To improve in vivo measurements for detecting internal exposure from transuranium radio nuclides, such as neptunium, plutonium, americium, the bioknetic model was studied. According to ICRP report (1993, 1995, 1997) and other research, the

  7. Americium product solidification and disposal

    International Nuclear Information System (INIS)

    The americium product from the TRUEX processing plant needs to be converted into a form suitable for ultimate disposal. An evaluation of the disposal based on safety, number of process steps, demonstrated operability of the processes, production of low-level alpha waste streams, and simplicity of maintenance with low radiation exposures to personnel during maintenance, has been made. The best process is to load the americium on a cation exchange resin followed by calcination or oxidation of the resin after loading

  8. Science and Technology for Americium Transmutation

    International Nuclear Information System (INIS)

    Americium could be seen as the most troublesome element that is present in nuclear fuel. This thesis offers different points of view on the possibility of americium transmutation. The first point of view elaborates simulations of americium-bearing facilities, namely nuclear data, a popular computational code and modeling techniques. The second point of view is focused on practical usage of the simulations to examine upper limit of americium in a specific reactor

  9. The Silver Halides

    Science.gov (United States)

    Sahyun, M. R. V.

    1977-01-01

    Illustrates the type of fractional bonding for solid silver halides. Treats the silver halides as electron excess compounds, and develops a model of a localized bonding unit that may be iterated in three dimensions to describe the bulk phase. (MLH)

  10. Transmutation of Americium in Fast Neutron Facilities

    OpenAIRE

    Zhang, Youpeng

    2011-01-01

    In this thesis, the feasibility to use a medium sized sodium cooled fast reactor fully loaded with MOX fuel for efficient transmutation of americium is investigated by simulating the safety performance of a BN600-type fast reactor loaded with different fractions of americium in the fuel, using the safety parameters obtained with the SERPENT Monte Carlo code. The focus is on americium mainly due to its long-term contribution to the radiotoxicity of spent nuclear fuel and its deterioration on c...

  11. Polynuclear technetium halide clusters

    International Nuclear Information System (INIS)

    Development of chemistry of polynuclear technetium halide clusters in works devoted to synthesis, structure and investigation of their chemical and physical properties is considered. The role of academician V.I. Spitsyn as an initiator of investigation of polynuclear technetium halide clusters in the Institute of Physical Chemistry of Academy of Science of USSR is noted. Reactions and stability of cluster halides, their molecular and electronic structures are analyzed. Prospects of development of polynuclear technetium halide clusters chemistry as a direction being on the junction of cluster chemistry and theory of metal-metal multiple bonds are appreciated

  12. Production of americium isotopes in France

    International Nuclear Information System (INIS)

    The program of productions of americium 241 and 243 isotopes is based respectively on the retreatment of aged plutonium alloys or plutonium dioxide and on the treatment of plutonium targets irradiated either in CELESTIN reactors for Pu-Al alloys or OSIRIS reactor for plutonium 242 dioxide. All the operations, including americium final purifications, are carried out in hot cells equipped with remote manipulators. The chemical processes are based on the use of extraction chromatography with hydrophobic SiO2 impregnated with extracting agents. Plutonium targets and aged plutonium alloys are dissolved in nitric acid using conventional techniques while plutonium dioxide dissolutions are performed routine at 300 grams scale with electrogenerated silver II in 4M HNO3 at room temperature. The separation between plutonium and americium is performed by extraction of Pu(IV) either on TBP/SiO2 or TOAHNO3/SiO2 column. Americium recovery from waste streams rid of plutonium is realized by chromatographic extraction of Am(III) using mainly TBP and episodically DHDECMP as extractant. The final purification of both americium isotopes uses the selective extraction of Am(VI) on HDDiBMP/SiO2 column at 60 grams scale. Using the overall process a total amount of 1000 grams of americium 241 and 100 grams of americium 243 has been produced nowadays and the AmO2 final product indicates a purity better than 98.5%

  13. Photofragmentation of metal halides

    International Nuclear Information System (INIS)

    The author deals with photodissociation of molecules of alkali halides. It is shown that the total absorption cross section consists of two contributions arising from transitions to excited states of total electronic angular momentum Ω=0+ and Ω=1. From the inversion of the absorption continua potential energy curves of the excited states can be constructed in the Franck-Condon region. It is found that for all alkali halides the 0+ state is higher in energy than the Ω=1 state. Extensive studies are reported on three thallium halides, TlI, TlBr and TlCl at various wavelengths covering the near ultraviolet region. (Auth.)

  14. Study of americium sorption by humic acids

    International Nuclear Information System (INIS)

    The results of investigation of influence of the cation content and acidity of soil solution on americium sorption by the humic acids have been shown. The most influence on the interphase distribution coefficient in the system 'humic acid - model soil solution' is caused by the presence of the iron (III), calcium ions and acidity of the solution. The increase of the sodium ions concentration in the solution makes an insignificant impact on the americium sorption. (Authors)

  15. Spectrochemical analysis of curium and americium samples

    International Nuclear Information System (INIS)

    Spectrochemical procedures have been developed to determine impurities in americium and curium samples. The simultaneous separation of many impurity elements from the base material (americium and curium) is carried out with extraction and extraction-chromatographic methods using di-2-ethylhexylphosphoric acid. It is shown that part of the elements are separated with extraction or sorption of americium and curium; the other part with the Talspeak process. Two fractions in the extraction chromatography and three fractions in the extraction separation of americium and curium, containing impurities, are analyzed separately by a.c. or d.c. arc spectrography. To increase the sensitivity of the spectrographic analysis and accelerate the burn-up of impurities from the crater of the carbon electrode bismuth fluoride and sodium chloride were used as chemically active substances. The extraction of impurities from weighed quantities of americium and curium samples of 5 to 10 mg permits the lower limit of determined impurity concentrations to be extended to 1 x 10-4 to 5 x 10-3% m/m. (author)

  16. Aqueous Chloride Operations Overview: Plutonium and Americium Purification/Recovery

    Energy Technology Data Exchange (ETDEWEB)

    Kimball, David Bryan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Skidmore, Bradley Evan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-06-22

    Acqueous Chloride mission is to recover plutonium and americium from pyrochemical residues (undesirable form for utilization and storage) and generate plutonium oxide and americium oxide. Plutonium oxide is recycled into Pu metal production flowsheet. It is suitable for storage. Americium oxide is a valuable product, sold through the DOE-OS isotope sales program.

  17. Pyrochemical technology of plutonium and americium preparation and purification

    International Nuclear Information System (INIS)

    Pyrochemical tecnology of metallic plutonium and americium preparation and purification is considered. Investigations into plutonium dioxide reduction up to metal; plutonium electrolytic refining in molten salts; plutonium extraction from the molten salts and preparation of americium dioxide and metallic americium from its tetrafluoride are described

  18. Formation of americium and europium humate complexes

    International Nuclear Information System (INIS)

    Binding constants of americium and europium with a humic acid were determined to study if complex formation of trivalent actinide-humates affects dissolved species of the actinides in hydrosphere. The purified humic acid was characterized by means of UV-vis, IR, and pH titration, indicating high carboxylate capacity and low aromaticity. Binding constants of americium and europium humates were determined at pH 4.6 and 6.0 by solvent extraction using 241Am or 152Eu as a tracer. The binding constants for americium-humate obtained preliminarily suggest that complexes with humic acid are not negligible in speciation of trivalent actinides in hydrosphere. The obtained binding constants were nearly identical with those determined previously by the same procedures, but with humic acids of different origin and compositions. (author)

  19. Preparation of americium source for smoke detector

    International Nuclear Information System (INIS)

    This report describes the method developed for the preparation of 241Am source for smoke detector. Americium was electrodeposited from iso-propyl alcohol medium on silver backing. Thin layer of gold (few hundred micro gram thick) was plated on the americium source to make it safe for handling. The thickness of plated gold was such that the alpha radiations from the 241Am source could escape out of the gold layer and cause ionisation in the surrounding air. The performance of the prepared sources were checked in a smoke detector and was found to be satisfactory and comparable to the imported sources. (author). 1 refs., 2 figs., 1 tab

  20. Recovery of americium-241 from raffinates of plutonium purification columns

    International Nuclear Information System (INIS)

    Recovery and purification of americium from ion exchange raffinates generated during purification of aged plutonium is described. The method consists of the following stages: (i) co-precipitation of americium with kilogramme quantities of rare earth oxalates, (ii) destruction of oxalate and removal of residual plutonium from nitric acid medium using anion exchange process, (iii) preliminary separation of americium making use of its preferential uptake on an anion exchange column from thiocyanate medium and (iv) extraction of americium and remaining rare earths into di-(2-ethyl hexyl) phosphoric acid followed by preferential back washing of americium by lactic acid medium containing DTPA. (author)

  1. 1976 Hanford americium exposure incident: psychological aspects

    International Nuclear Information System (INIS)

    Accidents involving exposure to radiation or radioactive materials may involve an unusual degree of emotional trauma. Methods that may be employed in dealing with such trauma are discussed in relation to a specific accident in which a radiation worker was injured and seriously contaminated with americium-241

  2. Americium separations from high salt solutions

    International Nuclear Information System (INIS)

    Americium (III) exhibits an unexpectedly high affinity for anion-exchange material from the high-salt evaporator bottoms solutions--an effect which has not been duplicated using simple salt solutions. Similar behavior is observed for its lanthanide homologue, Nd(III), in complex evaporator bottoms surrogate solutions. There appears to be no single controlling factor--acid concentration, total nitrate concentration or solution ionic strength--which accounts for the approximately 2-fold increase in retention of the trivalent ions from complex solutions relative to simple solutions. Calculation of species activities (i.e., water, proton and nitrate) in such concentrated mixed salt solutions is difficult and of questionable accuracy, but it is likely that the answer to forcing formation of anionic nitrate complexes of americium lies in the relative activities of water and nitrate. From a practical viewpoint, the modest americium removal needs (ca. 50--75%) from nitric acid evaporator bottoms allow sufficient latitude for the use of non-optimized conditions such as running existing columns filled with older, well-used Reillex HPQ. Newer materials, such as HPQ-100 and the experimental bifunctional resins, which exhibit higher distribution coefficients, would allow for either increased Am removal or the use of smaller columns. It is also of interest that one of the experimental neutral-donor solid-support extractants, DHDECMP, exhibits a similarly high level of americium (total alpha) removal from EV bottoms and is much less sensitive to total acid content than commercially-available material

  3. Decontaminaion of metals containing plutonium and americium

    International Nuclear Information System (INIS)

    Melt-slagging (melt-refining) techniques were evaluated as a decontamination and consolidation step for metals contaminated with oxides of plutonium and americium. Experiments were performed in which mild steel, stainless steel, and nickel contaminated with oxides of plutonium and americium were melted in the presence of silicate slags of various compositions. The metal products were low in contamination, with the plutonium and americium strongly fractionated to the slags. Partition coefficients (plutonium in slag/plutonium in steel) of 7 x 106 were measured with boro-silicate slag and of 3 x 106 with calcium, magnesium silicate slag. Decontamination of metals containing as much as 14,000 ppM plutonium appears to be as efficient as for metals with plutonium levels of 400 ppM. Staged extraction, that is, a remelting of processed metal with clean slag, results in further decontamination of the metal. The second extraction is effective with either resistance-furnace melting or electric-arc melting. Slag adhering to the metal ingots and in defects within the ingots is in the important contributors to plutonium retained in processed metals. If these sources of plutonium are controlled, the melt-refining process can be used on a large scale to convert highly contaminated metals to homogeneous and compact forms with very low concentrations of plutonium and americium. A conceptual design of a melt-refining process to decontaminate plutonium- and americium-contaminated metals is described. The process includes single-stage refining of contaminated metals to produce a metal product which would have less than 10 nCi/g of TRU-element contamination. Two plant sizes were considered. The smaller conceptual plant processes 77 kg of metal per 8-h period and may be portable.The larger one processes 140 kg of metal per 8-h period, is stationary, and may be near te maximum size that is practical for a metal decontamination process

  4. Status of Americium-241 recovery at Rocky Flats Plant

    International Nuclear Information System (INIS)

    This paper is presented in two parts: Part I, Molten Salt Extraction of Americium from Molten Plutonium Metal, and Part II, Aqueous Recovery of Americium from Extraction Salts. The Rocky Flats recovery process used for waste salts includes (1) dilute hydrochloric acid dissolution of residues; (2) cation exchange to convert from the chloride to the nitrate system and to remove gross amounts of monovalent impurities; (3) anion exchange separation of plutonium; (4) oxalate precipitation of americium; and (5) calcination of the oxalate at 6000C to yield americium oxide. The aqueous process portion describes attempts to improve the recovery of americium. The first part deals with modifications to the cation exchange step; the second describes development of a solvent extractions process that will recovery americium from residues containing aluminium as well as other common impurities. Results of laboratory work are described. 3 figures, 6 tables. (DP)

  5. Plutonium and americium in soil organic matter

    International Nuclear Information System (INIS)

    A gley soil from west Cumbria, with specific activities in its surface horizon of 5-10 kBq kg-1239,240Pu and comparable 241Am levels, has been used as a source of actinide-enriched organic fractions. Humic and fulvic acids were isolated by conventional alkali extraction and investigated by gel filtration, treatment with organic solvents and differential flocculation procedures. All these techniques are capable of resolving the organics into two or more fractions, with specific activities up to 80 kBq kg-239,240Pu. There is evidence for differentiation of plutonium and americium, with americium being concentrated, to some extent, in the lower molecular weight fractions from gel filtration. (author)

  6. PREPARATION OF HALIDES OF PLUTONIUM

    Science.gov (United States)

    Garner, C.S.; Johns, I.B.

    1958-09-01

    A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

  7. Incentives for transmutation of americium in thermal reactors

    International Nuclear Information System (INIS)

    This report describes possible benefits when americium is irradiated in a thermal reactor. If all plutonium is partitioned from spent fuel, americium is the main contributor to the radiotoxicity of spent fuel upto several thousands of years of storage. It is shown that americium can be transmuted to other nuclides upon irradiation in a thermal reactor, leading to a 50% reduction of the radiotoxicity of neptunium, which can be an important contributor to the dose due to leakage of nuclides after one million years of storage. The radiotoxicity of americium can be reduced considerably after irradiation for 3 to 6 years in a thermal reactor with thermal neutron flux of 1014 cm-2s-1. The strongly α and neutron emitting transmutation products can most probably not be recycled again, so a transmutation process is suggested in which americium is irradiated for 3 to 6 years and then put to final storage. It is shown that the radiotoxicity of the transmuation products after a storage time of about one hundred years can be considerably reduced compared to the radiotoxicity of the initial americium. The same holds for the α activity and heat emission of the transmutation products. Because plutonium in spent fuel contributes for about 80% to the radiotoxicity upto 105 years of storage, recycling and transmutation of plutonium has first priority. Transmutation of americium is only meaningful when the radiotoxicity of plutonium is reduced far below the radiotoxicity of americium. (orig.)

  8. Americium transfer studies using hollow fiber/extractant membranes

    International Nuclear Information System (INIS)

    Americium can be removed from low acid/high nitrate feeds using hollow fiber membrane modules. Americium can be concentrated in the stripping solution. (Maximum observed concentration was a factor of 3.1). Accurel hollow fibers are less prone to leakage problems

  9. Electronic structure of compressed americium metal

    Czech Academy of Sciences Publication Activity Database

    Kolorenč, Jindřich; Shick, Alexander; Caciuffo, R.

    Cambridge: Cambridge University Press,, 2012 - (Anderson, D.; Boot, C.; Burns, P.), s. 177-182. (Materials Research Society Symposium Proceedings. 1444). ISBN 978-1-60511-421-7. ISSN 0272-9172. [2012 MRS Spring Meeting. Sacramento (CA), 09.04.2012-13.04.2012] R&D Projects: GA ČR(CZ) GAP204/10/0330; GA AV ČR IAA100100912 Institutional research plan: CEZ:AV0Z10100520 Keywords : americium * X-ray spectroscopy * LDA+DMFT Subject RIV: BM - Solid Matter Physics ; Magnetism http://journals.cambridge.org/article_S1946427412009463

  10. METHOD OF PREPARING METAL HALIDES

    Science.gov (United States)

    Hendrickson, A.V.

    1958-11-18

    The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

  11. Electrochemical oxidation of americium in nitric medium: study of reaction mechanisms; Oxydation de l'americium par voie electrochimique: etude des mecanismes

    Energy Technology Data Exchange (ETDEWEB)

    Picart, S.; Chartier, D.; Donnet, L.; Adnet, J.M. [CEA Valrho, (DCC/DRRV/SPHA), 30 - Marcoule (France)

    2000-07-01

    One alternative selected by the CEA for partitioning minor actinides from aqueous solutions containing fission products is the selective extraction of oxidized americium. This is the SESAME process (Selective Extraction and Separation of Americium by Means of Electrolysis) aimed to convert americium to oxidation state (VI) and then extract it with a specific extractant of high valences. This paper presents the study of the electrochemical oxidation of americium in nitric medium which represents an important stage of the process. The reaction can be divided into two main steps: oxidation of americium (III) to americium (IV), and then of americium (IV) to americium (VI). For the first oxidation step, a ligand L is needed to stabilize the intermediate species americium (IV) which disproportionates in its free form into americium (III) and (V). Phospho-tungstate or silico-tungstate are appropriate ligands because they are stable in concentrated nitric acid and show a great affinity for metallic cations at oxidation state (IV) (Table 1 lists the stability constants of americium (IV) complexes). The presence of the lacunary poly-anion lowers the potential of the americium (IV) / americium (Ill) redox pair (see Figure 5 for the diagram of the apparent formal potential of americium versus ligand concentration). This makes it thermodynamically possible to oxidize americium (III) into americium (IV) at the anode of an electrolyzer in nitric acid. For the second oxidation step, a strong oxidant redox mediator, like silver (II), is needed to convert complexed americium at oxidation state (IV) to oxidation state (V). The AmVL complex is then hydrolyzed to yield americyle (V) aqua ion. A spectroscopic Raman study with {sup 18}O labeled species showed that the oxygen atoms of the americyle moiety came from water. This indicates that water hydrolyzes the americium (V) complex to produce americyle (V) aqua ion, AmO{sub 2}{sup +}. This cation reacts with silver (Il) to give

  12. Modelling of americium stripping in the EXAm process

    International Nuclear Information System (INIS)

    The EXAm process aims at recovering americium alone contained in the PUREX raffinate. The americium stripping model has been revised to take into account a change of stripping aqueous phase and up-to-date experimental results conducted within DRCP to improve knowledge about complexes. This work represents a first approximation at modelling americium stripping. The modelling work has led to synthesize the knowledge on chemical phenomenology and adopt assumptions that best reflect experimental results. The modelling has been implemented in PAREX code in order to simulate this step to prepare and understand tests to be carried out in mixer settlers. (authors)

  13. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  14. Mixed chelation therapy for removal of plutonium and americium

    International Nuclear Information System (INIS)

    Iron-binding compounds, 2,3-dihydroxybenzoic acid (DHBA), 2-hydroxybenzoic acid (HBA), and 2-(acetyloxy)benzoic acid (ABA), were tested for their ability to remove americium and plutonium from rats following intraperitioneal injection of the radionuclides as citrates (pH 5). Treatments, 2 mmol/kg, were given on days 3, 6, 10, 12 and 14 following the actinide injection. DHBA and HBA caused about a 20% decrease in liver retention of americium compared to the control value, and DHB caused a similar effect for plutonium. The above agents, co-administered with 0.5 mmol polyaminopolycarboxylic acid (PAPCA)-type chelons, did not change tissue retention of americium and plutonium from that due to the PAPCAs alone. Administration of americium and plutonium to the same rats is useful for studying removal agents since the two actinides behave independently in their biological disposition and response to removal

  15. Plutonium and Americium Geochemistry at Hanford: A Site Wide Review

    Energy Technology Data Exchange (ETDEWEB)

    Cantrell, Kirk J.; Felmy, Andrew R.

    2012-08-23

    This report was produced to provide a systematic review of the state-of-knowledge of plutonium and americium geochemistry at the Hanford Site. The report integrates existing knowledge of the subsurface migration behavior of plutonium and americium at the Hanford Site with available information in the scientific literature regarding the geochemistry of plutonium and americium in systems that are environmentally relevant to the Hanford Site. As a part of the report, key research needs are identified and prioritized, with the ultimate goal of developing a science-based capability to quantitatively assess risk at sites contaminated with plutonium and americium at the Hanford Site and the impact of remediation technologies and closure strategies.

  16. Americium/Curium Disposition Life Cycle Planning Study

    International Nuclear Information System (INIS)

    At the request of the Department of Energy Savannah River Office (DOE- SR), Westinghouse Savannah River Company (WSRC) evaluated concepts to complete disposition of Americium and Curium (Am/Cm) bearing materials currently located at the Savannah River Site (SRS)

  17. Radiochemical synthesis of pure anhydrous metal halides

    Science.gov (United States)

    Philipp, W. H.; Marsik, S. J.; May, C. E.

    1973-01-01

    Method uses radiation chemistry as practical tool for inorganic preparations and in particular deposition of metals by irradiation of their aqueous metal salt solutions with high energy electrons. Higher valence metal halide is dissolved in organic liquid and exposed to high energy electrons. This causes metal halide to be reduced to a lower valence metal halide.

  18. Preparation of cerium halide solvate complexes

    Science.gov (United States)

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  19. Gamma-sources on the basis of metallic americium-241

    International Nuclear Information System (INIS)

    A batch of gamma-radiation sources has been manufactured from metallic americium-241 of isotopic purity, its activity varying from 0.08 to 0.93 GBq. The cores of the sources are high-purity americium metal condensate on a tantalum or stainless steel substrate prepared by thermal decomposition of 241Pu-241Am alloy in a high vacuum. 7 refs., 1 tab

  20. Pyrochemical investigations into recovering plutonium from americium extraction salt residues

    International Nuclear Information System (INIS)

    Progress into developing a pyrochemical technique for separating and recovering plutonium from spent americium extraction waste salts has concentrated on selective chemical reduction with lanthanum metal and calcium metal and on the solvent extraction of americium with calcium metal. Both techniques are effective for recovering plutonium from the waste salt, although neither appears suitable as a separation technique for recycling a plutonium stream back to mainline purification processes. 17 refs., 13 figs., 2 tabs

  1. 1976 Hanford americium-exposure incident: external decontamination procedures

    International Nuclear Information System (INIS)

    An accident resulted in the deposition on an injured workman's skin surfaces, in acid-burned areas and in lacerations, of something in excess of 6 mCi americium-241. The external decontamination procedures used, the change in americium content of the skin during the course of treatment, and some of the unusual problems encountered from the extrusion of foreign material and flaking of skin and scar tissue are described

  2. Electronic conduction in molten halides

    Energy Technology Data Exchange (ETDEWEB)

    Heus, R.J.; Egan, J.J.

    1976-01-01

    Methods of measuring electronic conductivity in molten halides are reviewed. These include increase of total conductivity with addition of metal, polarization techniques, chronopotentiometry, and motion of colored subhalides in a potential gradient. The applicability of the Nernst-Einstein equation and the role of convection are considered. Results are presented for several halide melts. Applications of these results are elucidated, including self-discharge rate of molten salt batteries, measurement of alloy thermodynamics using molten salt electrolytes, and kinetics of tarnishing reactions with formation of liquid films.

  3. Thermodynamic properties of Alkali Halides

    International Nuclear Information System (INIS)

    The method of moments of [1], developed by the authors in [2] for strongly and harmonic crystals with f.c.c. structure is used here to investigate the main thermodynamic properties of the potassium halides. Their analytic expressions as functions of temperature are obtained and the comparison between the theoretical results and the experimental data is made. (author). 22 refs., 5 tabs

  4. Electrochemical oxidation of americium in nitric medium: study of reaction mechanisms

    International Nuclear Information System (INIS)

    One alternative selected by the CEA for partitioning minor actinides from aqueous solutions containing fission products is the selective extraction of oxidized americium. This is the SESAME process (Selective Extraction and Separation of Americium by Means of Electrolysis) aimed to convert americium to oxidation state (VI) and then extract it with a specific extractant of high valences. This paper presents the study of the electrochemical oxidation of americium in nitric medium which represents an important stage of the process. The reaction can be divided into two main steps: oxidation of americium (III) to americium (IV), and then of americium (IV) to americium (VI). For the first oxidation step, a ligand L is needed to stabilize the intermediate species americium (IV) which disproportionates in its free form into americium (III) and (V). Phospho-tungstate or silico-tungstate are appropriate ligands because they are stable in concentrated nitric acid and show a great affinity for metallic cations at oxidation state (IV) (Table 1 lists the stability constants of americium (IV) complexes). The presence of the lacunary poly-anion lowers the potential of the americium (IV) / americium (Ill) redox pair (see Figure 5 for the diagram of the apparent formal potential of americium versus ligand concentration). This makes it thermodynamically possible to oxidize americium (III) into americium (IV) at the anode of an electrolyzer in nitric acid. For the second oxidation step, a strong oxidant redox mediator, like silver (II), is needed to convert complexed americium at oxidation state (IV) to oxidation state (V). The AmVL complex is then hydrolyzed to yield americyle (V) aqua ion. A spectroscopic Raman study with 18O labeled species showed that the oxygen atoms of the americyle moiety came from water. This indicates that water hydrolyzes the americium (V) complex to produce americyle (V) aqua ion, AmO2+. This cation reacts with silver (Il) to give americyle (VI) ion. Figure

  5. Complexation of americium with humic acid

    International Nuclear Information System (INIS)

    As a part of the interlaboratory comparison exercise for the complexation of humic acid and colloid generation (COCO-Club activities) in the CEC project MIRAGE-II, the complexation of americium with humic acid has been studied in our laboratory. Two humic acids were used for the study: Aldrich-HA(H+) which is a reference humic acid of the COCO-Club and Bradford-HA(H+) from Lake Bradford, Florida. A wide concentration range of humic acid and different ratios of Am to humic acid have been investigated between pH 5 and 6 with the ionic strength of 0.1 M and 1.0 M. The complexation has been studied by UV-spectroscopy, Laser-induced Photoacoustic Spectroscopy (LPAS) and ultrafiltration. LPAS is used for the submicromolar concentration range where the sensitivity of UV spectroscopy is not accessible. Ultrafiltration is used for low Am to humic acid ratios where both spectroscopic methods are not applicable. Varying the humic acid concentration over three orders of magnitude, only a 1:1 type of binding is observed. No significant variation of the stability constant is found in the investigated range of pH and ionic strength. However, the precipitation tendency and the loading capacity of humic acid are found to depend sensitively on pH and ionic strength. The complexation study provides a deep insight into the influence of humic acid on the migration behaviour of fission products and actinides in the geosphere. (orig.)

  6. Analysis of BWR lattices to recycle americium

    International Nuclear Information System (INIS)

    This study was carried out to assess the ability to eliminate meaningful quantities of americium in a primarily thermal neutron flux by 'spiking' modern BWR fuel with this minor actinide (MA). The studies carried out so far include the simulation of modern 10 x 10 BWR lattices employing the Westinghouse lattice physics code PHOENIX-4 alongside validation studies using MCNP5 models of the same lattices that were spatially depleted via the MONTEBURNS code coupling to ORIGEN. When considering the total inventory of minor actinides in Am-spiked pins, excluding isotopes of uranium and plutonium, the results indicate that a reduction of approximately 50% or more in the total mass inventory of these minor actinides is viable within the selected pins. Therefore, these preliminary results have encouraged the extension of this work to the development of improved lattice designs to help optimize the transmutation rates as well as absolute MA inventory reductions. The ultimate goal being to design batches of these advanced BWR bundles alongside multi-cycle core reload strategies. (authors)

  7. Applicability of insoluble tannin to treatment of waste containing americium

    International Nuclear Information System (INIS)

    The applicability of insoluble tannin adsorbent to the treatment of aqueous waste contaminated with americium has been investigated. Insoluble tannin is considered highly applicable because it consists of only carbon, hydrogen and oxygen and so its volume can be easily reduced by incineration. This report describes measurements of the americium distribution coefficient in low concentration nitric acid. The americium distribution coefficients were found to decrease with increasing concentration of nitric acid and sodium nitrate, and with increasing temperature. At 25 C in 2.0 x 10-3 M HNO3, the distribution coefficient was found to be 2000 ml g-1. The adsorption capacity was determined by column experiments using europium as a simulant of americium, and found to be 7 x 10-3 mmol g-1-dried tannin in 0.01 M HNO3 at 25 C, which corresponds to approximately 1.7 mg-241Am/g-adsorbent(dried). The prospect of applying the adsorbent to the treatment of aqueous waste contaminated with americium appears promising. (orig.)

  8. Saucy-Marbet Rearrangements of Alkynyl Halides in the Synthesis of Highly Enantiomerically Enriched Allenyl Halides

    OpenAIRE

    Tang, Yu; Shen, Lichun; Dellaria, Becky J.; Richard P. Hsung

    2008-01-01

    A stereospecific Saucy-Marbet rearrangement of alkynyl halides is described here. These rearrangements provide an entry to highly enantiomerically enriched allenyl bromides and chlorides through excellent chirality transfer and the reservation of optical integrity of alkynyl halides.

  9. A TRUEX-based separation of americium from the lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Bruce J. Mincher; Nicholas C. Schmitt; Mary E. Case

    2011-03-01

    Abstract: The inextractability of the actinide AnO2+ ions in the TRUEX process suggests the possibility of a separation of americium from the lanthanides using oxidation to Am(V). The only current method for the direct oxidation of americium to Am(V) in strongly acidic media is with sodium bismuthate. We prepared Am(V) over a wide range of nitric acid concentrations and investigated its solvent extraction behavior for comparison to europium. While a separation is achievable in principal, the presence of macro amounts of cerium competes for the sparingly soluble oxidant and the oxidant itself competes for CMPO complexation. These factors conspire to reduce the Eu/Am separation factor from ~40 using tracer solutions to ~5 for extractions from first cycle raffinate simulant solution. To separate pentavalent americium directly from the lanthanides using the TRUEX process, an alternative oxidizing agent will be necessary.

  10. Salvage of plutonium-and americium-contaminated metals

    International Nuclear Information System (INIS)

    Melt-slagging techniques were evaluated as a decontamination and consolidation step for metals contaminated with oxides of plutonium and americium. Experiments were performed in which mild steel, stainless steel, and nickel metals contaminated with oxides of plutonium and americium were melted in the presence of silicate slags of various compositions. The metal products were low in contamination, with the plutonium and americium strongly fractionated to the slags. Partition coefficients (plutonium in slag/plutonium in steel) of 7*10/sup 6/ with borosilicate slag and 3*10/sup 6/ for calcium, magnesium silicate slag were measured. Decontamination of metals containing as much as 14,000 p.p.m. plutonium appears to be as efficient as that of metals with plutonium levels of 400 p.p.m. Staged extraction, that is, a remelting of processed metal with clean slag, results in further decontamination of the metal. 10 refs

  11. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    Science.gov (United States)

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  12. 40 CFR 721.4095 - Quaternary ammonium alkyltherpropyl trialkylamine halides.

    Science.gov (United States)

    2010-07-01

    ... trialkylamine halides. 721.4095 Section 721.4095 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4095 Quaternary ammonium alkyltherpropyl trialkylamine halides. (a... generically as quaternary ammonium alkyltherpropyl trialkylamine halides (PMNs...

  13. Halogen versus halide electronic structure

    Institute of Scientific and Technical Information of China (English)

    Willem-Jan; van; Zeist; F.Matthias; Bickelhaupt

    2010-01-01

    Halide anions X-are known to show a decreasing proton affinity(PA),as X descends in the periodic table along series F,Cl,Br and I.But it is also well-known that,along this series,the halogen atom X becomes less electronegative(or more electropositive).This corresponds to an increasing energy of the valence np atomic orbital(AO) which,somewhat contradictorily,suggests that the electron donor capability and thus the PA of the halides should increase along the series F,Cl,Br,I.To reconcile these contradictory observations,we have carried out a detailed theoretical analysis of the electronic structure and bonding capability of the halide anions X-as well as the halogen radicals X-,using the molecular orbital(MO) models contained in Kohn-Sham density functional theory(DFT,at SAOP/TZ2P as well as OLYP/TZ2P levels) and ab initio theory(at the HF/TZ2P level).We also resolve an apparent intrinsic contradiction in Hartree-Fock theory between orbital-energy and PA trends.The results of our analyses are of direct relevance for understanding elementary organic reactions such as nucleophilic substitution(SN2) and base-induced elimination(E2) reactions.

  14. Uptake of americium-241 by algae and bacteria

    International Nuclear Information System (INIS)

    The uptake of americium by three algae, scenedesmus obliquus, selenastrum capricomutum and chlorella pyrenosdosa and a bacterium aeromonas hydrophila was studied. Live and fixed cells of each algal species and live bacterial cells were used. it is shown that algae and bacteria concentrate americium 241 to a high degree which makes them important links in the biomagnification phenomenon which may ultimately lead to a human hazard and be potentially important in recycling Am 241 in the water column and mobilization from sediments. Chemical fixation of algal cells caused increased uptake which indicated that uptake is by passive diffusion and probably due to chemical alteration of surface binding sites. (U.K.)

  15. Americium incineration by recycling in target rods using coated particles

    International Nuclear Information System (INIS)

    This paper proposes a type of target rod based on the use of coated particles, for an efficient incineration of americium in nuclear reactors. The analysis takes advantage of the experience gained in the past from long duration irradiation without damage of coated particles with plutonium oxide kernels. A conservative theoretical evaluation of the gas pressure inside the coated particles at the end of irradiation allows comparing the well known conditions of the plutonium oxide particles which were successfully irradiated to high burn-up, with a preliminary design of americium oxide particles. (authors)

  16. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    Science.gov (United States)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  17. 1976 Hanford americium exposure incident: overview and perspective

    International Nuclear Information System (INIS)

    Salient features of the 1976 Hanford americium exposure incident are discussed. Comparisons are made with previous human and animal exposure data, and conclusions drawn relative to the injured workman, to health physics practices, and to the adequacy of current exposure limits

  18. Americium retention by the smectite hectorite

    International Nuclear Information System (INIS)

    Document available in extended abstract form only. Clay minerals may play an important role in a high level nuclear waste disposal site. Smectites may be major components of backfill material used to enhance the retention properties of engineered barriers. Furthermore, they have also been detected in the alteration layer of nuclear waste glass corroded in laboratory experiments. For example, the smectite hectorite (Na0.33[Mg2.67Li0.33Si4O10(OH)2]) was identified as phase forming upon waste matrix dissolution and subsequent reprecipitation. Smectites are known to be highly reactive with respect to cations in aqueous systems. Several distinct molecular scale binding mechanisms may operate, but the most effective retention may occur by incorporation in the bulk structure, especially if a (meta)stable solid solution forms. Investigations showed the possibility to incorporate Lu(III) in a clay-like octahedral site in hectorite by coprecipitation. Furthermore, luminescence studies on hectorite synthesized in the presence of Cm(III) or Eu(III) were consistent with an incorporation in the bulk structure. However, structural data such as coordination numbers and bond lengths are still missing for the actinides. In the present study, Am(III) was coprecipitated with and adsorbed on hectorite to decipher the actual retention mechanism(s). Hectorite was synthesized in the presence of Am(III) (sample AmCopHec) from an Am-containing brucite precursor phase. Briefly, brucite was freshly precipitated in the presence of Am(III) (Am:Mg molar ratio of 1:1175) and washed. The resulting sol was aged in a tightly closed vessel in the presence of LiF and silica sol for several days at 90 C. Separately, an Am-containing brucite phase (sample AmCopBru) was prepared under identical conditions as described above, and the americium aqua ions were adsorbed on hectorite (m/V = 2 g/L, [Am(III)]tot = 105 μmol/L, 0.5 mol/L NaClO4, pH = 6.4(1), sample AmSorbHec) and used as reference samples. X

  19. Synthesis and characterization of uranium-americium mixed oxides

    International Nuclear Information System (INIS)

    Americium isotopes represent a significant part of high-level and long-lived nuclear waste in spent fuels. Among the envisaged reprocessing scenarios, their transmutation in fast neutron reactors using uranium-americium mixed-oxide pellets (U1-xAmxO2±δ) is a promising option which would help decrease the ecological footprint of ultimate waste repository sites. In this context, this thesis is dedicated to the study of such compounds over a wide range of americium contents (7.5 at.% ≤ Am/(U+Am) ≤ 70 at.%), with an emphasis on their fabrication from single-oxide precursors and the assessment of their structural and thermodynamic stabilities, also taking self-irradiation effects into account. Results highlight the main influence of americium reduction to Am(+III), not only on the mechanisms of solid-state formation of the U1-xAmxO2±δ solid solution, but also on the stabilization of oxidized uranium cations and the formation of defects in the oxygen sublattice such as vacancies and cub-octahedral clusters. In addition, the data acquired concerning the stability of U1-xAmxO2±δ compounds (existence of a miscibility gap, vaporization behavior) were compared to calculations based on new thermodynamic modelling of the U-Am-O ternary system. Finally, α-self-irradiation-induced structural effects on U1-xAmxO2±δ compounds were analyzed using XRD, XAS and TEM, allowing the influence of americium content on the structural swelling to be studied as well as the description of the evolution of radiation-induced structural defects. (author)

  20. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  1. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich;

    of natural selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides......Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure...

  2. Liquid-liquid extraction separation and determination of plutonium and americium

    International Nuclear Information System (INIS)

    A procedure is described for the determination of plutonium and americium after their initial separation on barium sulfate. The barium sulfate is dissolved in perchloric acid and the antinides and lanthanides are extracted into bis(2-ethylhexyl)phosphoric acid (HDEHP). Americium along with other tervalent actinides and lanthanides is stripped from HDEHP with nitric acid. The lanthanides are removed on a column of HDEHP supported on Teflon powder, and the americium and other tervalent actinides are electrodeposited for their determination by α spectrometry. The plutonium is stripped with nitric acid after reduction to the tervalent state with 2,5-di-tert-butylhydroquinone and electrodeposited for α spectrometry. Decontamination factors for plutonium and americium from each other and from other α emitters are 104 to 105. Two hours are required for the liquid-liquid extraction separations of plutonium and americium from eight samples. Recoveries of americium and plutonium through the HDEHP separatons are 99% and 95%, respectively

  3. Calculational study on irradiation of americium fuel samples in the Petten High Flux Reactor

    International Nuclear Information System (INIS)

    A calculational study on the irradiation of americium samples in the Petten High Flux Reactor (HFR) has been performed. This has been done in the framework of the international EFTTRA cooperation. For several reasons the americium in the samples is supposed to be diluted with a neutron inert matrix, but the main reason is to limit the power density in the sample. The low americium nuclide density in the sample (10 weight % americium oxide) leads to a low radial dependence of the burnup. Three different calculational methods have been used to calculate the burnup in the americium sample: Two-dimensional calculations with WIMS-6, one-dimensional calculations with WIMS-6, and one-dimensional calculations with SCALE. The results of the different methods agree fairly well. It is concluded that the radiotoxicity of the americium sample can be reduced upon irradiation in our scenario. This is especially the case for the radiotoxicity between 100 and 1000 years after storage. (orig.)

  4. Neptunium and americium control for international non-proliferation regime

    International Nuclear Information System (INIS)

    It was decided in the IAEA Board of Governors Meeting held in Sept. 1999 that Neptunium and Americium could be diverted for manufacturing nuclear weapon or explosives, so that appropriate measures should be taken for the prevention of proliferation of these materials. It is expected to take relatively long time for settling down the aligned system dealing with the above materials because the present regulatory statement was prepared on the basis of voluntary offers from the States concerned. The necessity of preventive measures is being convinced among Member States, but it would not be easy to take voluntary participation in detail because of their respective interests. It is expected that this paper could contribute to the effective response as to the international commitments as well as for protecting the domestic nuclear industry and R and D area through analysis on the IAEA's approach on Neptunium and Americium

  5. Thermophysical properties of americium-containing barium plutonate

    International Nuclear Information System (INIS)

    Polycrystalline specimens of americium-containing barium plutonate have been prepared by mixing the appropriate amounts of (Pu0.91Am0.09)O2 and BaCO3 powders followed by reacting and sintering at 1600 K under the flowing gas atmosphere of dry-air. The sintered specimens had a single phase of orthorhombic perovskite structure and were crack-free. Elastic moduli were determined from longitudinal and shear sound velocities. Debye temperature was also determined from sound velocities and lattice parameter measurements. Thermal conductivity was calculated from measured density at room temperature, literature values of heat capacity and thermal diffusivity measured by laser flash method in vacuum. Thermal conductivity of americium-containing barium plutonate was roughly independent of temperature and registered almost the same magnitude as that of BaPuO3 and BaUO3. (author)

  6. Fullerenes doped with metal halides

    International Nuclear Information System (INIS)

    The cage-like structure of fullerenes is a challenge to every experimental to put something inside - to dope the fullerenes. In fact, the research team that first identified C60 as a football-like molecule quickly succeeded in trapping metal atoms inside and in shrinking the cage around this atom by photofragmentation. In this paper we report the results of ''shrink-wrapping'' the fullerenes around metal halide molecules. Of special interest is the critical size (the minimum number of carbon atoms) that can still enclose the dopant. A rough model for the space available inside a carbon cage gives good agreement with the measured shrinking limits. (author). 8 refs, 6 figs

  7. 1976 Hanford americium-exposure incident: decontamination and treatment facility

    International Nuclear Information System (INIS)

    An injured worker, contaminated with over 6 mCi of americium-241, required special treatment and housing for 4 months. This paper is a description of the design and management of the facility in which most of the treatment and housing occurred. The problems associated with contamination control, waste handling, supplies, and radiological concerns during the two-stage transfer of the patient from a controlled situation to his normal living environment are discussed in detail

  8. Recycling heterogeneous americium targets in a boiling water reactor

    International Nuclear Information System (INIS)

    One of the limiting contributors to the heat load constraint for a long term spent fuel repository is the decay of americium-241. A possible option to reduce the heat load produced by Am-241 is to eliminate it via transmutation in a light water reactor thermal neutron environment, in particular, by taking advantage of the large thermal fission cross section of Am-242 and Am-242m. In this study we employ lattice loading optimization techniques to define the loadings and arrangements of fuel pins with blended americium and uranium oxide in boiling water reactor bundles, specifically, by defining the incineration of pre-loaded americium as an objective function to maximize americium transmutation. Subsequently, the viability of these optimized lattices is tested by assembling them into bundles with Am-spiked fuel pins and by loading these bundles into realistic three-dimensional BWR core-wide simulations that model multiple reload cycles and observe standard operational constraints. These simulations are possible via our collaboration with the Westinghouse Electric Co. which facilitates the use of industrial-caliber design tools such as the PHOENIX-4/POLCA-7 sequence and the Core Master 2 GUI work environment for fuel management. The resulting analysis confirms the ability to axially uniformly eliminating roughly 90% of the pre-loaded inventory of recycled Am-241 in BWR bundles with heterogeneous target pins. This high level of incineration was achieved within three to four 18-month operational cycles, which is equivalent to a typical in-core residence time of a BWR bundle.

  9. Ingestion Pathway Transfer Factors for Plutonium and Americium

    Energy Technology Data Exchange (ETDEWEB)

    Blanchard, A.

    1999-07-28

    Overall transfer factors for major ingestion pathways are derived for plutonium and americium. These transfer factors relate the radionuclide concentration in a given foodstuff to deposition on the soil. Equations describing basic relationships consistent with Regulatory Guide 1.109 are followed. Updated values and coefficients from IAEA Technical Reports Series No. 364 are used when a available. Preference is given to using factors specific to the Savannah River Site.

  10. Gut uptake factors for plutonium, americium and curium

    International Nuclear Information System (INIS)

    Data on estimates of the absorption of plutonium, americium and curium from the human gut based on measurements of uptake in other mammalian species are reviewed. It is proposed that for all adult members of the public ingesting low concentrations of plutonium in food and water, 0.05% would be an appropriate value of absorption except when the conditions of exposure are known and a lower value can be justified. For dietary intakes of americium and curium, the available data do not warrant a change from the ICRP value of 0.05%. For newborn children ingesting americium, curium and soluble forms of plutonium, a value of 1% absorption is proposed for the first 3 months of life during which the infant is maintained on a milk diet. It is proposed that a value of 0.5% should be used for the first year of life to take account of the gradual maturation of the gut. In considering the ingestion of insoluble oxides of plutonium by infants, it is proposed that absorption is taken as 0.1% for the first 3 months and 0.05% for the first year. (author)

  11. PREPARATION OF ALKYL HALIDES VIA ORGANOTELLURIUMS

    OpenAIRE

    チカマツ, キヨフミ; オオツボ, テツオ; オグラ, フミオ; ヤマグチ, ハチロウ; Kiyofumi, CHIKAMATSU; Tetsuo, OTSUBO; Fumio, OGURA; Hachiro, YAMAGUCHI

    1982-01-01

    The conversion of phenyltelluroalkanes to haloalkanes was studied in connection with the homologation of alkyl halides. Similar reactions of 1,1-bis(phenyltelluro)alkanes provided a new synthetic method of aldehydes.

  12. Toxicity of organometal halide perovskite solar cells

    Science.gov (United States)

    Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc; Conings, Bert

    2016-03-01

    In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

  13. Copper Catalyzed Oceanic Methyl Halide Production

    OpenAIRE

    Robin Kim, Jae Yun; Rhew, Robert

    2014-01-01

    Methyl halides are found in all of Earth’s biomes, produced naturally or through manmade means. Their presence in the atmosphere is problematic, as they catalyze depletion of stratospheric ozone. To understand the full environmental impact of these compounds, it is important to identify their chemical cycling processes. Iron increases methyl halide production in soils and oceans, yet copper’s influence remains unknown despite its similar chemical oxidation properties to iron. I experimentally...

  14. Oxidation of hydrogen halides to elemental halogens

    Science.gov (United States)

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  15. Airborne plutonium-239 and americium-241 concentrations measured from the 125-meter Hanford Meteorological Tower

    International Nuclear Information System (INIS)

    Airborne plutonium-239 and americium-241 concentrations and fluxes were measured at six heights from 1.9 to 122 m on the Hanford meteorological tower. The data show that plutonium-239 was transported on nonrespirable and small particles at all heights. Airborne americium-241 concentrations on small particles were maximum at the 91 m height

  16. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    Science.gov (United States)

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  17. Effect of 241-americium on bone marrow stroma

    International Nuclear Information System (INIS)

    The regulation of haemopoiesis occurs via complex interactions between the stroma and the haemopoietic cells. An attempt to further clarifying the mechanisms and the exact role of the stroma in the regulation was made in a study. Results revealed that the murine bone marrow stromal cells are highly radiosensitive after injection with 241-americium and can thus be considered as a target population after internal contamination. In addition, observations are made which may be important for risk estimation for the developing animal and during pregnancy. Contamination in utero and by lactation shows persistent damage up to 1 year after contamination at an average annual dose of 5 cGy. (author)

  18. Recovery of americium-241 from aged plutonium metal

    International Nuclear Information System (INIS)

    After separation and purification, both actinides were precipitated as oxalates and calcined. A large-scale process was developed using dissolution, separation, purification, precipitation, and calcination. Efforts were made to control corrosion, to avoid product contamination, to keep the volume of process and waste solutions manageable, and to denitrate solutions with formic acid. The Multipurpose Processing Facility (MPPF), designed for recovery of transplutonium isotopes, was used for the first time for the precipitation and calcination of americium. Also, for the first time,, large-scale formic acid denitration was performed in a canyon vessel at SRP

  19. The Antimicrobial Action of Silver Halides in Calcium Phosphate

    OpenAIRE

    Kalniņa, D; Gross, K; Onufrijevs, P.; Daukšta, E; Nikolajeva, V; Stankeviciute, Z; Kareiva, A.

    2015-01-01

    Silver halides represent a yet unexplored avenue for imparting antimicrobial activity to calcium phosphates. Negtively charged silver halide colloids (AgI, AgBr and AgCl) were added to synthesized amorphous calcium phosphate. Concurrent melting of silver halides and crystallization to carbonated apatite at 700 oC increased the silver halide surface area available to bacteria and formed a lower solubility apatite. The effect of the matrix solubility on antimicrobial response could ...

  20. Preferential decorporation of americium by pulmonary administration of DTPA dry powder after inhalation of aged PuO2 containing americium in rats

    International Nuclear Information System (INIS)

    After inhalation of plutonium oxides containing various percentages of americium in rats, we identified an acellular transient pulmonary compartment, the epithelial lining fluid (ELF), in which a fraction of actinide oxides dissolve prior to absorption and subsequent extrapulmonary deposit. Chelation therapy is usually considered to be poorly efficient after inhalation of actinide oxides. However, in the present study, prompt pulmonary administration of diethylenetriaminepentaacetic acid (DTPA) as a dry powder led to a decrease in actinide content in ELF together with a limitation of bone and liver deposits. Because americium is more soluble than plutonium, higher amounts of americium were found in ELF, extrapulmonary tissues and urine. Our results also demonstrated that the higher efficacy of DTPA on americium compared to plutonium in ELF induced a preferential inhibition of extrapulmonary deposit and a greater urinary excretion of americium compared to plutonium. All together, our data justify the use of an early and local DTPA treatment after inhalation of plutonium oxide aerosols in which americium can be in high proportion such as in aged compounds. (authors)

  1. Method for recovering hydrocarbons from molten metal halides

    Science.gov (United States)

    Pell, Melvyn B.

    1979-01-01

    In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

  2. 40 CFR 721.575 - Substituted alkyl halide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  3. Harmonic dynamical behaviour of thallous halides

    Indian Academy of Sciences (India)

    Sarvesh K Tiwari; L J Shukla; K S Upadhyaya

    2010-05-01

    Harmonic dynamical behaviour of thallous halides (TlCl and TlBr) have been studied using the new van der Waals three-body force shell model (VTSM), which incorporates the effects of the van der Waals interaction along with long-range Coulomb interactions, three-body interactions and short-range second neighbour interactions in the framework of rigid shell model (RSM). Phonon dispersion curves (PDC), variations of Debye temperature with absolute temperature and phonon density of state (PDS) curves have been reported for thallous halides using VTSM. Comparison of experimental values with those of VTSM and TSM are also reported in the paper and a good agreement between experimental and VTSM values has been found, from which it may be inferred that the incorporation of van der Waals interactions is essential for the complete harmonic dynamical behaviour of thallous halides.

  4. Ultraviolet laser ablation of halides and oxides

    International Nuclear Information System (INIS)

    We compare and contrast recent measurements of the behavior of ions and excited ions desorbed from samples of alkali halides and oxide ferroelectrics by an excimer laser at 308 nm wavelength. At the intensities used in these experiments, the density of local electronic excitation is low in the halides and high in the ferroelectrics, corresponding to two- and one-photon band-to-band transitions, respectively. The observed desorption yields and changes in the sample surfaces are discussed in terms of the density of electronic excitation, the relative strengths of electron-lattice coupling, and the role of thermal relaxation processes in the two materials. (orig.)

  5. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich; Vegge, Tejs

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure....... In this project we are searching for improved mixed materials with optimal desorption temperatures and kinetics, optimally releasing all ammonia in one step. We apply Density Functional Theory, DFT, calculations on mixed compounds selected by a Genetic Algorithm (GA), relying on biological principles...

  6. Analytical performance of radiochemical method for americium determination in urine

    International Nuclear Information System (INIS)

    This paper presents an analytical method developed and adapted for separation and analysis of Plutonium (Pu) isotopes and Americium (Am) in urine samples. The proposed method will attend the demand of internal exposure monitoring program for workers involved mainly with dismantling rods and radioactive smoke detectors. In this experimental procedure four steps are involved as preparation of samples, sequential radiochemical separation, preparation of the source for electroplating and quantification by alpha spectrometry. In the first stage of radiochemical separation, plutonium is conventionally isolated employing the anion exchange technique. Americium isolation is achieved sequentially by chromatographic extraction (Tru.spec column) from the load and rinse solutions coming from the anion exchange column. The 243Am tracer is added into the sample as chemical yield monitors and to correct the results improving the precision and accuracy. The mean recovery obtained is 60%, and the detection limit for 24h urine sample is 1.0 mBq L-1 in accordance with the literature. Based in the preliminary results, the method is appropriate to be used in monitoring programme of workers with a potential risk of internal contamination. (author)

  7. Placental transfer of americium and plutonium in mice

    International Nuclear Information System (INIS)

    Actinide element release to the environment and subsequent transfer through food chains to pregnant women may present a radiation hazard to fetuses in utero. To measure americium incorporation, four groups of pregnant mice were intravenously dosed with four concentrations of 243Am citrate in late pregnancy. Concentrations of 243Am in fetuses, placentas, and maternal femur, liver, carcass and pelt were determined 48 hr after injection. Doses were chosen so that the number of atoms of 243Am in each injected dose was equal to the number of atoms of 239Pu used in an earlier study of transplacental movement. Results indicate that, atom for atom, americium is incorporated into fetal tissue in lesser amounts (10-25 times) than is plutonium when intravenously administered to pregnant mice in equal atom amounts. Tissue analyses indicated that, at low dose levels, the average fraction of the dose incorporated into the fetuses decreased as the dose to the pregnant mouse was increased. A similar pattern was noted for placentas and maternal femurs. Data indicate that one must make extrapolations from low dose data only to make reasonable and realistic estimates of the transplacental movement and fetal incorporation of environmental levels of actinide elements in man and other species. (author)

  8. Development of separation techniques of americium from reprocessing solution

    International Nuclear Information System (INIS)

    Americium(Am) and neptunium(Np) finally transfer to the waste stream in the current PUREX reprocessing process. As an option, some methods have been developed to recover Am and Np from the waste stream to decrease long-term toxicity of the high level waste. The most stable valence state of Am is III, but TBP (tri-n-butyl phosphate) which is an extractant used in the PUREX reprocessing does not extract Am(III). Therefore, some special extractants have been developed to recover Am(III). However, they also extract rare-earth elements(REs), which necessitates the separation process for Am from REs. We have been developing a separation process which consists of valence control of Am to the VI state and its extraction with TBP. This process allows Am recovery from reprocessing solution and Am separation from REs simultaneously. Americium(III) is oxidized to Am(VI) by electrochemical oxidation and chemical oxidation using peroxodisulfate ammonium and silver nitrate. The latter was adopted here because the chemical oxidation reaction proceeds faster than the electrochemical method. Reaction mechanisms of oxidation and extraction were investigated. Based on the mechanisms, we found that extraction efficiency could be improved and waste generation could be minimized. (author)

  9. Solubility of Plutonium (IV) Oxalate During Americium/Curium Pretreatment

    Energy Technology Data Exchange (ETDEWEB)

    Rudisill, T.S.

    1999-08-11

    Approximately 15,000 L of solution containing isotopes of americium and curium (Am/Cm) will undergo stabilization by vitrification at the Savannah River Site (SRS). Prior to vitrification, an in-tank pretreatment will be used to remove metal impurities from the solution using an oxalate precipitation process. Material balance calculations for this process, based on solubility data in pure nitric acid, predict approximately 80 percent of the plutonium in the solution will be lost to waste. Due to the uncertainty associated with the plutonium losses during processing, solubility experiments were performed to measure the recovery of plutonium during pretreatment and a subsequent precipitation process to prepare a slurry feed for a batch melter. A good estimate of the plutonium content of the glass is required for planning the shipment of the vitrified Am/Cm product to Oak Ridge National Laboratory (ORNL).The plutonium solubility in the oxalate precipitation supernate during pretreatment was 10 mg/mL at 35 degrees C. In two subsequent washes with a 0.25M oxalic acid/0.5M nitric acid solution, the solubility dropped to less than 5 mg/mL. During the precipitation and washing steps, lanthanide fission products in the solution were mostly insoluble. Uranium, and alkali, alkaline earth, and transition metal impurities were soluble as expected. An elemental material balance for plutonium showed that greater than 94 percent of the plutonium was recovered in the dissolved precipitate. The recovery of the lanthanide elements was generally 94 percent or higher except for the more soluble lanthanum. The recovery of soluble metal impurities from the precipitate slurry ranged from 15 to 22 percent. Theoretically, 16 percent of the soluble oxalates should have been present in the dissolved slurry based on the dilution effects and volumes of supernate and wash solutions removed. A trace level material balance showed greater than 97 percent recovery of americium-241 (from the beta dec

  10. Solubility of Plutonium (IV) Oxalate During Americium/Curium Pretreatment

    International Nuclear Information System (INIS)

    Approximately 15,000 L of solution containing isotopes of americium and curium (Am/Cm) will undergo stabilization by vitrification at the Savannah River Site (SRS). Prior to vitrification, an in-tank pretreatment will be used to remove metal impurities from the solution using an oxalate precipitation process. Material balance calculations for this process, based on solubility data in pure nitric acid, predict approximately 80 percent of the plutonium in the solution will be lost to waste. Due to the uncertainty associated with the plutonium losses during processing, solubility experiments were performed to measure the recovery of plutonium during pretreatment and a subsequent precipitation process to prepare a slurry feed for a batch melter. A good estimate of the plutonium content of the glass is required for planning the shipment of the vitrified Am/Cm product to Oak Ridge National Laboratory (ORNL).The plutonium solubility in the oxalate precipitation supernate during pretreatment was 10 mg/mL at 35 degrees C. In two subsequent washes with a 0.25M oxalic acid/0.5M nitric acid solution, the solubility dropped to less than 5 mg/mL. During the precipitation and washing steps, lanthanide fission products in the solution were mostly insoluble. Uranium, and alkali, alkaline earth, and transition metal impurities were soluble as expected. An elemental material balance for plutonium showed that greater than 94 percent of the plutonium was recovered in the dissolved precipitate. The recovery of the lanthanide elements was generally 94 percent or higher except for the more soluble lanthanum. The recovery of soluble metal impurities from the precipitate slurry ranged from 15 to 22 percent. Theoretically, 16 percent of the soluble oxalates should have been present in the dissolved slurry based on the dilution effects and volumes of supernate and wash solutions removed. A trace level material balance showed greater than 97 percent recovery of americium-241 (from the beta dec

  11. Americium Transmutation Feasibility When Used as Burnable Absorbers - 12392

    International Nuclear Information System (INIS)

    The use of plutonium in Mixed Oxide (MOX) fuel in traditional Pressurized Water Reactor (PWR) assemblies leads to greater americium production which is not addressed in MOX recycling. The transuranic nuclides (TRU) contribute the most to the radiotoxicity of nuclear waste and a reduction of the TRU stockpile would greatly reduce the overall radiotoxicity of what must be managed. Am-241 is a TRU of particular concern because it is the dominant contributor of total radiotoxicity for the first 1000 years in a repository. This research explored the feasibility of transmuting Am-241 by using varying amounts in MOX rods being used in place of burnable absorbers and evaluated with respect to the impact on incineration and transmutation of transuranics in MOX fuel as well as the impact on safety. This research concludes that the addition of americium to a non-uniform fuel assembly is a viable method of transmuting Am-241, holding down excess reactivity in the core while serving as a burnable poison, as well as reducing the radiotoxicity of high level waste that must be managed. The use of Am/MOX hybrid fuel assemblies to transmute americium was researched using multiple computer codes. Am-241 was shown in this study to be able to hold down excess reactivity at the beginning of cycle and shape the power distribution in the core with assemblies of varying americium content loaded in a pattern similar to the traditional use of assemblies with varying amounts of burnable absorbers. The feasibility, safety, and utility of using americium to create an Am/MOX hybrid non-uniform core were also evaluated. The core remained critical to a burnup of 22,000 MWD/MTM. The power coefficient of reactivity as well as the temperature and power defects were sufficiently negative to provide a prompt feedback mechanism in case of a transient and prevent a power excursion, thus ensuring inherent safety and protection of the core. As shown here as well as many other studies, this non

  12. Removal of americium from effluent generated during the purification of plutonium by anion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Noronha, Donald M.; Pius, Illipparambil C.; Chaudhury, Satyajeet [Bhabha Atomic Research Centre, Mumbai (India). Fuel Chemistry Div.

    2015-07-01

    Studies have been carried out on removal of americium from the effluent generated during anion exchange purification of plutonium. Americium 241, generated by the beta decay of Plutonium-241, is the major source of a activity in this highly acidic effluent and its removal would render the waste easily disposable. A simple and effective co-precipitation method, using thorium oxalate has been investigated for the treatment of this alpha active aqueous waste. Experiments have been carried out to identify optimum conditions to obtain high percentage co-precipitation with minimum amount of co-precipitant. Efforts were carried out to correlate the optimum conditions of co-precipitation of americium obtained in these experiments with solubility of thorium oxalate and americium oxalate calculated from solubility products of these compounds, stability constants of thorium and americium oxalate complexes taken from literature. The saturation capacity of thorium oxalate for Am(III) was also calculated by analyzing the K{sub d} value data using Langmuir adsorption equation. The strong tendency of americium to get co-precipitated and the high capacity exhibited by thorium oxalate for the uptake of americium indicate feasibility of using this method for the treatment of anion exchange effluent.

  13. Removal of americium from effluent generated during the purification of plutonium by anion exchange

    International Nuclear Information System (INIS)

    Studies have been carried out on removal of americium from the effluent generated during anion exchange purification of plutonium. Americium 241, generated by the beta decay of Plutonium-241, is the major source of a activity in this highly acidic effluent and its removal would render the waste easily disposable. A simple and effective co-precipitation method, using thorium oxalate has been investigated for the treatment of this alpha active aqueous waste. Experiments have been carried out to identify optimum conditions to obtain high percentage co-precipitation with minimum amount of co-precipitant. Efforts were carried out to correlate the optimum conditions of co-precipitation of americium obtained in these experiments with solubility of thorium oxalate and americium oxalate calculated from solubility products of these compounds, stability constants of thorium and americium oxalate complexes taken from literature. The saturation capacity of thorium oxalate for Am(III) was also calculated by analyzing the Kd value data using Langmuir adsorption equation. The strong tendency of americium to get co-precipitated and the high capacity exhibited by thorium oxalate for the uptake of americium indicate feasibility of using this method for the treatment of anion exchange effluent.

  14. The Additive Coloration of Alkali Halides

    Science.gov (United States)

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  15. Computational Screening of Mixed Metal Halide Ammines

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich; Vegge, Tejs

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. In this project we are searching for improved mixed materials with optimal desorption temperature and kinetics. We apply DFT calculations on mixed compounds...

  16. Selective leaching studies of deep-sea sediments loaded with americium, neptunium and plutonium

    International Nuclear Information System (INIS)

    A series of selective leaching experiments were undertaken to investigate the solid phase speciation and distribution of americium, neptunium and plutonium which had been experimentally loaded onto different marine sediment types. The chemical leaches employed showed rather poor selectivity but certain trends were evident. Adsorption was not by ion exchange. Americium showed a preferential affinity for carbonate and plutonium for organic matter. Neptunium appeared to have no preferential affinities. Americium was sorbed by acetic acid residues (CaCO3 removed) and by unleached carbonate-rich sediments with equal efficiency. This indicates that it is able to diversify its solid phase affinity/distribution depending upon which solid phases are available. (author)

  17. Solubility of americium collected on an aerosol filter

    International Nuclear Information System (INIS)

    Kinetics of dissolution of undefined americium aerosol in simulated serum ultrafiltrate was studied. 241Am was present in aerosol collected at a workplace, where an intake of 241Am had occurred formerly. Dissolution experiments in four parts of an aerosol filter were carried out either in ambient air or under CO2 and pH was kept within physiological range. Two?phase kinetics was found in both cases with dissolution half?times for rapid and slow phases ranging from 0.16 to 0.23 d and from 150 to 500 d, respectively. Regardless data dispersion, found half?times justify use of class M model in intake assessment. (author)

  18. The 1976 Hanford Americium Accident: Then and Now

    Energy Technology Data Exchange (ETDEWEB)

    Carbaugh, Eugene H.

    2013-10-02

    The 1976 chemical explosion of an 241Am ion exchange column at a Hanford Site waste management facility resulted in the extreme contamination of a worker with 241Am, nitric acid and debris. The worker underwent medical treatment for acid burns, as well as wound debridement, extensive personal skin decontamination and long-term DTPA chelation therapy for decorporation of americium-241. Because of the contamination levels and prolonged decontamination efforts, care was provided for the first three months at the unique Emergency Decontamination Facility with gradual transition to the patient’s home occurring over another two months. The medical treatment, management, and dosimetry of the patient have been well documented in numerous reports and journal articles. The lessons learned with regard to patient treatment and effectiveness of therapy still form the underlying philosophy of treatment for contaminated injuries. Changes in infrastructure and facilities as well as societal expectations make for interesting speculation as to how responses might differ today.

  19. Separation of americium from curium by oxidation and ion exchange.

    Science.gov (United States)

    Burns, Jonathan D; Shehee, Thomas C; Clearfield, Abraham; Hobbs, David T

    2012-08-21

    Nuclear energy has the potential to be a clean alternative to fossil fuels, but in order for it to play a major role in the US, many questions about the back end of the fuel cycle must be addressed. One of these questions is the difficult separation of americium from curium. Here, we report the oxidation of Am in two systems, perchloric acid and nitric acid and the affect of changing the acid has on the oxidation. K(d) values were observed and a direct separation factor was calculated and was seen to be as high as 20 for four metal(IV) pillared phosphate phosphonate inorganic organic hybrid ion exchange materials. These ion exchangers are characterized by very low selectivity for cations with low charge but extremely high uptake of ions of high charge. PMID:22827724

  20. Monte Carlo modeling of spallation targets containing uranium and americium

    International Nuclear Information System (INIS)

    Neutron production and transport in spallation targets made of uranium and americium are studied with a Geant4-based code MCADS (Monte Carlo model for Accelerator Driven Systems). A good agreement of MCADS results with experimental data on neutron- and proton-induced reactions on 241Am and 243Am nuclei allows to use this model for simulations with extended Am targets. It was demonstrated that MCADS model can be used for calculating the values of critical mass for 233,235U, 237Np, 239Pu and 241Am. Several geometry options and material compositions (U, U + Am, Am, Am2O3) are considered for spallation targets to be used in Accelerator Driven Systems. All considered options operate as deep subcritical targets having neutron multiplication factor of k∼0.5. It is found that more than 4 kg of Am can be burned in one spallation target during the first year of operation

  1. Pretreatment of americium/curium solutions for vitrification

    International Nuclear Information System (INIS)

    Vitrification will be used to stabilize an americium/curium (Am/Cm) solution presently stored in F-Canyon for eventual transport to the heavy isotope programs at Oak Ridge National Laboratory. Prior to vitrification, an in-tank oxalate precipitation and a series of oxalic/nitric acid washes will be used to separate these elements and lanthanide fission products from the bulk of the uranium and metal impurities present in the solution. Pretreatment development experiments were performed to understand the behavior of the lanthanides and the metal impurities during the oxalate precipitation and properties of the precipitate slurry. The results of these experiments will be used to refine the target glass composition allowing optimization of the primary processing parameters and design of the solution transfer equipment

  2. Plutonium and americium in sediments of Lithuanian lakes

    International Nuclear Information System (INIS)

    The assessment of contribution of the global and the Chernobyl NPP (Nuclear Power Plant) accident plutonium and americium to plutonium pollution in sediments of Lithuanian lakes is presented. Theoretical evaluation of activity ratios of 238Pu/239+240Pu and 241Pu/239+240Pu in the reactor of unit 4 of the Chernobyl NPP before the accident was performed by means of the ORIGEN-ARP code from the SCALE 4.4A program package. Non-uniform distribution of radionuclides in depositions on the Lithuanian territory after nuclear weapon tests and the Chernobyl NPP accident is experimentally observed by measuring the lake sediment pollution with actinides. The activity concentration of sediments polluted with plutonium ranges from 2.0 ± 0.5 Bq/kg d.w. (dry weight) in Lake Asavelis to 14 ± 2 Bq/kg d.w. in Lake Juodis. The ratio of activity concentrations of plutonium isotopes 238Pu/239+240Pu measured by α-spectrometry in the 10-cm-thick upper layer of bottom sediment varies from 0.03 in Lake Juodis to 0.3 in Lake Zuvintas. The analysis of the ratio values shows that the deposition of the Chernobyl origin plutonium is prevailing in southern and south-western regions of Lithuania. Plutonium of nuclear weapon tests origin in sediments of lakes is observed on the whole territory of Lithuania, and it is especially distinct in central Lithuania. The americium activity due to 241Pu decay after the Chernobyl NPP accident and global depositions in bottom sediments of Lithuanian lakes has been evaluated to be from 0.9 to 5.7 Bq/kg. (author)

  3. Kinetic parameters of transformation of americium and plutonium physicochemical forms in podsol soils

    International Nuclear Information System (INIS)

    Kinetic parameters of transformation of americium and plutonium physicochemical forms have been estimated and the prognosis of fixing and remobilization of these nuclides in podsol soils have been made on that basis in the work. (authors)

  4. Calibration procedures for in vivo sodium iodide spectrometry of plutonium and americium in the human lung

    International Nuclear Information System (INIS)

    This paper describes the calibration techniques and associated error analysis for the in vivo measurement by NaI spectrometry of heavy elements in the lung, specifically plutonium and americium. A very brief description of the instrumentation system is included

  5. Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

    Science.gov (United States)

    Zaitsevskii, Andréi; Mosyagin, Nikolai S.; Titov, Anatoly V.; Kiselev, Yuri M.

    2013-07-01

    The results of electronic structure modeling of plutonium and americium higher oxide molecules (actinide oxidation states VI through VIII) by two-component relativistic density functional theory are presented. Ground-state equilibrium molecular structures, main features of charge distributions, and energetics of AnO3, AnO4, An2On (An=Pu, Am), and PuAmOn, n = 6-8, are determined. In all cases, molecular geometries of americium and mixed plutonium-americium oxides are similar to those of the corresponding plutonium compounds, though chemical bonding in americium oxides is markedly weaker. Relatively high stability of the mixed heptoxide PuAmO7 is noticed; the Pu(VIII) and especially Am(VIII) oxides are expected to be unstable.

  6. Transport of Soil Halides through Rice Paddies: A Viable Mechanism for Rapid Dispersion of the Soil Halide Reservoir

    Science.gov (United States)

    Redeker, K. R.; Manley, S.; Wang, N.; Cicerone, R.

    2002-05-01

    On short time scales (1-10 years) soil halide concentrations have been assumed to be primarily driven by leaching and deposition processes. Recent results however, have shown that terrestrial plants volatilize soil halides in the form of methyl halides. Emissions of methyl chloride, methyl bromide and methyl iodide represent major pathways for delivery of inorganic halogen radicals to the atmosphere. Inorganic halogen radicals destroy ozone in the stratosphere and modify the oxidative capacity of the lower atmosphere. We have previously shown that rice paddies emit methyl halides and that emissions depend on growth stage of the rice plant as well as field water management. We show here that rice grown in a greenhouse at UCI is capable of volatilizing and/or storing up to 30%, 5%, and 10% of the available chloride, bromide and iodide within the top meter of soil. The percent of plant tissue halide volatilized as methyl halide over the course of the season is calculated to be 0.05%, 0.25% and 85.0% for chloride, bromide and iodide. We compare our greenhouse soil halide concentrations to other commercial rice fields around the world and estimate the e-folding time for soil halides within each region. We suggest that rice agriculture is the driving removal mechanism for halides within rice paddies and that terrestrial plants play a larger role in global cycling of halides than previously estimated.

  7. Distribution of uranium, americium and plutonium in the biomass of freshwater macrophytes

    Energy Technology Data Exchange (ETDEWEB)

    Zotina, T.A.; Kalacheva, G.S.; Bolsunovsky, A.YA. [Institute of Biophysics SB RAS, Akademgorodok, Krasnoyarsk (Russian Federation)

    2010-07-01

    Accumulation of uranium ({sup 238}U), americium ({sup 241}Am) and plutonium ({sup 242}Pu) and their distribution in cell compartments and biochemical components of the biomass of aquatic plants Elodea canadensis, Ceratophyllum demersum, Myrioplyllum spicatum and aquatic moss Fontinalis antipyretica have been investigated in laboratory batch experiments. Isotopes of uranium, americium and plutonium taken up from the water by Elodea canadensis apical shoots were mainly absorbed by cell walls, plasmalemma and organelles. A small portion of isotopes (about 6-13 %) could be dissolved in cytoplasm. The major portion (76-92 %) of americium was bound to cell wall cellulose-like polysaccharides of Elodea canadensis, Myriophyllum spicatum, Ceratophyllum demersum and Fontinalis antipyretica, 8-23 % of americium activity was registered in the fraction of proteins and carbohydrates, and just a small portion (< 1%) in lipid fraction. The distribution of plutonium in the biomass fraction of Elodea was similar to that of americium. Hence, americium and plutonium had the highest affinity to cellulose-like polysaccharides in Elodea biomass. Distribution of uranium in the biomass of Elodea differed essentially from that of transuranium elements: a considerable portion of uranium was recorded in the fraction of protein and carbohydrates (51 %). From our data we can assume that uranium has higher affinity to carbohydrates than proteins. (authors)

  8. Separation of curium and americium microquantities by chromatographic method with introduction of separating ions. 2. Effect of cadmium ion quantity and method of it introduction in the system on efficiency of curium and americium separation

    International Nuclear Information System (INIS)

    Effect of fractionating cadmium ion and a method of it introduction in the system on efficiency of separation of curium and americium with the use of NTA solutions as an eluent is investigated. It is established that in contrast to mutual sorption of curium, americium and cadmium their selective sorption contributes more complete separation of curium and americium. It is shown that growth of quantity of introduced cadmium increased efficiency of separation. Elution rate not products effect on separation process

  9. Flame inhibition by hydrogen halides - Some spectroscopic measurements

    Science.gov (United States)

    Lerner, N. R.; Cagliostro, D. E.

    1973-01-01

    The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

  10. Lanthanide-halide based humidity indicators

    Science.gov (United States)

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  11. Computational Screening of Mixed Metal Halide Ammines

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich;

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. In this project we are searching for improved mixed materials with optimal desorption temperature and kinetics. We apply DFT calculations on mixed compounds...... selected by a Genetic Algorithm (GA), relying on biological principles of natural selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d...... and 4d metals and the four lightest halides, giving in total almost two million combinations....

  12. Process and composition for drying of gaseous hydrogen halides

    Science.gov (United States)

    Tom, Glenn M.; Brown, Duncan W.

    1989-08-01

    A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

  13. Iridium-catalyzed intramolecular [4 + 2] cycloadditions of alkynyl halides

    OpenAIRE

    Andrew Tigchelaar; William Tam

    2012-01-01

    Iridium-catalyzed intramolecular [4 + 2] cycloadditions of diene-tethered alkynyl halides were investigated by using [IrCl(cod)]2 as catalyst, and dppe was found to be the most suitable phosphine ligand for the reaction. No oxidative insertion of the iridium into the carbon–halide bond was observed, and the reactions proceeded to provide the halogenated cycloadducts in good yield (75–94%). These results are the first examples of cycloadditions of alkynyl halides using an iridium c...

  14. Lanthanide doped strontium-barium cesium halide scintillators

    Science.gov (United States)

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  15. Americium(3) solvent extraction by oxides of dialkyl(diaryl)[dialkylcarbamoylmethyl]phosphines (CMPO) from perchloric acid solutions

    International Nuclear Information System (INIS)

    Extraction of americium(3) from perchloric acid solutions by CMPO was investigated. It is shown that americium(3) is much more effectively extracted from perchloric acid solutions, than from nitric acid ones, and increase in americium distribution coefficient depends considerably on reagent nature. As a consequence, anomalous aryl effect increases significantly in perchloric acid solutions. The value of anomalous aryl effect depends directly on stoichiometry of extracted complexes in nitric acid and perchloric acid media. Conditions for extractional concentration of americium up to the 100-fold one with small reagent consumption were suggested

  16. Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides

    OpenAIRE

    Biswas, Soumik; Weix, Daniel J.

    2013-01-01

    The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides w...

  17. Making and Breaking of Lead Halide Perovskites

    KAUST Repository

    Manser, Joseph S.

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80–150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic–inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  18. Making and Breaking of Lead Halide Perovskites.

    Science.gov (United States)

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  19. Extraction of Americium(III) by diglycolamides in ionic liquids

    International Nuclear Information System (INIS)

    In the present work, the extraction behavior of Am(lII) in the three isomeric DGAs, TODGA, DEHDODGA and TEHDGA in two ionic liquids, 1-butyl-3-methylimidazolium bis(triflouromethane sulphonyl)imide (C4mimNTf2) and 1-butyl-1-methylpyrrolidinium bis(triflouromethanesulphonyl)imide (C4mpyNTf2) is compared. The distribution ratio of americium was determined at various acidities ranging from 1M to 8M. The distribution values were found to decrease with increase in aqueous phase acidity upto 3M. The DAm values then marginally increased with increase of acidity from 3 to 4M followed by a decrease in distribution values. The distribution ratio obtained for various DGAs followed the order TEHDGA < TODGA < DEHDODGA at aqueous phase acidities ranging from 1-4 M. When the aqueous nitric acid concentration was higher than 4M, the distribution values followed the order DEHDODGA < TEHDGA < TODGA. The anomalous behaviour of unsymmetrical diglycolamide in ionic liquid medium was investigated by IR spectroscopy. The study revealed that the unprotonated fraction of DGA (i.e. the free DGA) increased in the order TEHDGA < TODGA < DEHDODGA, which seems to be responsible for the observed anomalous extraction trend in DEHDODGA in ionic liquid medium

  20. Extraction of americium and europium by CMPO-substituted adamantylcalixarenes

    International Nuclear Information System (INIS)

    Eight p-adamantylcalix[4]arene derivatives, bearing four CMPO-like functions [-(CH2)n-NH-C(O)-CH2-P(O)Ph2] at the wide (4a,b, n = 0, 1) or narrow (5a-c and 6a-c, n = 2-4) rims were synthesized for the first time. Studies of the extraction of americium(III) and europium(III) from 3 M HNO3 solutions to organic phases (dichloromethane, m-nitro-trifluoromethylbenzene) showed: (i) The extraction ability for all the adamantylcalixarene ligands is much better than for their monomeric analogues -N-(1-adamantyl)-, N-(1-adamantylmethyl)- and N,N-(dibutyl)carbamoylmethyldiphenylphosphine oxides 7a, 7b, 8; (ii) The extraction percentage increases strongly with increasing length of the spacer for all types of ligands 4-6, and best extraction results were found for 4b (n = 1) and 5c (n = 4); (iii) The separation coefficient DAm/DEu for the investigated compounds did not exceed 2, which is close to the narrow rim CMPO calixarenes, studied earlier; (iv) Variation of the spacer length between CMPO groups attached to the 1,3- and 2,4-positions of the calixarene platform in 6 did not lead to appreciably improved extractants, neither with respect to the extraction abilities (D) nor to the selectivities (DAm/DEu). (orig.)

  1. Effect of americium-241 on luminous bacteria. Role of peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Alexandrova, M., E-mail: maka-alexandrova@rambler.r [Siberian Federal University, Svobodny 79, 660041 Krasnoyarsk (Russian Federation); Rozhko, T. [Siberian Federal University, Svobodny 79, 660041 Krasnoyarsk (Russian Federation); Vydryakova, G. [Institute of Biophysics SB RAS, Akademgorodok 50, 660036 Krasnoyarsk (Russian Federation); Kudryasheva, N. [Siberian Federal University, Svobodny 79, 660041 Krasnoyarsk (Russian Federation); Institute of Biophysics SB RAS, Akademgorodok 50, 660036 Krasnoyarsk (Russian Federation)

    2011-04-15

    The effect of americium-241 ({sup 241}Am), an alpha-emitting radionuclide of high specific activity, on luminous bacteria Photobacterium phosphoreum was studied. Traces of {sup 241}Am in nutrient media (0.16-6.67 kBq/L) suppressed the growth of bacteria, but enhanced luminescence intensity and quantum yield at room temperature. Lower temperature (4 {sup o}C) increased the time of bacterial luminescence and revealed a stage of bioluminescence inhibition after 150 h of bioluminescence registration start. The role of conditions of exposure the bacterial cells to the {sup 241}Am is discussed. The effect of {sup 241}Am on luminous bacteria was attributed to peroxide compounds generated in water solutions as secondary products of radioactive decay. Increase of peroxide concentration in {sup 241}Am solutions was demonstrated; and the similarity of {sup 241}Am and hydrogen peroxide effects on bacterial luminescence was revealed. The study provides a scientific basis for elaboration of bioluminescence-based assay to monitor radiotoxicity of alpha-emitting radionuclides in aquatic solutions. - Highlights: {yields} Am-241 in water solutions (A = 0.16-6.7 kBq/L) suppresses bacterial growth.{yields} Am-241 (A = 0.16-6.7 kBq/L) stimulate bacterial luminescence. {yields} Peroxides, secondary radiolysis products, cause increase of bacterial luminescence.

  2. The coacervation of aqueous solutions of tetraalkylammonium halides

    International Nuclear Information System (INIS)

    The coacervation of aqueous solutions of tatraalkylammonium halides in the presence of not of inorganic halides and acids has been studied, considering thermodynamic and spectroscopic aspects. The importance of dispersion forces as well as forces resulting from hydrophobic hydration has been assessed. The analogy between these systems and anionic ion exchange resins has been shown especially for Uranium VI extraction

  3. Ultraviolet absorption spectra of mercuric halides.

    Science.gov (United States)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

  4. Elastic Properties of Potassium Halides under Pressure

    Institute of Scientific and Technical Information of China (English)

    K.Haddadi; L.Louail; D.Maouche

    2008-01-01

    The moderate-pressure elastic properties of potassium halides KX (X=F, CI, Br) was studied theoretically using the density functional theory (DFT) with normconserving pseudopotentials method. The phase transfor- mation from the B1 phase (NaCl-type structure) to the denser B2 phase (CsCl-type structure) occurred at 7.7, 3.46 and 2.96 GPa for KF, KCl and KBr, respectively. The elastic stiffness coefficients and bulk modulus of these materials were calculated as function of hydrostatic pressure and compared with both the experimental and theoretical values.

  5. Studies of rare gas halide lasers

    OpenAIRE

    Hogan, Daniel Christopher.; Webb, Colin E.; Dr. C. E. Webb

    1983-01-01

    This thesis presents the results of a study of the mechanisms responsible for limiting the laser pulse duration obtainable in xenon chloride lasers which are excited by UV-preionized, self-sustained gas discharges. The xenon chloride laser system, the principal emission band of which is centred around 308 nm, belongs to the class of high pressure gas lasers known as 'rare-gas halides'(RGH). RGH lasers are now well known for their high peak power output at a number of wavelen...

  6. Separation and determination of americium in low-level alkaline waste of NPP origin

    Science.gov (United States)

    Todorov, B.; Djingova, R.; Nikiforova, A.

    2006-01-01

    The aim of this work is to develop a short and cost-saving procedure for the determination of 241Am in sludge sample of the alkaline low-level radioactive waste (LL LRAW) collected from Nuclear Power Plant “Kozloduy”. The determination of americium was a part of a complex analytical approach, where group actinide separation was achieved. An anion exchange was used for separation of americium from uranium, plutonium and iron. For the separation of americium extraction with diethylhexyl phosphoric acid (DEHPA) was studied. The final radioactive samples were prepared by micro co-precipitation with NdF3, counted by alpha and gamma spectrometry. The procedure takes 2 hours. The recovery yield of the procedure amounts to (95 ± 1.5)% and the detection limit is 53 mBq/kg 241Am (t=150 000 s). The analytical procedure was applied for actual liquid wastes and results were compared to standard procedure.

  7. Americium 241 in vegetation of natural biocenoses and agrocenoses on Belarus territories contaminated with Chernobyl fall-out

    International Nuclear Information System (INIS)

    As a result of beta-decay of plutonium 241 the content of americium 241 increases progressively in soils, contaminated with Chernobyl trans uranium elements. Americium 241 displayed higher (0,5 - 1,5-fold) biological mobility than isotopes of plutonium 239, 240. Activity of americium 241 in surface phyto mass of wild and cultural plants varies from 0,04 to 5,9 Bq/kg of dry weight. Americium 241 contribution to the total trans uranium elements contamination of plants made up 60 - 80% in 1996 - 1998. Investigation of trials from the areas adjacent to the 30-km zone showed that mobility of americium 241 and plutonium was 5 - 15 times as high as in the zone

  8. Finding New Perovskite Halides via Machine learning

    Directory of Open Access Journals (Sweden)

    Ghanshyam ePilania

    2016-04-01

    Full Text Available Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning via building a support vector machine (SVM based classifier that uses elemental features (or descriptors to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  9. Finding New Perovskite Halides via Machine learning

    Science.gov (United States)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  10. Isotopic and elemental composition of plutonium/americium oxides influence pulmonary and extra-pulmonary distribution after inhalation in rats

    International Nuclear Information System (INIS)

    The biodistribution of plutonium and americium has been studied in a rat model after inhalation of two PuO2 powders in lungs and extra-pulmonary organs from 3 d to 3 mo. The main difference between the two powders was the content of americium (approximately 46% and 4.5% of total alpha activity). The PuO2 with a higher proportion of americium shows an accelerated transfer of activity from lungs to blood as compared to PuO2 with the lower americium content, illustrated by increased urinary excretion and higher bone and liver actinide retention. The total alpha activity measured reflects mostly the americium biological behavior. The activity contained in epithelial lining fluid, recovered in the acellular phase of broncho-alveolar lavages, mainly contains americium, whereas plutonium remains trapped in macrophages. Epithelial lining fluid could represent a transitional pulmonary compartment prior to translocation of actinides to the blood and subsequent deposition in extra-pulmonary retention organs. In addition, differential behaviors of plutonium and americium are also observed between the PuO2 powders with a higher dissolution rate for both plutonium and americium being obtained for the PuO2 with the highest americium content. Our results indicate that the biological behavior of plutonium and americium after translocation into blood differ two-fold: (1) for the two actinides for the same PuO2 aerosol, and (2) for the same actinide from the two different aerosols. These results highlight the importance of considering the specific behavior of each contaminant after accidental pulmonary intake when assessing extra-pulmonary deposits from the level of activity excreted in urine or for therapeutic strategy decisions. (authors)

  11. Determination of trace concentration of uranium in americium oxide samples by ICP-AES

    International Nuclear Information System (INIS)

    A solvent extraction method has been developed for the determination of uranium (200-2000 ppm) in americium oxide samples. The method involves the quantitative separation of uranium from americium matrix using mixed solvent comprising 1.1M tri-n-butyl phosphate (TBP) +1% trialkyl phosphine oxide (TRPO) + 0.3 M tertiary butyl hydroquinone (TBHQ) in n-dodecane. Uranium from the organic is stripped into the aqueous phase with 0.8 M oxalic acid and determined by ICP-AES. The reliability of the method was ascertained by analytical recovery, which is found to be nearly 100%. (author)

  12. Alkali metal and alkali earth metal gadolinium halide scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  13. Adsorption-desorption characteristics of plutonium and americium with sediment particles in the estuarine environment: studies using plutonium-237 and americium-241

    International Nuclear Information System (INIS)

    The particle formation of plutonium and americium, their adsorption onto fresh water sediments and the desorption from the sediments in sea water were studied in the Laboratory under simulated river-estuary conditions, using γ-emitting plutonium-237 and americium-241. The results of the experiments show that the particle formation of plutonium depends on its valence states, on pH and on the salinity of the medium. For river water at pH4, some 25%, 20% and 30% of the added 237Pu was in particulate form, larger than 0.45 μm, for Pu (III), Pu (IV) and Pu (VI), respectively, while 65%, 90% and 50% of the respective valence states was associated with particles at pH 8. In sea water the general pattern remains similar, although Pu (VI) is more soluble in sea water owing to higher ligand concentrations for carbonate and bicarbonate complexes. The pH-dependency of particle formation of Am (III) is more steep than that of plutonium and seems to be influenced by colloidal substances occurring in the experimental media. The adsorption-desorption characteristics of plutonium and americium with the sediment in river water as well as sea water reflect the characteristics of their particle formation, being dependent upon such properties as valence states, the pH and salinity of the medium. A sewage effluent added to the media has small but measurable effects on the adsorption-desorption processes of plutonium. (author)

  14. Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

    Science.gov (United States)

    Li, Chi; Wei, Jian; Sato, Mikio; Koike, Harunobu; Xie, Zhong-Zhi; Li, Yan-Qing; Kanai, Kaname; Kera, Satoshi; Ueno, Nobuo; Tang, Jian-Xin

    2016-05-11

    Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes. PMID:27101940

  15. Metal halide perovskites for energy applications

    Science.gov (United States)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  16. Thermoluminescence of alkali halides and its implications

    Science.gov (United States)

    Gartia, R. K.; Rey, L.; Tejkumar Singh, Th.; Basanta Singh, Th.

    2012-03-01

    Trapping levels present in some alkali halides namely NaCl, KCl, KBr, and KI are determined by deconvolution of the thermoluminescence (TL) curves. Unlike most of the studies undertaken over the last few decades, we have presented a comprehensive picture of the phenomenon of TL as an analytical technique capable of revealing the position of the trapping levels present in the materials. We show that for all practical purposes, TL can be described involving only the three key trapping parameters, namely, the activation energy (E), the frequency factor (s), and the order of kinetics (b) even for complex glow curves having a number of TL peaks. Finally, based on these, we logically infer the importance of TL in development and characterization of materials used in dosimetry, dating and scintillation.

  17. Impact of ionic liquids on europium and americium extraction by an upper rim phosphorylated calixarene

    International Nuclear Information System (INIS)

    The solvent extraction of europium and americium using the calixarene 5,11,17,23-tetrakis[dipropylphosphinylmethyl] 25,26,27,28-tetrapropoxycalix[4]arene (conical conformation) in the presence of ionic liquids with different natures was studied. It was shown that upper rim phosphorylated calixarene is able to extract europium and americium from nitric acid to dichloroethane by forming a 1:1 complex without the addition of ionic liquids. The distribution coefficients of americium are higher than those of europium in this case, but the isolation degrees of both elements are insufficient for this system to be useful in extraction technologies. The addition of the ionic liquid trihexyl(tetradecyl)phosphonium hexafluorophosphate increases the europium distribution coefficient by values ranging from twofold to more than two orders of magnitude at ionic liquid concentrations of 1 and 50 %, respectively. The values of the distribution coefficients for americium are increased by approximately 25-fold after a 50 % addition of the ionic liquid. (author)

  18. Understanding the Chemistry of Uncommon Americium Oxidation States for Application to Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Leigh Martin; Bruce J. Mincher; Nicholas C. Schmitt

    2007-09-01

    A spectroscopic study of the stability of Am(V) and Am(VI) produced by oxidizing Am(III) with sodium bismuthate is presented, varying the initial americium concentration, temperature and length of the oxidation was seen to have profound effects on the resultant solutions.

  19. Speciation and bioavailability of plutonium and americium in the Irish Sea and other marine ecosystems

    International Nuclear Information System (INIS)

    Since the late 1960s, the Irish Sea has become a repository for a variety of radio-elements originating mainly in discharges from the British Nuclear Fuels (BNF) plc. Sellafield reprocessing complex located on the Cumbrian coast. In particular, transuranium nuclides such as plutonium, americium and curium (the main constituents of the α-emitting discharges) have become incorporated into every marine compartment by a variety of mechanisms, many of which are not well understood. Although extensive studies have been carried out in the near-field (eastern Irish Sea, especially in the vicinity of the discharge point and collateral muddy sediments), comparatively little had been done to assess the long-term behaviour and bioavailability of plutonium and americium in the far-field, e.g., the western Irish Sea, prior to the present study. In this dissertation, the results of an extensive research programme, undertaken in order to improve and refine our understanding of the behaviour of plutonium and americium in the marine environment, are presented. Specifically, the thesis details the results of (and conclusions deduced from) a series of experiments in which the physical and chemical speciation, colloidal association, mobility and bioavailability of plutonium and americium were examined in diverse environments including the Irish Sea and the Mediterranean. (author)

  20. Evaluation of the readsorption of plutonium and americium in dynamic fractionations of environmental solid samples

    DEFF Research Database (Denmark)

    Petersen, Roongrat; Hou, Xiaolin; Hansen, Elo Harald

    2008-01-01

    extractions. The degree of readsorption in dynamic and conventional batch extraction systems are compared and evaluated by using a double-spiking technique. A high degree of readsorption of plutonium and americium (>75%) was observed in both systems, and they also exhibited similar distribution patterns...

  1. Extraction chromatographic recovery of americium from acidic raffinate solutions using CMPO adsorbed on Chromosorb-102

    International Nuclear Information System (INIS)

    Microgram amounts of americium have been separated and purified from large amounts of uranium present in effluent solutions resulting from the anion-exchange columns during the purification and recovery of plutonium by using TBP extraction followed by extraction chromatography using CMPO adsorbed on Chromosorb-102. (author). 4 refs., 1 tab

  2. Cesium-137 and americium-241 distribution by granulometric fractions of soil at Azgir test site grounds

    International Nuclear Information System (INIS)

    In measurements of radionuclide specific content in surface soil layer of contaminated territories it is important to determine in what agglomerations of soil particles there is the highest radionuclide concentration. For this purpose granulometric composition of soil at Azgir test site was studied and cesium-137 and americium-241 distribution by soil fractions was researched. (author)

  3. Development of analytical methods for the separation of plutonium, americium, curium and neptunium from environmental samples

    OpenAIRE

    Salminen, Susanna

    2009-01-01

    In this work, separation methods have been developed for the analysis of anthropogenic transuranium elements plutonium, americium, curium and neptunium from environmental samples contaminated by global nuclear weapons testing and the Chernobyl accident. The analytical methods utilized in this study are based on extraction chromatography. Highly varying atmospheric plutonium isotope concentrations and activity ratios were found at both Kurchatov (Kazakhstan), near the former Semipalatinsk...

  4. Determination of specific activity of americium and plutonium in selected environmental samples

    International Nuclear Information System (INIS)

    The aim of this work was development of method for determination of americium and plutonium in environmental samples. Developed method was evaluated on soil samples and after they was applied on selected samples of fishes (smoked mackerel, herring and fillet from Alaska hake). The method for separation of americium is based on liquid separation with Aliquate-336, precipitation with oxalic acid and using of chromatographic material TRU-SpecTM.The intervals of radiochemical yields were from 13.0% to 80.9% for plutonium-236 and from 10.5% to 100% for americium-241. Determined specific activities of plutonium-239,240 were from (2.3 ± 1.4) mBq/kg to (82 ± 29) mBq/kg, the specific activities of plutonium-238 were from (14.2 ± 3.7) mBq/kg to (708 ± 86) mBq/kg. The specific activities of americium-241 were from (1.4 ± 0.9) mBq/kg to (3360 ± 210) mBq/kg. The fishes from Baltic Sea as well as from North Sea show highest specific activities then fresh-water fishes from Slovakia. Therefore the monitoring of alpha radionuclides in foods imported from territories with nuclear testing is recommended

  5. Application of hollow fiber supported liquid membrane for the separation of americium from the analytical waste

    International Nuclear Information System (INIS)

    Americium from analytical solid waste containing U and metallic impurities was separated using hollow fiber supported liquid membrane (HFSLM) technique impregnated with DHOA-TODGA from nitric acid medium. An aliquot of 5 g of the solid waste containing Am (19.95 mg) as minor actinide and of U (2,588 mg), Fe (1,360 mg), Ca (1,810 mg) and Na (3,130 mg) as major impurities was processed. The feed solution obtained after the dissolution of the residue in ∼4 M HNO3 was passed through HFSLM module. In the first stage using 1 M DHOA-dodecane was used for the separation of Am from other impurities. Though, majority of the elements were separated in this cycle, Ca was co extracted along with the americium. CMPO extraction chromatographic technique was used for further separation of americium from Ca. Significant decontamination factors were achieved in this three step separation process with respect to U, Fe, Na and Ca with ∼77 % recovery of americium. (author)

  6. Determination of α-emitters (plutonium, americium, curium ...) in feces and urine ashes

    International Nuclear Information System (INIS)

    A description is given of the methods used to determine a number of radionuclides to be found in feces and urine, and obtain samples thin enough for counting and α-spectrometry. These methods can be applied to plutonium, americium and curium especially

  7. Upper Limits to Americium Concentration in Medium Size Sodium Cooled Fast Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Y.P.; Wallenius, J. [Royal Institute of Technology (KTH), AlbaNova University Centre, S-106 91, Stockholm (Sweden)

    2009-06-15

    The fastest way to realize transmutation of minor actinides would be using existing reactor types, adding some proper modifications to allow for insertion of MA in the fuel. According to calculations by Fazio and co-workers, the consumption rate of TRU in a low conversion ratio fast reactor may reach 70-75 % of that of an ADS with uranium free fuel [1]. However, americium introduction brings a negative influence on several safety parameters such as {beta}{sub eff}, Doppler coefficient, coolant temperature coefficient and void worth. Therefore the upper limit of americium that can be included into the fuel needs to be carefully evaluated. In this paper, fast reactor fuels with various minor actinide fractions are loaded into a SAS4A model of the semi-commercial BN600 reactor. Unprotected loss of flow (ULOF) and transient over power (UTOP) accidents are modelled using safety parameters obtained from Monte Carlo simulations as well as from the deterministic calculations published by Fazio et al. Applying the latter parameters (obtained with VARI3D), the upper limit to MA concentration in the fuel of a medium sized SFR of BN-600 type appears at 12%, corresponding to 8% of americium. We note however that the Doppler constants displayed by Fazio et al for MA concentrations above 10% have a considerably larger magnitude than those obtained with MCNP. Applying the safety parameters obtained with Monte Carlo simulations and updated nuclear data evaluations, we find that the upper limit to the americium concentration allowing to survive a ULOF is about half of that inferred by the use of parameters from VARI-3D. Since such a difference has a major impact on the predicted americium transmutation capability of SFR, it is of high priority to analyse the reasons for the apparent discrepancies. We note here that the major contribution to the Doppler feedback comes from capture resonance in U-238 and Pu-240 residing below the sodium scattering resonance located at 3 keV, and that

  8. Silver-catalyzed coupling reactions of alkyl halides with indenyllithiums

    OpenAIRE

    Someya, Hidenori; Yorimitsu, Hideki; Oshima, Koichiro

    2010-01-01

    Coupling reactions of tertiary and secondary alkyl halides with indenyllithiums proceeded effectively in the presence of a catalytic amount of silver bromide to provide tertiary- and secondary-alkyl-substituted indene derivatives in good yields.

  9. Theory of the late stage of radiolysis of alkali halides

    OpenAIRE

    Dubinko, V. I.; Turkin, A.A.; Vainshtein, D.I.; Hartog, H.W. den

    2000-01-01

    Recent results on heavily irradiated natural and synthetic NaCl crystals give evidence for the formation of large vacancy voids, which were not addressed by the conventional Jain-Lidiard model of radiation damage ill alkali halides. This model was constructed to describe metal colloids and dislocation loops formed in alkali halides during earlier stages of irradiation. We present a theory based on a new mechanism of dislocation climb, which involves the production of Vt centers (self-trapped ...

  10. Effect of bone-status on retention and distribution of americium-241 in bones of small rodents

    International Nuclear Information System (INIS)

    Forced physical exercise before and after application of americium-241 resulted in only small changes in bone-structure and behaviour of the radionuclide in bone. Feeding of a low phosphorus or low calcium diet resulted in an increased excretion of americium from bone, whereby Zn-DTPA as chelating agent removed an additional fraction of the radionuclide from bone. Low calcium diet and simultaneous continuous infusion of pharmacological doses of vitamin D-hormones didn't increase the excretion of americium more than the low calcium diet alone. (orig.)

  11. Interaction and diffusion transport of americium in soils

    International Nuclear Information System (INIS)

    The final disposal of High Level Radioactive Wastes (HLRW) is based on its long-term storage in underground facilities located in geological stable sites with a multi-barrier system, the so called Deep Geological Repositories (DGR), that will keep HLRW confined for >10.000 years. After this period of time, leachates rich in long-live radioisotopes might escape from DGR and start to transport towards the biosphere. There is still a lack of information concerning the interaction and transport in soils of some radionuclides present in HLRW, especially for radionuclides that present a high sorption, such as americium (Am). Having reliable information about the mobility of radionuclides in soils is crucial in order to develop risk assessment models and to take proper decisions in case of soil contamination. The aim of the present work was, by means of laboratory scale experiments, to study the interaction and, for first time, to evaluate the diffusion transport of 241Am in soils. The 241Am interaction in soils was assessed by applying sorption batch assays to 20 soil samples with contrasted edaphic properties which allowed us to quantify the solid-liquid distribution coefficient (Kd) and desorption percentage. Kd (Am) values ranged from 103 to 105 L kg-1 and desorption percentages were always less than 2% which denoted a high capacity of the soil to incorporate the Am and a low reversibility of the sorption process. The influence of soil properties in 241Am interaction was studied by means of multiple linear and multivariate regressions. Although a single correlation between Kd (Am) values and a soil property was not found, the main properties affecting 241Am interaction in soils were soil pH, carbonate and organic matter contents in the soil. Finally, additional batch assays at different controlled pH were done to study Am sorption as a function of the contact solution pH. A variation of the Am sorption capacity was observed in all soils due to the dissolution of soil

  12. Interaction and diffusion transport of americium in soils

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez-Guinart, Oriol; Rigol, Anna; Vidal, Miquel [Analytical Chemistry department, Faculty of Chemistry, University of Barcelona, Marti i Franques 1-11, 08028, Barcelona (Spain)

    2014-07-01

    The final disposal of High Level Radioactive Wastes (HLRW) is based on its long-term storage in underground facilities located in geological stable sites with a multi-barrier system, the so called Deep Geological Repositories (DGR), that will keep HLRW confined for >10.000 years. After this period of time, leachates rich in long-live radioisotopes might escape from DGR and start to transport towards the biosphere. There is still a lack of information concerning the interaction and transport in soils of some radionuclides present in HLRW, especially for radionuclides that present a high sorption, such as americium (Am). Having reliable information about the mobility of radionuclides in soils is crucial in order to develop risk assessment models and to take proper decisions in case of soil contamination. The aim of the present work was, by means of laboratory scale experiments, to study the interaction and, for first time, to evaluate the diffusion transport of {sup 241}Am in soils. The {sup 241}Am interaction in soils was assessed by applying sorption batch assays to 20 soil samples with contrasted edaphic properties which allowed us to quantify the solid-liquid distribution coefficient (K{sub d}) and desorption percentage. K{sub d} (Am) values ranged from 10{sup 3} to 10{sup 5} L kg{sup -1} and desorption percentages were always less than 2% which denoted a high capacity of the soil to incorporate the Am and a low reversibility of the sorption process. The influence of soil properties in {sup 241}Am interaction was studied by means of multiple linear and multivariate regressions. Although a single correlation between K{sub d} (Am) values and a soil property was not found, the main properties affecting {sup 241}Am interaction in soils were soil pH, carbonate and organic matter contents in the soil. Finally, additional batch assays at different controlled pH were done to study Am sorption as a function of the contact solution pH. A variation of the Am sorption

  13. SKIN DOSIMETRY IN CONDITIONS OF ITS CONSTANT SURFACE CONTAMINATION WITH SOLUTIONS OF PLUTONIUM-239 AND AMERICIUM-241

    Directory of Open Access Journals (Sweden)

    E. B. Ershov

    2012-01-01

    Full Text Available The article considers, on the basis of experimental data, the issue of assessing dose burdens to the skin basal layer in conditions of its permanent contamination with solutions of plutonium-239 and americium-241 and subsequent decontamination.

  14. Metabolism of americium-241 in man: an unusual case of internal contamination of a child and his father

    International Nuclear Information System (INIS)

    The metabolism of americium-241 was studied during an 8-yr period of an adult male and his son who, at the ages of 50 and 4, respectively, were accidentally and unknowingly contaminated within their home by means of inhalation. Chelation therapy with Na3(Ca-DTPA) was more effective in enhancing the removal of americium-241 from the child than from his father

  15. Influence of biofilms on migration of uranium, americium and europium in the environment; Einfluss von Biofilmen auf das Migrationsverhalten von Uran, Americium und Europium in der Umwelt

    Energy Technology Data Exchange (ETDEWEB)

    Baumann, Nils; Zirnstein, Isabel; Arnold, Thuro

    2015-07-01

    The report on the influence of biofilms on migration of uranium, americium and europium in the environment deals with the contamination problems of uranium mines such as SDAG WISMUT in Saxonia and Thuringia. In mine waters microorganisms form a complex microbiological biocoenosis in spite of low pH values and high heavy metal concentrations including high uranium concentrations. The analyses used microbiological methods like confocal laser scanning microscopy and molecular-biological techniques. The interactions of microorganism with fluorescent radioactive heavy metal ions were performed with TRLFS (time resolved laser-induced fluorescence spectroscopy).

  16. Color silver halide hologram production and mastering

    Science.gov (United States)

    Bjelkhagen, Hans I.; Huang, Qiang

    1997-04-01

    Color reflection holograms recorded with the Denisyuk geometry have been demonstrated by the recently formed HOLOS Corporation in New Hampshire. The Slavich red-green-blue (RGB) sensitized ultra-high resolution silver halide emulsion was used for the hologram recording. The employed laser wavelengths were 647 nm, 532 nm, and 476 nm, generated by an argon ion, a frequency doubled Nd:YAG, and a krypton ion laser, respectively. A beam combination mechanism with dichroic filters enabled a simultaneous RGB exposure, which made the color balance and overall exposure energy easy to control as well as simplifying the recording procedure. HOLOS has been producing limited edition color holograms in various sizes from 4' X 5' to 12' X 16'. A 30 foot long optical table and high power lasers will enable HOLOS to record color holograms up to the size of one meter square in the near future. Various approaches have been investigated in generating color hologram masters which have sufficiently high diffraction efficiency to contact copy the color images onto photopolymer materials. A specially designed test object including the 1931 CIE chromaticity diagram, a rainbow ribbon cable, pure yellow dots, and a cloisonne elephant was used for color recording experiments. In addition, the Macbeth Color Checker chart was used. Both colorimetric evaluation and scattering noise measurements were performed using the PR-650 Photo Research SpectraScan SpectraCalorimeter.

  17. Liquid-liquid extraction separation and sequential determination of plutonium and americium in environmental samples by alpha-spectrometry

    International Nuclear Information System (INIS)

    A procedure is described by which plutonium and americium can be determined in environmental samples. The sample is leached with nitric acid and hydrogen peroxide, and the two elements are co-precipitated with ferric hydroxide and calcium oxalate. The calcium oxalate is incinerated at 4500 and the ash is dissolved in nitric acid. Plutonium is extracted with tri-n-octylamine solution in xylene from 4M nitric acid and stripped with ammonium iodide/hydrochloric acid. Americium is extracted with thenoyltrifluoroacetone solution in xylene at pH 4 together with rare-earth elements and stripped with 1M nitric acid. Americium and the rare-earth elements thus separated are sorbed on Dowex 1 x 4 resin from 1M nitric acid in 93% methanol, the rare-earth elements are eluted with 0.1M hydrochloric acid/0.5M ammonium thiocyanate/80% methanol and the americium is finally eluted with 1.5M hydrochloric acid in 86% methanol. Plutonium and americium in each fraction are electro-deposited and determined by alpha-spectrometry. Overall average recoveries are 81% for plutonium and 59% for americium. (author)

  18. Vitrification of IFR and MSBR halide salt reprocessing wastes

    International Nuclear Information System (INIS)

    Both of the genuinely sustainable (breeder) nuclear fuel cycles (IFR - Integral Fast Reactor - and MSBR - Molten Salt Breeder Reactor -) studied by the USA's national laboratories would generate high level reprocessing waste (HLRW) streams consisting of a relatively small amount ( about 4 mole %) of fission product halide (chloride or fluoride) salts in a matrix comprised primarily (about 95 mole %) of non radioactive alkali metal halide salts. Because leach resistant glasses cannot accommodate much of any of the halides, most of the treatment scenarios previously envisioned for such HLRW have assumed a monolithic waste form comprised of a synthetic analog of an insoluble crystalline halide mineral. In practice, this translates to making a 'substituted' sodalite ('Ceramic Waste Form') of the IFR's chloride salt-based wastes and fluoroapatite of the MSBR's fluoride salt-based wastes. This paper discusses my experimental studies of an alternative waste management scenario for both fuel cycles that would separate/recycle the waste's halide and immobilize everything else in iron phosphate (Fe-P) glass. It will describe both how the work was done and what its results indicate about how a treatment process for both of those wastes should be implemented (fluoride and chloride behave differently). In either case, this scenario's primary advantages include much higher waste loadings, much lower overall cost, and the generation of a product (glass) that is more consistent with current waste management practices. (author)

  19. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    Science.gov (United States)

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature. PMID:27174223

  20. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    Science.gov (United States)

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  1. Process for oxidation of hydrogen halides to elemental halogens

    Science.gov (United States)

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  2. Electrodeposition of americium on a liquid cadmium cathode from a molten salt bath

    International Nuclear Information System (INIS)

    A high-activity experiment involving the electrode position of americium on a liquid cadmium cathode from a LiCl-KCl eutectic with about 3 g of AmO2 was conducted in a shielded cell in the ATALANTE complex. After describing the electrolyzer and the experimental conditions, the authors discuss the preparation of the LiCl-KCl-AmCl3 solution and briefly review its electrochemical properties. It was clearly confirmed that Am(III) reduction on an inert solid cathode occurs in two steps forming Am(II) before Am(0), whereas only one reduction step was observed on liquid cadmium. The main results of this study concern americium electrode position on the liquid cadmium cathode (recovery yields, current densities, problems encountered). The solvent properties of cadmium for actinide/lanthanide separation are discussed. (authors)

  3. Experimental Insight into the Radiation Resistance of Zirconia-Based Americium Ceramics

    International Nuclear Information System (INIS)

    Our works shows that the americium pyrochlore 241Am2Zr2O7 undergoes a phase transition to a defect-fluorite structure along with an unusual volume contraction when subjected to internal radiation from α-emitting actinides. Disorder relaxation proceeds through the simultaneous formation of cation anti sites and oxygen Frenkel pairs. X-ray absorption spectroscopy at the Am-LII and the Zr-K edges reveals that Am-O polyhedra show an increasing disorder with increasing exposure. In contrast, the Zr-O polyhedral units remain highly ordered, while rotating along edges and corners, thereby reducing the structural strain imposed by the growing disorder around americium. We believe it is this particular property of the compound that provides the remarkable resistance to radiation (≥9.4 * 1018) α-decay events g-1 or 0.80 dpa). (authors)

  4. Influence of some organic additives on the extractive separation of americium(III) by sulfoxides

    International Nuclear Information System (INIS)

    The solvent extraction behavior of americium(III) from aqueous nitrate media by two long-chain aliphatic sulfoxides has been examined systematically in the presence of several water-miscible organic solvents to study their possible synergistic effect on metal ion extraction. Methanol, ethanol, n- and isopropanol, n-butanol, dioxane, acetone, as well as acetonitrile, were employed as the organic component of the mixed (polar) phase. These additives affected the extraction to varying degrees. Extractability of Am increased 5 to 10-fold with increasing concentration of some of these additives, with the maximum enhancement being observed in the presence of acetone or acetonitrile. However, alcohols are generally very poor in this respect. Possible reasons for such behavior are briefly discussed. The distribution of several common contaminants was also investigated at the optimum condition for americium extraction

  5. Transmutation of americium and curium incorporated in zirconia-based host materials

    International Nuclear Information System (INIS)

    Presented are studies involving the incorporation of americium and curium in zirconia-based materials. First explored was the pseudo ternary system AmO2-ZrO2-Y2O3. It was determined that selected Y-CSZ materials can incorporate significant quantities of americium oxide and remain cubic single-phase. The cell parameters of these fluorite-type products were established to be linear with the AmO2 content. The Cm2O3-ZrO2 system was also investigated. It was found that at 25 mol% of CmO1.5, the Cm(III) stabilized zirconia in its cubic form (a = 5.21 ±0.01 Angstrom). At higher and lower concentrations, diphasic materials were encountered. At 50 mol% of CmO1.5, a pyrochlore oxide - Cm2Zr2O7 - is formed (a = 10.63 ±0.02 Angstrom). (author)

  6. Americium and samarium determination in aqueous solutions after separation by cation-exchange

    International Nuclear Information System (INIS)

    The concentration of trivalent americium and samarium in aqueous samples has been determined by means of alpha-radiometry and UV-Vis photometry, respectively, after chemical separation and pre-concentration of the elements by cation-exchange using Chelex-100 resin. Method calibration was performed using americium (241Am) and samarium standard solutions and resulted in a high chemical recovery for cation-exchange. Regarding, the effect of physicochemical parameters (e.g. pH, salinity, competitive cations and colloidal species) on the separation recovery of the trivalent elements from aqueous solutions by cation-exchange has also been investigated. The investigation was performed to evaluate the applicability of cation-exchange as separation and pre-concentration method prior to the quantitative analysis of trivalent f-elements in water samples, and has shown that the method could be successfully applied to waters with relatively low dissolved solid content. (author)

  7. Analysis of americium-beryllium neutron source composition using the FRAM code

    Energy Technology Data Exchange (ETDEWEB)

    Hypes, P. A. (Philip A.); Bracken, D. S. (David S.); Sampson, Thomas E.; Taylor, W. A. (Wayne A.)

    2002-01-01

    The FRAM code was originally developed to analyze high-resolution gamma spectra from plutonium items. Its capabilities have since been expanded to include analysis of uranium spectra. The flexibility of the software also enables a capable spectroscopist to use FRAM to analyze spectra in which neither plutonium nor uranium is present in significant amounts. This paper documents the use of FRAM to determine the {sup 239}Pu/{sup 241}Am, {sup 243}Am/{sup 241}Am, {sup 237}Np/{sup 241}Am, and {sup 239}Np/{sup 241}Am ratios in americium-beryllium neutron sources. The effective specific power of each neutron source was calculated from the ratios determined by FRAM in order to determine the americium mass of each of these neutron sources using calorimetric assay. We will also discuss the use of FRAM for the general case of isotopic analysis of nonplutonium, nonuranium items.

  8. Influence of environmental factors on the gastrointestinal absorption of plutonium and americium

    International Nuclear Information System (INIS)

    The absorption of plutonium and americium from the gastrointestinal tract was studied, using adult hamsters and rabbits. Both actinides were administered as inorganic compounds, as organic complexes with naturally occurring chelating agents, and in a biologically incorporated form in liver tissues. The absorption of the tetravalent and hexavalent forms of plutonium were compared and the effect of protracted administration at very low concentrations was investigated. In addition, plutonium uptake from contaminated sediments and grass, collected near a nuclear-fuel reprocessing plant, was measured. The results of these studies suggest that chronic exposure of man to plutonium and americium in food and water will not lead to any substantial increase in their gastrointestinal absorption above the values currently recommended by the International Commission on Radiological Protection to define the occupational exposure of workers

  9. Contemporary state of plutonium and americium in the soils of Palesse state radiation-ecological reserve

    International Nuclear Information System (INIS)

    Full text: At present, the most important alpha-emitting radionuclides of Chernobyl origin are Pu 238, Pu 239, Pu 240 and Am 241. They are classified as the most dangerous group of radionuclides in view of the long half-lives and high radiotoxicity. The main part of alpha-emitted radionuclides is located within the Palesse State Radiation-Ecological Reserve. One of the most important factors determining the radioecological situation in the contaminated ecosystems is the physicochemical forms of radionuclides in a soil medium. Radionuclide species determine the radionuclide entrance into the soil solutions, their redistribution in soil profiles and the 'soil - plant' and the 'soil - surface, ground or underground water' systems as well as spreading beyond the contaminated area. The present work is devoted to investigation of state and migration ability of plutonium and americium in soils of the Palesse state radiation-ecological reserve after more than 20 years from the Chernobyl accident. The objects of investigation were mineral and organic soils sampled in 2008 with the step of 5 cm to the depth of 25-30 cm. The forms of plutonium and americium distinguishing by association with the different components of soil and by potential for migration in the soil medium were studied using the method of sequential selective extraction according to the modified Tessier scheme. Activities of Pu 238, Pu 239, Pu 240 and Am 241 in the samples were determined by the method of radiochemical analysis with alpha-spectrometer radionuclide identification. The dominant part of plutonium and americium in the soils is in immobile forms. Nowadays, radionuclide portions in water soluble and reversibly bound forms do not exceed 9.4 % of radionuclide content in the soil. In mineral soil samples, the radionuclide portions in these fractions exceed the corresponding portions in organic ones. In both mineral and organic soils, the portions of mobile americium are higher than plutonium. The

  10. Standard test method for quantitative determination of americium 241 in plutonium by Gamma-Ray spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1994-01-01

    1.1 This test method covers the quantitative determination of americium 241 by gamma-ray spectrometry in plutonium nitrate solution samples that do not contain significant amounts of radioactive fission products or other high specific activity gamma-ray emitters. 1.2 This test method can be used to determine the americium 241 in samples of plutonium metal, oxide and other solid forms, when the solid is appropriately sampled and dissolved. 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  11. Fabrication of neptunium, plutonium, americium and curium metals for fuel research

    International Nuclear Information System (INIS)

    The techniques for the fabrication of actinide metals; neptunium, americium and curium called as minor actinides, and plutonium, are surveied in a viewpoint of the preparation of starting materials for fuel property measurements. In this report, the processes of the conversion to metals, purification et al. are reviewed. The concept related to the apparatus design is also proposed and the considerable subjects are discussed. (author)

  12. Final Radiological Assessment of External Exposure for CLEAR-Line Americium Recovery Operations

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Adam C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Belooussova, Olga N. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hetrick, Lucas Duane [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2014-11-12

    Los Alamos National Laboratory is currently planning to implement an americium recovery program. The americium, ordinarily isotopically pure 241Am, would be extracted from existing Pu materials, converted to an oxide and shipped to support fabrication of americium oxide-beryllium neutron sources. These operations would occur in the currently proposed Chloride Extraction and Actinide Recovery (CLEAR) line of glove boxes. This glove box line would be collocated with the currently-operational Experimental Chloride Extraction Line (EXCEL). The focus of this document is to provide an in-depth assessment of the currently planned radiation protection measures and to determine whether or not further design work is required to satisfy design-goal and ALARA requirements. Further, this document presents a history of americium recovery operations in the Department of Energy and high-level descriptions of the CLEAR line operations to provide a basis of comparison. Under the working assumptions adopted by this study, it was found that the evaluated design appears to mitigate doses to a level that satisfies the ALARA-in-design requirements of 10 CFR 835 as implemented by the Los Alamos National Laboratory procedure P121. The analyses indicate that extremity doses would also meet design requirements. Dose-rate calculations were performed using the radiation transport code MCNP5 and doses were estimated using a time-motion study developed in consort with the subject matter expert. A copy of this report and all supporting documentation are located on the Radiological Engineering server at Y:\\Rad Engineering\\2013 PROJECTS\\TA-55 Clear Line.

  13. High Biomass Specific Methyl Halide Production Rates of Selected Coastal Marsh Plants and its Relationship to Halide Content

    Science.gov (United States)

    Manley, S. L.; Wang, N.; Cicerone, R. J.

    2002-12-01

    Salt tolerant coastal marsh plants (halophytes) have previously been shown to be globally significant producers of methyl chloride (MeCl) and methyl bromide (MeBr). While halophytes are known for their high salt content, there are few reports of their halide content. Our studies have attempted to quantify biomass specific methyl halide (MeX) production from these plants and relate it to tissue halide levels. MeCl, MeBr and MeI production rates and tissue chloride, bromide and iodide concentrations from selected coastal marsh plants were measured for nearly a year. Certain halophyte species (i.e. Batis and Frankenia) have very high summer biomass specific production rates for MeX (e.g. Frankenia: 1 ug MeCl /gfwt/hr; 80 ng MeBr/gfwt/hr; 8 ng MeI/gfwt/hr). These rates of MeCl and MeBr production are much higher than those from other coastal marsh plants or seaweeds. Plant halide levels remain high throughout the year, while MeX production peaks at a high level in mid summer falling to low winter rates. This implies a linkage to plant growth. Higher levels of chloride and bromide were seen in the fleshy marsh plants such as Batis (saltwort, approximately 20 percent dry wt chloride, 0.4 percent dry wt bromide) and Salicornia (pickleweed) than in the others such as Frankenia (alkali heath) approx 7 percent dry wt chloride, 0.1 percent dry wt bromide) or Spartina (cordgrass). No such trend was seen for iodide, which ranged from 4 - 10 ppm. Calculations show the daily halide losses from MeX production are far less than the variability in tissue halide content. MeX production removes a small fraction of the total tissue halide from these plants suggesting that MeX production is not a mechanism used by these species to control internal halide levels. Saltwort cell-free extracts incubated with bromide or iodide in the presence of S-adenosyl-L-methionine (SAM) produced the corresponding MeX. MeBr production was inhibited by caffeic acid the substrate of lignin-specific O

  14. Fabrication of uranium–americium mixed oxide pellet from microsphere precursors: Application of CRMP process

    International Nuclear Information System (INIS)

    Highlights: • Dust free process for (U,Am)O2 transmutation target fabrication. • Synthesis of U0.9Am0.1O2 mixed oxide microspheres from ion exchange resin. • Fabrication of dense U0.9Am0.1O2 pellet with 95% TD from mixed oxide microspheres. - Abstract: Mixed uranium–americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Recently, several processes have been developed in order to validate fabrication flowchart in terms of material specifications such as density and homogeneity but also to suggest simplifications for lowering industrial costs and hazards linked to dust generation of highly contaminating and irradiating compounds. This study deals with the application of an innovative route using mixed oxide microspheres obtained from metal loaded resin bead calcination, called Calcined Resin Microsphere Pelletization (CRMP). The synthesis of mixed oxide microsphere precursor of U0.9Am0.1O2±δ is described as well as its characterisation. The use of this free-flowing precursor allows the pressing and sintering of one pellet of U0.9Am0.1O2±δ. The ceramic obtained was characterised and results showed that its microstructure is dense and homogeneous and its density attains 95% of the theoretical density. This study validates the scientific feasibility of the CRMP process applied to the fabrication of uranium and americium-containing materials

  15. Influence of dissolved organic substances in groundwater on sorption behavior of americium and neptunium

    International Nuclear Information System (INIS)

    Groundwaters typically contain dissolved organic carbon consisting largely of high molecular weight compounds of humic and fulvic acids. To evaluate whether these dissolved organic substances can enhance the tranport of radionuclides through the groundwater system, experiments were conducted to examine the sorption of americium and neptunium onto crushed basalt in the presence of dissolved humic- and fulvic-acid organic carbon introduced into synthetic groundwater. The partitioning experiments with synthetic groundwater show that increasing the concentration of either humic or fulvic acid in the water has a significant inhibiting effect on sorption of both americium and neptunium. At 220C, adsorption of these radionuclides, as measured by distribution ratios (the ratio of nuclide sorbed onto the solid to nuclide in solution at the end of the experiment), decreased by 25% to 50% by addition of as little as 1 mg/L dissolved organic carbon and by one to two orders of magnitude by addition of 100 to 200 mg/L dissolved organic carbon. Distribution ratios measured in solutions reacted at 900C similarly decreased with the addition of dissolved organic carbon but generally ranged from one to two orders of magnitude higher than those determined in the 220C experiment. These results suggest that organic carbon dissolved in deep groundwaters may significantly enhance the mobility of radionuclides of americium and neptunium. 23 references, 5 figures, 11 tables

  16. Bidentate organophosphorus extraction of americium and plutonium from Hanford Plutonium Reclamation Facility waste

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1974-09-01

    Applicability of bidentate organiphosphorus reagents to recovery of americium and plutonium from Hanford's Plutonium Reclamation Facility acid (approx. 2M HNO/sub 3/) waste stream (CAW solution) was studied. A solvent extraction process which employs a 30% DHDECMP (dihexyl-N, N-diethylcarbamylmethylene phosphonate)-CCl/sub 4/ extractant was devised and successfully tested in mixer-settler runs with actual CAW solution. Substitution of DHDECMP for DBBP eliminates the need to perform careful neutralization of unbuffered CAW soluton and increases overall americium recovery from the present 60 to 80% level to greater than or equal to 90%. Disadvantages to such substitution include the high cost (approx. $50/liter) of DHDECMP and the need to purify it (by acid (6M HCl) hydrolysis and alkaline washing) from small amounts of an unidentified impurity which prevents stripping of americium with dilute HNO/sub 3/. Distribution data obtained in this study confirm Siddall's earlier contention that bidentate organophosphorus regents can be used to remove actinides from concentrated high-level Purex process acid waste; a conceptual flowsheet for such an extraction process is given.

  17. Selective recovery of americium alone from PUREX or COEXTM raffinate by the EXAm process

    International Nuclear Information System (INIS)

    Americium is the main contributor to the long-term radiotoxicity and to the heat generation of glasses used for the HLW conditioning. To decrease both impact on the ultimate waste and to avoid the difficult recycling of curium, the CEA has developed the EXAm process for the the separation and the recovery of the sole americium directly from PUREX or COEXTM raffinates. The principle of the EXAm process is to extract americium and light lanthanides from high nitric acid media, leaving curium and heavy lanthanides in the raffinate. A water-soluble amide molecule, TEDGA, is added in aqueous phase to increase Am/Cm and Am/heavy lanthanides selectivity, because of the preferential complexation of curium and heavy lanthanides by this diglycolamide. Many experimental data have been acquired mainly at the extraction-scrubbing step (Am/Cm separation) and were used for the development of a phenomenological model implemented in the PAREX process simulation code. The scientific feasibility demonstration of the EXAm process was then performed on a genuine PUREX raffinate in Atalante CBP hot cell in 2010. (author)

  18. Uptake and effects of americium-241 on a brackish-water amphipod

    International Nuclear Information System (INIS)

    The present paper reports the results of experimental work undertaken using the brackish-water amphipod Gammarus duebeni duebeni and the transuranium nuclide americium-241. Data on the accumulation of this actinide showed that the larger fraction of the total body burden is associated with the exoskeleton. It was found that the body burden remained constant in the range pH 8.0-6.5 even though the water concentration changed markedly. It would thus appear that the concept of a concentration factor should be re-examined and it is proposed that a factor should be defined in terms of environmental and chemical parameters which represent the bioavailable fraction of the actinide. The effect of americium on survival and moulting was studied at two activity concentrations; the dose rates and absorbed doses under the experimental conditions employed have been estimated. The differences in survival rates between the control and irradiated groups were statistically analyzed and the significant difference at the higher concentration is believed to be due to a synergism between physiological stress and radiotoxicity of americium rather than the chemical toxicity of the element. (orig.)

  19. Solvated Positron Chemistry. Competitive Positron Reactions with Halide Ions in Water

    DEFF Research Database (Denmark)

    Christensen, Palle; Pedersen, Niels Jørgen; Andersen, J. R.;

    1979-01-01

    It is shown by means of the angular correlation technique that the binding of positrons to halides is strongly influenced by solvation effects. For aqueous solutions we find increasing values for the binding energies between the halide and the positron with increasing mass of the halide. This is...

  20. Halide-Dependent Electronic Structure of Organolead Perovskite Materials

    KAUST Repository

    Buin, Andrei

    2015-06-23

    © 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention both at the experimental and theoretical levels. These materials, in particular methylammonium triiodide, are still limited by poor chemical and structural stability under ambient conditions. Today this represents one of the major challenges for polycrystalline perovskite-based photovoltaic technology. In addition to this, the performance of perovskite-based devices is degraded by deep localized states, or traps. To achieve better-performing devices, it is necessary to understand the nature of these states and the mechanisms that lead to their formation. Here we show that the major sources of deep traps in the different halide systems have different origin and character. Halide vacancies are shallow donors in I-based perovskites, whereas they evolve into a major source of traps in Cl-based perovskites. Lead interstitials, which can form lead dimers, are the dominant source of defects in Br-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability in relation to the reaction enthalpies of mixtures of bulk precursors with respect to final perovskite product. Methylammonium lead triiodide is characterized by the lowest reaction enthalpy, explaining its low stability. At the opposite end, the highest stability was found for the methylammonium lead trichloride, also consistent with our experimental findings which show no observable structural variations over an extended period of time.

  1. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    Science.gov (United States)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  2. Thallous and cesium halide materials for use in cryogenic applications

    International Nuclear Information System (INIS)

    Certain thallous and cesium halides, either used alone or in combination with other ceramic materials, are provided in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous and cesium halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated or extruded onto substrates or wires. (author)

  3. About the reaction between uranium-americium mixed oxides and sodium

    International Nuclear Information System (INIS)

    The recycling and fission of the highly toxic minor actinides neptunium and americium is only possible in a liquid metal cooled fast breeder reactor, for nuclear physical reasons. The present work is part of a research program dealing with the fuel-coolant interaction. Fuel pellets with equal parts of americium and uranium and varying oxygen-metal ratio were investigated. A behaviour comparable to that of uranium-plutonium mixed oxides was suggested as a first approach. The reaction of sodium with (U0.5Am0.5)O2-x results in a complete desintegration of the sintered pellet whereas (U, Pu)O2-x pellets show a small increase in volume. A first explanation of the strong reaction of uranium-americium mixed oxides compared to (U, Pu)O2-x or (U, Np)O2-x could be provided by the less negative oxygen potential of the former. Ternary and polynary oxides which are possible products of the fuel-coolant reaction were prepared and characterised by X-ray diffraction. Their oxygen potentials were measured using a solid state e.m.f. cell. Neither Na2AmO3 nor Na3AmO4 can coexist with sodium metal. The measured ΔGO2 values of the Am(IV) and Am (V)-compounds are much higher than those of the sodium uranates(VI) or sodium neptunates(VI). Only Na2O seems to be likely as product of the fuel-coolant interactions. It could be determined in reacted samples by X-ray diffraction. The relatively high oxygen potentials of (U0.5Am0.5)O2-x that are responsible for the reaction could be explained by a binding model which is based on an americium valency state of + 3 and U5+. The existence of both valency states could be proved by XPS measurements. Due to the similar behaviour of neptunium and uranium the problems that are expected for the recycling of Np are much smaller than for americium

  4. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    Science.gov (United States)

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  5. Method for calcining nuclear waste solutions containing zirconium and halides

    Science.gov (United States)

    Newby, Billie J.

    1979-01-01

    A reduction in the quantity of gelatinous solids which are formed in aqueous zirconium-fluoride nuclear reprocessing waste solutions by calcium nitrate added to suppress halide volatility during calcination of the solution while further suppressing chloride volatility is achieved by increasing the aluminum to fluoride mole ratio in the waste solution prior to adding the calcium nitrate.

  6. Kinetic Studies of the Solvolysis of Two Organic Halides

    Science.gov (United States)

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  7. On the Boiling Points of the Alkyl Halides.

    Science.gov (United States)

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  8. A new mechanism for radiation damage processes in alkali halides

    NARCIS (Netherlands)

    Dubinko, V.I.; Turkin, A.A.; Vainshtein, D.I.; Hartog, H.W. den

    1999-01-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution o

  9. Halide glass containing trivalent uranium ions and its fabrication process

    International Nuclear Information System (INIS)

    This halide glass, showing an optical attenuation -1 in the near infrared from 2.2 to 304 micrometers, is prepared with a glass containing uranium ions as U4+ and/or U5+ reduced by ionizing radiations in U3+. Application is made to the fabrication of optical fibers and lasers doped with trivalent uranium

  10. Theory of the late stage of radiolysis of alkali halides

    NARCIS (Netherlands)

    Dubinko, V.I.; Turkin, A.A.; Vainshtein, D.I.; Hartog, H.W. den

    2000-01-01

    Recent results on heavily irradiated natural and synthetic NaCl crystals give evidence for the formation of large vacancy voids, which were not addressed by the conventional Jain-Lidiard model of radiation damage ill alkali halides. This model was constructed to describe metal colloids and dislocati

  11. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    Science.gov (United States)

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  12. Americium(3) coordination chemistry: An unexplored diversity of structure and bonding

    Energy Technology Data Exchange (ETDEWEB)

    Fedosseev, A.M.; Grigoriev, M.S.; Budantseva, N.A. [A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation); Guillaumont, D.; Den Auwer, Ch.; Moisy, Ph. [CEA Marcoule, Nuclear Energy Division, RadioChemistry and Processes Department, 30 (France); Le Naour, C.; Simoni, E. [CNRS, University Paris-11 Orsay, IPN, 91 - Orsay (France)

    2010-06-15

    The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic groups, namely the amino-tri-acetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH{sub 3}){sub 6}][M(NTA){sub 2}(H{sub 2}O)].8H{sub 2}O with M Nd, Yb and Am, and [Co(NH{sub 3}){sub 6}]{sub 2}K[M{sub 3}(Cit){sub 4}(H{sub 2}O){sub 3}].18H{sub 2}O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents. (authors)

  13. Americium(3) coordination chemistry: An unexplored diversity of structure and bonding

    International Nuclear Information System (INIS)

    The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic groups, namely the amino-tri-acetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH3)6][M(NTA)2(H2O)].8H2O with M Nd, Yb and Am, and [Co(NH3)6]2K[M3(Cit)4(H2O)3].18H2O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents. (authors)

  14. Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola.

    Science.gov (United States)

    Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo; Moisy, Philippe; Tribalat, Marie-Aude; Oberhaensli, François R; Dechraoui Bottein, Marie Yasmine; Thomas, Olivier P; Monfort, Marguerite; Moulin, Christophe; Den Auwer, Christophe

    2015-12-21

    The fate of radionuclides in the environment is a cause of great concern for modern society, seen especially in 2011 after the Fukushima accident. Among the environmental compartments, seawater covers most of the earth's surface and may be directly or indirectly impacted. The interaction between radionuclides and the marine compartment is therefore essential for better understanding the transfer mechanisms from the hydrosphere to the biosphere. This information allows for the evaluation of the impact on humans via our interaction with the biotope that has been largely undocumented up to now. In this report, we attempt to make a link between the speciation of heavy elements in natural seawater and their uptake by a model marine organism. More specifically, because the interaction of actinides with marine invertebrates has been poorly studied, the accumulation in a representative member of the Mediterranean coralligenous habitat, the sponge Aplysina cavernicola, was investigated and its uptake curve exposed to a radiotracer (241)Am was estimated using a high-purity Ge gamma spectrometer. But in order to go beyond the phenomenological accumulation rate, the speciation of americium(III) in seawater must be assessed. The speciation of (241)Am (and natural europium as its chemically stable surrogate) in seawater was determined using a combination of different techniques: Time-Resolved Laser-Induced Fluorescence (TRLIF), Extended X-ray Absorption Fine Structure (EXAFS) at the LIII edge, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and Scanning Electron Microscopy (SEM) and the resulting data were compared with the speciation modeling. In seawater, the americium(III) complex (as well as the corresponding europium complex, although with conformational differences) was identified as a ternary sodium biscarbonato complex, whose formula can be tentatively written as NaAm(CO3)2·nH2O. It is therefore this chemical form of americium that is

  15. Fabrication of uranium–americium mixed oxide pellet from microsphere precursors: Application of CRMP process

    Energy Technology Data Exchange (ETDEWEB)

    Remy, E. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Picart, S., E-mail: sebastien.picart@cea.fr [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Delahaye, T. [Fuel Cycle Technology Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Jobelin, I. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Lebreton, F.; Horlait, D. [Fuel Cycle Technology Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Bisel, I. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Blanchart, P. [Heterogeneous Materials Research Group, Centre Européen de la Céramique, F-87068 Limoges (France); Ayral, A. [Institut Européen des Membranes, CNRS-ENSCM-UM2, CC47, University Montpellier 2, F-34095 Montpellier cedex 5 (France)

    2014-10-15

    Highlights: • Dust free process for (U,Am)O{sub 2} transmutation target fabrication. • Synthesis of U{sub 0.9}Am{sub 0.1}O{sub 2} mixed oxide microspheres from ion exchange resin. • Fabrication of dense U{sub 0.9}Am{sub 0.1}O{sub 2} pellet with 95% TD from mixed oxide microspheres. - Abstract: Mixed uranium–americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Recently, several processes have been developed in order to validate fabrication flowchart in terms of material specifications such as density and homogeneity but also to suggest simplifications for lowering industrial costs and hazards linked to dust generation of highly contaminating and irradiating compounds. This study deals with the application of an innovative route using mixed oxide microspheres obtained from metal loaded resin bead calcination, called Calcined Resin Microsphere Pelletization (CRMP). The synthesis of mixed oxide microsphere precursor of U{sub 0.9}Am{sub 0.1}O{sub 2±δ} is described as well as its characterisation. The use of this free-flowing precursor allows the pressing and sintering of one pellet of U{sub 0.9}Am{sub 0.1}O{sub 2±δ}. The ceramic obtained was characterised and results showed that its microstructure is dense and homogeneous and its density attains 95% of the theoretical density. This study validates the scientific feasibility of the CRMP process applied to the fabrication of uranium and americium-containing materials.

  16. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    International Nuclear Information System (INIS)

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg−1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (∼0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13− coordination environment (e.g. >90%) and no (III XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO2 matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am3+ face an AmO813− coordination environment in the (Pu,U)O2 matrix. • The americium dioxide is reduced by the uranium dioxide matrix

  17. Recovery of Americium-241 from lightning rod by the method of chemical treatment

    International Nuclear Information System (INIS)

    About 95% of the lightning rods installed in the Peruvian territory have set in their structures, pose small amounts of radioactive sources such as Americium-241 (241Am), fewer and Radium 226 (226Ra) these are alpha emitters and have a half life of 432 years and 1600 years respectively. In this paper describes the recovery of radioactive sources of 241Am radioactive lightning rods using the conventional chemical treatment method using agents and acids to break down the slides. The 241Am recovered was as excitation source and alpha particle generator for analysing samples by X Ray Fluorescence, for fixing the stainless steel 241Am technique was used electrodeposition. (author)

  18. Report of scouting study on precipitation of strontium, plutonium, and americium from Hanford complexant concentrate waste

    International Nuclear Information System (INIS)

    A laboratory scouting test was conducted of precipitation methods for reducing the solubility of radionuclides in complexant concentrate (CC) waste solution. The results show that addition of strontium nitrate solution is effective in reducing the liquid phase activity of 90Sr (Strontium) in CC waste from tank 107-AN by 94% when the total strontium concentration is adjusted to 0.1 M. Addition of ferric nitrate solution effective in reducing the 241Am (Americium) activity in CC waste by 96% under the conditions described in the report. Ferric nitrate was also marginally effective in reducing the solubility of 239/240Pu (Plutonium) in CC waste

  19. Plutonium and americium in arctic waters, the North Sea and Scottish and Irish coastal zones

    DEFF Research Database (Denmark)

    Hallstadius, L.; Aarkrog, Asker; Dahlgaard, Henning;

    1986-01-01

    Plutonium and americium have been measured in surface waters of the Greenland and Barents Seas and in the northern North Sea from 1980 through 1984. Measurements in water and biota, Fucus, Mytilus and Patella, were carried out in North-English and Scottish waters in 1982 and Fucus samples were...... plutonium from the latter to Spitsbergen waters. Fallout plutonium in Arctic waters has a residence time of the order of several years, while for Pu from Sellafield we estimate mean residence times of 11–15 months in Scottish waters and, tentatively, 1·5-3 y during transport from the North Channel (north...

  20. Americium and curium heterogeneous transmutation in moderated S/ A in the framework of CNE scenarios studies

    International Nuclear Information System (INIS)

    This paper presents the transmutation of Americium and Curium in a heterogeneous mode in the framework of the 1991 French Law concerning waste management. Two scenarios with moderated targets are presented: a 100% frit reactor (EFR) scenario multi-recycling Pu+Np with targets of Am+Cm placed in core and a mixed PWR (UOX fuel) and fast reactor (50% of EFR) multi-recycling Pu+Np and containing targets in core and in the blanket region. The design of the target is based on classical fast fuel S/A technology (pins, spacer wires,...) and should reach the goal of 90% fission rate. (authors)

  1. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids.

    Science.gov (United States)

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William

    2015-10-01

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater-bentonite-fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L(-1)) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10(-10) M (241)Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k(f)) of 0.01-0.02 h(-1). Am recoveries in each column were 55-60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h(-1) in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. Our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because

  2. Purification of used scintillation liquids containing the alpha emitters americium and plutonium

    International Nuclear Information System (INIS)

    In Sweden, alpha radioactive waste liquids with an activity over some kBq per waste container cannot be sent for final storage. Therefore, in this work, a method for a purification of alpha active scintillation cocktails was developed. Until today (March, 2013) more than 20 L of scintillation liquids have successfully been purified from americium and plutonium. The products of the process are a solid fraction that can be sent to final storage and a practically non-radioactive liquid fraction that can be sent to municipal incineration. (author)

  3. Comparison of acid leachate and fusion methods to determine plutonium and americium in environmental samples

    International Nuclear Information System (INIS)

    The Analytical Chemistry Laboratory at Argonne National Laboratory performs radiochemical analyses for a wide variety of sites within the Department of Energy complex. Since the chemical history of the samples may vary drastically from site to site, the effectiveness of any analytical technique may also vary. This study compares a potassium fluoride-pyrosulfate fusion technique with an acid leachate method. Both normal and high-fired soils and vegetation samples were analyzed for both americium and plutonium. Results show both methods work well, except for plutonium in high-fired soils. Here the fusion method provides higher accuracy

  4. Plutonium and americium in arctic waters, the North Sea and Scottish and Irish coastal zones

    DEFF Research Database (Denmark)

    Hallstadius, L.; Aarkrog, Asker; Dahlgaard, Henning; Holm, E.; Boelskifte, S.; Duniec, S.; Persson, B.

    1986-01-01

    Plutonium and americium have been measured in surface waters of the Greenland and Barents Seas and in the northern North Sea from 1980 through 1984. Measurements in water and biota, Fucus, Mytilus and Patella, were carried out in North-English and Scottish waters in 1982 and Fucus samples were...... plutonium from the latter to Spitsbergen waters. Fallout plutonium in Arctic waters has a residence time of the order of several years, while for Pu from Sellafield we estimate mean residence times of 11–15 months in Scottish waters and, tentatively, 1·5-3 y during transport from the North Channel (north of...

  5. Influence of biofilms on migration of uranium, americium and europium in the environment

    International Nuclear Information System (INIS)

    The report on the influence of biofilms on migration of uranium, americium and europium in the environment deals with the contamination problems of uranium mines such as SDAG WISMUT in Saxonia and Thuringia. In mine waters microorganisms form a complex microbiological biocoenosis in spite of low pH values and high heavy metal concentrations including high uranium concentrations. The analyses used microbiological methods like confocal laser scanning microscopy and molecular-biological techniques. The interactions of microorganism with fluorescent radioactive heavy metal ions were performed with TRLFS (time resolved laser-induced fluorescence spectroscopy).

  6. Numerical simulation for concentration profiles of americium and lanthanides in the CMPO-TBP solvent extraction system

    International Nuclear Information System (INIS)

    A numerical simulation code is developed to predict the extraction behavior of americium and lanthanides in the TRUEX (TRansUranium EXtraction)process. This code gives the concentration profiles of the components at steady state. The stage efficiency is included in this code as a parameter in order to simulate the extraction behavior of the components accurately. Concentration profiles of americium and typical lanthanides in some counter current experiments are calculated by means of the present code. The calculated concentration profiles are compared with the experimental results. The efficiency value for the mixer-settlers, which gives good agreement between the calculated and the experimental profiles, is evaluated. (author)

  7. Numerical simulation for concentration profiles of americium and lanthanides in the CMPO-TBP solvent extraction system

    International Nuclear Information System (INIS)

    A numerical simulation code for the TRUEX (TRansUranium EXtraction) process is developed to predict the extraction behavior of americium and lanthanides. This code gives the concentrations of the components at the steady state of the TRUEX process. The stage efficiency is applied to this code in order to simulate the extraction behavior of the components accurately. Concentration profiles of americium and typical lanthanides in some counter current experiments are calculated by means of the present code. The calculated profiles are compared with the experimental ones. The efficiency value for the mixer-settlers, which gives the best agreement between the two profiles, is investigated

  8. Study of the extraction and the purification of americium and trivalent actinides contained in effluents with supported liquid membranes

    International Nuclear Information System (INIS)

    The supported liquid membrane technique is studied and developed for americium recovery from uranium or plutonium matrices and decontamination of liquid radioactive wastes. First tests on uranium-nickel solutions with a flat membrane showed the easiness of the operation and the efficiency of the process. Acid-resistant (10 N), interchangeable elements with hollow fibers, are developed and also a computerized automatic device. The different tests on americium solutions demonstrate the feasibility and the reliability of the system. Influence of various parameters on transfer kinetics is investigated

  9. Experimental and in situ investigations on americium, curium and plutonium behaviour in marine benthic species: transfer from water or sediments

    International Nuclear Information System (INIS)

    The tranfer of transuranic elements -americium, curium and plutonium- from the sediments containing them to some marine benthic species (endofauna and epifauna) was studied with a twofold approach - laboratory and in-situ investigation. The experimental investigations, divided into three parts, made it possible to specify concentration factors (F.C.), transfer factors (F.T.) and to understand the process involved for 5 benthic species. The result were refined by an in-situ study that brought new data on the marine distribution of the transuranic elements released by the La Hague plant. Finally, the localization of americium and plutonium in the tissues and cells of these species was determined by autoradiography

  10. Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

    Science.gov (United States)

    Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

    1982-01-01

    Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

  11. Vitrification of F-area americium/curium: feasibility study and preliminary process recommendation

    International Nuclear Information System (INIS)

    Work was performed to identify a process to vitrify the contents of F- canyon Tank 17.1. Tank 17.1 contains the majority of americium (Am) and curium (Cm) contained in the DOE Complex. Oak Ridge National Laboratory (ORNL) has made a formal request for this material as fuel for production of Cf252 and other transplutonium actinides. The Am and Cm (and associated lanthanide fission products) are currently in nitric acid solution. Transportation of the intensely radioactive Am/Cm in liquid form is not considered possible. As a result, the material will either be solidified and shipped to ORNL or discarded to the Tank Farm. Nuclear Materials Processing Technology (NMPT), therefore, requested Defense Waste Processing Technology (DWPT) to determine if the Tank 17.1 material could be vitrified, and if it was vitrified could the americium and curium be successfully recovered. Research was performed to determine if the Tank 17.1 contents could indeed be mixed with glass formers and vitrified. Additional studies identified critical process parameters such as heat loading, melter requirements, off-gas evolution, etc. Discussions with NMPT personnel were initiated to determine existing facilities where this work could be accomplished safely. A process has been identified which will convert the Am/Cm material into approximately 300kg of glass

  12. Transfer of radiocaesium, plutonium and americium to sheep after ingestion of contaminated soil

    International Nuclear Information System (INIS)

    A dual isotope method has been used to study the transfer of 137Cs, 239/240Pu and 241Am to sheep following ingestion of contaminated soil. Two soils were used; an alluvial gley contaminated by Sellafield discharges, and an organic soil, artificially contaminated in a lysimeter. Values of the true absorption coefficient of radiocaesium of 0.19 +/- 0.03 and 0.03 +/- 0.01 respectively were obtained for these soils. This implies an availability factor for soil-associated radiocaesium of up to about 20 pc compared to radiocaesium ingested in soluble form. The absorption of plutonium and americium was not significantly different for the two soils tested. Absorption of both plutonium and americium was in the range 10-5 - 10-4, with mean values of 7 x 10-5 and 4 x 10-5 obtained respectively. These values imply availability factors of around 10 pc, compared to the value of 5 x 10-4 recommended by ICRP for plutonium ingested in a comparatively available form. These results are compared with estimates of availability made using an in-vitro approach

  13. Transfer of radiocaesium, plutonium and americium to sheep after ingestion of contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Cooke, A.I.; Weekes, T.E.C. [Newcastle upon Tyne Univ. (United Kingdom). Dept. of Biological and Nutritional Sciences; Rimmer, D.L. [Newcastle upon Tyne Univ. (United Kingdom). Dept. of Agricultural and Environmental Science; Green, N.; Wilkins, B.T. [National Radiological Protection Board, Chilton (United Kingdom)

    1997-12-31

    A dual isotope method has been used to study the transfer of {sup 137}Cs, {sup 239/240}Pu and {sup 241}Am to sheep following ingestion of contaminated soil. Two soils were used; an alluvial gley contaminated by Sellafield discharges, and an organic soil, artificially contaminated in a lysimeter. Values of the true absorption coefficient of radiocaesium of 0.19 +/- 0.03 and 0.03 +/- 0.01 respectively were obtained for these soils. This implies an availability factor for soil-associated radiocaesium of up to about 20 pc compared to radiocaesium ingested in soluble form. The absorption of plutonium and americium was not significantly different for the two soils tested. Absorption of both plutonium and americium was in the range 10{sup -5} - 10{sup -4}, with mean values of 7 x 10{sup -5} and 4 x 10{sup -5} obtained respectively. These values imply availability factors of around 10 pc, compared to the value of 5 x 10{sup -4} recommended by ICRP for plutonium ingested in a comparatively available form. These results are compared with estimates of availability made using an in-vitro approach

  14. Americium and europium extraction from carbonate solutions by 1-phenyl-3-methyl-4-benzoylpyrazolone -5

    International Nuclear Information System (INIS)

    Trivalent TPEs and REEs are extractable from carbonate solutions by 1-pheny-3-methyl-4-benzoylpyrazolone-5 (PMBP). The effect of concentration of KHCO3 and K2CO3, extractant, metal, and other factors on the extent of extraction of the elements has been clarified. The kinetics of extraction of the elements from carbonate solutions has been studied. It has been shown that in the KHCO3 concentration range 0.2-2.0 M americium and europium are extracted by PMBP solutions in different diluents with distribution coefficients lying within n x 102-n x 103. From K2CO3 solutions the elements are extracted better by PMBP solutions in methyl isobutyl ketone (MIBK). It has been shown that metal concentration in the range 1x10-5. 5x10-3 g-ion x liter-1 does not affect extraction (log E = 3). Extracts based on PMBP with a metal content higher than 5x10-3g-ion x liter-1 were obtained by absolute concentrating method and were used for the study of 13C NMR spectra. The composition of thecompounds extracted by PMBP from carbonate solutions was determined by 13C NMR spectroscopy and extraction. The conditions of europium and americium reextraction from extracts based on PMBP by complexones, their mixtures with alkalis and other substances were studied. The scopes for using the system PMBP-carbonate solutions to separate and concentrate TPEs and REEs has been examined

  15. Evaluation of americium-241 toxicity influence on the microbial growth of organic wastes

    International Nuclear Information System (INIS)

    Available in abstract form only. Full text of publication follows: Since the licenses for using radioactive sources in radioactive lightning rods were lifted by the Brazilian national nuclear authority, in 1989, the radioactive devices have been replaced by Franklin type and collected as radioactive waste. However, only 20 percent of the estimated total number of installed rods was delivered to Brazilian Nuclear Commission. This situation causes concern, due to, first, the possibility of the rods being disposed as domestic waste, and second, the americium, the most commonly employed radionuclide, is classified as a high-toxicity element. In the present study, Am-241 migration experiments were performed by a lysimeter system, in order to evaluate the risk of contamination caused by radioactive lightning rods disposed as a common solid waste. Besides the risk evaluation, it is important to know the mechanism of the Am-241 release or retention in waste as well as its influence in the waste decomposition processes. Many factors are involved, but microorganisms present in the waste play an important role in its degradation, which control the physical and chemical processes. The objective of this work was to evaluate the Am-241 influence on the microbial population by counting number of cells in lysimeters leachate. Preliminary results suggest that americium may influence significantly the bacteria growth in organic waste, evidenced by culture under aerobiosis and an-aerobiosis and the antimicrobial resistance test. (authors)

  16. Contribution to the prediction of americium, plutonium and neptunium behaviour in the geosphere: chemical data

    International Nuclear Information System (INIS)

    An exhaustive bibliographic review on hydrolysis of americium gives the stability constants, at zero ionic strength. No evidence of Am(OH)4- formation was found by solubility studies up to pH 2 (CO3)3 characterised by its X-ray diffraction pattern is studied at a high ionic strength. All the published results on Am in carbonate media are reinterpreted using these stability constants (Am-OH-CO3 complexes are not needed). No evidence of Am(CO3)45- formation was found by spectrophotometry up to 3M. Literature results are used to determine the formal redox potentials at pH = 9.4 and to calculate the formation constants, at zero ionic strength. The formation of complexes between americium and humic materials (purified fulvic and humic acids) has been studied by a spectrophotometric technique. The results are interpreted by the formation of a 1:1 complexe. Solubility of the solid PuO2(CO3) is measured in bicarbonate media at high ionic strength, to obtain the solubility product and formation constants of the PuO2(CO3)i2-2i complexes

  17. Electrolytic systems and methods for making metal halides and refining metals

    Science.gov (United States)

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  18. Large methyl halide emissions from south Texas salt marshes

    Directory of Open Access Journals (Sweden)

    R. C. Rhew

    2014-06-01

    Full Text Available Coastal salt marshes are natural sources of methyl chloride (CH3Cl and methyl bromide (CH3Br to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  19. Alkali Halide Microstructured Optical Fiber for X-Ray Detection

    Science.gov (United States)

    DeHaven, S. L.; Wincheski, R. A.; Albin, S.

    2014-01-01

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  20. Facile Preparation of Silver Halide Nanoparticles as Visible Light Photocatalysts

    Directory of Open Access Journals (Sweden)

    Linfan Cui

    2015-07-01

    Full Text Available In this study, highly efficient silver halide (AgX-based photocatalysts were successfully fabricated using a facile and template-free direct-precipitation method. AgX nanoparticles, which included silver chloride (AgCl, silver bromide (AgBr and silver iodide (AgI, were synthesized using different potassium halides and silver acetate as reactive sources. The size distribution of the AgX nanopar‐ ticles was determined by the reaction time and ratio of the reagents, which were monitored by UV-vis spectra. The as- prepared AgX nanoparticles exhibited different photoca‐ talytic properties. This shows the differences for the photodegradation of methyl orange and Congo red dyes. In addition, the AgCl nanoparticle-based photocatalyst exhibited the best photocatalytic property among all three types of AgX nanoparticles that are discussed in this study. Therefore, it is a good candidate for removing organic pollutants.

  1. Correlations between entropy and volume of melting in halide salts

    International Nuclear Information System (INIS)

    Melting parameters and transport coefficients in the melt are collated for halides of monovalent, divalent and trivalent metals. A number of systems show a deficit of entropy of melting relative to the linear relationships between entropy change and relative volume change on melting that are found to be approximately obeyed by a majority of halides. These behaviours are discussed on the basis of structural and transport data. The deviating systems are classified into three main classes, namely (i) fast-ion conductors in the high-temperature crystal phase such as AgI, (ii) strongly structured network-like systems such as ZnCl2, and (iii) molecular systems melting into associated molecular liquids such as SbCl3. (author). 35 refs, 1 fig., 3 tabs

  2. Stability diagrams for complexes in molten mixtures of halide salts

    International Nuclear Information System (INIS)

    The stability of local fourfold coordination for divalent and trivalent metal ions in liquid mixtures of polyvalent metal halides and alkali halides is classified by means of structural coordinates obtained from properties of the elements. In parallel with earlier classifications of compound crystal structures and molecular shapes, the elemental properties are taken from first-principles calculations of valence electron orbitals in atoms, in the form of (i) the nodal radii of Andreoni, Baldereschi and Guizzetti or (ii) the pseudo-potential radii of Zunger and Cohen. As a third alternative we also consider a classification based on Pettifor's phenomenological chemical scale of the elements. The alternative structural classification schemes that are developed from these elemental properties are very successful in distinguishing molten mixtures in which the available experimental evidence indicates stability of ''complexes'', i.e. long-lived fourfold coordination of polyvalent metal ions. (author). 55 refs, 3 figs

  3. Alkali halide microstructured optical fiber for X-ray detection

    International Nuclear Information System (INIS)

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed

  4. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    Science.gov (United States)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31Р-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  5. Study of methyl halide fluxes in temperate and tropical ecosystems

    OpenAIRE

    Blei, Emanuel

    2010-01-01

    CH3Br and CH3Cl (methyl halides) are the most abundant natural vectors of bromine and chlorine into the stratosphere and play an important role in stratospheric ozone destruction. The current knowledge of their respective natural sources is incomplete leading to large uncertainties in their global budgets. Beside the issue of quantification, characterisation of possible sources is needed to assist modelling of future environmental change impacts on these sources and hence the s...

  6. Influence of the Print Run on Silver Halide Printing Plates

    Directory of Open Access Journals (Sweden)

    Tomislav Cigula

    2010-09-01

    Full Text Available The most common printing technique today is lithography. The difference between printing and nonprinting areason a printing plate is accomplished by opposite physical and chemical properties of those areas (MacPhee, 1998.The printing areas are made of photoactive layer that attracts oil and chemical substances with oil solvent – printinginks. The nonprinting areas are made of aluminium-oxide which attracts water based substances – the fountainsolution.There are many of various types of photoactive layer which are used for production of offset printing plates, amongothers is silver halide layer. The usage of the silver halide technology in the graphic reproduction is not a novelty.The filmmaking phase is based on the usage of the silver halide as the photographically active ingredient, for instance,AgBr (silver bromide. The new, digital plate making technology (Computer to Plate, CtP eliminates thefilmmaking phase and therefore enables control of the printing plate’s exposure made by computer. CtP technologyeliminates the filmmaking phase, but it also results with the reduction of needed material quantities and requiredtime for the production (Limburg, 1994; Seydel, 1996.In this paper the basis of the graphic reproduction by using the silver halide digital printing plates was described.The changes of the AgX copying layer and the surface of the aluminium base in the printing process have beenobserved. The surface characteristics were determined by measuring the relevant surface roughness parameters. Inaddition, measurements of coverage values on the prints, detailed at smaller print run, were conducted.Results showed that surface changes on the printing plate are changing during printing process and that thesechanges influence transfer of the printing ink on the printing substrate. These measurements proved to be of greatinterest in the graphic reproduction as they enable us to determine consistency of the printing plates during theprinting

  7. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    Science.gov (United States)

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  8. Semiphysical development of holograms recorded in silver halide emulsions

    Science.gov (United States)

    Banyasz, Istvan; Belendez, Augusto; Pascual, Inmaculada V.; Fimia, Antonio

    2000-10-01

    In the course of experiments on measurement of the effects of processing on nonlinear characteristics of silver halide holograms recorded in Agfa-gevaert 8E75HD emulsions we found that, under certain circumstances, the AAC developer acted as a semi-physical developer instead of the normal chemical developing action. The developed and fixed holograms were of low optical density (carbonate of purest grade with that of for analysis grade of the same company.

  9. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    Directory of Open Access Journals (Sweden)

    Bijay Shrestha

    2015-12-01

    Full Text Available We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1 as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields.

  10. Effects of Halides on Plasmid-Mediated Silver Resistance in Escherichia coli

    OpenAIRE

    Gupta, Amit; Maynes, Maria; Silver, Simon

    1998-01-01

    Silver resistance of sensitive Escherichia coli J53 and resistance plasmid-containing J53(pMG101) was affected by halides in the growth medium. The effects of halides on Ag+ resistance were measured with AgNO3 and silver sulfadiazine, both on agar and in liquid. Low concentrations of chloride made the differences in MICs between sensitive and resistant strains larger. High concentrations of halides increased the sensitivities of both strains to Ag+.

  11. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    OpenAIRE

    Weix, Daniel J.

    2015-01-01

    Conspectus Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C–H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, th...

  12. Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

    OpenAIRE

    Sourish Chatterjee

    2013-01-01

    Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of...

  13. Environmental controls over methyl halide emissions from rice paddies

    Science.gov (United States)

    Redeker, K. R.; Cicerone, R. J.

    2004-03-01

    This paper examines primary controlling factors that affect methyl halide emissions from rice paddy ecosystems. Observations of four cultivars under multiple growth conditions during studies in commercial fields and the University of California, Irvine, greenhouse lead to the conclusion that daily emissions of methyl halides are primarily determined by the growth stage of the rice plant, with the exception that methyl chloride emissions show no clear seasonal pattern. Methyl chloride emissions appear to be more from the paddy water and/or soil as opposed to the plants; however, in soils with high chloride content, these emissions appear to peak during the reproductive phase. Strong secondary influences include air temperature, soil halide concentration, and soil pore water saturation. The cultivars studied had statistically separate seasonally integrated emissions. Irradiant light and aboveground biomass appear to have little effect on emissions. Emissions of methyl chloride, methyl bromide, and methyl iodide are estimated to be 3.5, 2.3, and 48 mg/m2/yr, or 5.3, 3.5, and 72 Gg/yr, from rice paddies globally.

  14. Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets.

    Science.gov (United States)

    Sichert, Jasmina A; Tong, Yu; Mutz, Niklas; Vollmer, Mathias; Fischer, Stefan; Milowska, Karolina Z; García Cortadella, Ramon; Nickel, Bert; Cardenas-Daw, Carlos; Stolarczyk, Jacek K; Urban, Alexander S; Feldmann, Jochen

    2015-10-14

    Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites. PMID:26327242

  15. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    Science.gov (United States)

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  16. Systematic analysis of the unique band gap modulation of mixed halide perovskites.

    Science.gov (United States)

    Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

    2016-02-14

    Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition. PMID:26791587

  17. EURADOS intercomparison on measurements and Monte Carlo modelling for the assessment of Americium in a USTUR leg phantom

    International Nuclear Information System (INIS)

    A collaboration of the EURADOS working group on 'Internal Dosimetry' and the United States Transuranium and Uranium Registries (USTUR) has taken place to carry out an intercomparison on measurements and Monte Carlo modelling determining americium deposited in the bone of a USTUR leg phantom. Preliminary results and conclusions of this intercomparison exercise are presented here. (authors)

  18. An economic analysis of a light and heavy water moderated reactor synergy: burning americium using recycled uranium

    International Nuclear Information System (INIS)

    An economic analysis is presented for a proposed synergistic system between 2 nuclear utilities, one operating light water reactors (LWR) and another running a fleet of heavy water moderated reactors (HWR). Americium is partitioned from LWR spent nuclear fuel (SNF) to be transmuted in HWRs, with a consequent averted disposal cost to the LWR operator. In return, reprocessed uranium (RU) is supplied to the HWRs in sufficient quantities to support their operation both as power generators and americium burners. Two simplifying assumptions have been made. First, the economic value of RU is a linear function of the cost of fresh natural uranium (NU), and secondly, plutonium recycling for a third utility running a mixed oxide (MOX) fuelled reactor fleet has been already taking place, so that the extra cost of americium recycling is manageable. We conclude that, in order for this scenario to be economically attractive to the LWR operator, the averted disposal cost due to partitioning americium from LWR spent fuel must exceed 214 dollars per kg, comparable to estimates of the permanent disposal cost of the high level waste (HLW) from reprocessing spent LWR fuel. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, C H; Barney, G S

    1983-03-01

    To judge the feasibility of continued storage of high-level waste solutions in existing tanks, effects of chemical waste components on the sorption of hazardous radioelements were determined. Experiments identified the effects of 12 Hanford high-level waste-solution components on the sorption of cobalt, strontium, neptunium, plutonium, and americium on 3 Hanford 200 Area sediments. The degree of sorption of strontium, neptunium, plutonium, and americium on two Hanford sediments was then quantified in terms of the concentrations of the influential waste components. Preliminary information on the influence of the waste components on radioelement solubility was gathered. Of the 12 Hanford waste-solution components studied, the most influential on radioelement sorption were NaOH, NaAlO/sub 2/, HEDTA, and EDTA. The chelating complexants, HEDTA and EDTA, generally decreased sorption by complexation of the radioelement metal ions. The components NaOH and NaAlO/sub 2/ decreased neptunium and plutonium sorption and increased cobalt sorption. Americium sorption was increased by NaOH. The three Hanford sediments' radioelement sorption behaviors were similar, implying that their sorption reactions were also similar. Sorption prediction equations were generated for strontium, neptunium, plutonium, and americium sorption reactions on two Hanford sediments. The equations yielded values of the distribution coefficient, K/sub d/, as quadratic functions of waste-component concentrations and showed that postulated radioelement migration rates through Hanford sediment could change by factors of 13 to 40 by changes in Hanford waste composition.

  20. Effects of Hanford high-level waste components on sorption of cobalt, strontium, neptunium, plutonium, and americium on Hanford sediments

    International Nuclear Information System (INIS)

    To judge the feasibility of continued storage of high-level waste solutions in existing tanks, effects of chemical waste components on the sorption of hazardous radioelements were determined. Experiments identified the effects of 12 Hanford high-level waste-solution components on the sorption of cobalt, strontium, neptunium, plutonium, and americium on 3 Hanford 200 Area sediments. The degree of sorption of strontium, neptunium, plutonium, and americium on two Hanford sediments was then quantified in terms of the concentrations of the influential waste components. Preliminary information on the influence of the waste components on radioelement solubility was gathered. Of the 12 Hanford waste-solution components studied, the most influential on radioelement sorption were NaOH, NaAlO2, HEDTA, and EDTA. The chelating complexants, HEDTA and EDTA, generally decreased sorption by complexation of the radioelement metal ions. The components NaOH and NaAlO2 decreased neptunium and plutonium sorption and increased cobalt sorption. Americium sorption was increased by NaOH. The three Hanford sediments' radioelement sorption behaviors were similar, implying that their sorption reactions were also similar. Sorption prediction equations were generated for strontium, neptunium, plutonium, and americium sorption reactions on two Hanford sediments. The equations yielded values of the distribution coefficient, K/sub d/, as quadratic functions of waste-component concentrations and showed that postulated radioelement migration rates through Hanford sediment could change by factors of 13 to 40 by changes in Hanford waste composition

  1. Anomalous aryl strengthening of americium and europium complexes during extraction by alkylenediphosphine dioxides from perchloric acid media

    International Nuclear Information System (INIS)

    Extraction of americium and europium from perchlorate environments by solutions of three types of methylenediphosphine dioxides, namely (C6H5)P(O)(CH2)sub(n)(O)P(C6H5)2, (C6H5)2P(O)CH2(O)P(C8H17)2 and (C8H17)2P(O)(CH2)sub(n)(O)P(C8H17)2 has been studied (n is 1 or 2 ) The diluents used have been dichlorethane and chloroform. In perchlorate environments the distribuiton coefficients of americium and europium have proved to be by about 3 orders of magnitude higher than in nitric acid environments, i.e. in perchlorate media the complexes are far more stable. Separation coefficients of americium and REE in perchloric acid soutions are much higher than in nitrate environments. The average value of Am/Eu separation coeffecient at 1-5 M acidity was about 6 (with dichlorethane as diluent) or about 7 (with chloroform as diluent). The complexes essentially exist as trisolvated. Americium complexes display anomalous stability increase upon being diluted: by about 2 orders of magnitude with dichlorethane and by up to 3 orders of magnitude with chloroform used as diluent

  2. Investigations of neutron characteristics for salt blanket models; integral fission cross section measurements of neptunium, plutonium, americium and curium isotopes

    International Nuclear Information System (INIS)

    Neutron characteristics of salt blanket micromodels containing eutectic mixtures of sodium, zirconium, and uranium fluorides were measured on FKBN-2M, BIGR and MAKET facilities. The effective fission cross sections of neptunium, plutonium, americium, and curium isotopes were measured on the neutron spectra formed by micromodels. (author)

  3. The distribution of plutonium-239 and americium-241 in the Syrian hamster following its intravenous administration as citrate

    International Nuclear Information System (INIS)

    Actinide distribution in various tissues and the skeleton of hamsters by liquid scintillation counting or isotope dilution. For plutonium 57% of activity was concentrated in the skeleton and more than 90% in the liver and skeleton after seven days. For americium the liver retained more than 50% of total activity and 25% was excreted in urine within seven days. (U.K.)

  4. Application of ion-exchange chromatography to eliminate the curium from americium by his determination by the method of liquid scintillation spectrometry

    International Nuclear Information System (INIS)

    The aim of this work is to eliminate curium in determining of americium by the method of liquid scintillation spectrometry. The paper introduces a method that has been done to eliminate curium from americium by determining of americium with liquid scintillation spectrometry method. In the research we used ion-exchange chromatography and ion-exchange sorbents DOWEX. We also observed the effect of geometry organization of column on the separation course. Resources for alpha spectrometry were prepared by micro-precipitation with neodymium chloride. High radiochemical yields were achieved, but separation did not take place according to a pre-separation scheme. (authors)

  5. Purification of scintillation cocktails containing the alpha emitters americium and plutonium

    International Nuclear Information System (INIS)

    One efficient way of measuring alpha emitters is by the usage of liquid scintillation counting (LSC). A liquid sample is placed in a vial containing a scintillation cocktail. The alpha particles excite electrons in the surrounding liquid, and when they are de-excited photons are emitted. The photons are detected and the activity can be quantified. LSC has a high efficiency for alpha radiation and is therefore a fast and easy way for measuring alpha emitting samples. One drawback is that it does not differentiate very well between alpha energies; measurements of for example curium and plutonium simultaneously are impossible and demand other techniques. Another drawback is the production of a liquid alpha active waste. In Sweden alpha radioactive waste liquids with an activity over some kBq per waste container cannot be sent for final storage. If, however, the activity of the liquids could be reduced by precipitation of the actinides, it would be possible to send away the liquid samples to municipal incineration. In this work a method for a purification of alpha active scintillation cocktails was developed. The method was first tried on a lab scale, and then scaled up. Until today (March, 2013) more than 20 liters of scintillation liquids have successfully been purified from americium and plutonium at Chalmers University of Technology in Sweden. The four scintillation cocktails used were Emulsifier Safe®, Hionic-Fluor®, Ultima Gold AB® and Ultima Gold XR®. The scintillation cocktails could all be purified from americium with higher yield than 95%. The yield was kept when the liquids were mixed. Also plutonium could be precipitated with a yield over 95% in all cocktails except in Hionic-Fluor® (>55%). However, that liquid in particular could be purified (>95%) by mixing it with the three other cocktails. Up-scaling was performed to a batch size of 6-8 L of scintillation cocktail. In neither the americium nor the plutonium system, adverse effects of increasing the

  6. Involvement of S-adenosylmethionine-dependent halide/thiol methyltransferase (HTMT) in methyl halide emissions from agricultural plants: isolation and characterization of an HTMT-coding gene from Raphanus sativus (daikon radish)

    OpenAIRE

    Taniguchi Tomokazu; Negishi Takashi; Matsuda Michiko; Toda Hiroshi; Itoh Nobuya; Ohsawa Noboru

    2009-01-01

    Abstract Background Biogenic emissions of methyl halides (CH3Cl, CH3Br and CH3I) are the major source of these compounds in the atmosphere; however, there are few reports about the halide profiles and strengths of these emissions. Halide ion methyltransferase (HMT) and halide/thiol methyltransferase (HTMT) enzymes concerning these emissions have been purified and characterized from several organisms including marine algae, fungi, and higher plants; however, the correlation between emission pr...

  7. Seasonal variations in halides in marine brown algae from Porbandar and Okha coasts (NW coast of India)

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, Ch.K.; Singbal, S.Y.S.

    Seasonal variation of halides and their ratios were estimated in three brown algae, namely Cystoseira indica, Sargassum tenerrimum) and S. johnstonii from Porbandar and Okha Coasts. Halides were found to be higher in early stages of growth. The Br...

  8. Imitators of plutonium and americium in a mixed uranium- plutonium nitride fuel

    Science.gov (United States)

    Nikitin, S. N.; Shornikov, D. P.; Tarasov, B. A.; Baranov, V. G.; Burlakova, M. A.

    2016-04-01

    Uranium nitride and mix uranium nitride (U-Pu)N is most popular nuclear fuel for Russian Fast Breeder Reactor. The works in hot cells associated with the radiation exposure of personnel and methodological difficulties. To know the main physical-chemical properties of uranium-plutonium nitride it necessary research to hot cells. In this paper, based on an assessment of physicochemical and thermodynamic properties of selected simulators Pu and Am. Analogues of Pu is are Ce and Y, and analogues Am - Dy. The technique of obtaining a model nitride fuel based on lanthanides nitrides and UN. Hydrogenation-dehydrogenation- nitration method of derived powders nitrides uranium, cerium, yttrium and dysprosium, held their mixing, pressing and sintering, the samples obtained model nitride fuel with plutonium and americium imitation. According to the results of structural studies have shown that all the samples are solid solution nitrides rare earth (REE) elements in UN.

  9. Recovery of plutonium and americium from chloride salt wastes by solvent extraction

    International Nuclear Information System (INIS)

    Plutonium and americium can be recovered from aqueous waste solutions containing a mixture of HCl and chloride salt wastes by the coupling of two solvent extraction systems: tributyl phosphate (TBP) in tetrachloroethylene (TCE) and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in TCE. In the flowsheet developed, the salt wastes are dissolved in HCl, the Pu(III) is oxidized to the IV state with NaClO2 and recovered in the TBP-TCE cycle, and the Am is then removed from the resultant raffinate by the CMPO-TCE cycle. The consequences of the feed solution composition and extraction behavior of these species on the process flowsheet design, the Pu-product purity, and the decontamination of the aqueous raffinate from transuranic elements are discussed. 16 refs., 6 figs

  10. Recovery of plutonium and americium from chloride salt wastes by solvent extraction

    International Nuclear Information System (INIS)

    Plutonium and americium can be recovered from aqueous waste solutions containing a mixture of HCl and chloride salt wastes by the coupling of two solvent extraction systems: tributyl phosphate (TBP) in tetrachloroethylene (TCE) and octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) in TCE. In the flowsheet developed, the salt wastes are dissolved in HCl, the Pu(III) is oxidized to the IV state with NaClO2 and recovered in the TBP-TCE cycle, and the Am is then removed from the resultant raffinate by the CMPO-TCE cycle. The consequences of the feed solution composition and extraction behavior of these species on the process flowsheet design, the Pu-product purity, and the decontamination of the aqueous raffinate from transuranic elements are discussed

  11. The uptake of plutonium-239, 240, americium-241, strontium-90 into plants

    International Nuclear Information System (INIS)

    This report describes the results of measurements on the uptake of plutonium, americium, strontium-90 and caesium-137 into peas, beet, oats, sweet corn, tomatoes and vegetable marrow grown in tubs containing radioactively-contaminated silts. The silts had been taken from an area of West Cumbria commonly referred to as the Ravenglass estuary. The experiments are categorised as being carried out under non-standard conditions because of the manner in which the radioactivity came to be incorporated into the growth medium. The growth medium was representative of conditions which could arise when the estuarine silt moves inland under the influence of wind and tide and mixes with the adjacent farm land. The silt had been contaminated by radioactive effluents from the nuclear fuels reprocessing plant at Sellafield and this contamination had been brought about by natural means. (Auth.)

  12. Mutual separation of americium(III) and europium(III) using glycolamic acid and thioglycolamic acid

    International Nuclear Information System (INIS)

    The extractants, bis(2-ethylhexyl)diglycolamicacid (HDEHDGA) and bis(2-ethylhexy)thiodiglycolamic acid (HDEHSDGA) were synthesized and characterized by 1H and 13C NMR, mass and IR spectroscopy. The extraction behaviour of (152+154)Eu(III) and 241Am(III) from nitric acid medium by a solution of HDEHDGA (or HDEHSDGA) in n-dodecane (n-DD) was studied for the mutual separation of actinides and lanthanides. The effect of various parameters such as the pH, concentrations of HDEHDGA, HDEHSDGA, sodium nitrate, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) and diethylenetriaminepentaacetic acid (DTPA) on the separation factor (SF) of americium(III) over europium(III) and vice versa was studied, and the conditions needed for the preferential separation were optimised. The results show that HDEHDGA exhibits higher extraction for (152+154)Eu(III) and HDEHSDGA shows the superior selectivity for 241Am(III). (orig.)

  13. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids

    International Nuclear Information System (INIS)

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L−1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10−10 M 241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (kf) of 0.01–0.02 h−1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h−1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. Our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance

  14. Comparative study of plutonium and americium bioaccumulation from two marine sediments contaminated in the natural environment

    International Nuclear Information System (INIS)

    Plutonium and americium sediment-animal transfer was studied under controlled laboratory conditions by exposure of the benthic polychaete Nereis diversicolor (O. F. Mueller) to marine sediments contaminated by a nuclear bomb accident (near Thule, Greenland) and nuclear weapons testing (Enewetak Atoll). In both sediment regimes, the bioavailability of plutonium and 241Am was low, with specific activity in the tissues 241Am occurred and 241Am uptake from the Thule sediment was enhanced compared to that from lagoon sediments of Enewetak Atoll. Autoradiography studies indicated the presence of hot particles of plutonium in the sediments. The results highlight the importance of purging animals of their gut contents in order to obtain accurate estimates of transuranic transfer from ingested sediments into tissue. It is further suggested that enhanced transuranic uptake by some benthic species could arise from ingestion of highly activity particles and organic-rich detritus present in the sediments. (author)

  15. A thermodynamic study of actinide oxide targets/fuels for americium transmutation

    International Nuclear Information System (INIS)

    A thermodynamic study was performed on the systems Am-O, AmOx-MgO, AmOx-MgAl2O4, Pu-Mg-O and U-Mg-O. Both experimental work (X-ray analyses, oxygen potential measurements etc.) and calculations on the phase diagrams involved were made. The reaction between americium oxide and spinel is expected to form the compound AmAlO3. Isothermal sections have been calculated for AmOx-(MgO, Al2O3), Pu-Mg-O and U-Mg-O at 2000 K using the software package ''Thermo-Calc''. Thermodynamic equilibrium data were used to predict the behaviour of actinide oxides in a reactor. The implication of the results for the technological application is discussed, with emphasis on the effects of the high oxygen potential of AmO2 as compared to the conventional fuel, i.e. UO2. (author)

  16. EURADOS action for determination of americium in skull measures in vivo and Monte Carlo simulation

    International Nuclear Information System (INIS)

    From the Group of WG7 internal dosimetry of the EURADOS Organization (European Radiation Dosimetry group, e.V.) which It coordinates CIEMAT, international action for the vivo measurement of americium has been conducted in three mannequins type skull with detectors of Germanium by gamma spectrometry and simulation by Monte Carlo methods. Such action has been raised as two separate exercises, with the participation of institutions in Europe, America and Asia. Other actions similar precede this vivo intercomparison of measurement and modeling Monte Carlo1. The preliminary results and associated findings are presented in this work. The laboratory of the body radioactivity (CRC) of service counter of dosimetry staff internal (DPI) of the CIEMAT, it has been one of the participants in vivo measures exercise. On the other hand part, the Group of numerical dosimetry of CIEMAT is participant of the Monte Carlo2 simulation exercise. (Author)

  17. Ab initio modelling of the behaviour of helium in americium and plutonium oxides

    International Nuclear Information System (INIS)

    By means of an ab initio plane wave pseudo potential method, plutonium dioxide and americium dioxide are modelled, and the behaviour of helium in both these materials is studied. We first show that a pseudo potential approach in the Generalized Gradient Approximation (GGA) can satisfactorily describe the cohesive properties of PuO2 and AmO2. We then calculate the formation energies of point defects (vacancies and interstitials), as well as the incorporation and solution energies of helium in PuO2 and AmO2. The results are discussed according to the incorporation site of the gas atom in the lattice and to the stoichiometry of PuO2±x and AmO2±x. (authors)

  18. Removal of plutonium and americium from hydrochloric acid waste stream using extraction chromatography

    International Nuclear Information System (INIS)

    Extraction chromatography is under development as a method to lower actinide activity levels in hydrochloric acid (HCl) effluent streams. Successful application of this technique would allow recycle of the largest portion of HCl, while lowering the quantity and improving the form of solid waste generated. The extraction of plutonium and americium from HCl solutions was examined for several commercial and similar laboratory-produced resins coated with n-octyl(phenyl)-N,N-diisobutylcarbamoylmethyphosphine oxide (CMPO) and either tributyl phosphate (TBP), or diamyl amylphosphonate (DAAP). Distribution coefficients for Pu and Am were measured by contact studies in hydrochloric acid solutions over the range of 0.1 - 10.0 N HCl, whole varying REDOX conditions, actinide loading levels, and contact time intervals. Significant differences in the actinide distribution coefficients, and in the kinetics of actinide removal were observed as a function of resin formulation. The usefulness of these resins for actinide removal from HCl effluent streams is discussed

  19. Complex formation of trivalent americium with salicylic acid at very low concentrations

    International Nuclear Information System (INIS)

    For the first time, the complexation of americium(III) with salicylic acid was studied at trace metal concentrations using a 2.0 m Long Path Flow Cell for UV-vis spectroscopy. The detection limit of Am(III) in aqueous solution at pH 3.0 was found to be 5 x 10-9 M. Two Am(III)-salicylate complexes were formed at pH 5.0 in 0.1 M NaClO4, indicated by a clear red shift of the absorption maximum. The absorption spectra obtained from spectrophotometric titration were analyzed by means of factor analysis and complex stabilities were calculated to be log β110 = 2.56 ± 0.08 and log β120 = 3.93 ± 0.19. (author)

  20. Standard practice for The separation of americium from plutonium by ion exchange

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2001-01-01

    1.1 This practice describes the use of an ion exchange technique to separate plutonium from solutions containing low concentrations of americium prior to measurement of the 241Am by gamma counting. 1.2 This practice covers the removal of plutonium, but not all the other radioactive isotopes that may interfere in the determination of 241Am. 1.3 This practice can be used when 241Am is to be determined in samples in which the plutonium is in the form of metal, oxide, or other solid provided that the solid is appropriately sampled and dissolved (See Test Methods C758, C759, and C1168). 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  1. Transportability Class of Americium in K Basin Sludge under Ambient and Hydrothermal Processing Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Schmitt, Bruce E.; Schmidt, Andrew J.

    2006-08-01

    This report establishes the technical bases for using a ''slow uptake'' instead of a ''moderate uptake'' transportability class for americium-241 (241Am) for the K Basin Sludge Treatment Project (STP) dose consequence analysis. Slow uptake classes are used for most uranium and plutonium oxides. A moderate uptake class has been used in prior STP analyses for 241Am based on the properties of separated 241Am and its associated oxide. However, when 241Am exists as an ingrown progeny (and as a small mass fraction) within plutonium mixtures, it is appropriate to assign transportability factors of the predominant plutonium mixtures (typically slow) to the Am241. It is argued that the transportability factor for 241Am in sludge likewise should be slow because it exists as a small mass fraction as the ingrown progeny within the uranium oxide in sludge. In this report, the transportability class assignment for 241Am is underpinned with radiochemical characterization data on K Basin sludge and with studies conducted with other irradiated fuel exposed to elevated temperatures and conditions similar to the STP. Key findings and conclusions from evaluation of the characterization data and published literature are summarized here. Plutonium and 241Am make up very small fractions of the uranium within the K Basin sludge matrix. Plutonium is present at about 1 atom per 500 atoms of uranium and 241Am at about 1 atom per 19000 of uranium. Plutonium and americium are found to remain with uranium in the solid phase in all of the {approx}60 samples taken and analyzed from various sources of K Basin sludge. The uranium-specific concentrations of plutonium and americium also remain approximately constant over a uranium concentration range (in the dry sludge solids) from 0.2 to 94 wt%, a factor of {approx}460. This invariability demonstrates that 241Am does not partition from the uranium or plutonium fraction for any characterized sludge matrix. Most

  2. Plutonium and americium concentrations and vertical profiles in some Italian mosses used as bioindicators

    International Nuclear Information System (INIS)

    We have examined the uptake of actinide elements Am and Pu by different species of lichen and moss collected in two locations (Urbino, Central Italy; Alps region, North-east Italy). Plutonium and americium were separated and determined by extraction chromatography, electrodeposition and alpha-spectrometry. This paper summarizes our results with a special emphasis on the vertical profiles of these actinides in two different species of mosses. Several 1-2 cm depth sections were obtained and dated by 210Pb method. A typical peak for 239,240Pu and 241Am was found in the very old moss species ('Sphagnum Compactum') at a depth corresponding to the period 1960-1970 which was the period characterized by the maximum nuclear weapon tests. In a younger moss species ('Neckeria Crispa') no peak was observed and the regression curves showed that Am is more mobile than 239,240Pu and 238Pu. (author)

  3. Artificial Synapses: Organometal Halide Perovskite Artificial Synapses (Adv. Mater. 28/2016).

    Science.gov (United States)

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    A synapse-emulating electronic device based on organometal halide perovskite thin films is described by T.-W. Lee and co-workers on page 5916. The device successfully emulates important characteristics of a biological synapse. This work extends the application of organometal halide perovskites to bioinspired electronic devices, and contributes to the development of neuromorphic electronics. PMID:27442971

  4. Formal Nucleophilic Boryl Substitution of Organic Halides with Silylborane/Alkoxy Base System

    OpenAIRE

    Yamamoto, Eiji; Izumi, Kiyotaka; Horita, Yuko; Ukigai, Satoshi; Ito, Hajime

    2014-01-01

    Boryl substitution of organohalides with a silylborane and alkoxy bases is described. This reaction can be applied to various functionalized aryl halides. Alkyl and alkenyl halides, and even sterically congested aryl bromides also provided the corresponding borylated products in high yields. Mechanistic studies indicated that neither trace transition-metal impurities nor aryl radical species involved in this reaction.

  5. Temperature effects in the absorption spectra and exciton luminescence in ammonium halides

    International Nuclear Information System (INIS)

    Warm-up behavior of the first maximum exciton absorption bands in ammonium halides is explored. Under phase transition occurs offset of bands, bound both with changing a parameter of lattice, and efficient mass of exciton. Warm-up dependency of quantum leaving a luminescence of self-trapped excitons in ammonium halides is measured. (author)

  6. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    KAUST Repository

    Moore, David T.

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt\\'s anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films. © 2014 Author(s).

  7. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    International Nuclear Information System (INIS)

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films

  8. Structural, dynamical, and transport properties of the hydrated halides: How do At− bulk properties compare with those of the other halides, from F− to I−?

    OpenAIRE

    Réal, Florent; Severo Pereira Gomes, Andre; Guerrero Martínez, Yansel Omar; Galland, Nicolas; Vallet, Valérie; Masella, Michel; Ayed, Tarah

    2016-01-01

    International audience The properties of halides from the lightest, uoride (F−), to the heaviest, astatide (At−), have been studied in water using a polarizable force- eld approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force- eld explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force- eld parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-o...

  9. Silylaryl Halides Can Replace Triflates as Aryne Precursors.

    Science.gov (United States)

    Mesgar, Milad; Daugulis, Olafs

    2016-08-01

    Silylaryl bromides and iodides can be prepared in one step from commercially available starting materials. Arynes can be generated from these compounds under conditions nearly identical to those employed for silylaryl triflates. Three distinct transformations, ortho-arylation of N-tritylanilines, intermolecular addition of arynes to amides, and reaction of ureas with arynes, were shown to be successful for the new aryne precursors. The main advantage of silylaryl halides relative to silyl aryl triflates is their one-step preparation from commercially available starting materials. PMID:27415183

  10. A new mechanism for radiation damage processes in alkali halides

    OpenAIRE

    Dubinko, V. I.; Turkin, A.A.; Vainshtein, D.I.; Hartog, H.W. den

    1999-01-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface o...

  11. Thermal conductivity of halide solid solutions: measurement and prediction.

    Science.gov (United States)

    Gheribi, Aïmen E; Poncsák, Sándor; St-Pierre, Rémi; Kiss, László I; Chartrand, Patrice

    2014-09-14

    The composition dependence of the lattice thermal conductivity in NaCl-KCl solid solutions has been measured as a function of composition and temperature. Samples with systematically varied compositions were prepared and the laser flash technique was used to determine the thermal diffusivity from 373 K to 823 K. A theoretical model, based on the Debye approximation of phonon density of state (which contains no adjustable parameters) was used to predict the thermal conductivity of both stoichiometric compounds and fully disordered solid solutions. The predictions obtained with the model agree very well with our measurement. A general method for predicting the thermal conductivity of different halide systems is discussed. PMID:25217938

  12. A new mechanism for radiation damage processes in alkali halides

    Science.gov (United States)

    Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I.; den Hartog, H. W.

    1999-12-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface of halogen bubbles. Voids can ignite a back reaction between the radiolytic products resulting in decomposition of the irradiated material.

  13. Coordination chemistry of halides and oxohalides of tungsten (6)

    International Nuclear Information System (INIS)

    Literature data on the structure of molecular complexes of halides, exo- and dioxohalides of tungsten (6), as well as results of the study of WX6, WOX4 and WO2X2 structures in gaseous phase, crystal state and in solutions of organic solvents, were generalized. The greatest volume of structural studies involved complexes W6 with oxygen-containing ligands. The presence of cis- and trans- effects of aliquotly bound oxygen atoms in complexes of exo- and dioxohalides of tungsten is pointed out

  14. RENUW - A dry halide process for nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    The RENUW Dry Halide Process for reprocessing nuclear fuel will be described. Analysis has shown that the RENUW process will significantly reduce the waste produces from processing irradiated nuclear fuel compared to aqueous processes. Waste reduction is accomplished by recovering the zirconium and uranium for reuse. The RENUW process uses hot chlorine gas to chlorinate the feed; separation is accomplished by exploiting the large differences between the relative volatilities of the fission products and the uranium and zirconium. The flow sheet is quite simple and uses readily commercial technologies

  15. RENUW - A dry halide process for nuclear fuel reprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Lahoda, E.J.; McLaughlin, D.F.; Peterson, S.H.; Burgman, H.A. [Westinghouse Electric Corporation, Pittsburgh, PA (United States); Behrens, R. Jr.; Johnston, S.C.; Vosen, S.R. [Sandia National Laboratories, Livermore, CA (United States); Christian, J.D. [Westinghouse Idaho Nuclear Company, Idaho Falls, ID (United States)

    1993-12-31

    The RENUW Dry Halide Process for reprocessing nuclear fuel will be described. Analysis has shown that the RENUW process will significantly reduce the waste produces from processing irradiated nuclear fuel compared to aqueous processes. Waste reduction is accomplished by recovering the zirconium and uranium for reuse. The RENUW process uses hot chlorine gas to chlorinate the feed; separation is accomplished by exploiting the large differences between the relative volatilities of the fission products and the uranium and zirconium. The flow sheet is quite simple and uses readily commercial technologies.

  16. Optical Properties of Photovoltaic Organic-Inorganic Lead Halide Perovskites.

    Science.gov (United States)

    Green, Martin A; Jiang, Yajie; Soufiani, Arman Mahboubi; Ho-Baillie, Anita

    2015-12-01

    Over the last several years, organic-inorganic lead halide perovskites have rapidly emerged as a new photovoltaic contender. Although energy conversion efficiency above 20% has now been certified, improved understanding of the material properties contributing to these high performance levels may allow the progression to even higher efficiency, stable cells. The optical properties of these new materials are important not only to device design but also because of the insight they provide into less directly accessible properties, including energy-band structures, binding energies, and likely impact of excitons, as well as into absorption and inverse radiative recombination processes. PMID:26560862

  17. Analysis and modeling of alkali halide aqueous solutions

    DEFF Research Database (Denmark)

    Kim, Sun Hyung; Anantpinijwatna, Amata; Kang, Jeong Won;

    2016-01-01

    calculations for various electrolyte properties of alkali halide aqueous solutions such as mean ionic activity coefficients, osmotic coefficients, and salt solubilities. The model covers highly nonideal electrolyte systems such as lithium chloride, lithium bromide and lithium iodide, that is, systems that are...... very soluble in water, for example, up to more than 30 mol kg-1. Phase behaviors for the systems are analyzed at concentrations of salt up to the solubility in water at temperatures between 273 and 373 K by comparing calculated results with available experimental data and available models....

  18. An electrochemical oxidation process of Am (III) into Am (VI) used to separate the americium of spent fuels reprocessing solutions

    International Nuclear Information System (INIS)

    The aim of this invention is to oxidize by an electrochemical process Am (III) to Am (VI). This process can be used to separate the americium of spent fuels reprocessing solutions. The method consists to add to the aqueous nitric solution containing Am (III) an heteropolyanion able to complex the americium (as for instance the potassium tungstophosphate) and the Ag (II) ion. The Ag (II) ion oxidizes the Am (III) and is reduced into an Ag (I) ion. It is then regenerated by the electrolysis of the solution. After the oxidation of Am (III) into Am (VI), this last ion can be extracted by an adapted organic solvent. With this electrochemical method a yield of 100% Am (VI) is obtained in half a hour. (O.M.). 5 refs., 5 figs., 2 tabs

  19. Separation of oxidized americium from lanthanides by use of pillared metal(IV) phosphate-phosphonate hybrid materials

    International Nuclear Information System (INIS)

    Closing the nuclear fuel cycle in the US poses many challenges, one of which is found in the waste streams, which contain both trivalent lanthanides and actinides. The separation of americium from the raffinate will dramatically reduce the long-term radiotoxicity of the waste. The sorption of americium in both the tri- and pentavalent oxidation states was observed for four M(IV) phosphate-phosphonate ion exchange materials in nitric acid at pH 2. High selectivity was observed for reduced Am(III) with Kd values ca. 6 x 105 mL/g, while the Kd values for Am(V) were much lower. A new method of synthesizing and stabilizing AmO2+ to yield a lifetime of at least 24 h in acidic media using a combination of sodium persulfate and calcium hypochlorite will be described.

  20. Effects of impurities on the size and form of crystals of thorium and americium oxalates and oxides

    International Nuclear Information System (INIS)

    The influence of impurity salts and certain surfactants on the shape and size of thorium and americium oxalate crystals, as well as crystals of their dioxides, prepared at thermolysis of oxalate precipitates, has been investigated. It is shown that during thorium oxalate deposition from solutions, containing 0.8 mol/l thorium and 2 mol/l nitric acid at 96 deg C in the presence of ammonium salts or surfactants larger and monodisperse crystals are grown than in the absence of the above-mentioned substances. Addition of ammonium nitrate in the amount of 0.6 mol/l to solution containing 7.6x10-3 mol/l of americium dioxide particles coincides with the shape of oxalate crystals but their size is reduced by (20-25)% as compared with the initial ones

  1. Combined radiochemical procedure for determination of plutonium, americium and strontium-90 in the soil samples from SNTS

    International Nuclear Information System (INIS)

    The results of combined radiochemical procedure for the determination of plutonium, americium and 90Sr (via measurement of 90Y) in the soil samples from SNTS (Semipalatinsk Nuclear Test Site) are presented. The processes of co-precipitation of these nuclides with calcium fluoride in the strong acid solutions have been investigated. The conditions for simultaneous separation of americium and yttrium using extraction chromatography have been studied. It follows from analyses of real soil samples that the procedure developed provides the chemical recovery of plutonium and yttrium in the range of 50-95 % and 60-95 %, respectively. The execution of the procedure requires 3.5 working days including a sample decomposition study. (author)

  2. Halide salts accelerate degradation of high explosives by zerovalent iron

    International Nuclear Information System (INIS)

    Zerovalent iron (Fe0, ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe0 (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24 h also restored ZVI reactivity, resulting in complete degradation within 8 h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl- and Br- was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br- was present in solution. - The addition of halide ions promotes the degradation of high explosives by zerovalent iron

  3. Structure and Bonding in Small Neutral Alkali-Halide Clusters

    CERN Document Server

    Aguado, A; López, J M; Alonso, J A

    1997-01-01

    The structural and bonding properties of small neutral alkali-halide clusters (AX)n, with n less than or equal to 10, A=Li, Na, K, Rb and X=F, Cl, Br, I, are studied using the ab initio Perturbed Ion (aiPI) model and a restricted structural relaxation criterion. A trend of competition between rock-salt and hexagonal ring-like isomers is found and discussed in terms of the relative ionic sizes. The main conclusion is that an approximate value of r_C/r_A=0.5 (where r_C and r_A are the cationic and anionic radii) separates the hexagonal from the rock-salt structures. The classical electrostatic part of the total energy at the equilibrium geometry is enough to explain these trends. The magic numbers in the size range studied are n= 4, 6 and 9, and these are universal since they occur for all alkali-halides and do not depend on the specific ground state geometry. Instead those numbers allow for the formation of compact clusters. Full geometrical relaxations are considered for (LiF)n (n=3-7) and (AX)_3 clusters, an...

  4. Melting and liquid structure of polyvalent metal halides

    International Nuclear Information System (INIS)

    A short review is given of recent progress in determining and understanding liquid structure types and melting mechanisms for halides of polyvalent metals. The nature of the preferred local coordination for the polyvalent metal ion in the melt can usually be ascertained from data on liquid mixtures with halogen-donating alkali halides. The stability of these local coordination states and the connectivity that arises between them in the approach to the pure melt determines the character of its short-range and possible medium-range order. A broad classification of structural and melting behaviours can be given on the basis of measured melting parameters and transport coefficients for many compounds, in combination with the available diffraction data on the liquid structure of several compounds. Correlations have been shown to exist with a simple indicator of the nature of the chemical bond and also with appropriate parameters of ionic models, wherever the latter are usefully applicable for semiquantitative calculations of liquid structure. Consequences on the mechanisms for valence electron localization in solutions of metallic elements into strongly structured molten salts are also briefly discussed. (author). 46 refs, 4 figs, 2 tabs

  5. Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

    Science.gov (United States)

    Lai, May L; Tay, Timothy Y S; Sadhanala, Aditya; Dutton, Siân E; Li, Guangru; Friend, Richard H; Tan, Zhi-Kuang

    2016-07-21

    Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications. PMID:27336412

  6. A new polarizable force field for alkali and halide ions

    International Nuclear Information System (INIS)

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r−6 attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed

  7. Dislocation unpinning model of acoustic emission from alkali halide crystals

    Indian Academy of Sciences (India)

    B P Chandra; Anubha S Gour; Vivek K Chandra; Yuvraj Patil

    2004-06-01

    The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations. Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate, the time constant $_{\\text{s}}$ for surface annihilation of dislocations and the pinning time $_{\\text{p}}$ of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related to the AE from alkali halide crystals.

  8. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects.

    Science.gov (United States)

    Liu, Yuanyue; Xiao, Hai; Goddard, William A

    2016-05-11

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them. PMID:27100910

  9. Extraction of americium(III) from nitric acid medium by CMPO-TBP extractants in ionic liquid diluent

    International Nuclear Information System (INIS)

    Extraction of americium(III) from nitric acid medium by a solution of tri-n-butylphosphate (TBP) and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in room temperature ionic liquid, l-butyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide (bmimNTf2), was studied and the results were compared with that obtained with CMPO-TBP in n-doddecane (n-DD). The distribution ratio of 241Am(III) in TBP-CMPO/bmimNTf2 was measured as a function of various parameters such as concentrations of nitric acid, CMPO, bmimNO3, NaNO3 and TBP and temperature. Remarkably large distribution ratios were observed for the extraction of americium(III) when bmimNTf2 acted as diluent and the extraction was insignificant in the absence of CMPO. The stoichiometry of metal-solvate in organic phase was determined by the slope analysis of extraction data and it indicated the formation of 1:3 (Am: CMPO) complex in organic phase. Viscosity of TBP-CMPO/bmimNTf2 at various temperatures and enthalpy change accompanied by the extraction of americium(III) were determined and reported in this paper. (orig.)

  10. The behaviour under irradiation of molybdenum matrix for inert matrix fuel containing americium oxide (CerMet concept)

    Science.gov (United States)

    D'Agata, E.; Knol, S.; Fedorov, A. V.; Fernandez, A.; Somers, J.; Klaassen, F.

    2015-10-01

    Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors or Accelerator Driven System (ADS, subcritical reactors dedicated to transmutation) of long-lived nuclides like 241Am is therefore an option for the reduction of radiotoxicity of waste packages to be stored in a repository. In order to safely burn americium in a fast reactor or ADS, it must be incorporated in a matrix that could be metallic (CerMet target) or ceramic (CerCer target). One of the most promising matrix to incorporate Am is molybdenum. In order to address the issues (swelling, stability under irradiation, gas retention and release) of using Mo as matrix to transmute Am, two irradiation experiments have been conducted recently at the High Flux Reactor (HFR) in Petten (The Netherland) namely HELIOS and BODEX. The BODEX experiment is a separate effect test, where the molybdenum behaviour is studied without the presence of fission products using 10B to "produce" helium, the HELIOS experiment included a more representative fuel target with the presence of Am and fission product. This paper covers the results of Post Irradiation Examination (PIE) of the two irradiation experiments mentioned above where molybdenum behaviour has been deeply investigated as possible matrix to transmute americium (CerMet fuel target). The behaviour of molybdenum looks satisfying at operating temperature but at high temperature (above 1000 °C) more investigation should be performed.

  11. Consideration of the effect of lymph-node deposition upon the measurement of plutonium and americium in the lungs

    International Nuclear Information System (INIS)

    Measurement of an inhaled radionuclide by external photon counting includes quantities which may be contained in lymph nodes, as well as quantities in the lungs. An overestimate of the lung burden can result, if a portion of the radionuclide were present in the lymph nodes. This problem is analyzed with respect to the measurement of inhaled plutonium containing plutonium-241 and americium-241, when americium-241 has been used as a tracer for the plutonium. Equations are derived which yield the amounts of americium and of plutonium in the lungs and in the lymph nodes as a function of time after exposure and for various translocation and retention parameters. Count histories (count profiles) of actual exposure cases are compared with calculated count profiles in order to gain insight into possible values of the translocation and retention parameters. Comparison is also made with calculated count profiles using values of translocation and retention parameters recommended by the International Commission on Radiological Protection (ICRP) for use with the Task Group Lung Model. The magnitude of the possible overestimate (error factor) was calculated for combinations o

  12. HELIOS: the new design of the irradiation of U-free fuels for americium transmutation

    Energy Technology Data Exchange (ETDEWEB)

    D' Agata, E. [European Commission, Joint Research Centre, Institute for Energy, P.O. Box 2, 1755 ZG Petten (Netherlands); Klaassen, F.; Sciolla, C. [Nuclear Research and Consultancy Group, Dept. Life Cycle and Innovations, P.O. Box 25 1755 ZG Petten (Netherlands); Fernandez-Carretero, A. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Bonnerot, J.M. [Commissariat a l' Energie Atomique, DEC/SESC/LC2I CEA-Cadarache, 13108 St. Paul lez Durance Cedex (France)

    2009-06-15

    Americium is one of the radioactive elements that mostly contribute to the radiotoxicity of the nuclear spent fuel. Transmutation of long-lived nuclides like Americium is an option for the reduction of the mass, the radiotoxicity and the decay heat of nuclear waste. The HELIOS irradiation experiment is the last evolution in a series of experiments on americium transmutation. The previous experiments, EFTTRA-T4 and T4bis, have shown that the release or trapping of helium is the key issue for the design of such kind of target. In fact, the production of helium, which is characteristic of {sup 241}Am transmutation, is quite significant. The experiment is carried out in the framework of the 4-year project EUROTRANS of the EURATOM 6. Framework Programme (FP6). Therefore, the main objective of the HELIOS experiment is to study the in-pile behaviour of U-free fuels such as CerCer (Pu, Am, Zr)O{sub 2} and Am{sub 2}Zr{sub 2}O{sub 7}+MgO or CerMet (Pu, Am)O{sub 2}+Mo in order to gain knowledge on the role of the fuel microstructure and of the temperature on the gas release and on the fuel swelling. The experiment was planned to be conducted in the HFR (High Flux Reactor) in Petten (The Netherlands) starting the first quarter of 2007. Because of the innovative aspects of the fuel, the fabrication has had some delays as well as the final safety analyses of the original design showed some unexpected deviation. Besides, the HFR reactor has been unavailable since August 2008. Due to the reasons described above, the experiment has been postponed. HELIOS should start in the first quarter of 2009 and will last 300 full power days. The paper will cover the description of the new design of the irradiation experiment HELIOS. The experiment has been split in two parts (HELIOS1 and HELIOS2) which will be irradiated together. Moreover, due to the high temperature achieved in cladding and to the high amount of helium produced during transmutation the experiment previously designed for a

  13. Formability of ABX3 (X = F, Cl, Br, I) halide perovskites.

    Science.gov (United States)

    Li, Chonghea; Lu, Xionggang; Ding, Weizhong; Feng, Liming; Gao, Yonghui; Guo, Ziming

    2008-12-01

    In this study a total of 186 complex halide systems were collected; the formabilities of ABX3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF2) without perovskite structure and six systems (RbF-PbF2, CsF-BeF2, KCl-FeCl2, TlI-MnI2, RbI-SnI2, TlI-PbI2) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. PMID:19029699

  14. Uptake of americium-241 by plants from contaminated Chernobyl exclusive zone test site soils

    International Nuclear Information System (INIS)

    Americium-241 was found to accumulate in soils and biological objects of the environment. Its concentration has increased many times after the Chernobyl disaster and can be expected to increase about 40 times in the future. This research concentrated on the contaminated exclusive Chernobyl zone polluted by trace radionuclides, their behavior and accumulation by various plant species. Special attention is devoted to the bioavailability of 241Am to the plants Galium rivale, G. tinctorium, G. aparine, G. intermedium, Berteroa incana, Artemisia absinthium, A. vulgaris, Centaurea borysthenica, C. arenaria, Cirsium arvense, Succissa pratensis, Solidago virgaurea, Linaria vulgaris, Lepidium ruderale, Stenactis annua, Veronica maxima, Verbascum lychnitis, Euphorbia cyparissias, Genista tinctoria, Erigeron canadensis, Oenothera biennis, Betula pendula and Quercus robur, which were collected from the Chernobyl, Kopachi, and Yanov districts. The plant samples of Oenothera biennis, Betula pendula and Quercus robur were collected from the Yanov district, where the soil contamination by 241Am and 137Cs was at the level of 660 and 27 MBq/m2, respectively. Gamma spectroscopy and radiochemical methods were used to estimate the activity concentration of 137Cs, 90Sr, 238Pu, 239+240Pu, 241Am. The radionuclides were measured in the dry green mass of the plant samples and in the dry soils. The contamination of the Oenothera biennis, Betula pendula and Quercus robur samples by 137Cs was (5.8±1,5)x106, (7.4±1.1)x105, and (2.6±0.2)x106 Bq/kg dry mass, respectively, and contamination by 241Am was 47±5, 45±3 and 3.2±0.2 Bq/kg, respectively. The soil-to-plant transfer ratio for 137Cs ranged lay within the interval of 0.2 to 0.03 Bq/kg : Bq/m2, the the transfer ratio for 241Am did not exceed 7x10-5 Bq/kg : Bq/m2. The coefficient of the relative contents of the 241Am/239+240Pu radionuclides in the various plant samples varied from 3.2 to 8.3, while for soil from the Yanov district this

  15. Anomalous aryl strengthening of complexes at americium and europium extraction with alkylenediphospine dioxide from perchloric media

    International Nuclear Information System (INIS)

    Studied was the extraction of americium(3) and europium(3) from perchlorate solutions(0.001 M) with dioxides of alkylenediphosphines of three types: aryl Ph2P(O)CH2(O)PPh2(briefly 4P), and Ph2P(O)(CH2)2(O)PPh2, mixed Ph2P(O)CH2(O)P(C8H17)2 (or 2Ph2Oct) and alkyl (C8H17)2P(O)CH2(O)P(C8H17)2 (or 4 Oct). Trisolvates of MeS3x(ClO4)3 are predominantly formed but americium disolvates are also present upon dilution with dichloroethane. For 4Ph,2Ph2Oct and 4 Oct the concentration is, respectively, 1015, 2x1014, and 1013; for disolvates by 4 orders of magnitude lower which is, nevertheless, by 2 orders of magnitude higher than for nitric acid solutions. The separation coefficient of β Am/Eu for 4Ph attains 6-8. As in the case of nitrate solutions, an anomalous aryl strengthening of the complexes is observed: an increase in the distribution coefficients and extraction constants in the series of 4 Oct - 2Ph 2 Oct - 4Ph, in spite of the introduction of electronegative aryl substituents into the dioxide molecule, which reduce electron density on oxygen atoms and basicity of dioxides. In contrast to nitric acid solutions, observed is a nonlinear effect of a change in basicity on extraction properties upon dilution with dichloroethane (dioxide of 2Ph2 Oct does not occupy an intermediate position but is close to 4Ph). Upon dilution with chloroform the dependence is linear and anomalous effect rises due to a different nature of interactions of dioxides with chloroform. When the bridge increases up to ethylene, an anomalous strengthening of the complexes disappears. However, the distribution coefficients upon extraction with alkyl dioxide are considerably lower, which can be explained by a stronger extraction of perchloric acid

  16. Investigation of change regularity of energy states of Mn2+ in halides

    International Nuclear Information System (INIS)

    Data on 4E, 4A1 (4G) and 4T1 (4G) energy states of Mn2+ ion in some halides have been obtained and analyzed. With use of the dielectric theory of the chemical bond for complex crystals, several chemical bond parameters were calculated. The change regularity of the energy states of Mn2+ in halides has been studied. The results show that the covalence, the coordination number and the radius of the central ion are the main factors influencing the energy states of Mn2+ ion in halides. The relationships between these factors and the energy state 4T1 (4G), the energy difference ΔE (ΔE=4E, 4A1 (4G)→4T1 (4G)) of Mn2+ ion in halides were established: E=2.0898+0.8618 exp (−F/0.2431); ΔE=0.3201+0.9713⁎F. These relationships allow us to predict the position of energy state 4T1 (4G) and the energy difference ΔE of Mn2+ in halides. This work can be significant for further understanding the luminescent properties of Mn2+ and can be used to develop new Mn2+-doped phosphors. - Highlights: ► Relationship between F and energy state 4T1(4G) of Mn2+ in halides was set up. ► Relationship between F and energy difference ΔE of Mn2+ in halides was set up. ► Site occupation of Mn2+-doped halides with two or more cations can be made clear. ► Energy state 4T1(4G) and emission band of Mn2+ in halides can be predicted.

  17. Mild Palladium-Catalyzed Cyanation of (Hetero)aryl Halides and Triflates in Aqueous Media

    OpenAIRE

    Cohen, Daniel T.; Buchwald, Stephen L.

    2015-01-01

    A mild, efficient, and low-temperature palladium-catalyzed cyanation of (hetero)aryl halides and triflates is reported. Previous palladium-catalyzed cyanations of (hetero)aryl halides have required higher temperatures to achieve good catalytic activity. This current reaction allows the cyanation of a general scope of (hetero)aryl halides and triflates at 2–5 mol % catalyst loadings with temperatures ranging from rt to 40 °C. This mild method was applied to the synthesis of lersivirine, a reve...

  18. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  19. Neutron Activation Analysis of Lead Halide Pollution Aerosols

    International Nuclear Information System (INIS)

    Iodine, bromine and chlorine have been determined by neutron activation analysis in atmospheric samples of both natural and pollution origin, and a comparison of the two sources provides the basis of a technique described in this paper for determining the composition and possible source of lead halide pollution aerosols. The activation analysis procedure employed consists of reactor neutron irradiation of aqueous samples and comparators for 20 min followed by radiochemical separation of iodine, bromine and chlorine and automatic counting of beta radioactivity from solid silver halide sources. Determination of lead by anodic stripping voltammetry (inverse polarography) consists of deposition of Pb++ from the solution onto a composite paraffin- impregnated graphite and mercury electrode at -1.00 V versus the standard calomel electrode, and then stripping by increasing the potential continuously. A significant question of public health interest in the air chemistry of lead is the source of the lead. Ethyl fluid, a mixture of organic lead, bromine and chlorine compounds, burns to form inorganic lead halide particles with Cl/Pb = 0.34 and Br/Pb = 0.39 by weight. In Cambridge, Massachusetts, analyses of cascade impactor aerosols were compared with similarly collected samples from the unpolluted air of Hawaii. The pollution bromine component ranged from 0.4 to 0.1 or less of the lead concentration, indicating in most cases either automotive lead with a bromine deficiency or a mixture of lead from automotive and other sources. In Fairbanks, Alaska, during winter, atmospheric conditions favour high local concentrations of air pollutants. Aerosols collected by Millipore filters show that pollution chlorine averages very nearly the value predicted from the observed lead and the known composition of ethyl fluid, and the automotive source for both chlorine and lead is strongly indicated. Pollution bromine, however, was less than predicted, and the bromine deficiency was about

  20. Americium and plutonium in water, biota, and sediment from the central Oregon coast

    International Nuclear Information System (INIS)

    Plutonium-239, 240 and americium-241 were measured in the mussel Mytilus californianus from the region of Coos Bay, OR. The flesh of this species has a plutonium concentration of about 90 fCi/kg, and an Am-241/Pu-239, 240 ratio that is high relative to mixed fallout, ranging between two and three. Transuranic concentrations in sediment, unfiltered water, and filterable particulates were also measured; none of these materials has an Am/Pu ratio as greatly elevated as the mussels, and there is no apparent difference in the Am/Pu ratio of terrestrial runoff and coastal water. Sediment core profiles do not allow accumulation rates or depositional histories to be identified, but it does not appear that material characterized by a high Am/Pu ratio has ever been introduced to this estuary. Other bivalves (Tresus capax and Macoma nasuta) and a polychaete (Abarenicola sp.) do not have an elevated Am/Pu ratio, although the absolute activity of plutonium in the infaunal bivalves is roughly four times that in the mussels

  1. Americium-based oxides: Dense pellet fabrication from co-converted oxalates

    Energy Technology Data Exchange (ETDEWEB)

    Horlait, Denis; Lebreton, Florent [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze (France); Gauthé, Aurélie [CEA, DEN, DRCP/SERA/LCAR, 30207 Bagnols-sur-Cèze (France); Caisso, Marie [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze (France); Arab-Chapelet, Bénédicte; Picart, Sébastien [CEA, DEN, DRCP/SERA/LCAR, 30207 Bagnols-sur-Cèze (France); Delahaye, Thibaud, E-mail: thibaud.delahaye@cea.fr [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze (France)

    2014-01-15

    Mixed oxides are used as nuclear fuels and are notably envisaged for future fuel cycles including plutonium and minor actinide recycling. In this context, processes are being developed for the fabrication of uranium–americium mixed-oxide compounds for transmutation. The purpose of these processes is not only the compliance with fuel specifications in terms of density and homogeneity, but also the simplification of the process for its industrialization as well as lowering dust generation. In this paper, the use of a U{sub 0.85}Am{sub 0.15}O{sub 2±δ} powder synthesized by oxalate co-conversion as a precursor for dense fuel fabrications is assessed. This study notably focuses on sintering, which yielded pellets up to 96% of the theoretical density, taking advantage of the high reactivity and homogeneity of the powder. As-obtained pellets were further characterized to be compared to those obtained via processes based on the UMACS (Uranium Minor Actinide Conventional Sintering) process. This comparison highlights several advantages of co-converted powder as a precursor for simplified processes that generate little dust.

  2. Influence of organic additives on the colour reaction between trivalent americium and arsenazo III

    International Nuclear Information System (INIS)

    The colour reaction of Am(III) with arsenazo III in several hydroorganic media has been examined systematically on the addition of certain polar water-miscible organic solvents in the course of a search for improved and simple spectrophotometric methods for the estimation of americium. Addition of these substances resulted in the stabilization of colour and brought about a drastic enhancement in the absorbance values. The organic additives studied include acetone, acetonitrile, dimethylformamide, dioxane and ethanol. Among the many solvents tested, alcohol and dioxane proved to be the most effective, the highest sensitivity is obtained by using a 60% dioxane-ethanol (1:1) mixture. The apparent molar absorptivity based on Am content is 184616+-9931 mol-1 cm-1 at 655 nm which is about 3 times higher than that attained for the reaction in aqueous medium (65178+-1243). Moreover, this is the highest value reported as yet for its determination. Beer's law is obeyed both in mixed and aqueous media. The effects of some experimental variables on colour development have also been studied to optimize the conditions for the assay of Am. (author)

  3. Speciation and bioavailability of Americium-241 in the fresh water environment

    International Nuclear Information System (INIS)

    Due to its anthropogenic origin, the transuranic americium 241 confronts physiologists with the intriguing question, which mechanisms are involved in the incorporation or elimination of such artificial elements in biological cycles. The investigations on the speciation and bioavailability of 241Am in the freshwater environment aim to establish a relation between the behavior of 241Am in freshwater ecosystems and its availability for biota. In the limnic environment, most often characterized by a high organic load and a low conductivity, the effect of complexation of 241Am with humic acids and competition with trivalent cations such as A1 and Fe, were proven to be significant on the speciation of 241Am. Based on the registration of the 241Am uptake by a large number of freshwater organisms, the crayfish Astacus leptodactylus Eschscholtz was chosen to study the whole-body uptake of 241Am, its corresponding organ distribution and its retention in the animal. The share of external fixation and ingestion in the global uptake, and the effect of speciation on it, were studied more carefully. Other aspects in this physiological part were: the kinetics of 241Am in the hemolymph and the hepatopancreas, and its subcellular distribution in the digestive gland. Finally, by comparing the physiology of 241Am with some other metals (240Pu, 64Cu, 198Au) with analogous or contradictional properties, we tried to find out whether the behavior of 241Am in organisms can be explained from its chemical characteristics

  4. Development and Testing of an Americium/Lanthanide Separation Flowsheet Using Sodium Bismuthate

    Energy Technology Data Exchange (ETDEWEB)

    Jack Law; Bruce Mincher; Troy Garn; Mitchell Greenhalgh; Nicholas Schmitt; Veronica Rutledge

    2014-04-01

    The separation of Am from the lanthanides and curium is a key step in proposed advanced fuel cycle scenarios. The partitioning and transmutation of Am is desirable to minimize the long-term heat load of material interred in a future high-level waste repository. A separation process amenable to process scale-up remains elusive. Given only subtle chemistry differences within and between the ions of the trivalent actinide and lanthanide series this separation is challenging ; however, higher oxidation states of americium can be prepared using sodium bismuthate and separated via solvent extraction using diamylamylphosphonate (DAAP) extraction. Among the other trivalent metals only Ce is also oxidized and extracted. Due to the long-term instability of Am(VI) , the loaded organic phase is readily selectively stripped to partition the actinide to a new acidic aqueous phase. Batch extraction distribution ratio measurements were used to design a flowsheet to accomplish this separation. Additionally, crossflow filtration was investigated as a method to filter the bismuthate solids from the feed solution prior to extraction. Results of the filtration studies, flowsheet development work and flowsheet performance testing using a centrifugal contactor are detailed.

  5. Determination of plutonium americium and curium in soil samples by solvent extraction with trioctylphosphine oxide

    International Nuclear Information System (INIS)

    A method of Pu, Am and Cm determination in soil samples, which was developed for analyzing samples from territories subjected to radioactive contamination as a result of the Chernobyl accident is described. After preliminary treatment the samples were leached by solution of 7 mol/l HNO23+0.3 mol/l KBrO3 during heating. Pu was isolated by extraction with 0.05 mol TOPO from 7 mol/l HNO3. 144Ce and partially remaining in water phase isotopes of Zr, U and Th were isolated in an extraction-chromatographic column with TOPO and PbO2. Then Am and Cm were extracted by 0.2 mol/l TOPO from solution 1 mol/l HLact+0.07 mol/l DTPA+1 mol/l Al(NO3)3. Alpha-activity of both extracted products was determined in liquid scintillation counter. Chemical yield of plutonium counted to 85±10%, that of americium and curium -75±10%. 17 refs

  6. Assessment of radiation doses from residential smoke detectors that contain americium-241

    International Nuclear Information System (INIS)

    External dose equivalents and internal dose commitments were estimated for individuals and populations from annual distribution, use, and disposal of 10 million ionization chamber smoke detectors that contain 110 kBq (3 μCi) americium-241 each. Under exposure scenarios developed for normal distribution, use, and disposal using the best available information, annual external dose equivalents to average individuals were estimated to range from 4 fSv (0.4 prem) to 20 nSv (2 μrem) for total body and from 7 fSv to 40 nSv for bone. Internal dose commitments to individuals under post disposal scenarios were estimated to range from 0.006 to 80 μSv (0.0006 to 8 mrem) to total body and from 0.06 to 800 μSv to bone. The total collective dose (the sum of external dose equivalents and 50-year internal dose commitments) for all individuals involved with distribution, use, or disposal of 10 million smoke detectors was estimated

  7. NMR Evidence for the 8.5 K Phase Transition in Americium Dioxide

    Science.gov (United States)

    Tokunaga, Yo; Nishi, Tsuyoshi; Kambe, Shinsaku; Nakada, Masami; Itoh, Akinori; Homma, Yoshiya; Sakai, Hironori; Chudo, Hiroyuki

    2010-05-01

    We report here the first NMR study of americium dioxide (AmO2). More than 30 years ago, a phase transition was suggested to occur in this compound at 8.5 K based on magnetic susceptibility data, while no evidence had been obtained from microscopic measurements. We have prepared a powder sample of 243AmO2 containing 90 at. % 17O and have performed 17O NMR at temperatures ranging from 1.5 to 200 K. After a sudden drop of the 17O NMR signal intensity below 8.5 K, at 1.5 K we have observed an extremely broad spectrum covering a range of ˜14 kOe in applied field. These data provide the first microscopic evidence for a phase transition as a bulk property in this system. In addition, the 17O NMR spectrum has been found to split into two peaks in the paramagnetic state, an effect which has not been reported for actinide dioxides studied up to now. We suggest that the splitting is induced by self-radiation damage from the alpha decay of 243Am.

  8. Study of biosorbents application on the treatment of radioactive liquid wastes with americium-241

    International Nuclear Information System (INIS)

    The use of nuclear energy for many different purposes has been intensified and highlighted by the benefits that it provides. Medical diagnosis and therapy, agriculture, industry and electricity generation are examples of its application. However, nuclear energy generates radioactive wastes that require suitable treatment ensuring life and environmental safety. Biosorption and bioaccumulation represent an emergent alternative for the treatment of radioactive liquid wastes, providing volume reduction and physical state change. This work aimed to study biosorbents for the treatment of radioactive liquid wastes contaminated with americium-241 in order to reduce the volume and change the physical state from liquid to solid. The biosorbents evaluated were Saccharomyces cerevisiae immobilized in calcium alginate beads, inactivated and free cells of Saccharomyces cerevisiae, calcium alginate beads, Bacillus subtilis, Cupriavidus metallidurans and Ochrobactrum anthropi. The results were quite satisfactory, achieving 100% in some cases. The technique presented in this work may be useful and viable for implementing at the Waste Management Laboratory of IPEN - CNEN/SP in short term, since it is an easy and low cost method. (author)

  9. In Vitro Dissolution Tests of Plutonium and Americium Containing Contamination Originating From ZPPR Fuel Plates

    Energy Technology Data Exchange (ETDEWEB)

    William F. Bauer; Brian K. Schuetz; Gary M. Huestis; Thomas B. Lints; Brian K. Harris; R. Duane Ball; Gracy Elias

    2012-09-01

    Assessing the extent of internal dose is of concern whenever workers are exposed to airborne radionuclides or other contaminants. Internal dose determinations depend upon a reasonable estimate of the expected biological half-life of the contaminants in the respiratory tract. One issue with refractory elements is determining the dissolution rate of the element. Actinides such as plutonium (Pu) and Americium (Am) tend to be very refractory and can have biological half-lives of tens of years. In the event of an exposure, the dissolution rates of the radionuclides of interest needs to be assessed in order to assign the proper internal dose estimates. During the November 2011 incident at the Idaho National Laboratory (INL) involving a ZPPR fuel plate, air filters in a constant air monitor (CAM) and a giraffe filter apparatus captured airborne particulate matter. These filters were used in dissolution rate experiments to determine the apparent dissolution half-life of Pu and Am in simulated biological fluids. This report describes these experiments and the results. The dissolution rates were found to follow a three term exponential decay equation. Differences were noted depending upon the nature of the biological fluid simulant. Overall, greater than 95% of the Pu and 93% of the Am were in a very slow dissolving component with dissolution half-lives of over 10 years.

  10. Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

    Science.gov (United States)

    Ikeda-Ohno, Atsushi; Harrison, Jennifer J; Thiruvoth, Sangeeth; Wilsher, Kerry; Wong, Henri K Y; Johansen, Mathew P; Waite, T David; Payne, Timothy E

    2014-09-01

    During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed. PMID:25126837

  11. Comparative study of plutonium and americium bioaccumulation from two marine sediments contaminated in the natural environment

    Energy Technology Data Exchange (ETDEWEB)

    Hamilton, T.F.; Smith, J.D. (Melbourne Univ., Parkville (Australia). Dept. of Inorganic Chemistry); Fowler, S.W.; LaRosa, J.; Holm, E. (International Atomic Energy Agency, Monaco-Ville (Monaco). Lab. of Marine Radioactivity); Aarkrog, A.; Dahlgaard, H. (Risoe National Lab., Roskilde (Denmark))

    1991-01-01

    Plutonium and americium sediment-animal transfer was studied under controlled laboratory conditions by exposure of the benthic polychaete Nereis diversicolor (O. F. Mueller) to marine sediments contaminated by a nuclear bomb accident (near Thule, Greenland) and nuclear weapons testing (Enewetak Atoll). In both sediment regimes, the bioavailability of plutonium and {sup 241}Am was low, with specific activity in the tissues <1% (dry wt) than in the sediments. Over the first three months, a slight preference in transfer of plutonium over {sup 241}Am occurred and {sup 241}Am uptake from the Thule sediment was enhanced compared to that from lagoon sediments of Enewetak Atoll. Autoradiography studies indicated the presence of hot particles of plutonium in the sediments. The results highlight the importance of purging animals of their gut contents in order to obtain accurate estimates of transuranic transfer from ingested sediments into tissue. It is further suggested that enhanced transuranic uptake by some benthic species could arise from ingestion of highly activity particles and organic-rich detritus present in the sediments. (author).

  12. Theoretical study of the scandium and yttrium halides

    Science.gov (United States)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Partridge, Harry

    1988-01-01

    The X1Sigma(+) ground states and a3Delta excited states of the diatomic halides of Sc and Y are characterized theoretically, using the SDCI coupled-pair functional method and the state-averaged CASSCF method to determine the spectroscopic constants and related properties. The techniques employed are discussed, and the results are presented in extensive tables. The dissociation energies are given as D0 = 6.00 eV for ScF, 4.55 eV for ScCl, 3.90 eV for ScBr, 6.72 eV for YF, 5.36 eV for YCl, and 4.74 eV for YBr.

  13. Material Innovation in Advancing Organometal Halide Perovskite Functionality.

    Science.gov (United States)

    Zheng, Fan; Saldana-Greco, Diomedes; Liu, Shi; Rappe, Andrew M

    2015-12-01

    Organometal halide perovskites (OMHPs) have garnered much attention recently for their unprecedented rate of increasing power conversion efficiency (PCE), positioning them as a promising basis for the next-generation photovoltaic devices. However, the gap between the rapid increasing PCE and the incomplete understanding of the structure-property-performance relationship prevents the realization of the true potential of OMHPs. This Perspective aims to provide a concise overview of the current status of OMHP research, highlighting the unique properties of OMHPs that are critical for solar applications but still not adequately explained. Stability and performance challenges of OMHP solar cells are discussed, calling upon combined experimental and theoretical efforts to address these challenges for pioneering commercialization of OMHP solar cells. Various material innovation strategies for improving the performance and stability of OMHPs are surveyed, showing that the OMHP architecture can serve as a promising and robust platform for the design and optimization of materials with desired functionalities. PMID:26631361

  14. Quasielastic neutron scattering study of silver selenium halides

    CERN Document Server

    Major, A G; Barnes, A C; Howells, W S

    2002-01-01

    Both silver chalcogenides (Ag sub 2 S, Ag sub 2 Se, and Ag sub 2 Te) and silver halides (AgCl, AgBr, and AgI) are known to be fast-ion solids in which the silver ions can diffuse quickly in a sublattice formed by the other ions. To clarify whether mixtures of these materials (such as Ag sub 3 SeI) possess comparable properties and whether a systematic dependence on the cation-to-anion ratio can be observed, some of these mixtures were studied by quasielastic neutron scattering both in the solid and the liquid phases. To identify the diffusion mechanisms and constants, a new data-analysis method based on a two-dimensional maximum-likelihood fit is proposed. This method has the potential to give more reliable information on the diffusion mechanism than the traditional Bayesian method. (orig.)

  15. Theory of freezing of alkali halides and binary alloys

    International Nuclear Information System (INIS)

    Using the basic equations of classical statistical mechanics relating the singlet densities rho1 and rho2 of a binary system to the three partial direct correlation functions csub(ij), a theory of freezing is developed. Though the theory is set up for arbitrary concentration, we focus on the freezing of the alkali halides. In particular, we show that periodic solutions of the equations for rho1 and rho2 can coexist with homogeneous solutions. The difference in free energy between periodic and homogeneous phases is built up in terms of (i) the volume difference and (ii) the Fourier components of rho1, rho2 and csub(ij). To lowest order, it is stressed that the freezing transition is determined by the charge-charge structure factor at the principal peak and by the compressibility. (author)

  16. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Brendel' , V M; Bukin, V V; Garnov, Sergei V; Bagdasarov, V Kh; Denisov, N N; Garanin, Sergey G; Terekhin, V A; Trutnev, Yurii A

    2012-12-31

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation. (laser technologies)

  17. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    Science.gov (United States)

    Brendel', V. M.; Bukin, V. V.; Garnov, Sergei V.; Bagdasarov, V. Kh; Denisov, N. N.; Garanin, Sergey G.; Terekhin, V. A.; Trutnev, Yurii A.

    2012-12-01

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation.

  18. Games people play with interstitials (in alkali halides)

    International Nuclear Information System (INIS)

    A survey is given of the various ways in which interstitial halogen atoms produced by ionising radiation can be trapped in alkali halides. First, the fundamental interstitial halogen atom center, the H-center, is discussed. Then, interstitial centers trapped by, or in the neighbourhood of, various impurities are presented. Particular attention is given to trapping by the following impurities: foreign halogen ions, foreign alkali ions or pairs of both. The discussion is limited to a description of the production and the models of these H-type centers and little is said about their sometimes interesting physical properties. A few speculations are offered why certain interstitial centers have not yet been observed. The models of a few paramagnetic diinterstitial centers are also presented

  19. Giant photostriction in organic-inorganic lead halide perovskites

    Science.gov (United States)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-04-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices.

  20. Mechanical properties of silver halide core/clad IR fibers

    Science.gov (United States)

    Shalem, Shaul; German, Alla; Moser, Frank; Katzir, Abraham

    1996-04-01

    We have developed core/clad polycrystalline silver halide optical fibers with a loss of roughly 0.3 dB/m at 10.6 micrometers. Such fibers, with core diameters 0.3 - 0.6 mm and lengths of 1 to 2 meters are capable of continuously delivering output power densities as high as 14 KW/cm2. The fibers were repetitively bent in the plastic and elastic regimes and the optical transmission monitored during bending. The mechanical properties of the core/clad fibers and of the core only fibers are similar. It was also demonstrated that the 'bending' properties of the core/clad fibers are determined by the cladding material. Our investigations suggest that proper design of the core/clad structure may give significant improvement in mechanical properties such as more cycles to optical failure. This will be very important especially for endoscopic laser surgery and other medical applications.

  1. Strong Turbulence in Alkali Halide Negative Ion Plasmas

    Science.gov (United States)

    Sheehan, Daniel

    1999-11-01

    Negative ion plasmas (NIPs) are charge-neutral plasmas in which the negative charge is dominated by negative ions rather than electrons. They are found in laser discharges, combustion products, semiconductor manufacturing processes, stellar atmospheres, pulsar magnetospheres, and the Earth's ionosphere, both naturally and man-made. They often display signatures of strong turbulence^1. Development of a novel, compact, unmagnetized alkali halide (MX) NIP source will be discussed, it incorporating a ohmically-heated incandescent (2500K) tantulum solenoid (3cm dia, 15 cm long) with heat shields. The solenoid ionizes the MX vapor and confines contaminant electrons, allowing a very dry (electron-free) source. Plasma densities of 10^10 cm-3 and positive to negative ion mass ratios of 1 Fusion 4, 91 (1978).

  2. Ultraviolet optical absorption of alkali cyanides and alkali halide cyanides

    International Nuclear Information System (INIS)

    The ultraviolet absorption spectra of alkali cyanide and mixed alkali halide cyanide crystals were measured at temperatures ranging from 300K down to 4.2K. A set of small absorption peaks was observed at energies near 6 eV and assigned to parity forbidden X1Σ+→a'3Σ+ transitions of the CN- molecular ions. It was observed that the peak position depends on the alkali atom while the absorption cross section strongly depends on the halogen and on the CN- concentration of the mixed crystals. These effects are explained in terms of an interaction between the triplet molecular excitons and charge transfer excitons. The experimental data were fit with a coupling energy of a few meV. The coupling mechanism is discussed and it is found to be due to the overlap between the wave functions of the two excitations. (Author)

  3. Two-photon pumped lead halide perovskite nanowire lasers

    CERN Document Server

    Gu, Zhiyuan; Sun, Wenzhao; Li, Jinakai; Liu, Shuai; Song, Qinghai; Xiao, Shumin

    2015-01-01

    Solution-processed lead halide perovskites have shown very bright future in both solar cells and microlasers. Very recently, the nonlinearity of perovskites started to attract considerable research attention. Second harmonic generation and two-photon absorption have been successfully demonstrated. However, the nonlinearity based perovskite devices such as micro- & nano- lasers are still absent. Here we demonstrate the two-photon pumped nanolasers from perovskite nanowires. The CH3NH3PbBr3 perovskite nanowires were synthesized with one-step solution self-assembly method and dispersed on glass substrate. Under the optical excitation at 800 nm, two-photon pumped lasing actions with periodic peaks have been successfully observed at around 546 nm. The obtained quality (Q) factors of two-photon pumped nanolasers are around 960, and the corresponding thresholds are about 674?J=cm2. Both the Q factors and thresholds are comparable to conventional whispering gallery modes in two-dimensional polygon microplates. Ou...

  4. Giant photostriction in organic–inorganic lead halide perovskites

    Science.gov (United States)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic–inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge–orbital–lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  5. Phase space investigation of the lithium amide halides

    Energy Technology Data Exchange (ETDEWEB)

    Davies, Rosalind A. [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Hydrogen and Fuel Cell Group, School of Chemical Engineering, University of Birmingham, Edgbaston B15 2TT (United Kingdom); Hewett, David R.; Korkiakoski, Emma [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Thompson, Stephen P. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Anderson, Paul A., E-mail: p.a.anderson@bham.ac.uk [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2015-10-05

    Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li{sub 3}(NH{sub 2}){sub 2}I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li{sub 7}(NH{sub 2}){sub 6}Cl. • New low-chloride phase maintained improved H{sub 2} desorption properties of Li{sub 4}(NH{sub 2}){sub 3}Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH{sub 2}). It was found that the lithium amide iodide Li{sub 3}(NH{sub 2}){sub 2}I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li{sub 7}(NH{sub 2}){sub 6}Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li{sub 4}(NH{sub 2}){sub 3}Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li{sub 7}(NH{sub 2}){sub 6}Cl was observed. In comparison to LiNH{sub 2}, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li{sub 4}(NH{sub 2}){sub 3}Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful.

  6. Phase space investigation of the lithium amide halides

    International Nuclear Information System (INIS)

    Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li3(NH2)2I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li7(NH2)6Cl. • New low-chloride phase maintained improved H2 desorption properties of Li4(NH2)3Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH2). It was found that the lithium amide iodide Li3(NH2)2I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li7(NH2)6Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li4(NH2)3Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li7(NH2)6Cl was observed. In comparison to LiNH2, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li4(NH2)3Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful

  7. NEW THIO S2- ADDUCTS WITH ANTIMONY (III AND V HALIDE: SYNTHESIS AND INFRARED STUDY

    Directory of Open Access Journals (Sweden)

    HASSAN ALLOUCH

    2013-12-01

    Full Text Available Five new S2- adducts with SbIII and SbV halides have been synthesized and studied by infrared. Discrete structures have been suggested, the environment around the antimony being tetrahedral, trigonal bipyramidal or octahedral.

  8. Methods for synthesizing alane without the formation of adducts and free of halides

    Science.gov (United States)

    Zidan, Ragaiy; Knight, Douglas A; Dinh, Long V

    2013-02-19

    A process is provided to synthesize an alane without the formation of alane adducts as a precursor. The resulting product is a crystallized .alpha.-alane and is a highly stable product and is free of halides.

  9. Palladium-catalyzed Cascade Cyclization-Coupling Reaction of Benzyl Halides with N,N-Diallylbenzoylamide

    Institute of Scientific and Technical Information of China (English)

    Yi Min HU; Yu ZHANG; Jian Lin HAN; Cheng Jian ZHU; Yi PAN

    2003-01-01

    A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.

  10. Efficiency of energy transfer from γ-irradiated ammonium halides in aqueous iodide and nitrate solutions

    International Nuclear Information System (INIS)

    It is well known that ammonium halide (NH4X) crystals, on γ-exposure, store energy in the form of primary and secondary radiolytic products. Such crystals on dissolution in aqueous iodide and nitrate solutions result in oxidation of iodide and reduction of nitrate, respectively. The yields of iodine and nitrite are determined by chemical methods under varying conditions of the amount, dose and particle size of the irradiated ammonium halide salts. The maximum values of the efficiency of energy transfer for oxidation and reduction processes for ammonium halide salts correspond to 40% and 10%, respectively. At low doses, an empirical relation proposed between the percent efficiency of energy transfer and the absorbed dose is valid. The concentrations of inherent oxidizing and reducing species initially present are 7.0*1018 and 1.0*1018 per mol of ammonium halide, respectively. (author) 21 refs.; 7 figs.; 2 tabs

  11. Approaching Bulk Carrier Dynamics in Organo-Halide Perovskite Nanocrystalline Films by Surface Passivation.

    Science.gov (United States)

    Stewart, Robert J; Grieco, Christopher; Larsen, Alec V; Maier, Joshua J; Asbury, John B

    2016-04-01

    The electronic properties of organo-halide perovskite absorbers described in the literature have been closely associated with their morphologies and processing conditions. However, the underlying origins of this dependence remain unclear. A combination of inorganic synthesis, surface chemistry, and time-resolved photoluminescence spectroscopy was used to show that charge recombination centers in organo-halide perovskites are almost exclusively localized on the surfaces of the crystals rather than in the bulk. Passivation of these surface defects causes average charge carrier lifetimes in nanocrystalline thin films to approach the bulk limit reported for single-crystal organo-halide perovskites. These findings indicate that the charge carrier lifetimes of perovskites are correlated with their thin-film processing conditions and morphologies through the influence these have on the surface chemistry of the nanocrystals. Therefore, surface passivation may provide a means to decouple the electronic properties of organo-halide perovskites from their thin-film processing conditions and corresponding morphologies. PMID:26966792

  12. Space-dependent self-diffusion processes in molten copper halides: a molecular dynamics study

    OpenAIRE

    Alcaraz Sendra, Olga; Trullàs Simó, Joaquim

    2001-01-01

    This work is concerned with single ion dynamics in molten copper halides (CuI and CuCl) which exhibit fast ionic conduction before melting. The self-dynamic structure factor of the two ionic species in each melt have been calculated by molecular dynamics simulations and the corresponding effective wavelength-dependent self-diffusion coefficients have been studied. The results have been compared with those obtained for molten alkali halides (KCl and RbCl).

  13. Atomistic simulation of ion solvation in water explains surface preference of halides

    OpenAIRE

    Caleman, C.; Hub, J. S.; van Maaren, P.; van der Spoel, D

    2011-01-01

    Water is a demanding partner. It strongly attracts ions, yet some halide anions—chloride, bromide, and iodide—are expelled to the air/water interface. This has important implications for chemistry in the atmosphere, including the ozone cycle. We present a quantitative analysis of the energetics of ion solvation based on molecular simulations of all stable alkali and halide ions in water droplets. The potentials of mean force for Cl-, Br-, and I- have shallow minima near the surface. We demons...

  14. Influence of electrode, buffer gas and control gear on metal halide lamp performance

    International Nuclear Information System (INIS)

    In this paper the influence of electrode composition, buffer gas fill pressure and control gear on the performance of metal halide lamps is investigated. It is shown that pure tungsten electrodes improve lumen maintenance and reduce voltage rise over lamp life. An optimum buffer gas fill pressure condition is discovered which allows for reduced electrode erosion during lamp starting as well as under normal operating conditions. Use of electronic control gear is shown to improve the performance of metal halide lamps

  15. Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2016-02-18

    The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu, and X is a halide. The method comprises the use of two reservoirs containing different precursors and allowing the vapor diffusion from one reservoir to the other one. A solar cell comprising said crystal is also disclosed.

  16. The effect of low solublility organic acids on the hygroscopicity of sodium halide aerosols

    OpenAIRE

    L. Miñambres; Méndez, E; Sánchez, M. N.; Castaño, F.; F. J. Basterretxea

    2014-01-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be performed in this study. The hygroscopic properties of sodium halide submicrometer particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were gen...

  17. The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

    OpenAIRE

    L. Miñambres; Méndez, E; Sánchez, M. N.; Castaño, F.; F. J. Basterretxea

    2014-01-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles w...

  18. Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

    OpenAIRE

    Bretschneider, Simon A.; Jonas Weickert; James A. Dorman; Lukas Schmidt-Mende

    2014-01-01

    The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We...

  19. Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

    Science.gov (United States)

    Rohrmann, Charles A.

    1978-01-01

    A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

  20. Nickel-Catalyzed Regiodivergent Opening of Epoxides with Aryl Halides: Co-Catalysis Controls Regioselectivity

    OpenAIRE

    Zhao, Yang; Weix, Daniel J.

    2013-01-01

    Epoxides are versatile intermediates in organic synthesis, but have rarely been employed in cross-coupling reactions. We report that bipyridine-ligated nickel can mediate the addition of functionalized aryl halides, a vinyl halide, and a vinyl triflate to epoxides under reducing conditions. For terminal epoxides, the regioselectivity of the reaction depends upon the co-catalyst employed. Iodide co-catalysis results in opening at the less hindered position via an iodohydrin intermediate. Titan...

  1. Effect of replacing calcium oxide with calcium halide on crystallization and some physical properties of calcium vanadium phosphate glass ceramics

    International Nuclear Information System (INIS)

    The effect of halide ions on density, electrical, magnetic and crystallization kinetics for (20X-50P2O5-30V2O5) mole% has been investigated, where X=CaO, CaF2, CaCl2 and CaBr2. Halide ions reduce the glass transition temperature, crystallization temperature and activation energy of crystallization. Density, electrical conductivity and magnetic susceptibility increase while molar volume, glass thermal stability and interatomic distance between transition metal ions decrease as the halide ions replace the oxygen ions in these glasses. -- Research Highlights: → Replacing oxygen ions by halide ions decreases glass transition temperature and thermal stability. → Replacing oxygen ions by halide ions increases electrical conductivity and decreases activation energy. → Replacing oxygen ions by halide ions enhances the tendency of glass ceramic and decreases the crystallization activation energy.

  2. Effect of replacing calcium oxide with calcium halide on crystallization and some physical properties of calcium vanadium phosphate glass ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Assem, E.E., E-mail: e_assem_2000@sci.kfs.edu.e [Physics Department, Faculty of Science, Kafrelsheikh University, Kafrelsheikh (Egypt)

    2011-02-01

    The effect of halide ions on density, electrical, magnetic and crystallization kinetics for (20X-50P{sub 2}O{sub 5}-30V{sub 2}O{sub 5}) mole% has been investigated, where X=CaO, CaF{sub 2}, CaCl{sub 2} and CaBr{sub 2}. Halide ions reduce the glass transition temperature, crystallization temperature and activation energy of crystallization. Density, electrical conductivity and magnetic susceptibility increase while molar volume, glass thermal stability and interatomic distance between transition metal ions decrease as the halide ions replace the oxygen ions in these glasses. -- Research Highlights: {yields} Replacing oxygen ions by halide ions decreases glass transition temperature and thermal stability. {yields} Replacing oxygen ions by halide ions increases electrical conductivity and decreases activation energy. {yields} Replacing oxygen ions by halide ions enhances the tendency of glass ceramic and decreases the crystallization activation energy.

  3. Use of radioisotopes in the study of tetracycline analytical application. Extraction of compounds formed between tetracycline and neptunium and americium elements

    International Nuclear Information System (INIS)

    The behavior of tetracycline as complexing agent, in solvent extraction studies of neptunium and americium, using benzyl alcohol as the organic phase, is presented. By using radioactive tracers of 239Np and 241Am the extraction percent of these elements were determined as a function of pH in the absence and in the presence of several masking agents. The influence of shaking time and the use of different types of supporting eletrolytes upon the extraction behavior was also studied. The extraction curves obtained using EDTA as masking agent show that tetracycline can be used for neptunium and americium separation. In this condition neptunium is extracted into the organic phase and americium remains in the aqueous phase. (Author)

  4. Sorption of plutonium and americium on repository, backfill and geological materials relevant to the JNFL low-level radioactive waste repository at Rokkasho-Mura

    International Nuclear Information System (INIS)

    An integrated program of batch sorption experiments and mathematical modeling has been carried out to study the sorption of plutonium and americium on a series of repository, backfill and geological materials relevant to the JNFL low-level radioactive waste repository at Rokkasho-Mura. The sorption of plutonium and americium on samples of concrete, mortar, sand/bentonite, tuff, sandstone and cover soil has been investigated. In addition, specimens of bitumen, cation and anion exchange resins, and polyester were chemically degraded. The resulting degradation product solutions, alongside solutions of humic and isosaccharinic acids were used to study the effects on plutonium sorption onto concrete, sand/bentonite and sandstone. The sorption behavior of plutonium and americium has been modeled using the geochemical speciation program HARPHRQ in conjunction with the HATCHES database

  5. Biosorption of Americium-242 by saccharomyces cerevisiae: preliminary evaluation and mechanism

    International Nuclear Information System (INIS)

    As an important radioisotope in nuclear industry and other fields, americium-241 is one of the most serious contamination concerns duo to its high radiation toxicity and long half-life. In this experiment, the biosorption of 241Am from solution by a fungus, Saccharomyces cerevisiae (S. cerevisiae), and the effects of various experimental conditions on the biosorption and the mechanism were explored. The preliminary results showed that S. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total 241Am could be removed by S. cerevisiae of 2.1g/L (dry weight) from 241Am solutions of 2.22MBq/L -555 MBq/L (Co). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1-3. The culture times of more than 16 hours were suitable and the efficient adsorption of 241Am by the S. cerevisiae could be noted. The biosorption of 241Am by the decomposed cell wall, protoplasm or cell membrane of S. cerevisiae was same efficient as by the intact fungus, but the some components of S. cerevisiae, such as protein and acylation group had obvious effect on adsorption. When the concentrations of coexistent Eu3+, Nd3+ were 100 times more than that of 241Am, the adsorption rates would drop to 65%. However, most of the investigated acidic ions have no significant influence on the 241Am adsorption but minute change of pH value, while the saturated EDTA can strong inhibit the biosorption of 241Am.. (authors)

  6. Characterization of uranium, plutonium, neptunium, and americium in HLW supernate for LLW certification

    International Nuclear Information System (INIS)

    The 1S Manual requires that High Level Waste (HLW) implement a waste certification program prior to sending waste packages to the E-Area vaults. To support the waste certification plan, the HLW supernate inventory of uranium, plutonium, neptunium and americium have been characterized. This characterization is based on the chemical, isotopic and radiological properties of these elements in HLW supernate. This report uses process knowledge, solubility data, isotopic inventory data and sample data to determine if any isotopes of the aforementioned elements will exceed the minimum reportable quantity (MRQ) for waste packages contaminated with HLW supernate. If the MRQ can be exceeded for a particular nuclide, then a method for estimating the waste package content is provided. Waste packages contaminated from HLW supernate do not contain sufficient U-233, U-234, U-235, U-236, U-238, Pu-239, Pu-240, Pu-241, Pu-242 or Am-241 to warrant separate reporting on the shipping manifest. Calculations show that, on average, more than 100 gallons of supernate is required to exceed the PAC (package acceptance criteria) for each of these nuclides. Thus it is highly unlikely that the PAC would be exceeded for these nuclides and unlikely that the MRQ would be exceeded. These nuclides should be manifested as zero for waste packages contaminated with HLW supernate. The only actinide isotopes that may exceed the MRQ are Np-237 and Pu-238. The recommended method to calculate the amount of these two isotopes in waste packages contaminated with HLW supernate is to ratio them to the measured Cs-137 activity

  7. Some elements for a revision of the americium reference biokinetic model

    International Nuclear Information System (INIS)

    The interpretation of individual activity measurement after a contamination by 241Am or its parent nuclide 241Pu is based on the reference americium (Am) biokinetic model published by the International Commission on Radiological Protection in 1993 [International Commission on Radiological Protection. Age-dependent doses to members of the public from intake of radionuclides: Part 2 Ingestion dose coefficients. ICRP Publication 67. Ann. ICRP 23(3/4) (1993)]. The authors analysed the new data about Am biokinetics reported afterwards to propose an update of the current model. The most interesting results, from the United States Transuranium and Uranium Registries post-mortem measurement database [Filipy, R. E. and Russel, J. J. The United States Transuranium and Uranium Registries as sources for actinide dosimetry and bio-effects. Radiat. Prot. Dosim. 105(1-4), 185-187 (2003)] and the long-term follow-up of cases of inhalation intake [Malatova, I., Foltanova, S., Beckova, V., Filgas, R., Pospisilova, H. and Hoelgye, Z. Assessment of occupational doses from internal contamination with 241Am. Radiat. Prot. Dosim. 105(1-4), 325-328 (2003)], seemed to show that the current model underestimates the retention in the massive soft tissues and overestimates the retention in the skeleton and the late urinary excretion. However, a critical review of the data demonstrated that all were not equally reliable and suggested that only a slight revision of the model, possibly involving a change in the balance of activity between massive soft tissues, cortical and trabecular bone surfaces, may be required. (authors)

  8. The treatment of liquid radioactive waste containing Americium by using a cation exchange method

    International Nuclear Information System (INIS)

    A research in the treatment of a liquid radioactive waste containing americium has been done. The liquid radioactive waste used in this research was standard solution of U dan Ce with the initial activity of 100 ppm. The experimental investigation is aimed at a study of the effects of the waste pH, the column dimension of IR-120 cation exchanger which is expressed as L/D, the flow rate of a liquid waste and the influence of thiocyanate as a complex agent against the efficiency of a decontamination for uranium and cerium element. The experiment was done by passing downward the feed of uranium and cerium solution into an IR-120 type of cation exchanger with the L/D of 11.37. From the experimental parameters done in this research where the influence of waste pH was varied from 3 - 8, the geometric column (L/D) 11.37, the liquid flow rate was from 2.5 - 10 ml/m and the thiocyanate concentration was between 100 ppm-500 ppm can be concluded that the optimum operational condition for the ion exchange achieved were the waste pH for uranium = 4 and the waste pH for cerium = 6, the flow rate = 2.5 ml/men. From the given maximum value of DF for uranium = 24 (DE = 95.83%) and of DF for cerium = 40 (DE = 97.5%), it can also be concluded that this investigation is to be continued in order that the greater value of DF/DE can be achieved

  9. A study of plutonium and americium concentrations in seaspray on the southern Scottish coast

    International Nuclear Information System (INIS)

    Seaspray and seawater have been collected from the southern Scottish coast and, for comparison, Cumbria in northwest England during 1989 and 1991. The occurrence of sea-to-land transfer of the actinides plutonium and americium in seaspray was observed on these coasts using muslin screens (a semi-quantitative technique most efficient for collecting large spray droplets) and high volume conventional air samplers. The actinides and fine particulate in the spray were present in relatively higher concentrations than measured in the adjacent seawater, i.e. the spray was enriched in particulate actinides. The net efficiency of the muslim screens in collecting airborne plutonium isotopes and 241Am generally appeared to be about 20%. A review of earlier published concentrations of 239+240Pu and 241Am measured in aerosol and deposition for over a year several tens of metres inland was carried out. This suggested that airborne activities are up to a factor of 5 times higher in Cumbria than southern Scotland. However, neither the new data collected in 1989 and 1991 nor this older data suggests any enhancement of seaspray actinide enrichment in southern Scotland compared to Cumbria. This finding contrasts with earlier, more limited, comparisons that have been carried out which suggested such a difference. There is clear evidence of considerable localised spatial and temporal variability in aerosol actinide enrichment over the beaches in both areas. Enrichments varies between 20 and 500 relative to the adjacent surf zone waters. However, the average enrichment in spray based on the continuous measurements made further inland is likely to be at the lower end of this range. (author)

  10. Reduction of. systematic error of In-vivo measurement of americium 241 activity in the skull

    International Nuclear Information System (INIS)

    Excretion analysis and in vivo measuring methods are used for estimation of internal contamination by 241Am. In vivo measurements of the lung are suitable in short time after time of intake when the way of the intake is inhalation. In vivo measurements of the activity in the liver or in the skeleton could be performed at a later time. Detection of radionuclide activity in the liver is quite difficult because it is necessary to distinguish liver activity from the activity of surrounding tissues i.e. lung and skeleton. The skull or knees are the most suitable., for activity assessment in the skeleton. The skull is the most appropriate for measurements because it represents about 15% of total skeleton mass and contributions to measured activity of surrounding tissues are small. Americium activity in the skull could be measured with different instrumentation and in various geometries. Setting of two semiconductors detectors placed 3 cm over temporal region of the skull is used in NRPI. Calibration of the system was done by several head phantoms, in this process was observed that detection efficiencies depend on size of the phantoms. The aim of the paper is to express character of the efficiency as function of the size of skull in order to obtain more accurate value of the activity and decrees its uncertainty. Simulations of head by simplified geometric shapes, i.e. spheres and rotary ellipsoids, is in coherence with phantoms of big size (UCIN, BPAM-0001), but for small phantoms occurred quite serious discrepancy. Activity of real cases determined by calibration with phantom BPAM-0001 (reference phantom) is reduced from 9 to 44 %, when eq. 2 is used and relative uncertainty is reduced from 32% to maximum 12%. (authors)

  11. Transport of plutonium, americium, and curium from soils into plants by roots

    International Nuclear Information System (INIS)

    For assessing the dose from radionuclides in agricultural products by ingestion it is necessary to know the soil to plant transfer factors. The literature was entirely investigated, in order to judge the size of the soil to plant transfer factors. In total, 92 publications - from 1948 to 1978 -have been evaluated. As result, transfer factors from 10-9 to 10-3 have been found for Plutonium, and from 10-6 to 1 for Americium. For Curium only few data are available in literature. The considerable variation of the measured transfer factors is based on the dependence of these transfer factors from the ion exchange capacity of soils, from the amount of organic materials, from the pH-value, and from the mode of contamination. There are, in any case, contradictory data, although there has been detected a dependence of the transfer factors from these parameters. Chelating agenst increase the transfer factors to approximately 1300. As well, fertilizers have an influence on the size of the transfer factors - however, the relationships have been scarcely investigated. The distribution of actinides within the individual parts of plants has been investigated. The highest concentrations are in the roots; in the plant parts above ground the concentration of actinides decreases considerably. The most inferior transfer factors were measured for the respective seed or fruits. The soil to plant transfer factors of actinides are more dependend on the age of the plants within one growing period. At the beginning of the period, the transfer factor is considerably higher than at the end of this period. With respect to plants with a growing period of several years, correlations are unknown. (orig.)

  12. Reactivity of TEMPO anion as a nucleophile and its applications for selective transformations of haloalkanes or acyl halides to aldehydes

    OpenAIRE

    Inokuchi, Tsutomu; Kawafuchi, Hiroyuki

    2004-01-01

    Sodium 2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO−Na+), generated by reduction of TEMPO· with sodium naphthalenide in THF, reacted with alkyl halides or acyl halides to produce O-alkylated or acylated TEMPOs, which were in turn oxidized with mCPBA or reduced with DIBAL-H to afford the corresponding aldehydes, thus accomplishing a new protocol for the halides-carbonyls conversion.

  13. Inert matrices, uranium-free plutonium fuels and americium targets. Synthesis of CAPRA, SPIN and EFTTRA studies

    International Nuclear Information System (INIS)

    A first selection of inert-matrix materials, actinide support alone (Pu and Am based), and compound materials, U free plutonium burning fuels and heterogeneous americium targets are discussed. Basic properties, fabrication, and reprocessing studies, European in-pile and out-of-pile tests, performed recently in the framework of CAPRA, SPIN and EFTTRA programs, are reviewed here. Taking into account these studies and on the bases of the different requirements to be met in each of the fuels and targets, a number of materials have been selected as 'promising candidates'. Trends for further research on these materials are established. (author)

  14. Final Report on the Demonstration of Disposal of Americium and Curium Legacy Material Through the High Level Waste System

    International Nuclear Information System (INIS)

    This report provides the results of experimental demonstrations related to processing of a legacy solution containing americium and curium through the High Level Waste (HLW) system. The testing included eight experiments covering the baseline, mitigation, and enhanced nitrate processing studies. In general, each experiment studied the mixtures generated over a period of time to emulate the lifecycle of actual sludge in the High Level Waste system. While the data in previous reports remain valid, this report supercedes all the previous reports and provides a collective overview of the work

  15. Effect of a long-term release of plutonium and americium into an estuarine and coastal sea ecosystem

    International Nuclear Information System (INIS)

    This paper discusses the general problem of speciation of plutonium and americium in aquatic ecosystems and the implications relative to their fate in those systems. The following conclusions were reached: several oxidation states of plutonium coexist in the natural environment; the effect of environmental changes such as pH and Esub(h) values and complexes are probably the cause of these various oxidation states; a clearer definition of the 'concentration factor' should be given in view of the important role the sediments play in supplying plutonium for transfer through the food web. (author)

  16. Microstructure and elemental distribution of americium-containing MOX fuel under the short-term irradiation tests

    International Nuclear Information System (INIS)

    In order to investigate the effect of americium addition to MOX fuels on the irradiation behavior, the 'Am-1' program is being conducted in JAEA. The Am-1 program consists of two short-term irradiation tests of 10-minute and 24-hour irradiations and a steady-state irradiation test. The short-term irradiation tests were successfully completed and the post irradiation examinations (PIEs) are in progress. The PIEs for Am-containing MOX fuels focused on the microstructural evolution and redistribution behavior of Am at the initial stage of irradiation and the results to date are reported. (author)

  17. Double-Diffusive Convection During Growth of Halides and Selenides

    Science.gov (United States)

    Singh, N. B.; Su, Ching-Hua; Duval, Walter M. B.

    2015-01-01

    Heavy metal halides and selenides have unique properties which make them excellent materials for chemical, biological and radiological sensors. Recently it has been shown that selenohalides are even better materials than halides or selenides for gamma-ray detection. These materials also meet the strong needs of a wide band imaging technology to cover ultra-violet (UV), midwave infrared wavelength (MWIR) to very long wavelength infrared (VLWIR) region for hyperspectral imager components such as etalon filters and acousto-optic tunable filters (AO). In fact AOTF based imagers based on these materials have some superiority than imagers based on liquid crystals, FTIR, Fabry-Perot, grating, etalon, electro-optic modulation, piezoelectric and several other concepts. For example, broadband spectral and imagers have problems of processing large amount of information during real-time observation. Acousto-Optic Tunable Filter (AOTF) imagers are being developed to fill the need of reducing processing time of data, low cost operation and key to achieving the goal of covering long-wave infrared (LWIR). At the present time spectral imaging systems are based on the use of diffraction gratings are typically used in a pushbroom or whiskbroom mode. They are mostly used in systems and acquire large amounts of hyperspectral data that is processed off-line later. In contrast, acousto-optic tunable filter spectral imagers require very little image processing, providing new strategies for object recognition and tracking. They are ideally suited for tactical situations requiring immediate real-time image processing. But the performance of these imagers depends on the quality and homogeneity of acousto-optic materials. In addition for many systems requirements are so demanding that crystals up to sizes of 10 cm length are desired. We have studied several selenides and halide crystals for laser and AO imagers for MWIR and LWIR wavelength regions. We have grown and fabricated crystals of

  18. STUDY ON THE CATIONIC POLYMERIZATION OF 1,3-PENTADIENE INITIATED BY AlCl3/ALKYL HALIDE SYSTEMS

    Institute of Scientific and Technical Information of China (English)

    PENG Yuxing; LIU Jialin; DAI Hansong; CUN Linfeng

    1996-01-01

    The cationic polymerizations of 1, 3-pentadiene were initiated by AlCl3 in n-hexane at 30℃ in the presence of alkyl halides, i.e., tert-butyl chloride, tert-butyl bromide and isobutyl chloride. The effects of these halides on the polymer yield, molecular weight,crosslinking reaction, cyclization and polymer microstructure, have been investigated. Two main side reactions, crosslinking and cyclization, were suppressed and reduced by the addition of the halides. The proportion of 1, 4 units of polymer chains was increased by the presence of the halides, which reduced the polymer yield and the molecular weight of polymers.

  19. Development of a methodology for the determination of americium and thorium by ICP-AES and their inter-element effect

    International Nuclear Information System (INIS)

    Due to the scarcity of good quality uranium resources, the growth of nuclear technology in India is dependent on the utilization of the vast thorium resources. Therefore, Advance Heavy Water Reactor is going to acquire significant role in the scenario of Indian nuclear technology, where (Th, Pu)O2 will be utilized as fuel in the outermost ring of the reactor core. This will lead to a complex matrix containing thorium as well as americium, which is formed due to β-decay of plutonium. The amount of americium is dependent on the burn up and the storage time of the Pu based fuels. In the present case, attempt was made to develop a method for the determination of americium as well as thorium by ICP-AES. Two emission lines of americium were identified and calibration curves were established for determination of americium. Though the detection limit of 283.236 nm line (5 ng mL-1) of americium was found to be better than that of 408.930 nm (11 ng mL-1), the former line is significantly interfered by large amount of thorium. Three analytical lines (i.e. 283.242, 283.730 and 401.913 nm) of thorium were identified and calibration curves were established along with their detection limits. It was observed that 283.242 and 401.913 nm line are having similar detection limits (18 and 13 ng mL-1, respectively) which are better than that of 283.730 nm (60 ng mL-1). This can be attributed to the high background of 283.273 nm channel of thorium. The spectral interference study revealed that even small amount of americium has significant contribution on 283.242 nm channel of thorium while the other two channels remain practically unaffected. Considering both these facts, spectral interference and analytical performance (detection limits and sensitivity), it was concluded that 401.913 nm line is the best analytical line out of the three lines for determination of thorium in presence of americium. (author)

  20. Photophysics of Hybrid Lead Halide Perovskites: The Role of Microstructure.

    Science.gov (United States)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-03-15

    Since the first reports on high efficiency, solution processed solar cells based on hybrid lead halide perovskites, there has been an explosion of activities on these materials. Researchers with interests spanning the full range from conventional inorganic to emerging organic and hybrid optoelectronic technologies have been contributing to the prolific research output. This has led to solar cell power conversion efficiencies now exceeding 20% and the demonstration of proofs of concept for electroluminescent and lasing devices. Hybrid perovskites can be self-assembled by a simple chemical deposition of the constituent units, with the possibility of integrating the useful properties of organic and inorganic compounds at the molecular scale within a single crystalline material, thus enabling a fine-tuning of the electronic properties. Tellingly, the fundamental properties of these materials may make us think of a new, solution processable, GaAs-like semiconductor. While this can be true to a first approximation, hybrid perovskites are intrinsically complex materials, where the presence of various types of interactions and structural disorder may strongly affect their properties. In particular, a clear understanding and control of the relative interactions between the organic and inorganic moieties is of paramount importance to properly disentangle their innate physics. In this Account we review our recent studies which aim to clarify the relationship between structural and electronic properties from a molecular to mesoscopic level. First we identify the markers for local disorder at the molecular level by using Raman spectroscopy as a probe. Then, we exploit such a tool to explore the role of microstructure on the absorption and luminescence properties of the semiconductor. Finally we address the controversy surrounding electron-hole interactions and excitonic effects. We show that in hybrid lead-halide perovskites dielectric screening also depends on the local

  1. Effects of isoelectronic and halide surfactants on compound semiconductors

    Science.gov (United States)

    Howard, Alexander David

    Isoelectronic surfactants Sb, Bi, and N, have proven to increase the doping efficiency of Zn while concurrently reducing the unintentional impurities C, Si, and S in GaP. Additionally, surfactant Sb and N have demonstrated that altering the incorporation efficiency in GaP is also possible with a surfactant surface coverage of less than one. Halide surfactants Br and Cl were shown to systematically destroy ordering in GaInP. Furthermore, a distinct correlation between increasing surfactant Br or Cl in the vapor and surface roughness was evident. This work is presented in three main sections. First, surfactants Sb and Bi, from the pyrolysis of TMSb and TMBi, were examined to determine the effect on Zn doping in GaP. The data demonstrate that the incorporation of Zn can be increased by an order of magnitude in GaP to a value of approximately 1020 cm-3, the highest value reported to date. Additionally, these same surfactants lead to significant decreases in carbon contamination during growth. At high growth temperatures, the reduction can be as large as 100 x in GaP. Second, the role of steps versus the singular surface between steps was studied by using a surfactant fractional surface coverage of less than one. When surfactant Sb was used, the Zn concentration was increased and C was reduced. However, there was no discernable change in incorporation efficiency over the entire range of surfactant Sb studied. Interestingly, surfactant N showed a linear increase in the Zn doping the with amount of surfactant present during growth resulting in an increase of 2 x at the highest flow rate used. Third, halide surfactants Br and Cl, carbon-tetrabromide and carbon-tetrachloride, were studied for their effects on ordering in GaInP. Bromine systematically decreased the amount of CuPt ordering observed by photoluminescence and transmission electron microscopy. Both surfactants Br and Cl were shown to significantly increase the surface roughness, which is postulated to be the

  2. Silver nanoparticles from silver halide photography to plasmonics

    CERN Document Server

    Tani, Tadaaki

    2015-01-01

    This book provides systematic knowledge and ideas on nanoparticles of Ag and related materials. While Ag and metal nanoparticles are essential for plasmonics, silver halide (AgX) photography relies to a great extent on nanoparticles of Ag and AgX which have the same crystal structure and have been studied extensively for many years. This book has been written to combine the knowledge of nanoparticles of Ag and related materials in plasmonics and AgX photography in order to provide new ideas for metal nanoparticles in plasmonics. Chapters 1–3 of this book describe the structure and formation of nanoparticles of Ag and related materials. Systematic descriptions of the structure and preparation of Ag, Au, and noble-metal nanoparticles for plasmonics are followed by and related to those of nanoparticles of Ag and AgX in AgX photography. Knowledge of the structure and preparation of Ag and AgX nanoparticles in photography covers nanoparticles with widely varying sizes, shapes, and structures, and formation proce...

  3. Superconducting state in bromium halide at high pressure

    Science.gov (United States)

    Szczȩśniak, R.; Zemła, T. P.; Szczȩśniak, D.

    2016-08-01

    The thermodynamic properties of the superconducting state in bromium halide (HBr) compound have been analyzed in the framework of the Eliashberg formalism. In particular, for the range of the pressure (p) from 140 GPa to 200 GPa, it has been shown that the critical temperature increases significantly: TC(p) ∈ K, whereas the Coulomb pseudopotential (μ⋆) is equal to 0.1. Together with the increase of p, the values of the thermodynamic parameters such as: the ratio of the energy gap at the temperature of zero Kelvin to the critical temperature (RΔ ≡ 2 Δ (0) /kB TC), the ratio of the specific heat jump at the critical temperature to the electronic specific heat of the normal state (RC ≡ ΔC (TC) /CN (TC)), and the ratio related to the thermodynamic critical field (RH ≡TC CN (TC) / HC2 (0)) increasingly deviate from the predictions of the BCS model: RΔ(p) ∈ , RC(p) ∈ , and RH(p) ∈ . It should be noted that the increase of μ⋆ visibly lowers TC and significantly reduces the difference between the results of the Eliashberg and BCS theory.

  4. Electron–phonon coupling in hybrid lead halide perovskites

    Science.gov (United States)

    Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.; Eperon, Giles E.; Pérez-Osorio, Miguel A.; Snaith, Henry J.; Giustino, Feliciano; Johnston, Michael B.; Herz, Laura M.

    2016-01-01

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron–phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites. PMID:27225329

  5. Two dimensional condensation of argon adsorbed on lamellar halides

    International Nuclear Information System (INIS)

    Lamellar halides such as NiCl2, FeCl2, NiBr2, MnBr2, MgBr2, CdBr2, CoI2, FeI2, MnI2, CaI2 and PbI2 were sublimed in a rapid stream of dry nitrogen. The adsorption of argon on such materials shows stepped isotherms which reveal two dimensional condensations. From sets of isotherms the Helmholtz free energy, the internal energy and the entropy of the successive layers are determined. From the entropy of the first layer the role of the potential relief of the adsorbent surface on the structure of the adsorbed layer may be determined while the Helmholtz free energy reveals how the ionic character of the adsorbent governs the attractive force of adsorption. The study of the second third and fourth layers shows that their growth follows quite a different behaviour depending on whether the Van der Waals diameter of argon is greater or smaller than the distance between adjacent anions on the crystal surface. A proposition is made to account for the difference in the critical temperatures of the first and second dense layers in terms of the vibrationnal state of their respective substrate. The occurence for the maximum critical temperature observed of corresponding to a triangular layer 3% more expanded than the (111) plane of solid argon is discussed

  6. Photography: enhancing sensitivity by silver-halide crystal doping

    International Nuclear Information System (INIS)

    The physical chemistry of the silver photography processes, exposure, development and fixing, is briefly summarized. The mechanism of the autocatalytic development by the developer of the clusters produced in silver bromide crystals during the exposure which is controlled by the critical nuclearity of these clusters was understood from pulse radiolysis studies. The effective quantum yield PHIeff of photoinduced silver cluster formation in silver halide microcrystals is usually much lower than the photoionization theoretical limit PHItheor=1 electron-hole pair per photon absorbed, owing to a subsequent very fast intra-crystal recombination of a part of the electron-hole pairs. In order to inhibit this recombination and favor the silver reduction by photo-electrons, the AgX crystals were doped with the formate HCO2- as a specific hole scavenger. First, the dopant scavenges the photoinduced hole, thus enhancing the electron escape from the pair recombination. Second, the CO2·- radical so formed transfers an electron to another silver cation, so that the PHIeff limit may be of 2Ag0 per photon. This Photoinduced Bielectronic Transfer mechanism is strictly proportional to the light quanta absorbed and induces an exceptional efficiency for enhancing the radio- or photographic sensitivity insofar as it totally suppresses the electron-hole recombination

  7. Photography: enhancing sensitivity by silver-halide crystal doping

    Energy Technology Data Exchange (ETDEWEB)

    Belloni, Jacqueline

    2003-06-01

    The physical chemistry of the silver photography processes, exposure, development and fixing, is briefly summarized. The mechanism of the autocatalytic development by the developer of the clusters produced in silver bromide crystals during the exposure which is controlled by the critical nuclearity of these clusters was understood from pulse radiolysis studies. The effective quantum yield PHI{sub eff} of photoinduced silver cluster formation in silver halide microcrystals is usually much lower than the photoionization theoretical limit PHI{sub theor}=1 electron-hole pair per photon absorbed, owing to a subsequent very fast intra-crystal recombination of a part of the electron-hole pairs. In order to inhibit this recombination and favor the silver reduction by photo-electrons, the AgX crystals were doped with the formate HCO{sub 2}{sup -} as a specific hole scavenger. First, the dopant scavenges the photoinduced hole, thus enhancing the electron escape from the pair recombination. Second, the CO{sub 2}{sup {center_dot}}{sup -} radical so formed transfers an electron to another silver cation, so that the PHI{sub eff} limit may be of 2Ag{sup 0} per photon. This Photoinduced Bielectronic Transfer mechanism is strictly proportional to the light quanta absorbed and induces an exceptional efficiency for enhancing the radio- or photographic sensitivity insofar as it totally suppresses the electron-hole recombination.

  8. Synthetic and structural chemistry of amidinate-substituted boron halides.

    Science.gov (United States)

    Hill, Nicholas J; Findlater, Michael; Cowley, Alan H

    2005-10-01

    The following new amidinate-substituted boron halides are reported: [PhC{N(SiMe(3))}(2)]BCl(2)(6), [MeC{NCy}(2)]BCl(2)(10), [Mes*C{NCy}(2)]BCl(2)(11), [MeC{N(i)Pr}(2)]BCl(2)(12), and [FcC{NCy}(2)]BBr(2)(13). Compound 6 was prepared via the trimethylsilyl chloride elimination reaction of BCl(3) with N,N,N'-tris(trimethylsilyl)benzamidine, and compounds 10-12 were prepared by salt metathesis between the lithium amidinates [RC(NR')(2)]Li and BX(3). Compound 13 was prepared via the insertion of 1,3-dicyclohexylcarbodiimide into the B-C bond of ferrocenyldibromoborane FcBBr(2). The molecular structures of 6, 10, 11, 13 and the known compound [PhC{N(SiMe(3))}(2)]BBr(2)(1) were established by single-crystal X-ray diffraction. PMID:16172649

  9. Infrared continuum radiation from metal halide high intensity discharge lamps

    Energy Technology Data Exchange (ETDEWEB)

    Herd, M T; Lawler, J E [Department of Physics, University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2007-06-07

    Infrared (IR) continuum radiation from the arc of a metal halide high intensity discharge lamp was measured and modelled. There are three contributions to the near IR continuum from free electrons: electron-Hg atom bremsstrahlung, electron-ion bremsstrahlung and electron-ion recombination radiation. Electron-Hg atom bremsstrahlung is the most important of these. The radiation transport model utilized empirical Hg density, arc temperature and electron density maps. The line width of the Hg 7{sup 1}S{sub 0} to 6{sup 1}P{sub 1} resonance broadened transition was used to determine the arc core Hg density. The arc temperature as a function of radius was determined using the radiance of the Hg 9860, 7311 and 7166 cm{sup -1} lines. Relative densities of neutral Dy atoms and Dy ions as a function of radius were found using an Abel inversion of the relative line radiance of selected Dy I and Dy II lines. A Saha analysis was used to determine the electron density in the lamp. The continuum is 73% of the total near IR radiation in the 4000-12 800 cm{sup -1} range.

  10. Hysteresis, Stability, and Ion Migration in Lead Halide Perovskite Photovoltaics.

    Science.gov (United States)

    Miyano, Kenjiro; Yanagida, Masatoshi; Tripathi, Neeti; Shirai, Yasuhiro

    2016-06-16

    Ion migration has been suspected as the origin of various irreproducible and unstable properties, most notably the hysteresis, of lead halide perovskite photovoltaic (PV) cells since the early stage of the research. Although many evidence of ionic movement have been presented both numerically and experimentally, a coherent and quantitative picture that accounts for the observed irreproducible phenomena is still lacking. At the same time, however, it has been noticed that in certain types of PV cells, the hysteresis is absent or at least within the measurement reproducibility. We have previously shown that the electronic properties of hysteresis-free cells are well represented in terms of the conventional inorganic semiconductors. The reproducibility of these measurements was confirmed typically within tens of minutes under the biasing field of -1 V to +1.5 V. In order to probe the effect of ionic motion in the hysteresis-free cells, we extended the time scale and the biasing rage in the electronic measurements, from which we conclude the following: (1) From various evidence, it appears that ion migration is inevitable. However, it does not cause detrimental effects to the PV operation. (2) We propose, based on the quantitative characterization, that the degradation is more likely due to the chemical change at the interfaces between the carrier selective layers and perovskite rather than the compositional change of the lead iodide perovskite bulk. Together, they give much hope in the use of the lead iodide perovskite in the use of actual application. PMID:27227427

  11. Molecular structure and thermodynamic properties of scandium halides

    International Nuclear Information System (INIS)

    Experimental data on molecular constants of mono-, di- and trihalides of scandium, as well as di-scandium hexahalides of the composition ScXn and Sc2X6 (X = F - I; n = 1 - 3), have been analyzed. Specific features of the compounds molecule structure are considered. The values of molecular constants have been evaluated by the methods of statistical thermodynamics and thermodynamic properties of all scandium halides mentioned in the temperature range of 100 - 6000 K and 298.15 - 1000 K respectively for scandium monohalides and for di-, tri-, hexahalides have been calculated. The values of thermodynamic functions Cp Deg, Φ Deg (T), H Deg (T) - H Deg (0) at 298.15 K published for the first time equal respectively for ScF: 32.734; 192.186; 222.232; 8.958; for ScCl: 45.782; 203.351; 237.356; 10.138; for ScBr: 49.449; 215.090; 252.783; 11.238; for ScI: 42.605; 227.517; 265.635; 12.259

  12. Cerium doped lanthanum halides: fast scintillators for medical imaging

    International Nuclear Information System (INIS)

    This work is dedicated to two recently discovered scintillating crystals: cerium doped lanthanum halides (LaCl3:Ce3+ and LaBr3:Ce3+).These scintillators exhibit interesting properties for gamma detection, more particularly in the field of medical imaging: a short decay time, a high light yield and an excellent energy resolution. The strong hygroscopicity of these materials requires adapting the usual experimental methods for determining physico-chemical properties. Once determined, these can be used for the development of the industrial manufacturing process of the crystals. A proper comprehension of the scintillation mechanism and of the effect of defects within the material lead to new possible ways for optimizing the scintillator performance. Therefore, different techniques are used (EPR, radioluminescence, laser excitation, thermally stimulated luminescence). Alongside Ce3+ ions, self-trapped excitons are involved in the scintillation mechanism. Their nature and their role are detailed. The knowledge of the different processes involved in the scintillation mechanism leads to the prediction of the effect of temperature and doping level on the performance of the scintillator. A mechanism is proposed to explain the thermally stimulated luminescence processes that cause slow components in the light emission and a loss of light yield. Eventually the study of afterglow reveals a charge transfer to deep traps involved in the high temperature thermally stimulated luminescence. (author)

  13. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles

    International Nuclear Information System (INIS)

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large ArN and (H2O)N, N¯≈ 102–103, clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX)n clusters on ArN upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H2O)N. The photodissociation on ArN leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on ArN are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H2O)N also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H3O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H3O. The corresponding Cl-cofragment from the photoexcitation of the HCl·(H2O)N is trapped in the ice nanoparticle

  14. Effects of halides on reaction of nucleosides with ozone.

    Science.gov (United States)

    Suzuki, Toshinori; Kaya, Eriko; Inukai, Michiyo

    2012-01-01

    Ozone (O(3)), a major component of photochemical oxidants, is used recently as a deodorizer in living spaces. It has been reported that O(3) can directly react with DNA, causing mutagenesis in human cells and carcinogenesis in mice. However, little is known about the effects of coexistent ions in the reaction of O(3). In the present study, we analyzed the effects of halides on the reaction of O(3) with nucleosides using reversed-phase high-performance liquid chromatography with ultraviolet detection. When aqueous O(3) solution was added to a nucleoside mixture in potassium phosphate buffer (pH 7.3), the nucleosides were consumed with the following decreasing order of importance: dGuo > Thd > dCyd > dAdo. The effects of addition of fluoride and chloride in the system were slight. Bromide suppressed the reactions of dGuo, Thd, and dAdo but enhanced the reaction of dCyd. The major products were 5-hydroxy-2'-deoxycytidine, 5-bromo-2'-deoxycytidine, and 8-bromo-2'-deoxyguanosine. The time course and pH dependence of the product yield indicated formation of hypobromous acid as the reactive agent. Iodide suppressed all the reactions effectively. The results suggest that bromide may alter the mutation spectrum by O(3) in humans. PMID:22646086

  15. Emission Enhancement and Intermittency in Polycrystalline Organolead Halide Perovskite Films

    Directory of Open Access Journals (Sweden)

    Cheng Li

    2016-08-01

    Full Text Available Inorganic-organic halide organometal perovskites have demonstrated very promising performance for opto-electronic applications, such as solar cells, light-emitting diodes, lasers, single-photon sources, etc. However, the little knowledge on the underlying photophysics, especially on a microscopic scale, hampers the further improvement of devices based on this material. In this communication, correlated conventional photoluminescence (PL characterization and wide-field PL imaging as a function of time are employed to investigate the spatially- and temporally-resolved PL in CH3NH3PbI3−xClx perovskite films. Along with a continuous increase of the PL intensity during light soaking, we also observe PL blinking or PL intermittency behavior in individual grains of these films. Combined with significant suppression of PL blinking in perovskite films coated with a phenyl-C61-butyric acid methyl ester (PCBM layer, it suggests that this PL intermittency is attributed to Auger recombination induced by photoionized defects/traps or mobile ions within grains. These defects/traps are detrimental for light conversion and can be effectively passivated by the PCBM layer. This finding paves the way to provide a guideline on the further improvement of perovskite opto-electronic devices.

  16. Phase holograms in silver halide emulsions without a bleaching step

    Science.gov (United States)

    Belendez, Augusto; Madrigal, Roque F.; Pascual, Inmaculada V.; Fimia, Antonio

    2000-03-01

    Phase holograms in holographic emulsions are usually obtained by two bath processes (developing and bleaching). In this work we present a one step method to reach phase holograms with silver-halide emulsions. Which is based on the variation of the conditions of the typical developing processes of amplitude holograms. For this, we have used the well-known chemical developer, AAC, which is composed by ascorbic acid as a developing agent and sodium carbonate anhydrous as accelerator. Agfa 8E75 HD and BB-640 plates were used to obtain these phase gratings, whose colors are between yellow and brown. In function of the parameters of this developing method the resulting diffraction efficiency and optical density of the diffraction gratings were studied. One of these parameters studied is the influence of the grain size. In the case of Agfa plates diffraction efficiency around 18% with density emulsion, whose grain is smaller than that of the Agfa, diffraction efficiency near 30% has been obtained. The resulting gratings were analyzed through X-ray spectroscopy showing the differences of the structure of the developed silver when amplitude and transmission gratings are obtained. The angular response of both (transmission and amplitude) gratings were studied, where minimal transmission is showed at the Braggs angle in phase holograms, whilst a maximal value is obtained in amplitude gratings.

  17. Alternative translocation of protons and halide ions by bacteriorhodopsin

    International Nuclear Information System (INIS)

    Bacteriorhodopsin (bR568) in purple membrane near pH 2 shifts its absorption maximum from 568 to 605 nm forming the blue protein bRacid605, which no longer transports protons and which shows no transient deprotonation of the Schiff base upon illumination. Continued acid titration with HCl or HBr but not H2SO4 restores the purple chromophore to yield bRHCl564 or bRHBr568. These acid purple forms also regain transmembrane charge transport, but no transient Schiff base deprotonation is observed. In contrast to bR568, no rate decrease of the bRacidpurple transport kinetics is detected in 2H2O; however, the transport rate decreases by a factor of ∼ 2 in bRHBr568 compared with bRHCl564. The data indicate that in the acid purple form bR transports the halide anions instead of protons. The authors present a testable model for the transport mechanism, which should also be applicable to halorhodopsin

  18. Electron-phonon coupling in hybrid lead halide perovskites.

    Science.gov (United States)

    Wright, Adam D; Verdi, Carla; Milot, Rebecca L; Eperon, Giles E; Pérez-Osorio, Miguel A; Snaith, Henry J; Giustino, Feliciano; Johnston, Michael B; Herz, Laura M

    2016-01-01

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron-phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites. PMID:27225329

  19. Effect of radiolysis on leachability of plutonium and americium from 76-101 glass. [Glass containing 2 mole % plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L.; Fried, S.; Friedman, A.M.; Susak, N.; Rickert, P.; Sullivan, J.C.; Karim, D.P.; Lam, D.J.

    1982-01-01

    One aspect of the leachability of actinide-bearing glass which has not been adequately addressed is the effect of radiolysis of the system (glass-water) on the amount of actinides liberated from the glass. In the present study, we have investigated the leaching of plutonium and americium from 76-101 glass samples (containing 2 mole % plutonium) in the presence of a one megaRad/hour gamma-radiation field. The presence of the radiation field was found to increase the leaching rate of both plutonium and americium by a factor of five. Speciation studies of the plutonium in the leachate indicate that the plutonium is present predominantly in the higher oxidation states, Pu(V) and Pu(VI) and that it is significantly associated with colloidal particles. Examination of the glass surfaces with x-ray photoemission spectroscopy, XPS, both before and after leaching was carried out; these studies showed lower surface concentrations of plutonium in the samples of glass leached in the radiation field. 1 figure, 3 tables.

  20. Osteosarcoma induction by plutonium-239, americium-241 and neptunium-237 : the problem of deriving risk estimates for man

    International Nuclear Information System (INIS)

    Spontaneous bone cancer (osteosarcoma) represents only about 0.3% of all human cancers, but is well known to be inducible in humans by internal contamination with radium-226 and radium-224. plutonium-239, americium-241 and neptunium-237 form, or will form, the principal long-lived alpha particle emitting components of high activity waste and burnt-up nuclear fuel elements. These three nuclides deposit extensively in human bone and although, fortunately, no case of a human osteosarcoma induced by any of these nuclides is known, evidence from animal studies suggests that all three are more effective than radium-226 in inducing osteosarcoma. The assumption that the ratio of the risk factors, the number of osteosarcoma expected per 10000 person/animal Gy, for radium-226 and any other bone-seeking alpha-emitter will be independent of animal species has formed the basis of all the important studies of the radiotoxicity of actinide nuclides in experimental animals. The aim of this communication is to review the risk factors which may be calculated from the various animal studies carried out over the last thirty years with plutonium-237, americium-241 and neptunium-237 and to consider the problems which may arise in extrapolating these risk factors to homo sapiens

  1. Plutonium and americium in Arctic waters, the North Sea and Scottish and Irish coastal zones (in Fucus, Mytilus and Patella)

    International Nuclear Information System (INIS)

    Plutonium and americium have been measured in surface waters of the Greenland and Barents Seas and in the northern North Sea from 1980 through 1984. Measurements in water and biota, Fucus, Mytilus and Patella, were carried out in North-English and Scottish waters in 1982 and Fucus samples were collected from the Irish coast in 1983. Fallout is found to dominate as a source of 239+240Pu north of latitude 650N, while for 238Pu a substantial fraction originates from European nuclear fuel reprocessing facilities. The 238Pu/239+240Pu isotope ratio provides clear evidence of the transport of effluent plutonium from the latter to Spitsbergen waters. Fallout plutonium in Arctic waters has a residence time of the order of several years, while for Pu from Sellafield we estimate mean residence times of 11-15 months in Scottish waters and, tentatively, 1.5-3 y during transport from the North Channel (north of the Irish Sea) to Spitsbergen. 241Am found in Arctic waters probably originates from the decay of fallout 241Pu and, like Pu, tentatively has a residence time of the order of several years. Americium from Sellafield has an estimated mean residence time of 4-6 months in Scottish waters. (author)

  2. Experimental Study on Behavior of Americium in Pyrochemical Process of Nitride Fuel Cycle

    International Nuclear Information System (INIS)

    R and D on the transmutation of long-lived minor actinides (MA) by the accelerator-driven system (ADS) using nitride fuels is underway at JAEA. In regard to reprocessing technology, pyrochemical process has several advantages in case of treating spent fuel with large decay heat and fast neutron emission, and recovering highly enriched N-15. In the pyrochemical reprocessing, plutonium and MA are dissolved in LiCl-KCl eutectic melts and selectively recovered into liquid cadmium (Cd) cathode by molten salt electrorefining. The electrochemical behavior in LiCl-KCl eutectic melts and the subsequent nitride formation behavior of plutonium and MA recovered in liquid Cd cathode are investigated. In this paper, recent results on electrochemical study of americium (Am) on electrolyses of AmN in LiCl-KCl eutectic melts and nitride formation of Am recovered in the liquid Cd cathode are presented. Electrochemical behavior of Am on anodic dissolution of AmN and recovery of Am into a liquid Cd cathode by electrolyses in LiCl-KCl eutectic melts was investigated by transient electrochemical techniques. The formal standard potential of Am(III)/Am(0) obtained with the liquid Cd electrode is more positive than that calculated for the solid metal electrode. The potential shift is considered to be attributed to the lowering of the activity of Am by the formation of the intermetallic compound with Cd. Potentiostatic electrolyses of AmN in LiCl-KCl eutectic melts containing AmCl3 at 773 K were carried out. Nitrogen gas generated by the anodic dissolution of AmN was observed, and the current efficiency was obtained from the ratio of the amount of released nitrogen gas and the passed electric charge to be 20 - 28 %. Am was recovered as Am-Cd alloy in the liquid Cd cathode, in which AmCd6 type phase was identified besides Cd phase. The recovered Am was converted to AmN by the nitridation-distillation combined method, in which the Am-Cd alloy was heated in nitrogen gas stream at 973 K. These

  3. Effects of halide ions on photodegradation of sulfonamide antibiotics: Formation of halogenated intermediates.

    Science.gov (United States)

    Li, Yingjie; Qiao, Xianliang; Zhang, Ya-Nan; Zhou, Chengzhi; Xie, Huaijun; Chen, Jingwen

    2016-10-01

    The occurrence of sulfonamide antibiotics (SAs) in estuarine waters urges insights into their environmental fate for ecological risk assessment. Although many studies focused on the photochemical behavior of SAs, yet the effects of halide ions relevant to estuarine and marine environments on their photodegradation have been poorly understood. Here, we investigated the effects of halide ions on the photodegradation of SAs with sulfapyridine, sulfamethazine, and sulfamethoxazole as representative compounds. Results showed that halide ions did not significantly impact the photodegradation of sulfapyridine and sulfamethoxazole, while they significantly promoted the photodegradation of sulfamethazine. Further experiments found that ionic strength applied with NaClO4 significantly enhanced the photodegradation of the SAs, which was attributed to the decreased quenching rate constant of the triplet-excited SAs ((3)SA(∗)). Compared with ionic strength, specific Cl(-) effects retarded the photodegradation of the SAs. Our study found that triplet-excited sulfamethazine can oxidize halide ions to produce halogen radicals, subsequently leading to the halogenation of sulfamethazine, which was confirmed by the identification of both chlorinated and brominated intermediates. These results indicate that halide ions play an important role in the photochemical behavior of some SAs in estuarine waters and seawater. The occurrence of halogenation for certain organic pollutants can be predicted by comparing the oxidation potentials of triplet-excited contaminants with those of halogen radicals. Our findings are helpful in understanding the photochemical behavior and assessing the ecological risks of SAs and other organic pollutants in estuarine and marine environment. PMID:27393965

  4. Graphitic cage transformation by electron-beam-induced catalysis with alkali-halide nanocrystals

    Science.gov (United States)

    Fujita, Jun-ichi; Tachi, Masashi; Ito, Naoto; Murakami, Katsuhisa; Takeguchi, Masaki

    2016-05-01

    We found that alkali-halide nanocrystals, such as KCl and NaCl, have strong catalytic capability to form graphitic carbon cages from amorphous carbon shells under electron beam irradiation. In addition to the electron beam irradiation strongly inducing the decomposition of alkali-halide nanocrystals, graphene fragments were formed and linked together to form the final product of thin graphitic carbon cages after the evaporation of alkali-halide nanocrystals. The required electron dose was approximately 1 to 20 C/cm2 at 120 keV at room temperature, which was about two orders of magnitude smaller than that required for conventional beam-induced graphitization. The “knock-on” effect of primary electrons strongly induced the decomposition of the alkali-halide crystal inside the amorphous carbon shell. However, the strong ionic cohesion quickly reformed the crystal into thin layers inside the amorphous shell. The bond excitation induced by the electron beam irradiation seemed to enhance strongly the graphitization at the interface between the outer amorphous carbon shell and the inner alkali-halide crystal.

  5. Preconcentration of low levels of americium and plutonium from waste waters by synthetic water-soluble metal-binding polymers with ultrafiltration

    International Nuclear Information System (INIS)

    A preconcentration approach to assist in the measurement of low levels of americium and plutonium in waste waters has been developed based on the concept of using water-soluble metal-binding polymers in combination with ultrafiltration. The method has been optimized to give over 90% recovery and accountability from actual waste water. (author)

  6. Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

    OpenAIRE

    Aiichiro Nagaki; Yuki Uesugi; Yutaka Tomida; Jun-ichi Yoshida

    2011-01-01

    The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

  7. Copper(I)-catalyzed carbon-halogen bond-selective boryl substitution of alkyl halides bearing terminal alkene moieties

    OpenAIRE

    Iwamoto, Hiroaki; Kubota, Koji; Yamamoto, Eiji; Ito, Hajime

    2015-01-01

    The selective boryl substitution of alkyl halides bearing terminal C=C double bonds has been achieved using a copper(I)/tricyclohexylphosphine or copper(I)/o-diphenylphosphinophenol catalyst. This reaction represents a useful complementary approach to conventional procedures for the hydroboration of C=C double bonds or the borylative cyclization of alkyl halides bearing terminal alkenes.

  8. Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

    OpenAIRE

    Nagaki, Aiichiro; Uesugi, Yuki; Tomida, Yutaka; Yoshida, Jun-ichi

    2011-01-01

    The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

  9. 10 CFR 431.324 - Uniform test method for the measurement of energy efficiency of metal halide ballasts.

    Science.gov (United States)

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Uniform test method for the measurement of energy efficiency of metal halide ballasts. 431.324 Section 431.324 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts...

  10. Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

    Directory of Open Access Journals (Sweden)

    Aiichiro Nagaki

    2011-08-01

    Full Text Available The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

  11. Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun; Wang, Yafeng; Hu, Tao; Wu, Lin; Shen, Xuechu; Chen, Zhanghai, E-mail: lujian@fudan.edu.cn, E-mail: zhanghai@fudan.edu.cn [State Key Laboratory of Surface Physics, Key Laboratory of Micro and Nano Photonic Structures (Ministry of Education), Department of Physics, Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China); Cao, Runan; Xu, Fei [Department of Physics, Shanghai University, Shanghai 200444 (China); Da, Peimei; Zheng, Gengfeng [Laboratory of Advanced Materials, Department of Chemistry, Fudan University, Shanghai 200433 (China); Lu, Jian, E-mail: lujian@fudan.edu.cn, E-mail: zhanghai@fudan.edu.cn [State Key Laboratory of Surface Physics, Key Laboratory of Micro and Nano Photonic Structures (Ministry of Education), Department of Physics, Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China); Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China)

    2016-01-11

    Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources.

  12. Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

    International Nuclear Information System (INIS)

    Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources

  13. Self-Correction of Lanthanum-Cerium Halide Gamma Spectra (pre-print)

    Energy Technology Data Exchange (ETDEWEB)

    Ding Yuan, Paul Guss, and Sanjoy Mukhopadhyay

    2009-04-01

    Lanthanum-cerium halide detectors generally exhibit superior energy resolutions for gamma radiation detection compared with conventional sodium iodide detectors. However, they are also subject to self-activities due to lanthanum-138 decay and contamination due to beta decay in the low-energy region and alpha decay in the high-energy region. The detector’s self-activity and crystal contamination jointly contribute a significant amount of uncertainties to the gamma spectral measurement and affect the precision of the nuclide identification process. This paper demonstrates a self-correction procedure for self-activity and contamination reduction from spectra collected by lanthanum-cerium halide detectors. It can be implemented as an automatic self-correction module for the future gamma radiation detector made of lanthanum-cerium halide crystals.

  14. Self-Correction of Lanthanum-Cerium Halide Gamma Spectra (pre-print)

    International Nuclear Information System (INIS)

    Lanthanum-cerium halide detectors generally exhibit superior energy resolutions for gamma radiation detection compared with conventional sodium iodide detectors. However, they are also subject to self-activities due to lanthanum-138 decay and contamination due to beta decay in the low-energy region and alpha decay in the high-energy region. The detector's self-activity and crystal contamination jointly contribute a significant amount of uncertainties to the gamma spectral measurement and affect the precision of the nuclide identification process. This paper demonstrates a self-correction procedure for self-activity and contamination reduction from spectra collected by lanthanum-cerium halide detectors. It can be implemented as an automatic self-correction module for the future gamma radiation detector made of lanthanum-cerium halide crystals.

  15. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.;

    2014-01-01

    electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) – almost 27000 combinations, and have identified novel mixtures, with significantly improved storage......Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be...... supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer...

  16. Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

    Directory of Open Access Journals (Sweden)

    Sourish Chatterjee

    2013-11-01

    Full Text Available Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of CMH lamp demands the use of current control device in the lamp circuit and perfect matching of lamp ballast combination is required for efficient lamp operation. The electrical and photometric performance of two sets of commercial 70 watt CMH lamp and intregated ballast units were measured to investigate their compatibility for optimum lamp operation. The measured data were utilized to develop an electrical model for lamp ballast combination. Using this model a compatibility index is proposed which can be used for assessment of lamp performance.

  17. Effects of halides on plasmid-mediated silver resistance in Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, A.; Maynes, M.; Silver, S. [Univ. of Illinois, Chicago, IL (United States). Dept. of Microbiology and Immunology

    1998-12-01

    Silver resistance of sensitive Escherichia coli J53 and resistance plasmid-containing J53(pMG101) was affected by halides in the growth medium. The effects of halides on Ag{sup +} resistance were measured with AgNO{sub 3} and silver sulfadiazine, both on agar and in liquid. Low concentrations of chloride made the differences in MICs between sensitive and resistant strains larger. High concentrations of halides increased the sensitivities of both strains to Ag{sup +}. The purpose of this report is to set out easy-to-use conditions for measuring silver sensitivity and resistance in familiar and widely used media, Luria-Bertani (LB) agar and broth, so as to facilitate wider identification of silver resistance in nature.

  18. Studies on radiation-sensitive nonsilver halide materials, (1)

    International Nuclear Information System (INIS)

    In order to discover new radiation-sensitive nonsilver halide materials, the coloration based on the formation of Stenhouse salts was studied in the following three systems: (a) furfural-amine/HCl aq/methanol solution, (b) furfural-amine/polyhalogenide/PMMA matrix, (c) furfural-amine/PVC matrix. Firstly, forty-five aromatic amines were surveyed to find out the amines suitable for the color precursors (reactant from furfural and amine) in the system (a). As a result, the five amines, which gave the precursors in good yields by the reaction with furfural, were selected: m-nitroaniline, N-methylaniline, m-methyl-N-methylaniline, aniline, and o-methoxyaniline. Secondly, the coloration induced by electron beam bombardment was studied in the systems (b) and (c) containing the color precursors (the reactants from these amines and furfural). Although the PMMA films containing the color precursors and polyhalogenides were sensitive to electron beam, they were not stable when standing under daylight at room temperature. The PVC films containing the color precursors were very stable and colored to reddish yellow (lambda sub(max) 498 - 545 nm) by electron beam bombardment. The PVC film containing N-methylaniline-furfural was the most sensitive and the increase in absorbance at 498 nm was 0.78 by electron beam bombardment of 60 kV - 7.5 x 10-7C/cm2. A good linear relationship existed between the degree of coloration and the amounts of electron beam bombardment in the range from 0 to 10-6C/cm2. (author)

  19. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles.

    Science.gov (United States)

    Poterya, V; Lengyel, J; Pysanenko, A; Svrčková, P; Fárník, M

    2014-08-21

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large ArN and (H2O)N, N̄ ≈ 10(2)-10(3), clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX)n clusters on ArN upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H2O)N. The photodissociation on ArN leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on ArN are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H2O)N also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H3O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H3O. The corresponding Cl-cofragment from the photoexcitation of the HCl·(H2O)N is trapped in the ice nanoparticle. PMID:25149788

  20. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    International Nuclear Information System (INIS)

    We have studied a reaction between the reduced form of titanocene dichloride (Cp2TiCl2) and a group of organic halides: benzyl derivatives (4-X-C6H4CH2Cl, X = H, NO2, CH3; 4-X-C6H4CH2Br, X = H, NO2, PhC(O); 4-X-C6H4CH2SCN, X = H, NO2) as well as three aryl halides (4-NO2C6H4Hal, Hal = Cl, Br; 4-CH3O-C6H4Cl). It has been shown that the electrochemical reduction of Cp2TiCl2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

  1. Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

    Directory of Open Access Journals (Sweden)

    Simon A. Bretschneider

    2014-04-01

    Full Text Available The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We discuss the crystal and band structure of perovskite materials currently implemented in solar cells and the impact of the crystal properties on ferroelectricity, ambipolarity, and the properties of excitons.

  2. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  3. The electronic structure of the F-center in alkali-halides-The Bethe cluster - lattice

    International Nuclear Information System (INIS)

    The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Bethe Cluster lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second-neighbors to it, respectively cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides. (Author)

  4. Mid-infrared planar silver halide waveguides with integrated grating couplers.

    Science.gov (United States)

    Schädle, Thomas; Eifert, Alexander; Kranz, Christine; Raichlin, Yosef; Katzir, Abraham; Mizaikoff, Boris

    2013-09-01

    Grating couplers for planar silver halide waveguides were designed and fabricated by using focused ion beam (FIB) milling technology, facilitating coupling of mid-infrared radiation from quantum cascade lasers into thin-film waveguide structures. An optimized rectangular grating structure for an emitted wavelength of 10.4 μm, with a grating constant of 16.4 μm was integrated into a silver halide waveguide substrate via an optimized FIB fabrication procedure. Efficient incoupling and radiation propagation through the waveguide was confirmed by analyzing droplets of acetic acid at different concentrations, deposited at the waveguide surface via evanescent field absorption spectroscopy. PMID:24067637

  5. Propensity of heavier halides for the water/vapor interface revisited using the Amoeba force field

    Science.gov (United States)

    Tůma, Lukáš; Jeníček, Dominik; Jungwirth, Pavel

    2005-08-01

    Molecular dynamics simulations of aqueous sodium halide solutions in slab geometry were performed using the state-of-the-art polarizable Amoeba force field. The present calculations reveal a propensity of halide anions for the water/vapor interface, which correlates with the ionic size and polarizability and, therefore, increases in the series Cl - < Br - < I -. These results are in a quantitative agreement with previous calculations employing much simpler polarizable potentials and are supported by a mounting experimental evidence from photoelectron and non-linear optical and vibrational spectroscopies.

  6. Surface tension of molten alkali metal halides as a function of ion sizes

    International Nuclear Information System (INIS)

    The analysis of the experimental data on the surface tension of the liquid/vapor interphase boundary of the molten alkali metal halides MX (M Li-Cs, X = F-I) near the melting temperature, accounting for the cation and anion dimensional differences, is presented. The main attention is focused at the manifestation of the effects of the interphase boundary of the effects of the interphase boundary thickness and twofold electric layer. It is shown, that the experimental data on the whole MX series may be represented in the form of the electrocapillary curve on the graph of the surface tension dependence on the degree of the halides dimensional asymmetry

  7. High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

    Science.gov (United States)

    Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

    2016-06-01

    Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed. PMID:26669326

  8. Nickel-catalyzed regiodivergent opening of epoxides with aryl halides: co-catalysis controls regioselectivity.

    Science.gov (United States)

    Zhao, Yang; Weix, Daniel J

    2014-01-01

    Epoxides are versatile intermediates in organic synthesis, but have rarely been employed in cross-coupling reactions. We report that bipyridine-ligated nickel can mediate the addition of functionalized aryl halides, a vinyl halide, and a vinyl triflate to epoxides under reducing conditions. For terminal epoxides, the regioselectivity of the reaction depends upon the cocatalyst employed. Iodide cocatalysis results in opening at the less hindered position via an iodohydrin intermediate. Titanocene cocatalysis results in opening at the more hindered position, presumably via Ti(III)-mediated radical generation. 1,2-Disubstituted epoxides are opened under both conditions to form predominantly the trans product. PMID:24341892

  9. Nickel-catalyzed electrochemical couplings of vinyl halides: synthetic and stereochemical aspects

    Science.gov (United States)

    Cannes; Condon; Durandetti; Perichon; Nedelec

    2000-07-28

    Homo- and cross-coupling involving alkenyl halides have been performed efficiently using an electroassisted nickel-complex catalysis. Valuable product such as conjugated dienes, beta,gamma- or gamma,delta-unsaturated esters, ketones, or nitriles, as well as alkenylated aryl compounds are thus prepared with high yields and high stereoselectivity. Partial isomerization is only observed in a few cases, when the alkenyl halide is involved in a late step of the catalytic cycle. This is the case in the preparation of (Z,Z)-1,3-diene. PMID:10959862

  10. Chemical behaviour of trivalent and pentavalent americium in saline NaCl-solutions. Studies of transferability of laboratory data to natural conditions. Interim report. Reported period: 1.2.1993-31.12.1993; Chemisches Verhalten von drei- und fuenfwertigem Americium in Salinen NaCl-Loesungen. Untersuchung der Uebertragbarkeit von Labordaten auf natuerliche Verhaeltnisse. Zwischenbericht. Berichtszeitraum 1.2.1993-31.12.1993

    Energy Technology Data Exchange (ETDEWEB)

    Runde, W.; Kim, J.I.

    1994-09-15

    In order to clarify the chemical behaviour of Americium in saline aqueous systems relevant for final storage this study deals with the chemical reactions of trivalent and pentavalent Americium in NaCl-solutions under the influence of radiolysis from its own alpha radiation. The focus of the study was on investigating the geologically relevant reactions, such as hydrolysis or carbonate- and chloride complexing in solid-liquid equilibriums. Comprehensive measurements on solubility and spectroscopic studies in NaCl-solutions were carried out in a CO{sub 2}-free atmosphere and 10{sup -2} atm CO{sub 2} partial pressure. Identification and characterisation of the AM (III) and AM(V) solid phases were supplemented by structural research with the chemically analogue EU (III) and Np(V) compounds. The alpha-radiation induced radiolysis in saline NaCl solutions and the redox behaviour of Americium which was influenced thereby were spectroscopically quantified. (orig.) [Deutsch] Zur Klaerung des chemischen Verhaltens von Americium in endlagerrelevanten salinen aquatischen Systemen befasst sich die vorliegende Arbeit mit den chemischen Reaktionen des drei- und fuenfwertigen Americiums in NaCl-Loesungen unter dem Einfluss der Radiolyse durch die eigene {alpha}-Strahlung. Der Schwerpunkt dieser Arbeit lag auf der Untersuchung der geologisch relevanten Reaktionen, wie Hydrolyse sowie Carbonat- und Chloridkomplexierung in fest-fluessig Gleichgewichtssystemen. Hierzu wurden umfassende Loeslichkeitsmessungen und spektroskopische Untersuchungen in NaCl-Loesungen, sowohl unter CO{sub 2}-freier Atmosphaere als auch unter 10{sup -2} atm CO{sub 2}-Partialdruck, durchgefuehrt. Die Identifizierung und Charakterisierung der Am(III)- und Am(V)-Festphasen wurde ergaenzt durch strukturelle Untersuchungen mit den chemisch analogen Eu(III)- und Np(V)-Verbindungen. Die von der {alpha}-Strahlung induzierte Radiolyse in salinen NaCl-Loesungen und das dadurch beeinflusste Redoxverhalten von Americium

  11. Influence of an alkoxy group on bis-triazinyl-pyridines for selective extraction of americium(III)

    International Nuclear Information System (INIS)

    The extraction of americium(III), curium(III), and lanthanides(III) from nitric acid by 2,6-bis-(5,6-dimethyl-[1,2,4]-triazin-3-yl)-pyridine and 2,6-bis-(5,6-dimethyl-[1,2,4]-triazin- 3-yl)-4-methoxy-pyridine was studied. The physico-chemical properties of these ligands, such as the protonation and complexation constants, were also determined to describe the influence of different substituent groups. The selectivity of substituted-BTP was confirmed both in complexation and in solvent extraction experiments. The presence of an alkoxy-group in position 4 of the pyridine decreases the BTP selectivity. Influence of a long alkyl chain on protonation and complexation constants was also studied with 2,6-bis-(5,6-dimethyl-[1,2,4]- triazin-3-yl)-4-dodecyloxy-pyridine. (authors)

  12. Solvent extraction of europium and americium into phenyltrifluoromethyl sulfone by using synergistic mixture of hydrogen dicarbollylcobaltate and 'classical' CMPO

    International Nuclear Information System (INIS)

    Extraction of microamounts of europium and americium by a phenyltrifluoromethyl sulfone (FS 13) solution of hydrogen dicarbollylcobaltate (H+B-) in the presence of octyl-phenyl-N,N-diisobutylcarbamoylmethyl phosphine oxide ('classical' CMPO, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL+, HL2+, ML23+, ML33+ and ML43+ (M3+ Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the cationic complex species in FS 13 saturated with water have been determined. It was found that the stability constants of the corresponding complexes EuLn3+ and AmLn3+, where n 2, 3, 4 and L is 'classical' CMPO, in water-saturated FS 13 are comparable. (author)

  13. Recovery, purification and concentration of plutonium and americium from the aqueous wastes discharged in the reprocessing process studies

    International Nuclear Information System (INIS)

    For recovering and purifying plutonium and americium from the aqueous wastes occurring in the process studies on reprocessing, a standard procedure has been established for use in the laboratory works, through the preliminary tests of the precipitation as hydroxides and the anion exchange in nitrate media. The procedure was proven in the treatment of actual wastes, of which the results were contributed to determine the process conditions in the plutonium purification and product concentration of the JAERI Reprocessing Test Plant. The preliminary tests also include washing of U and Am recovery from the anion-exchanger in nitrate media, direct ion-exchange recovery of Pu from the TBP phase and elution of Am from the cation-exchanger. (auth.)

  14. Plutonium and americium in fish, shellfish and seaweed in the Irish environment and their contribution to dose

    International Nuclear Information System (INIS)

    Plutonium and americium activity concentrations in fish and shellfish landed in Ireland in the period 1988 to 1997 are presented. Activity concentrations in fish are low and often below detection limits, while those in mussels and oysters sampled on the northeast coast show no significant signs of decline. The estimated doses to hypothetical typical and heavy seafood consumers remain below 1 μSv yr-1 (committed effective dose).Plutonium activity concentrations measured in Fucus vesiculosus around the Irish coastline have not fallen appreciably in the ten year period between 1986 and 1996. Furthermore, the mean 238Pu/239,240Pu ratio of 0.17±0.05 in Fucus vesiculosus from the west coast of Ireland demonstrates the increasing significance of Sellafield-derived plutonium in those waters. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  15. The bone volume effect on the dosimetry of plutonium-239 and americium-241 in the skeleton of man and baboon

    International Nuclear Information System (INIS)

    Studies were undertaken using bone removed from young adult baboons, which had been contaminated with plutonium-239 at various times prior to sacrifice, and human bone from adult male (USTR Case 246), who had received an internal deposition of americium-241 as a result of a glove-box explosion 11 years prior to his death. The baboon bone was supplied by the CEA, France, and the human bone by the United States Transuranium registry. The bone samples, examined by qualitative and quantitative autoradiography with CR 39 detectors, demonstrated the rapid redistribution of bone surface-seeking radionuclides in younger primates due to growth and the slower, bone turnover driven redistribution in the adult human bone. In both species, primary and secondary surface deposits of radionuclide remained conspicious despite bone activity; true volumization of radionuclide was seldom seen. The dosimetric implications of these findings are discussed. (author) 21 refs.; 6 figs.; 4 tabs

  16. GaN nanotubes grown by halide vapor phase epitaxy

    International Nuclear Information System (INIS)

    Full text: Wide-band gap GaN nanostructures such as quantum dots, nanorods, nanowires, nano columns and nanotubes have a strong potential within areas of biochemical sensing, nanofluidics, and optoelectronics. GaN nanotubes play a role of the building blocks for several applications such as solution-based transistors and highly sensitive nanotube molecular sensors. We have studied non-catalytic and Au-assisted growth of GaN nanotubes using halide vapor phase epitaxy (HVPE) technique. The growth was performed in the temperature range 480 degrees Celsius to 520 degrees Celsius using pure N2 as a carrier gas at atmospheric pressure. The nanotubes size, shape, density and the selectivity of growth have been studied depending on V/III ratio, growth temperature and substrate material. By increasing the GaCl partial pressure, the structure changed from dot-like to nanotubes. The nanotubes were about 1 μm long with a diameter of typically 200 nm. In addition, it was observed that the nanostructures were spontaneously nucleated at droplets of Ga or, when using Au-coated Al2O3, on droplets of Au/Ga alloy. By varying the growth temperature, the inner diameter of the nanotubes could be controlled. A growth model is suggested, where the nanotubes are nucleated at droplets of Ga or an Au/Ga alloy. Our experimental results suggest that the approach with pre-patterned Au-coated Al2O3 substrates has the potential for fabrication of well-organized nanotubes with a high density. Nanostructures were characterized using electron microscopy methods and by low temperature time-resolved photoluminescence (TRPL). Studies were performed on samples with different wall thickness in the range of 35-75 nm. Two recombination processes with different dynamics contribute to the emission spectra of the GaN nanotubes. The photoluminescence peak shifts rapidly to the higher energy from 3.47 eV to 3.75 eV within a very short time of 30 ps. The origin of the emission having a short lifetime is related

  17. Regioselective chlorination and bromination of unprotected anilines under mild conditions using copper halides in ionic liquids

    OpenAIRE

    Han Wang; Kun Wen; Nurbiya Nurahmat; Yan Shao; He Zhang; Chao Wei; Ya Li; Yongjia Shen; Zhihua Sun

    2012-01-01

    By using ionic liquids as solvents, the chlorination or bromination of unprotected anilines at the para-position can be achieved in high yields with copper halides under mild conditions, without the need for potentially hazardous operations such as supplementing oxygen or gaseous HCl.

  18. A study on the electrochemical behaviour of polypyrrole films in concentrated aqueous alkali halide electrolytes

    DEFF Research Database (Denmark)

    Jafeen, M. J. M.; Careem, M.A.; Skaarup, Steen

    2014-01-01

    difference. In highly concentrated aqueous electrolytes, the mass of the PPy/DBS film at the end of each redox cycle is found to drift, which can be controlled by changing the concentration of the electrolyte. The PPy/DBS films were also cycled at different scan rates in various alkali halide aqueous...

  19. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    Science.gov (United States)

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-01

    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions. PMID:27490708

  20. Magnetic Silica Supported Copper: A Modular Approach to Aqueous Ullmann-type Amination of Aryl Halides

    Science.gov (United States)

    One-pot synthesis of magnetic silica supported copper catalyst has been described via in situ generated magnetic silica (Fe3O4@SiO2); the catalyst can be used for the efficacious amination of aryl halides in aqueous medium under microwave irradiation.

  1. Concentration dependence of halide fluxes and selectivity of the anion pathway in toad skin

    DEFF Research Database (Denmark)

    Harck, A F; Larsen, Erik Hviid

    1986-01-01

    mV (apical bath negative). The active sodium currents were eliminated by replacing external Na+ with K+. With [Cl-]o varying between 1.45 mM and 110 mM (gluconate substitution) and [I-]o = 3 mM, the total clamping current (y) and the sum of halide currents (x), estimated from flux measurements, were...

  2. Regioselective chlorination and bromination of unprotected anilines under mild conditions using copper halides in ionic liquids

    Directory of Open Access Journals (Sweden)

    Han Wang

    2012-05-01

    Full Text Available By using ionic liquids as solvents, the chlorination or bromination of unprotected anilines at the para-position can be achieved in high yields with copper halides under mild conditions, without the need for potentially hazardous operations such as supplementing oxygen or gaseous HCl.

  3. Amination of Aryl Halides and Esters Using Intensified Continuous Flow Processing

    OpenAIRE

    Thomas M. Kohl; Christian H. Hornung; John Tsanaktsidis

    2015-01-01

    Significant process intensification of the amination reactions of aryl halides and esters has been demonstrated using continuous flow processing. Using this technology traditionally difficult amination reactions have been performed safely at elevated temperatures. These reactions were successfully conducted on laboratory scale coil reactor modules with 1 mm internal diameter (ID) and on a preparatory scale tubular reactor with 6 mm ID containing static mixers.

  4. Iron-Catalyzed Acylation of Polyfunctionalized Aryl- and Benzylzinc Halides with Acid Chlorides.

    Science.gov (United States)

    Benischke, Andreas D; Leroux, Marcel; Knoll, Irina; Knochel, Paul

    2016-08-01

    FeCl2 (5 mol %) catalyzes a smooth and convenient acylation of functionalized arylzinc halides at 50 °C (2-4 h) and benzylic zinc chlorides at 25 °C (0.5-4 h) with a variety of acid chlorides leading to polyfunctionalized diaryl and aryl heteroaryl ketones. PMID:27457108

  5. Epitaxial Growth of a Methoxy-Functionalized Quaterphenylene on Alkali Halide Surfaces

    DEFF Research Database (Denmark)

    Balzer, Frank; Sun, Rong; Parisi, Jürgen;

    2015-01-01

    The epitaxial growth of the methoxy functionalized para-quaterphenylene (MOP4) on the (001) faces of the alkali halides NaCl and KCl and on glass is investigated by a combination of lowenergy electron diffraction (LEED), polarized light microscopy (PLM), atomic force microscopy (AFM), and X...

  6. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing.

    Science.gov (United States)

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka

    2016-04-01

    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature. PMID:27451628

  7. Chemistry of gaseous lower-valent actinide halides. Technical progress report

    International Nuclear Information System (INIS)

    Objective is to provide thermochemical data for key actinide halide and oxyhalide systems. Progress is reported on bond dissociation energies of gaseous ThCl4, ThCl3, ThCl2, and ThCl; bond dissociation energies of ruthenium fluorides; and mass spectroscopy of UF6

  8. New Condensation Reaction of β-keto-δ-valerolactones, Carbon Disulfide and Alkyl Halides

    Institute of Scientific and Technical Information of China (English)

    You Ming WANG; Yu Xin LI; Su Hua WANG; Zheng Ming LI

    2004-01-01

    β-Keto-δ-valerolactones, which were obtained by reaction of acetoacetate with aldehydes or ketones, reacted with carbon disulfide, alkyl halides and a new condensation reaction was developed. The structures of the products 3 were confirmed by 1HNMR spectra and elemental analysis.

  9. Synthesis of Cyclic Carbonates from CO2 and Epoxides Catalyzed by Hexaalkylguanidinium Halides

    Institute of Scientific and Technical Information of China (English)

    DUAN Hai-feng; LI Sheng-hai; LIN Ying-jie; XIE Hai-bo; ZHANG Suo-bo; WANG Zong-mu

    2004-01-01

    Hexaalkylguanidinium halides exhibit an efficient catalytic activity in the synthesis of cyclic carbonates from epoxides and carbon dioxide. By this method cyclic carbonates can be obtained in a high yield and a high selectivity at a low temperature and atmospheric pressure. This procedure is easy for the product isolation and recycling of the catalyst.

  10. Palladium-catalyzed Coupling between Aryl Halides and Trimethylsilylacetylene Assisted by Dimethylaminotrimethyltin

    Institute of Scientific and Technical Information of China (English)

    Cai Liangzhen; Yang Dujuan; Sun Zhonghua; Tao Xiaochun; Cai Lisheng; Pike Victor W

    2011-01-01

    Palladium-catalyzed coupling between aryl halides, especially less reactive ones or N-heteroaryls, and trimethylsilylacetylene in the presence of dimethylaminotrimethyltin generated the coupled products in high yields. The reaction does not need CuI and base as auxiliary agents.

  11. Luminescent decay and spectra of impurity-activated alkali halides under high pressure

    International Nuclear Information System (INIS)

    The effect of high pressure on the luminescence of alkali halides doped with the transition-metal ions Cu+ and Ag+ and the heavy-metal ions In+ and Tl+ was investigated to 140 kbar. Measurement of spectra allowed the prediction of kinetic properties, and the predictions agree with lifetime data

  12. An Improved Protocol for the Pd-catalyzed α-Arylation of Aldehydes with Aryl Halides

    OpenAIRE

    Martín, Rubén; Buchwald, Stephen L.

    2008-01-01

    An improved protocol for the Pd-catalyzed α-arylation of aldehydes with aryl halides has been developed. The new catalytic system allows for the coupling of an array of substrates including challenging electron-rich aryl bromides and less reactive aryl chlorides. The utility of this method has been demonstrated in a new total synthesis of (±)-sporochnol.

  13. Exciton Binding Energy in Organic-Inorganic Tri-Halide Perovskites.

    Science.gov (United States)

    Askar, Abdelrahman M; Shankar, Karthik

    2016-06-01

    The recent dramatic increase in the power conversion efficiencies of organic-inorganic tri-halide perovskite solar cells has triggered intense research worldwide and created a paradigm shift in the photovoltaics field. It is crucial to develop a solid understanding of the photophysical processes underlying solar cell operation in order to both further improve the photovoltaic performance of perovskite solar cells as well as to exploit the broader optoelectronic applications of the tri-halide perovskites. In this short review, we summarize the main research findings about the binding energy of excitons in tri-halide perovskite materials and find that a value in the range of 2-22 meV at room temperature would be a safe estimate. Spontaneous free carrier generation is the dominant process taking place directly after photoexcitation in organic-inorganic tri-halide perovskites at room temperature, which eliminates the exciton diffusion bottleneck present in organic solar cells and constitutes a major contributing factor to the high photovoltaic performance of this material. PMID:27427650

  14. Ionic liquids as solvent for efficient esterification of carboxylic acids with alkyl halides

    OpenAIRE

    carboxylic, Ionic liquids as solvent for efficient e

    2010-01-01

    The selective esterification of carboxylic acid derivatives with a variety of alkyl halides was carried out using ionic liquid as solvent in the presence of triethylamine. The reaction was found to proceed under relatively mild conditions with excellent conversions (up to 99%) and selectivities. The ionic liquid was recycled and reused.

  15. Correlated linear response calculations of the C6 dispersion coefficients of hydrogen halides

    Czech Academy of Sciences Publication Activity Database

    Sauer, S. P. A.; Paidarová, Ivana

    2007-01-01

    Roč. 3, 2-4 (2007), s. 399-421. ISSN 1574-0404 R&D Projects: GA AV ČR IAA401870702 Institutional research plan: CEZ:AV0Z40400503 Keywords : hydrogen halides * C6 dospersion coefficients * van der Waals coefficients * polarizability at imaginary frequences * SOPPA Subject RIV: CF - Physical ; Theoretical Chemistry

  16. Synthesis and Spectroscopic studies on cadmium halide complexes of isonicotinic acid

    International Nuclear Information System (INIS)

    In this study infrared spectra (4000-400cm-1) are reported for the cadmium(II) halide isonicotinic acid complexes. Vibrational assignments are given for all observed bands. Some structure spectra correlations and frequency shifts were found. It's found the frequency shifts depends on the halogen for a given metal. Certain chemical formulas were determined using elemental analysis results

  17. Direct ToF-SIMS analysis of organic halides and amines on TLC plates

    International Nuclear Information System (INIS)

    It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups

  18. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao

    2012-08-01

    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  19. Viabilization of a new aluminium grain refiner based on Zirconium halide salt

    International Nuclear Information System (INIS)

    A new aluminium grain refiner based on Zirconium halide salt is proposed. Its efficiency, as grain refiner is analysed varying the salt amount, the inoculation temperature and holding time. The grain size reduction shows to be dependent on the salt amount and independent on the inoculation temperature. The holding time effects is dependent on the innoculated salt amount. (Author)

  20. Halocyclization of Unsaturated Guanidines Mediated by Koser's Reagent and Lithium Halides.

    Science.gov (United States)

    Daniel, Marion; Blanchard, Florent; Nocquet-Thibault, Sophie; Cariou, Kevin; Dodd, Robert H

    2015-11-01

    The synthesis of halogenated cyclic guanidines through iodine(III)-mediated umpolung of halide salts is described. Cyclic guanidines of various sizes can be obtained with generally excellent regioselectivities through either a chloro- or a bromocyclization, using Koser's reagent and the corresponding lithium salt. PMID:26492553

  1. Effects of Alloying on the Optical Properties of Organic-Inorganic Lead Halide Perovskite Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Ndione, Paul F.; Li, Zhen; Zhu, Kai

    2016-09-07

    Complex refractive index and dielectric function spectra of organic-inorganic lead halide perovskite alloy thin films are presented, together with the critical-point parameter analysis (energy and broadening) of the respective composition. Thin films of methylammonium lead halide alloys (MAPbI3, MAPbBr3, MAPbBr2I, and MAPbBrI2), formamidinium lead halide alloys (FAPbI3, FAPbBr3, and FAPbBr2I), and formamidinium cesium lead halide alloys [FA0.85Cs0.15PbI3, FA0.85Cs0.15PbBrI2, and FA0.85Cs0.15Pb(Br0.4I0.6)3] were studied. The complex refractive index and dielectric functions were determined by spectroscopic ellipsometry (SE) in the photon energy range of 0.7-6.5 eV. Critical point energies and optical transitions were obtained by lineshape fitting to the second-derivative of the complex dielectric function data of these thin films as a function of alloy composition. Absorption onset in the vicinity of the bandgap, as well as critical point energies and optical band transition shift toward higher energies as the concentration of Br in the films increases. Cation alloying (Cs+) has less effect on the optical properties of the thin films compared to halide mixed alloys. The reported optical properties can help to understand the fundamental properties of the perovskite materials and also be used for optimizing or designing new devices.

  2. Vibrational spectra of discrete UO22+ halide complexes in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Gary S. Groenewold; Michael J. van Stipdonk; Wibe A. de Jong; Jos Oomens; Garold L. Gresham

    2010-11-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions, that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition [UO2(X)(ACO)3]+ (X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric v3 UO2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter the binding in the complex. The v3 peak in the spectrum of the F-containing complex was ~ 10 cm-1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to the blue was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the v1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes were conducted by measuring the v3 UO2 frequencies of [UO2X3]-, where X = Cl-, Br- and I-. The trifluoro complex could not be photodissociated. In these negatively charged complexes, the UO2 v3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that dissociation

  3. The ultraviolet photodissociation dynamics of the hydrogen halides

    International Nuclear Information System (INIS)

    The first electronic absorption bands of hydrogen halide (HX) molecules - HI, HBr, HCl and DCl - have been studied using two experimental, laser-based techniques. Each band of HX consists of absorption of ultraviolet (UV) radiation and leads to fragmentation into two sets of products: H(2S) + X(2Pj); j=3/2, 1/2. Numerous measurements that cover most of the UV absorption bands (λ∼200-300 nm) of HI and HBr were made using H Rydberg atom photofragment translational spectroscopy (HRPTS). The results comprise two important properties: the branching between the accessible product channels and the spatial distributions of the recoil velocities of the photofragments. These extensive observations afford a detailed interpretation of the featureless absorption bands in terms of the relative influences of transitions and dissociations involving multiple electronic states: 3Π(1), 3Π(0+), 1Π(1) and 3Σ+(1). The photolysis of HCl between 201 and 210 nm was also studied by HRPTS to provide a number of direct determinations of the relative product yield for comparison with the best available theoretical predictions based on ab initio electronic structure calculations and a time-independent treatment of the photodissociation dynamics. The good agreement between the calculations and observations provided encouraging support for the theoretical description. The second experimental method combined resonance enhanced multiphoton ionization (REMPI) and a time-of-flight mass spectrometer (TOF MS) to quantify the relative production of die spin-orbit components of the halogen photoproducts from HI, DCl and vibrationally-excited HCl. Relating the observed REMPI yields for each quantum state to the nascent populations required a scaling factor to account for the different ionization probabilities. This was derived for the ground state of the chlorine atom by comparing the Cl(2Pj) REMPI signal recorded following photolysis of HCl at λ=205.5 nm with a direct determination obtained by

  4. Molten lanthanide halide systems: experimental, modeling and thermodynamic computation

    International Nuclear Information System (INIS)

    Molten lanthanide halide based systems were studied using two approaches: experiments and calculations. Liquid mixing enthalpies of chloride europium systems (MCl-EuCl2; M = Na, K, Rb) were measured at 1138 K. They can be represented (in kJ.mol-1) as a function of the molar fraction of EuCl2 (x) with the polynomials: ΔmixHm0 (NaCl - EuCl2) = x(1 - x)(-1.6634 - 5.4964x + 6.3324x2), ΔmixHm0 (KCl - EuCl2 = x(1 - x)(-21.262 + 17.196x- 6.6293x2), ΔmixHm0 (RbCl - EuCl2 = x(1 - x)(-25.286 + 15.786x). The NaCl-EuCl2 phase diagram was experimentally determined. It exhibits an eutectic equilibrium (x(EuCl2) = 0.49; Teut = 847 ± 2 K). Temperatures and enthalpies effusion and transition of EuCl2 were also measured (Ttrs= 1014 ± 2 K, ΔtrsHm0 = 11.5 ± 0.7 kJ.mol1, TfUs = 1125 ± 2 K, ΔfusHm0 = 18.7 ± 1,1 kJ.mol-1) as well as heat capacities (Cpm0(EuCl2, ortho.) = 76.26 + 8.08 x 10-3 T between 310

  5. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium-americium mixed oxides

    Science.gov (United States)

    Prieur, D.; Lebreton, F.; Martin, P. M.; Caisso, M.; Butzbach, R.; Somers, J.; Delahaye, T.

    2015-10-01

    Uranium-americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U1-xAmxO2±δ samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U1-xAmxO2±δ leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions.

  6. Stability of penta- and hexavalent americium in the solutions of sodium peroxydisulfate and sodium bromate at intensive internal α-irradiation

    International Nuclear Information System (INIS)

    The spectrometric method has been used for studying the dependence of the rates of radiolytic reduction of Am(5) and (6) on the initial concentration of sodium persulfate and bromate, Am(5) and (6), acidity, and the dose rate of inner alpha-irradiation of the solutions. The high dose rates of inner alpha-irradiation of solutions (up to 3.25x1021 eV/lxmin-250Ci/l) have been attained with the aid of curium isotopes. The stability of americium (6) ions towards the action of ionizing radiation in solutions of sodium persulfate and bromate has been shown to be considerable lower than that of americium (5). The chemical difference has been shown in radiolytic behaviour between Am(5) and Am(6) ions in solutions of sodium persulfate and bromate. The equations have been derived showing the dependence of the rates of Am(6) and Am(5) reduction of different variables

  7. A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorption on the Relaxed (0001) Surface of Double Hexagonal Close Packed Americium

    OpenAIRE

    Dholabhai, P. P.; Atta-Fynn, R.; A.K. Ray

    2009-01-01

    Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorption on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals method. Chemisorption energies were optimized with respect to the distance of the adatom from the relaxed surface for three adsorption sites, namely top, bridge, and hollow hcp sites, the adlayer str...

  8. Distribution, retention and dosimetry of plutonium and americium in the rat, dog and monkey after inhalation of an industrial-mixed uranium and plutonium oxide aerosol

    International Nuclear Information System (INIS)

    This study provides information on patterns of radiation dose in laboratory animals after inhalation exposure to an aerosol of one form of mixed uranium and plutonium oxide. The aerosol contained a mixture of UO2 and 750 deg C heat-treated PuO2 obtained from the ball milling operation in a mixed-oxide fuel fabrication process. Americium-241 from the decay of 241Pu was also present in the PuO2 matrix. Fischer-344 rats, Beagle dogs, and Cynomolgus and Rhesus monkeys inhaled aerosols re-generated from dry mixed oxide powders with particle size distribution characteristics similar to those observed in samples collected at the industrial site. Clearance from the lung and distribution in other tissues of the plutonium from this UO2 + PuO2 admixture was similar to what has been observed for PuO2 from laboratory-produced aerosols. The UO2-PuO2 aerosol was relatively insoluble in the lungs of all species. Monkeys and rats cleared plutonium and americium from their lungs faster than dogs. Very little plutonium or americium translocated within the first 2 yr after exposure to tissues other than tracheobronchial lymph nodes. The greater accumulation of plutonium and americium in the tracheobronchial lymph nodes of dogs as compared to monkeys and rats combined with the more rapid initial clearance of these radionuclides from the lungs of rats and monkeys suggests that errors could result from using data from a single animal species to estimate risk to humans from inhalation of these industrial aerosols. (author)

  9. Experimental study of Americium-241 biokinetics in Homarus Gammarus lobster. Analysis of the accumulation and detoxication mechanisms at the sub-cellular level

    International Nuclear Information System (INIS)

    The Americium 241 radioelement accumulation and elimination rate and mechanisms in the lobster organism have been experimentally studied; incorporation and detoxification capacities of each organ are evaluated. The existence of various biological compartments is shown; the major role of the digestive gland in accumulation of the radioelement, its distribution towards the various organs, and its resorption is comprehensively described, with an analysis at the subcellular and molecular levels. 401 p., 65 fig., 43 tab., 428 ref

  10. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Prieur, D., E-mail: dam.prieur@gmail.com [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Lebreton, F. [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze cedex (France); Martin, P.M. [CEA, DEN, DEC/SESC/LLCC, 13108 Saint-Paul-Lez-Durance cedex (France); Caisso, M. [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze cedex (France); Butzbach, R. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Radiochemistry, P.O. Box 10119, 01314 Dresden (Germany); Somers, J. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Delahaye, T. [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze cedex (France)

    2015-10-15

    Uranium–americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U{sub 1−x}Am{sub x}O{sub 2±δ} samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U{sub 1−x}Am{sub x}O{sub 2±δ} leads to the formation of similar fluorite solid solution indicating the presence of Am{sup +III} and U{sup +V} in equimolar proportions. - Graphical abstract: Formation of (U{sup IV/V},Am{sup III})O{sup 2} solid solution by sol–gel and by powder metallurgy. - Highlights: • Uranium–americium mixed oxides were synthesized by sol–gel and powder metallurgy. • Fluorite solid solutions with similar local environment have been obtained. • U{sup V} and Am{sup III} are formed in equimolar proportions.

  11. An experimental study of americium-241 biokinetics in the Lobster Homarus Gammarus. Analysis of the accumulation/storage and detoxification processes at the subcellular level

    International Nuclear Information System (INIS)

    An experimental study of americium-241 kinetics has been conducted in the lobster Homarus gammmarus. The investigations were conducted at all the levels from the whole body to the subcellular and molecular levels. The animals were contaminated by a single or chronic ingestion of 241 Am labelled mussels. Assessments of accumulation, elimination and distribution of the radionuclide were established on organisms kept in the laboratory; they made it possible to demonstrate the importance of the digestive gland in the radionuclide transfer pathways. The preliminary results led to structural then ultrastructural investigations of the digestive gland in association with radioautographic studies and cellular extractions methods. Four cellular types were demonstrated, only two of them being implied in the radionuclide retention, the former being responsible for americium intake and the latter for its long-term retention. By means of biochemical techniques, subcellular accumulation was studied and the organelles implied in the nuclide retention were specified. Finally, a method of cellular nuclei dissociation was developed; it made it possible to analyse the molecular nature of americium ligands and to demonstrate the function of the protein nuclear matrix in the nuclide retention

  12. A new method for the determination of plutonium and americium using high pressure microwave digestion and alpha-spectrometry or ICP-SMS

    International Nuclear Information System (INIS)

    Plutonium and americium are radionuclides particularly difficult to measure in environmental samples because they are a-emitters and therefore necessitate a careful separation before any measurement, either using radiometric methods or ICP-SMS. Recent developments in extraction chromatography resins such as EichromR TRU and TEVA have resolved many of the analytical problems but drawbacks such as low recovery and spectral interferences still occasionally occur. Here, we report on the use of the new EichromR DGA resin in association with TEVA resin and high pressure microwave acid leaching for the sequential determination of plutonium and americium in environmental samples. The method results in average recoveries of 83 ± 15% for plutonium and 73 ± 22% for americium (n = 60), and a less than 10% deviation from reference values of four IAEA reference materials and three samples from intercomparisons exercises. The method is also suitable for measuring 239Pu in water samples at the μBq/l level, if ICP-SMS is used for the measurement. (author)

  13. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides

    International Nuclear Information System (INIS)

    Uranium–americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U1−xAmxO2±δ samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U1−xAmxO2±δ leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions. - Graphical abstract: Formation of (UIV/V,AmIII)O2 solid solution by sol–gel and by powder metallurgy. - Highlights: • Uranium–americium mixed oxides were synthesized by sol–gel and powder metallurgy. • Fluorite solid solutions with similar local environment have been obtained. • UV and AmIII are formed in equimolar proportions

  14. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    Science.gov (United States)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  15. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    Science.gov (United States)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-07-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials.

  16. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells.

    Science.gov (United States)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  17. Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

    International Nuclear Information System (INIS)

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO2(X)(ACO)3)+ (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν3 UO2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν3 peak in the spectrum of the F-containing complex was 9 cm-1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO2X3)- (where X = Cl-, Br- and I-) compared the ν3 UO2 modes versus halide, and showed that the ν3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO2X2)--X, and (UO2X2)·-X- dissociation energies decreased on the order F > Cl > Br > I

  18. Vibrational Spectra of Discrete UO₂²⁺ Halide Complexes in the Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Groenewold, G S; Van Stipdonk, Michael J; Oomens, Jos; De Jong, Wibe A; Gresham, Garold L; Mcilwain, Michael

    2010-11-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition [UO₂(X)(ACO)₃]+ (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν₃ UO₂ frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν₃ peak in the spectrum of the F-containing complex was 9 cm-1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes [UO₂X₃]- (where X = Cl-, Br- and I-) compared the ν₃ UO₂ modes versus halide, and showed that the ν₃ values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that [UO

  19. Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

    Science.gov (United States)

    Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

    2016-02-16

    Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation

  20. Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

    OpenAIRE

    Cheung, Chi Wai; Ren, Peng; Hu, Xile

    2014-01-01

    A simple protocol for iron-catalyzed cross-coupling of nonactivated secondary alkyl bromides and iodides with alkynyl Grignard reagents at room temperature has been developed. A wide range of secondary alkyl halides and terminal alkynes are tolerated to afford the substituted alkynes in good yields. A slight modification of the reaction protocol also allows for cross-coupling with a variety of primary alkyl halides.

  1. Palladium-Catalyzed Hydroxylation of Aryl and Heteroaryl Halides Enabled by the Use of a Palladacycle Precatalyst

    OpenAIRE

    Cheung, Chi Wai; Buchwald, Stephen L.

    2014-01-01

    A method for the hydroxylation of aryl and heteroaryl halides, promoted by a catalyst based on a biarylphosphine ligand tBuBrettPhos (L5) and its corresponding palladium precatalyst (1), is described. The reactions allow the cross-coupling of both potassium and cesium hydroxides with (hetero)aryl halides to afford a variety of phenols and hydroxylated heteroarenes in high to excellent yield.

  2. Fine structures in the optical absorption spectra of photochemical silver in silver halides? A call for further research

    OpenAIRE

    Georgiev, Mladen

    2007-01-01

    A survey is presented of the work done so far to check earlier claims that a fine structure may be observed to occur under certain circumstances in the impurity spectral range of the optical absorption spectra of silver halides following photostimulation in the intrinsic range. This structure, associated with the photochemical formation of silver specks, has been questioned over the years. We now weigh carefully the experimental evidence on the silver halides against a background of similar d...

  3. Fluorogenic derivatization of aryl halides based on the formation of biphenyl by Suzuki coupling reaction with phenylboronic acid.

    OpenAIRE

    Kishikawa, Naoya; Kubo, Kimiko; Hammad, Sherin Farouk; Mabrouk, Mokhtar Mohamed; Habib, Ahmed; Elfatatry, Hamed; Ohyama, Kaname; Nakashima, Kenichiro; Kuroda, Naotaka

    2009-01-01

    The fluorogenic derivatization method for aryl halide was developed for the first time. This method was based on the formation of fluorescent biphenyl structure by Suzuki coupling reaction between aryl halides and non-fluorescent phenylboronic acid (PBA). We measured the fluorescence spectra of the products obtained by the reaction of p-substituted aryl bromides (i.e., 4-bromobenzonitrile, 4-bromoanisole, 4-bromobenzoic acid ethyl ester and 4-bromotoluene) with PBA in the presence of palladiu...

  4. Structural, dynamical, and transport properties of the hydrated halides: How do At- bulk properties compare with those of the other halides, from F- to I-?

    Science.gov (United States)

    Réal, Florent; Severo Pereira Gomes, André; Guerrero Martínez, Yansel Omar; Ayed, Tahra; Galland, Nicolas; Masella, Michel; Vallet, Valérie

    2016-03-01

    The properties of halides from the lightest, fluoride (F-), to the heaviest, astatide (At-), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I- and At-, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I- and At- in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F-, Cl-, and Br- ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At- in liquid water at ambient conditions to be 68 kcal mol-1, a value also close the I- one, about 70 kcal mol-1. In all, our simulation results for I- are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At- ion are predictive, as no theoretical or experimental data are available to date.

  5. Structural, dynamical, and transport properties of the hydrated halides: How do At(-) bulk properties compare with those of the other halides, from F(-) to I(-)?

    Science.gov (United States)

    Réal, Florent; Gomes, André Severo Pereira; Guerrero Martínez, Yansel Omar; Ayed, Tahra; Galland, Nicolas; Masella, Michel; Vallet, Valérie

    2016-03-28

    The properties of halides from the lightest, fluoride (F(-)), to the heaviest, astatide (At(-)), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I(-) and At(-), were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I(-) and At(-) in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F(-), Cl(-), and Br(-) ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At(-) in liquid water at ambient conditions to be 68 kcal mol(-1), a value also close the I(-) one, about 70 kcal mol(-1). In all, our simulation results for I(-) are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At(-) ion are predictive, as no theoretical or experimental data are available to date. PMID:27036467

  6. Preliminary results from uranium/americium affinity studies under experimental conditions for cesium removal from NPP ''Kozloduy'' simulated wastes solutions

    International Nuclear Information System (INIS)

    We use the approach described by Westinghouse Savannah River Company using ammonium molybdophosphate (AMP) to remove elevated concentrations of radioactive cesium to facilitate handling waste samples from NPP Kozloduy. Preliminary series of tests were carried out to determine the exact conditions for sufficient cesium removal from five simulated waste solutions with concentrations of compounds, whose complexing power complicates any subsequent processing. Simulated wastes solutions contain high concentrations of nitrates, borates, H2C2O4, ethylenediaminetetraacetate (EDTA) and Citric acid, according to the composition of the real waste from the NPP. On this basis a laboratory treatment protocol was created. This experiment is a preparation for the analysis of real waste samples. In this sense the results are preliminary. Unwanted removal of non-cesium radioactive species from simulated waste solutions was studied with gamma spectrometry with the aim to find a compromise between on the one hand the AMP effectiveness and on the other hand unwanted affinity to AMP of Uranium and Americium. Success for the treatment protocol is defined by proving minimal uptake of U and Am, while at the same time demonstrating good removal effectiveness through the use of AMP. Uptake of U and Am were determined as influenced by oxidizing agents at nitric acid concentrations, proposed by Savannah River National laboratory. It was found that AMP does not significantly remove U and Am when concentration of oxidizing agents is more than 0.1M for simulated waste solutions and for contact times inherent in laboratory treatment protocol. Uranium and Americium affinity under experimental conditions for cesium removal were evaluated from gamma spectrometric data. Results are given for the model experiment and an approach for the real waste analysis is chosen. Under our experimental conditions simulated wastes solutions showed minimal affinity to AMP when U and Am are most probably in the

  7. Reactions between cold methyl halide molecules and alkali-metal atoms

    CERN Document Server

    Lutz, Jesse J

    2013-01-01

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH$_{3}X$ ($X$ = F, Cl, Br, I) and alkali-metal atoms $A$ ($A$ = Li, Na, K, Rb) using high-level {\\it ab initio} calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, ${\\rm CH}_{3}X+A\\rightarrow{\\rm CH}_{3}+AX$. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  8. Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez M, R.; Perez S, R. [Universidad de Sonora, Departamento de Investigacion en Fisica, Apdo. Postal 5-088, 83190 Hermosillo, Sonora (Mexico); Vazquez P, G.; Riveros, H. [UNAM, Instituto de Fisica, Apdo. Postal 20-364, 01000 Mexico D. F. (Mexico); Gonzalez M, P., E-mail: mijangos@cifus.uson.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2014-08-15

    Ionic crystals, mainly alkali halide crystals have been the subject of intense research for a better understanding of the luminescence properties of defects induced by ionizing radiation. The defects in crystals can be produced in appreciable concentration due to elastic stresses, radiation, and addition of impurities. These defects exhibit remarkable thermoluminescence properties. This work is concerned with the Tl properties of a ternary alkali halide crystal after being irradiated with gamma and beta rays. It has been found that the Tl glow peak of the crystal follows a rule of average associated to the Tl Temperatures of the components of the mixture, similarly to the response of europium doped binary mixed crystals KCl{sub x}KBr{sub 1-x} and KBr{sub x}RbBr{sub 1-x}. (Author)

  9. XAFS investigations of aqueous zinc halide solutions up to supercritical conditions

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, A.J. [Saint Francis Xavier Univ., Antigonish, NS (Canada). Dept. of Geology; Mayanovic, R.A. [Southwest Missouri State Univ., Springfield, MO (United States). Dept. of Physics; Chou, I.M. [US Geological Survey, Reston, VA (United States); Bassett, W.A. [Cornel Univ., Ithica, NY (United States). Dept. of Geological Sciences

    2000-07-01

    The molecular properties of aqueous zinc halide complexes in ore-forming hydrothermal brines was investigated using high temperature zinc (Zn) and bromide (Br) potassium (K)-edge X-ray absorption fine structure (XAFS) measurements of an aqueous zinc bromide solution. The main objective of the study was to determine if there is a relationship between complex hydration and zinc and halide bond distances as a function of temperature. A modified hydrothermal diamond-anvil cell was used as an autoclave. The spectra showed that ZnBr{sub 4}{sup 2-} is the dominant complex up to the supercritical conditions and that the Zn-Br bond lengths decrease as the temperature increases. The Br K-edge data also suggests that an increase in temperature reduces the number of waters surrounding the bromide ligand. 17 refs., 2 tabs., 5 figs.

  10. Reactions of 1,4-bis(tetrazole)benzenes: formation of long chain alkyl halides

    OpenAIRE

    Kelleher, Fintan; Bond, Andrew; Fleming, Adrienne; McGinley, John; Prajapati, Vipa

    2006-01-01

    The reactions of 1,4-bis[2-(tributylstannyl)tetrazol-5-yl]benzene with α,ω-dibromoalkanes were carried out in order to synthesise pendant alkyl halide derivatives of the parent bis-tetrazole. This led to the formation of several alkyl halide derivatives, substituted variously at N1 or N2 on the tetrazole ring. The crystal structures of 1,4-bis[(2-(4-bromobutyl)tetrazol-5-yl)]benzene (2-N,2-N′), 1,4-bis[(2-(4-bromobutyl)tetrazol-5-yl)]benzene (1-N,2-N′) and 1,4-bis[(2-(8-bromooctyl)tetra...

  11. Electric properties of stannous and stannic halides: How good are the experimental values?

    Science.gov (United States)

    Kalugina, Yulia N.; Thakkar, Ajit J.

    2015-04-01

    Coupled-cluster calculations are reported for the electric and vibrational properties of the stannous halides SnX2 and stannic halides SnX4 with X = F, Cl, Br, and I. Comparison with experiment, where available, is made. Our best values of the static mean dipole polarizability for SnF2, SnCl2, SnBr2, and SnI2, are 39.98, 71.93, 91.37, and 125.8 atomic units, respectively. Our best values of the static mean dipole polarizability for SnF4, SnCl4, SnBr4, and SnI4, are 32.82, 93.04, 126.9, and 191.2 atomic units, respectively.

  12. A study of some calcium dihalides and strontium fluoride halides systems

    International Nuclear Information System (INIS)

    The CaX2-CaY2 and SrF2-SrX2 (where X and Y represent halide anions) systems were investigated by the Guinier powder X-ray diffraction technique. In the calcium dihalide systems only solid solutions were found. In the strontium fluoride - strontium chloride and strontium fluoride - strontium bromide systems the dihalides and the PbFCl-type SrFX phases were observed. The preparation, crystallographic data and atom distribution of the mixed halides, SrFCl/sub 0.5/Br/sub 0.5/, Ca/sub 0.5/Sr/sub 0.5/FCl, Ca/sub 0.5/Yb/sub 0.5/FCl and Sr/sub 0.5/Eu/sub 0.5/FBr are presented and discussed. (author)

  13. Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides.

    Science.gov (United States)

    Cheung, Chi Wai; Hu, Xile

    2016-01-01

    (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon-nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C-N coupling method provides general and step-economical access to aryl amines. PMID:27515391

  14. Core-clad silver halide fibers for CO2 laser power transmission

    Science.gov (United States)

    Paiss, Idan; Moser, Frank; Katzir, Abraham

    1991-07-01

    Core-clad optical fibers with efficient IR power delivery are essential components in the development of laser ensoscope systems for surgical applications. The fabrication of such clad fibers of high quality is still an unsolved technical problem. We have investigated parameters of the fabrication of core-clad polyscrystalline silver halide optical fibers and found conditions that yield fibers with relatively good transmittance at 10.6 micrometers (about 3 dB/meter loss) and capable of delivering output power densities up to 3 kwatt/cm2 in CW operation. This performance is lower than what we achieved in core-only silver halide fibers, but the advantage of the protection provided by the clad and a subsequent plastic overcoat, make these core-clad fibers useful in a number of CO2 power transmission applications in laser surgery.

  15. Microscopic Investigation of Grain Boundaries in Organolead Halide Perovskite Solar Cells.

    Science.gov (United States)

    Li, Jiang-Jun; Ma, Jing-Yuan; Ge, Qian-Qing; Hu, Jin-Song; Wang, Dong; Wan, Li-Jun

    2015-12-30

    Grain boundaries (GBs) play an important role in organic-inorganic halide perovskite solar cells, which have generally been recognized as a new class of materials for photovoltaic applications. To definitely understand the electrical structure and behavior of GBs, here we present Kelvin probe force microscopy and conductive atomic force microscopy (c-AFM) measurements of both typical and inverted planar organolead halide perovskite solar cells. By comparing the contact potential difference (CPD) of these two devices in the dark and under illumination, we found that a downward band bending exists in GBs that predominantly attract photoinduced electrons. The c-AFM measurements observed that higher photocurrents flow through GBs when a low bias overcomes the barrier created by the band bending, indicating that GBs act as effective charge dissociation interfaces and photocurrent transduction pathways rather than recombination sites. PMID:26633192

  16. Reactions between cold methyl halide molecules and alkali-metal atoms

    International Nuclear Information System (INIS)

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A → CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow

  17. A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Neus Mesquida

    2012-04-01

    Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

  18. Solid-State Nanopore Confinement for Band Gap Engineering of Metal-Halide Perovskites

    CERN Document Server

    Demchyshyn, Stepan; Groiss, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus; Nickel, Bert; Sariciftci, Niyazi Serdar; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

    2016-01-01

    Tuning the band gap of semiconductors via quantum size effects launched a technological revolution in optoelectronics, advancing solar cells, quantum dot light-emitting displays, and solid state lasers. Next generation devices seek to employ low-cost, easily processable semiconductors. A promising class of such materials are metal-halide perovskites, currently propelling research on emerging photovoltaics. Their narrow band emission permits very high colour purity in light-emitting devices and vivid life-like displays paired with low-temperature processing through printing-compatible methods. Success of perovskites in light-emitting devices is conditional upon finding reliable strategies to obtain tunability of the band gap. So far, colour can be tuned chemically by mixed halide stoichiometry, or by synthesis of colloidal particles. Here we introduce a general strategy of controlling shape and size of perovskite nanocrystallites (less than 10 nm) in domains that exhibit strong quantum size effects. Without ma...

  19. Coloration of cadmium halide crystals due to reactor irradiation at low temperature

    International Nuclear Information System (INIS)

    The optical absorption spectra and ESR spectra of cadmium halide crystals were measured after the reactor irradiation at low temperature to study the coloration. The irradiated neutron dose was about 5 x 1017 n/cm2. In the measurement of ESR spectra, the crystal was rotated around the v-axis (the two-fold axis) in the magnetic field of fixed direction. The optical absorption spectra showed that the Cd3+ center was generated. From the analysis of the angular dependence of ESR spectra, the centers of C(2h) symmetry and the centers of D(3d) symmetry were considered to be generated. The models of these centers were considered, and the angular dependence was analyzed. It can be concluded from the present experiment that the coloration of cadmium halide crystals is recognized as the results of the reactor irradiation at low temperature. (Kato, T.)

  20. Energetics and dynamics in organic-inorganic halide perovskite photovoltaics and light emitters.

    Science.gov (United States)

    Sum, Tze Chien; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-08-28

    The rapid transcendence of organic-inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley-Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic-inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted. PMID:26234397

  1. Correlations for calculating the surface tension and enthalpies of sublimation of alkali halides

    International Nuclear Information System (INIS)

    The capability of a new model on predicting the surface tension of molten alkali halides is described. A relationship, with a simple form of calculation, exists between the surface tension (γ) at the melting point, molar volume (V), inter-nuclear distance (D) and the enthalpy of sublimation (Es). The basic idea results from the assumption that all the parameters are constants that are usually easy to acquire. Moreover, two previous models (Furth and Schytil equations) were also checked and applied for calculating surface tension of molten salts. The three formulas have been examined for 20 salts and showed remarkable agreement between calculated and experimental data with a difference of less than 10% for most of the salts studied. The heats of sublimation of alkali halides were, theoretically, calculated and compared to literature values.

  2. Enhanced phosphorescence emission by incorporating aromatic halides into an entangled coordination framework based on naphthalenediimide.

    Science.gov (United States)

    Martínez-Martínez, Virginia; Sola Llano, Rebeca; Furukawa, Shuhei; Takashima, Yohei; López Arbeloa, Iñigo; Kitagawa, Susumu

    2014-08-25

    Phosphorescence emission at room temperature is turned on in an entangled porous coordination polymer (PCP) with naphthalenediimide (NDI) as chromophore, by incorporating halogenated guests into the pores. The phosphorescent efficiency is drastically increased by the incorporation of aromatic halide guests in comparison with the incorporation of nonaromatic derivatives. Aromatic halide guests trigger a structural transformation, which allows a strong interaction with the NDI ligand in the framework through charge-transfer complexation, and provides an extra population process of the triplet state. The long-lived photoinduced triplet states, with an emission wavelength in the red region of the visible spectrum, demonstrated by this PCP, may open the door for potential uses, for example, as singlet-oxygen generators or for bio-imaging applications. PMID:24953198

  3. Stability diagrams for fourfold coordination of polyvalent metal ions in molten mixtures of halide salts

    International Nuclear Information System (INIS)

    The stability of local fourfold coordination for divalent and trivalent metal ions in liquid mixtures of polyvalent metal halides and alkali halides is classified by means of structural coordinates obtained from properties of the elements. In parallel with earlier classifications of compound crystal structures and molecular shapes, the elemental properties are taken from first-principles calculations of valence electron orbitals in atoms, in the form of (i) the nodal radii of Andreoni, Baldereschi and Guizzetti or (ii) the pseudopotential radii or Zunger and Cohen. As a third alternative a classification based on Pettifor's phenomenological chemical scale of the elements is also considered. The alternative structural classification schemes that are developed from these elemental properties are generally successfully in distinguishing molten mixtures in which the available experimental evidence indicates long-lived fourfold coordination of polyvalent metal ions. In addition, Pettifor's chemical scale scheme is useful in sorting out finer details of local coordination in the liquid state. 3 figs., 71 refs

  4. Tuning the thermal conductivity of methylammonium lead halide by the molecular substructure.

    Science.gov (United States)

    Caddeo, Claudia; Melis, Claudio; Saba, Maria Ilenia; Filippetti, Alessio; Colombo, Luciano; Mattoni, Alessandro

    2016-09-21

    By using state-of-the-art atomistic methods we provide an accurate estimate of thermal conductivity of methylammonium lead halide as a function of sample size and temperature, in agreement with experimental works. We show that the thermal conductivity of methylammonium lead halide is intrinsically low, due to the low sound velocity of the PbI lattice. Furthermore, by selectively analyzing the effect of different molecular degrees of freedom, we clarify the role of the molecular substructure by showing that the internal modes above 150 cm(-1) (in addition to rotations) are effective in reducing the thermal conductivity of hybrid perovskites. This analysis suggests strategies to tailor the thermal conductivity by modifying the internal structure of organic cations. PMID:27531063

  5. Spacial Structure of Cationic Phosphorus Ligand-Ru (Ⅱ) Halide Complexes-by DFT Study

    Institute of Scientific and Technical Information of China (English)

    Yi Xin ZHAO; Shu Guang WANG

    2005-01-01

    The full-parameter geometry optimization of cationic (S)-BINAP-Ru (Ⅱ) halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis sets is found to be the most suitable method with consideration of both precision and efficiency. The dihedral angles (θ) of the binaphthyl or biphenyl with different phosphorus ligand-Ru (Ⅱ) halide complexes were found changing from 59.9 to 79.3 degree, while the natural bite angle (βn) of those complexes only changes from 87.4to 90.3 degree. It is different from the common view of asymmetric organic chemists' that θ directly influences βn.

  6. Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

    KAUST Repository

    Chawla, Mohit

    2015-01-14

    Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

  7. Intermolecular interactions and proton transfer in the hydrogen halide-superoxide anion complexes.

    Science.gov (United States)

    Lee, Sebastian J R; Mullinax, J Wayne; Schaefer, Henry F

    2016-02-17

    The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the hydrogen halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 Å) hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier hydrogen halides with the resulting complexes characterized as long (>1.89 Å) hydrogen bonds between halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier hydrogen halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI. PMID:26852733

  8. Temperature Dependence of Interatomic Separation and Bulk Modulus for Alkali Halides

    Science.gov (United States)

    Liu, Quan

    2016-07-01

    The values of interatomic separation r with the change of temperature T for seven alkali halides have been investigated with the help of an isobaric equation of state. The calculated results are used to predict the values of bulk modulus at different temperatures. The results are compared with the available experimental data and other theoretical results and are further discussed in view of recent research in the field of high temperature physics.

  9. Mössbauer Emission-Spectra of Impurity Cobalt-57 in a Halide Matrix

    DEFF Research Database (Denmark)

    Maddock, A. G.; Williams, A. F.; Siekierska, K. E.;

    1976-01-01

    The Mössbauer emission spectra of 57Co in low concentrations in KF, NaCl, NaF, LiF, and MgF2, and the effects of doping NaF and LiF with La3+ ions are reported. The monovalent halides all give similar spectra showing a broad single line or a doublet at 2.19mm/s and two overlapping doublets at 0...

  10. Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

    DEFF Research Database (Denmark)

    Bae, Dowon; Palmstrom, Axel; Roelofs, Katherine;

    2016-01-01

    Wide-band-gap mixed-halide CH3NH3PbI3–XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently...

  11. Theoretical analysis of the kinetics of low-temperature defect recombination in alkali halide crystals

    Science.gov (United States)

    Kuzovkov, V. N.; Popov, A. I.; Kotomin, E. A.; Moskina, A. M.; Vasilchenko, E.; Lushchik, A.

    2016-07-01

    We analyzed carefully the experimental kinetics of the low-temperature diffusion-controlled F, H center recombination in a series of irradiated alkali halides and extracted the migration energies and pre-exponential parameters for the hole H centers. The migration energy for the complementary electronic F centers in NaCl was obtained from the colloid formation kinetics observed above room temperature. The obtained parameters were compared with data available from the literature.

  12. Dielectric relaxation of alkyl chains in graphite oxide and n-alkylammonium halides

    OpenAIRE

    Xiaoqian Ai; Yuchen Tian; Min Gu; Ji Yu; Tong B. Tang

    2016-01-01

    The dynamic of n-alkylammonium halides and n-alkylammonium cations (n = 12, 14, 16, 18) intercalated in graphite oxide (GO) have been investigated with complex impedance spectroscopy. X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, elemental analysis and thermogravimetry served to characterize the materials. The intercalated alkylammonium cations distributes as monolayers (when n = 12, 14 or 16) or bilayers (when n = 18), with their long axis para...

  13. Thick phase holographic gratings recorded on BB-640 and PFG-01 silver halide materials

    OpenAIRE

    Neipp López, Cristian; Márquez Ruiz, Andrés; Pascual Villalobos, Inmaculada; Beléndez Vázquez, Augusto

    2002-01-01

    Photographic emulsions are still widely used to record holographic optical elements. In particular, if high diffraction efficiencies are needed, phase volume holograms are preferably recorded on these emulsions. Two particular techniques producing high-quality volume phase holograms are fixation-free rehalogenating bleaching and the use of silver-halide-sensitized gelatin. In this work we compare these two particular techniques applied to three different red-sensitive emulsions: Agfa 8E75 HD,...

  14. Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

    International Nuclear Information System (INIS)

    Europium (Eu)-activated barium halide nanocrystals in fluorozirconate based glass ceramics represent a promising class of Xray scintillators. The scintillation in these glass ceramics is mainly caused by the emission of divalent Eu incorporated in hexagonal BaCl2 nanocrystals which are formed in the glass matrix upon appropriate annealing. Experiments with cerium (Ce)-activated fluorozironate glass ceramics showed that Ce is an interesting alternative. In order to get a better understanding of the scintillation mechanism in Eu- or Ce-activated barium halide nanocrystals, an investigation of the processes in the corresponding bulk material is essential. The objective of this thesis is the investigation of undoped, Eu-, and Ce-doped barium halides by X-ray excited luminescence (XL), pulse height, and scintillation decay spectra. That will help to figure out which of these crystals has the most promising scintillation properties and would be the best nanoparticles for the glass ceramics. Furthermore, alternative dopants like samarium (Sm) and manganese (Mn) were also investigated. Besides the above-mentioned optical investigation electron paramagnetic resonance (EPR) and Moessbauer measurements were carried out in order to complete the picture of Eu-doped barium halides. The EPR data of Eu-doped BaI2 is anticipated to yield more information about the crystal field and crystal structure that will help to understand the charge carrier process during the scintillation process. The main focus of the Moessbauer investigations was set on the Eu-doped fluorochlorozirconate glass ceramics. The results of this investigation should help to improve the glass ceramics. The Eu2+/Eu3+ ratio in the glass ceramics should be determined and optimize favor of the Eu2+. We also want to distinguish between Eu2+ in the glass matrix and Eu2+ in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a CaF2 host lattice were carried out. (orig.)

  15. Propensity of heavier halides for the water/vapor interface revisited using the Amoeba force field

    Czech Academy of Sciences Publication Activity Database

    Tůma, L.; Jeníček, D.; Jungwirth, Pavel

    2005-01-01

    Roč. 411, - (2005), s. 70-74. ISSN 0009-2614 R&D Projects: GA MŠk(CZ) LC512 Grant ostatní: NSF(US) CHE0431312; NSF(US) CHE0209719 Institutional research plan: CEZ:AV0Z4055905 Keywords : halide anions * water/vapor interface * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.438, year: 2005

  16. An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

    KAUST Repository

    Weng, Zhiqiang

    2012-12-12

    A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

    OpenAIRE

    Di, Dawei; Musselman, Kevin P.; Li, Guangru; Sadhanala, Aditya; Ievskaya, Yulia; Song, Qilei; Tan, Zhi-Kuang; Lai, May Ling; MacManus-Driscoll, Judith L; Greenham, Neil C.; Friend, Richard H

    2015-01-01

    In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskit...

  18. Calculation of shear angles in holographic gratings recorded in bleached silver-halide emulsions

    OpenAIRE

    Beléndez Vázquez, Augusto; Pascual Villalobos, Inmaculada; Fuentes Rosillo, Rosa; Fimia Gil, Antonio

    1993-01-01

    Shearing phenomena in holographic gratings formed in bleached silver-halide emulsions due to chemical processing are evaluated. These effects are introduced because of the inability of emulsion-thickness changes to explain the anomalous detuning of the peak diffraction efficiency from the expected Bragg condition. Experimental results obtained with transmission and reflection gratings are presented and discussed considering shearing effects, and the values of the shear angles calculated from ...

  19. Three-Component Halo Aldol Condensation of Thioacrylates with Aldehydes Mediated by Titanium (IV Halide

    Directory of Open Access Journals (Sweden)

    Guigen Li

    2002-01-01

    Full Text Available a,b-Ethyl thioacrylate was difuctionalized by a tandem X-C/C=C bond formation reaction. The new system uses Ti (IV halide as both the Lewis acidic promoter and the halogen source for the Michael-type addition onto the thioacrylate. The titanium enolate species resulting from Michael-type addition react with aldehydes followed by dehydration to afford trisubstituted olefin products. Complete geometric selectivity (>95% and up to 72% yield have been obtained for 7 examples.

  20. Three-Component Halo Aldol Condensation of Thioacrylates with Aldehydes Mediated by Titanium (IV) Halide

    OpenAIRE

    Guigen Li; Gao, Joe J.; Han-Xun Wei; Sun Hee Kim

    2002-01-01

    a,b-Ethyl thioacrylate was difuctionalized by a tandem X-C/C=C bond formation reaction. The new system uses Ti (IV) halide as both the Lewis acidic promoter and the halogen source for the Michael-type addition onto the thioacrylate. The titanium enolate species resulting from Michael-type addition react with aldehydes followed by dehydration to afford trisubstituted olefin products. Complete geometric selectivity (>95%) and up to 72% yield have been obtained for 7 examples.