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Sample records for americium halides

  1. 1976 Hanford americium accident

    International Nuclear Information System (INIS)

    Heid, K.R.; Breitenstein, B.D.; Palmer, H.E.; McMurray, B.J.; Wald, N.

    1979-01-01

    This report presents the 2.5-year medical course of a 64-year-old Hanford nuclear chemical operator who was involved in an accident in an americium recovery facility in August 1976. He was heavily externally contaminated with americium, sustained a substantial internal deposition of this isotope, and was burned with concentrated nitric acid and injured by flying debris about the face and neck. The medical care given the patient, including the decontamination efforts and clinical laboratory studies, are discussed. In-vivo measurements were used to estimate the dose rates and the accumulated doses to body organs. Urinary and fecal excreta were collected and analyzed for americium content. Interpretation of these data was complicated by the fact that the intake resulted both from inhalation and from solubilization of the americium embedded in facial tissues. A total of 1100 μCi was excreted in urine and feces during the first 2 years following the accident. The long-term use of diethylenetriaminepentate (DTPA), used principally as the zinc salt, is discussed including the method, route of administration, and effectiveness. To date, the patient has apparently experienced no complications attributable to this extensive course of therapy, even though he has been given approximately 560 grams of DTPA. 4 figures, 1 table

  2. 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)

  3. Americium in water and sediments

    International Nuclear Information System (INIS)

    Coughtrey, P.J.; Jackson, D.; Jones, C.H.; Thorne, M.C.

    1984-01-01

    Data for americium 241 in aquatic environments are presented derived from areas contaminated solely by global fallout, and also from areas contaminated by radioactive waste discharges. For several water bodies, in particular the Mediterranean, comprehensive data are given characterising the inputs, distribution, geochemical behaviour and biological availability of americium. Many data are also reported for concentrations of americium in North European coastal waters (e.g. English Channel, North Sea, Irish Sea, Baltic Sea, Barents Sea and the Eastern Atlantic). Much of the discussion in this section is in terms of the behaviour of americium relative to plutonium. (Auth.)

  4. Recycling of americium

    International Nuclear Information System (INIS)

    Hagstroem, Ingela

    1999-12-01

    Separation of actinides from spent nuclear fuel is a part of the process of recycling fissile material. Extracting agents for partitioning the high level liquid waste (HLLW) from conventional PUREX reprocessing is studied. The CTH-process is based on three consecutive extraction cycles. In the first cycle protactinium, uranium, neptunium and plutonium are removed by extraction with di-2-ethylhexyl-phosphoric acid (HDEHP) from a 6 M nitric acid HLLW solution. Distribution ratios for actinides, fission products and corrosion products between HLLW and 1 M HDEHP in an aliphatic diluent have been investigated. To avoid addition of chemicals the acidity is reduced by a tributylphosphate (TBP) extraction cycle. The distribution ratios of elements present in HLLW have been measured between 50 % TBP in an aliphatic diluent and synthetic HLLW in range 0.1-6 M nitric acid. In the third extraction cycle americium and curium are extracted. To separate trivalent actinides from lanthanides a method based on selective stripping of the actinides from 1 M HDEHP is proposed. The aqueous phase containing ammonia, diethylenetriaminepentaacetic acid (DTPA) and lactic acid is recycled in a closed loop after reextraction of the actinides into a second organic phase also containing 1 M HDEHP. Distribution ratios for americium and neodymium have been measured at varying DTPA and lactic acid concentrations and at varying pH. Nitrogen-donor reagents have been shown to have a potential to separate trivalent actinides from lanthanides. 2,2':6,2''-terpyridine as extractant follows the CHON-principle and can in synergy with 2-bromodecanoic acid separate americium from europium. Distribution ratios for americium and europium, in the range of 0.02-0.12 M nitric acid, between nitric acid and 0.02 M terpyridine with 1 M 2-bromodecanoic acid in tert-butylbenzene (TBB) was investigated. Comparison with other nitrogen-donor reagents show that increasing lipophilicity of the molecule, by substitution of

  5. Americium-241 - ED 4308

    International Nuclear Information System (INIS)

    Ammerich, M.; Frot, P.; Gambini, D.; Gauron, C.; Moureaux, P.; Herbelet, G.; Lahaye, T.; Le Guen, B.; Pihet, P.; Rannou, A.; Vidal, E.

    2012-12-01

    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. Plutonium and americium separation from salts

    International Nuclear Information System (INIS)

    Hagan, P.G.; Miner, F.J.

    1976-01-01

    Salts or materials containing plutonium and americium are dissolved in hydrochloric acid, heated, and contacted with an alkali metal carbonate solution to precipitate plutonium and americium carbonates which are thereafter readily separable from the solution

  7. 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...

  8. Metabolism of americium-241 in dairy animals

    International Nuclear Information System (INIS)

    Sutton, W.W.; Patzer, R.G.; Mullen, A.A.; Hahn, P.B.; Potter, G.D.

    1978-10-01

    Groups of lactating cows and goats were used to examine americium-241 metabolism in dairy animals. Following either single oral or intravenous nuclide doses, samples of milk, urine, blood, and feces were taken over a 168-hr collection period and the americium concentrations were determined by gamma counting. Gastrointestinal uptake of americium by both cows and goats was estimated to be 0.014% of the respective oral doses. The cumulative percentage of oral dose transported to milk and urine was 4.4 x 10 -4 and 1.1 x 10 -3 respectively for cows and 4.4 x 10 -3 and 1.2 x 10 -3 respectively for goats. The relatively high americium concentrations noted in caprine milk following the oral doses are discussed. Plasma concentrations of americium decreased rapidly following all intravenous injections. The average percentage of injected americium transferred to milk, urine, and feces was 3, 6, and 2% respectively for cows and 2, 4, and 2% respectively for goats. In both intravenously dosed groups, approximately 30% of all americium released from the body was found in the urine during the first 24 hrs after injection. All animals were sacrificed 8 to 9 days after dosing. Bovine bone retained the greatest fraction of the administered dose followed by the liver. However, liver retained the greatest amount of americium in the goats following both oral and intravenous doses. Comparisons are presented between americium-241 and plutonium-238 transport in dairy cows

  9. Production of americium isotopes in France

    International Nuclear Information System (INIS)

    Koehly, G.; Bourges, J.; Madic, C.; Nguyen, T.H.; Lecomte, M.

    1984-12-01

    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 SiO 2 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 HNO 3 at room temperature. The separation between plutonium and americium is performed by extraction of Pu(IV) either on TBP/SiO 2 or TOAHNO 3 /SiO 2 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/SiO 2 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 AmO 2 final product indicates a purity better than 98.5%

  10. 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.

  11. Formation of americium and europium humate complexes

    International Nuclear Information System (INIS)

    Minai, Y.; Tominaga, T.; Meguro, Y.

    1991-01-01

    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 241 Am or 152 Eu 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)

  12. Biosorption of americium by alginate beads

    International Nuclear Information System (INIS)

    Borba, Tania Regina de; Marumo, Julio Takehiro; Goes, Marcos Maciel de; Ferreira, Rafael Vicente de Padua; Sakata, Solange Kazumi

    2009-01-01

    The use of biotechnology to remove heavy metals from wastes plays great potential in treatment of radioactive wastes and therefore the aim of this study was to evaluate the biosorption of americium by alginate beads. Biosorption has been defined as the property of certain biomolecules to bind and remove selected ions or other molecules from aqueous solutions. The calcium alginate beads as biosorbent were prepared and analyzed for americium uptaking. The experiments were performed in different solution activity concentrations, pH and exposure time. The results suggest that biosorption process is more efficient at pH 4 and for 75, 150, 300 Bq/mL and 120 minutes were necessary to remove almost 100% of the americium-241 from the solution. (author)

  13. New Fecal Method for Plutonium and Americium

    International Nuclear Information System (INIS)

    Maxwell, S.L. III

    2000-01-01

    A new fecal analysis method that dissolves plutonium oxide was developed at the Westinghouse Savannah River Site. Diphonix Resin (Eichrom Industries), is used to pre-concentrate the actinides from digested fecal samples. A rapid microwave digestion technique is used to remove the actinides from the Diphonix Resin, which effectively extracts plutonium and americium from acidic solutions containing hydrofluoric acid. After resin digestion, the plutonium and americium are recovered in a small volume of nitric acid that is loaded onto small extraction chromatography columns, TEVA Resin and TRU Resin (Eichrom Industries). The method enables complete dissolution of plutonium oxide and provides high recovery of plutonium and americium with good removal of thorium isotopes such as thorium-228

  14. New fecal method for plutonium and americium

    International Nuclear Information System (INIS)

    Maxwell, S.L.; Fauth, D.J.; Nichols, S.T.

    2001-01-01

    A new fecal analysis method that dissolves plutonium oxide was developed at the Westinghouse Savannah River Site. Diphonix Resin R (Eichrom Technologies), is used to pre-concentrate the actinides from digested fecal samples. A rapid microwave digestion technique is used to remove the actinides from the Diphonix Resin R , which effectively extracts plutonium and americium from acidic solutions containing hydrofluoric acid. After resin digestion, the plutonium and americium are recovered in a small volume of nitric acid that is loaded onto small extraction chromatography columns, TEVA Resin and TRU Resin (Eichrom Technologies). The method enables complete dissolution of plutonium oxide and provides high recovery of plutonium and americium with good removal of thorium isotopes such as 228 Th. (author)

  15. Transmutation of Americium in Fast Neutron Facilities

    International Nuclear Information System (INIS)

    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 core's safety parameters. Applying the SAS4A/SASSYS transient analysis code, it is demonstrated that the power rating needs to be reduced by 6% for each percent additional americium introduction into the reference MOX fuel, maintaining 100 K margin to fuel melting, which is the most limiting failure mechanism. Safety analysis of a new Accelerator Driven System design with a smaller pin pitch-to-diameter ratio comparing to the reference EFIT-400 design, aiming at improving neutron source efficiency, was also performed by simulating performance for unprotected loss of flow, unprotected transient overpower, and protected loss-of-heat-sink transients, using neutronic parameters obtained from MCNP calculations. Thanks to the introduction of the austenitic 15/15Ti stainless steel with enhanced creep rupture resistance and acceptable irradiation swelling rate, the suggested ADS design loaded with nitride fuel and cooled by lead-bismuth eutectic could survive the full set of transients, preserving a margin of 130 K to cladding rupture during the most limiting transient. The thesis concludes that efficient transmutation of americium in a medium sized sodium cooled fast reactor loaded with MOX fuel is possible but leads to a severe power penalty. Instead, preserving transmutation rates of minor actinides up to 42 kg/TWh th , the suggested ADS design with enhanced proton source efficiency appears like a better option for americium transmutation

  16. Preparation of americium source for smoke detector

    International Nuclear Information System (INIS)

    Ramaswami, A.; Singh, R.J.; Manohar, S.B.

    1994-01-01

    This report describes the method developed for the preparation of 241 Am 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 241 Am 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

  17. Photofragmentation of metal halides

    International Nuclear Information System (INIS)

    Veen, N.J.A. van.

    1980-01-01

    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.)

  18. Redox chemistry of americium in nitric acid media

    International Nuclear Information System (INIS)

    Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM.

    2004-01-01

    The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

  19. 1976 Hanford americium exposure incident: psychological aspects

    International Nuclear Information System (INIS)

    Brown, W.R.

    1982-01-01

    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

  20. Ternary Silver Halide Nanocrystals.

    Science.gov (United States)

    Abeyweera, Sasitha C; Rasamani, Kowsalya D; Sun, Yugang

    2017-07-18

    Nanocrystalline silver halides (AgX) such as AgCl, AgBr, and AgI, a class of semiconductor materials with characteristics of both direct and indirect band gaps, represent the most crucial components in traditional photographic processing. The nanocrystal surfaces provide sensitivity specks that can turn into metallic silver, forming an invisible latent image, upon exposure to light. The photographic processing implies that the AgX nanoparticles possess unique properties. First, pristine AgX nanoparticles absorb light only at low efficiency to convert surface AgX into tiny clusters of silver atoms. Second, AgX nanoparticles represent an excellent class of materials to capture electrons efficiently. Third, small metallic silver clusters can catalyze the reduction of AgX nanoparticles to Ag nanoparticles in the presence of mild reducing reagents, known as self-catalytic reduction. These properties indicate that AgX nanoparticles can be partially converted to metallic silver with high precision, leading to the formation of hybrid AgX/Ag nanoparticles. The nanosized metallic Ag usually exhibit intense absorption bands in the visible spectral region due to their strong surface plasmon resonances, which make the AgX/Ag nanoparticles a class of promising visible-light-driven photocatalysts for environmental remediation and CO 2 reduction. Despite the less attention paid to their ability of capturing electrons, AgX nanoparticles might be a class of ideal electron shuttle materials to bridge light absorbers and catalysts on which electrons can drive chemical transformations. In this Account, we focus on ternary silver halide alloy (TSHA) nanoparticles, containing two types of halide ions, which increase the composition complexity of the silver halide nanoparticles. Interdiffusion of halide ions between two types of AgX at elevated temperatures has been developed for fabricating ternary silver halide alloy crystals, such as silver chlorobromide optical fibers for infrared

  1. Americium migration in basalt and implications to repository risk analysis

    International Nuclear Information System (INIS)

    Rickert, P.G.

    1980-01-01

    Experiments were performed with americium as a minor component in groundwater. Batch adsorption, migration through column, and filtration experiments were performed. It was determined in batch experiments that americium is strongly adsorbed from solution. It was determined with filtration experiments that large percentages of the americium concentrations suspended by the contact solutions in batch experiments and suspended by the infiltrating groundwater in migration experiments were associated with particulate. Filtration was determined to be the primary mode of removal of americium from infiltrating groundwater in a column of granulated basalt (20 to 50 mesh) and an intact core of permeable basalt. Fractionally, 0.46 and 0.22 of the americium component in the infiltrating groundwater was transported through the column and core respectively. In view of these filtration and migration experiment results, the concept of K/sub d/ in the chromatographic sense is meaningless for predicting americium migration in bedrock by groundwater transport at near neutral pH

  2. Procedure for the analysis of americium in complex matrices

    International Nuclear Information System (INIS)

    Knab, D.

    1978-02-01

    A radioanalytical procedure for the analysis of americium in complex matrices has been developed. Clean separations of americium can be obtained from up to 100 g of sample ash, regardless of the starting material. The ability to analyze large masses of material provides the increased sensitivity necessary to detect americium in many environmental samples. The procedure adequately decontaminates from rare earth elements and natural radioactive nuclides that interfere with the alpha spectrometric measurements

  3. The relative physiological and toxicological properties of americium and plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Carter, R.E.; Busch, E.; Johnson, O. [and others

    1951-11-15

    The relative physiological and toxicological properties of americium and plutonium have been studied following their intravenous administration to rats. The urinary and fecal excretion of americium was similar to that of plutonium administered as Pu(N0{sub 3}){sub 4}. The deposition of americium the tissues and organs of the rat was also similar to that observed for plutonium. The liver and the skeleton were the major sites of deposition. Zirconium citrate administered 15 minutes after injection of americium increased the urinary excretion of americium and decreased the amount found in the liver and the skeleton at 4 and 16 days. LD{sub 30}{sup 50} studies showed americium was slightly less toxic when given in the acute toxic range than was plutonium. The difference was, however, too slight to be important in establishing a larger tolerance does for americium. Survival studies, hematological observations, bone marrow observations, comparison of tumor incidence and the incidence of skeletal abnormalities indicated that americium and plutonium have essentially the same chronic toxicity when given on an equal {mu}c. basis. These studies support the conclusion that the tolerance values for americium should be essentially the same as those for Plutonium.

  4. Investigation of americium-241 metal alloys for target applications

    International Nuclear Information System (INIS)

    Conner, W.V.; Rockwell International Corp., Golden, CO

    1982-01-01

    Several 241 Am metal alloys have been investigated for possible use in the Lawrence Livermore National Laboratory Radiochemical Diagnostic Tracer Program. Several properties were desired for an alloy to be useful for tracer program applications. A suitable alloy would have a fairly high density, be ductile, homogeneous and easy to prepare. Alloys investigated have included uranium-americium, aluminium-americium, and cerium-americium. Uranium-americium alloys with the desired properties proved to be difficult to prepare, and work with this alloy was discontinued. Aluminium-americium alloys were much easier to prepare, but the alloy consisted of an aluminium-americium intermetallic compound (AmAl 4 ) in an aluminum matrix. This alloy could be cast and formed into shapes, but the low density of aluminum, and other problems, made the alloy unsuitable for the intended application. Americium metal was found to have a high solid solubility in cerium and alloys prepared from these two elements exhibited all of the properties desired for the tracer program application. Cerium-americium alloys containing up to 34 wt% americium have been prepared using both co-melting and co-reduction techniques. The latter technique involves co-reduction of cerium tetrafluoride and americium tetrafluoride with calcium metal in a sealed reduction vessel. Casting techniques have been developed for preparing up to eight 2.2 cm (0.87 in) diameter disks in a single casting, and cerium-americium metal alloy disks containing from 10 to 25 wt% 241 Am have been prepared using these techniques. (orig.)

  5. Surface complexation modeling of americium sorption onto volcanic tuff.

    Science.gov (United States)

    Ding, M; Kelkar, S; Meijer, A

    2014-10-01

    Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways. Published by Elsevier Ltd.

  6. Self-irradiation and oxidation effects on americium sesquioxide and Raman spectroscopy studies of americium oxides

    Energy Technology Data Exchange (ETDEWEB)

    Horlait, Denis [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Caraballo, Richard [CEA, DEN, DTCD/SECM/LMPA, F-30207 Bagnols-sur-Cèze Cedex (France); Lebreton, Florent [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Jégou, Christophe [CEA, DEN, DTCD/SECM/LMPA, F-30207 Bagnols-sur-Cèze Cedex (France); Roussel, Pascal [Unité de Catalyse et Chimie du Solide, UMR 8012 CNRS, Ecole Nationale Supérieure de Chimie de Lille BP 90108, 59652 Villeneuve d’Ascq Cedex (France); Delahaye, Thibaud, E-mail: thibaud.delahaye@cea.fr [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France)

    2014-09-15

    Americium oxides samples were characterized by X-ray diffraction (XRD) and Raman spectroscopy, with an emphasis on their structural behavior under oxidation and self-irradiation. Raman spectra of americium dioxide (AmO{sub 2}) and sesquioxide (Am{sub 2}O{sub 3}) were obtained for the first time. With the help of literature data on isostructural oxides, Raman signatures of Ia-3 C-type Am{sub 2}O{sub 3} and P-3m1 A-type Am{sub 2}O{sub 3} are identified. For AmO{sub 2,} a clear band is noted at 390 cm{sup −1}. Its nature is compared to that of the other actinide dioxides. Am{sub 2}O{sub 3} evolution under ambient conditions and against {sup 241}Am α self-irradiation was monitored by powder XRD. The sample, initially composed of A-type Am{sub 2}O{sub 3} as major phase as well as C2/m B-type and C-type structures as minor phases, progressively oxidizes to Fm-3m AmO{sub 2−δ} over a few months. On the basis of diffractogram refinements, evolutions of unit cell volumes caused by self-irradiation are also determined and discussed. - Graphical abstract: The evolution of americium oxide under ambient conditions was monitored using XRD (X-ray diffraction) and Raman spectroscopy. After a thermal treatment under reducing conditions, a polyphasic sample mainly composed of A- and C-type americium sesquioxides is evidenced by XRD and Raman spectroscopy. The sample then evolves through two processes: oxidation and self-irradiation. The first one provokes the progressive appearance of F-type americium dioxide while the initial phases disappear, whereas the main effect of the second is a structural swelling with time. - Highlights: • The first Raman spectroscopy measurements on americium oxides were performed. • Observed Am{sub 2}O{sub 3} Raman bands were identified thanks to data on analogue compounds. • AmO{sub 2} assumed T{sub 2g} band presents a shift compared to the actinide dioxide series. • Am{sub 2}O{sub 3} evolution under self-irradiation and oxidation was also

  7. Halide laser glasses

    Energy Technology Data Exchange (ETDEWEB)

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  8. 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

  9. Feasibility of the fabrication of americium targets

    International Nuclear Information System (INIS)

    Haas, D.; Somers, J.

    1999-01-01

    The paper compares the processes used at ITU for the fabrication of americium targets for transmutation: powder mixing process, sol-gel method and the infiltration by an active solution of inactive pellets. The advantages of the latter process, related mainly to the lower level of dust formation, are stressed. Moreover, the radiological constraints on the fabrication as a function of Am content and of selected fabrication process are evaluated. As conclusion, the feasibility of Am target fabrication has been demonstrated on a laboratory scale, based on experimental results evaluation. The penalties due to radiological constraints in a semi-industrial process are acceptable. The future developments consist in the construction of a laboratory fully dedicated to minor actinides fuel pins or targets fabrication. (author)

  10. Americium/Curium Disposition Life Cycle Planning Study

    International Nuclear Information System (INIS)

    Jackson, W.N.; Krupa, J.; Stutts, P.; Nester, S.; Raimesch, R.

    1998-01-01

    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)

  11. 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.

  12. Americium/Curium Disposition Life Cycle Planning Study

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, W.N. [Westinghouse Savannah River Company, AIKEN, SC (United States); Krupa, J.; Stutts, P.; Nester, S.; Raimesch, R.

    1998-04-30

    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).

  13. PROCESS FOR SEPARATING AMERICIUM AND CURIUM FROM RARE EARTH ELEMENTS

    Science.gov (United States)

    Baybarz, R.D.; Lloyd, M.H.

    1963-02-26

    This invention relates to methods of separating americium and curium values from rare earth values. In accordance with the invention americium, curium, and rare earth values are sorbed on an anion exchange resin. A major portion of the rare earth values are selectively stripped from the resin with a concentrated aqueous solution of lithium chloride, and americium, curium, and a minor portion of rare earth values are then stripped from the resin with a dilute aqueous solution of lithium chloride. The americium and curium values are further purified by increasing the concentration of lithium chloride in the solution to at least 8 molar and selectively extracting rare earth values from the resulting solution with a monoalkylphosphoric acid. (AEC)

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

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, Kyle Shelton [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); 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)

    2016-09-28

    These are a set of slides intended for an information session as part of recruiting activities at Brigham Young University. It gives an overview of aqueous chloride operations, specifically on plutonium and americium purification/recovery. This presentation details the steps taken perform these processes, from plutonium size reduction, dissolution, solvent extraction, oxalate precipitation, to calcination. For americium recovery, it details the CLEAR (chloride extraction and actinide recovery) Line, oxalate precipitation and calcination.

  15. 1976 Hanford americium-exposure incident: external decontamination procedures

    International Nuclear Information System (INIS)

    Jech, J.J.; Berry, J.R.; Breitenstein, B.D.

    1982-01-01

    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

  16. Preparation of americium metal of high purity and determination of the heat of formation of the hydrated trivalent americium ion

    International Nuclear Information System (INIS)

    Spirlet, J.C.

    1975-10-01

    In order to redetermine some physical and chemical properties of americium metal, several grams of Am-241 have been prepared by two independent methods: lanthanum reduction of the oxide and thermal dissociation of the intermetallic compound Pt 5 Am. After its separation from excess lanthanum or alloy constituent by evaporation, americium metal was further purified by sublimation at 1100 deg C and 10 -6 Torr. Irrespective of the method of preparation, the americium samples displayed the same d.h.c.p. crystal structure. As determined by vacuum hot extraction, the oxygen, nitrogen and hydrogen contents are equal to or smaller than 250, 50 and 20 ppm, respectively. The heats of solution of americium metal (d.c.h.p. structure) in aqueous hydrochloric acid solutions have been measured at 298.15+-0.05K. The standard enthalpy of formation of Am 3+ (aq) is obtained as -616.7+-1.2 kJ mol -1 [fr

  17. Citric complexes, neodymium citrate and americium citrate

    International Nuclear Information System (INIS)

    Bouhlassa, Saidati.

    1981-06-01

    The behaviour of neodymium and americium has been studied in citric aqueous medium by two methods: solvent extraction of elements at tracer scale as chelates and by potentiometry. So range of pH and concentrations of elements and citric acid never reached before have been explored: 10 -7 -1 M, 10 -10 -3 , Csub(H3 Cit) -1 M, 1 2 O; AmCit, xH 2 O; NdCit 2 Co(NH 3 ) 6 , 8H 2 O; AmCit 2 Co(NH 3 ) 6 , xH 2 O and Nd 3 (OH) 4 (Cit) 4 NH 4 (Co(NH 3 ) 6 ) 2 , 18H 2 O. Their spectroscopic and crystallographic characteristics have been listed and studied. The nephelauxetic effect has been estimated from citric complexes as well as from citrates of these elements. The structure of the complexes in solution has been discussed on the basis of analysis of hypersensitive transition in different complexes [fr

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

    International Nuclear Information System (INIS)

    Matsumura, T.; Usuda, S.

    1998-01-01

    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 HNO 3 , 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 HNO 3 at 25 C, which corresponds to approximately 1.7 mg- 241 Am/g-adsorbent(dried). The prospect of applying the adsorbent to the treatment of aqueous waste contaminated with americium appears promising. (orig.)

  19. Methyl Halide Production by Fungi

    Science.gov (United States)

    Dailey, G. D.; Varner, R. K.; Blanchard, R. O.; Sive, B. C.; Crill, P. M.

    2005-12-01

    Methyl chloride (CH3Cl), methyl bromide (CH3Br) and methyl iodide (CH3I) are methyl halide gases that contribute significant amounts of halogen radicals to the atmosphere. In an effort to better understand the global budget of methyl halides and their impact on the atmosphere, we need to identify the natural sources in addition to the known anthropogenic sources of these compounds. We are investigating the role of fungi in the production of methyl halides in the soils and wetlands in southern New Hampshire, USA. Previous research has shown that wood decay fungi and ectomycorrhizal fungi, which are within a group of fungi called basidiomycetes, emit methyl halides. In our study, measurements of headspace gas extracted from flasks containing fungi grown in culture demonstrate that a variety of fungi, including basidiomycetes and non-basidiomycetes, emit methyl halides. Our research sites include four ecosystems: an agricultural field, a temperate forest, a fresh water wetland, and coastal salt marshes. We have collected and isolated fungi at each site by culturing tissue samples of fruiting bodies and plant material, by using wood baits, and from the direct culture of soil. We compared the rates of methyl halide emissions from the fungi in the four ecosystems. In addition, we measured emissions from previously assayed fungal isolates after reintroducing them to sterilized soils that were collected from their original environments. Fungal biomass was determined by substrate-induced respiration (SIR). The emission rate by the fungus was determined by a linear regression of the concentration of methyl halide in the sample headspace over time divided by the fungal biomass.

  20. A process for the recovery of americium from analytical wastes

    International Nuclear Information System (INIS)

    Brossard, P.; Kwinta, J.; Schwander, Y.

    1984-12-01

    The object of the present work is to define a procedure for the extraction of americium contained in hundreds of liters of liquid analytical wastes. The main objective is to produce wastes for which the americium concentration is lower than 0,5 mg/l, the operations being carried out in glove boxes. Dihexyl N, N-diethylcarbamylmethylene phosphonate (DHDECMP) is used for the extraction of americium. Experimental laboratory results and procedure design are described. Distribution coefficient, DHDECMP concentration, addition of TBP, influence of PH and temperature are studied. A bank of mixer-settlers appears to be the most appropriate laboratory equipment to handle large volume of solution with a good efficiency

  1. The selective extraction of americium from high level liquid wastes

    Energy Technology Data Exchange (ETDEWEB)

    Adnet, J.M.; Donnet, L.; Brossard, P.; Bourges, J.

    1996-12-31

    One of the possible ways selected by CEA for the partitioning of minor actinides from solutions containing fission products is the selective extraction of the oxidized species. This papers deals with the latest developments in the electrochemical oxidation of americium in nitric media to the oxidation states (IV) and (VI). Oxidized americium is generated and stabilized through the use of poly anionic ligands such as the phospho tungstate. With in view the use of such ligands in the treatment of real liquid wastes, the complexation of several metallic ions has been investigated A first experiment done with a real liquid waste to prove the possibility to selectively extract the oxidized americium is presented. (authors). 8 refs.

  2. Synergistic extraction behaviour of americium from simulated acidic waste solutions

    International Nuclear Information System (INIS)

    Pathak, P.N.; Veeraraghavan, R.; Mohapatra, P.K.; Manchanda, V.K.

    1998-01-01

    The extraction behaviour of americium has been investigated with mixtures of 3-phenyl-4-benzoyl-5-isoxazolone (PBI) and oxodonors viz. tri-n-butyl phosphate (TBP), tri-n-octyl phosphine oxide (TOPO) and di-n-butyl octanamide (DBOA) using dodecane as the diluent from 1-6 M HNO 3 media. It is observed that D Am remains unaltered with PBI concentration (in the range 0.06-0.1 M) at 1.47 M TBP in the entire range of HNO 3 concentration. PBI and TBP in combination appears more promising compared to other synergistic systems. The possibility of using this mixture for americium removal from high level liquid waste solution has been explored. Extraction studies indicated that prior removal of uranium by 20% TBP in dodecane is helpful in the quantitative recovery of americium in three contacts. Effect of lanthanides on D Am is found to be marginal. (orig.)

  3. Covalency in Americium(III) Hexachloride.

    Science.gov (United States)

    Cross, Justin N; Su, Jing; Batista, Enrique R; Cary, Samantha K; Evans, William J; Kozimor, Stosh A; Mocko, Veronika; Scott, Brian L; Stein, Benjamin W; Windorff, Cory J; Yang, Ping

    2017-06-28

    Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance of orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by Seaborg and co-workers ( Diamond, R. M.; Street, K., Jr.; Seaborg, G. T. J. Am. Chem. Soc. 1954 , 76 , 1461 ) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in-arguably-one of the most difficult systems to study, the Am-Cl interaction within AmCl 6 3- . We observed both 5f- and 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl 6 3- indicated that the amount of Cl 3p-mixing with Eu III 5d-orbitals was similar to that observed with the Am III 6d-orbitals. Meanwhile, the results confirmed Seaborg's 1954 hypothesis that Am III 5f-orbital covalency was more substantial than 4f-orbital mixing for Eu III .

  4. The ingestion of plutonium and americium by range cattle

    International Nuclear Information System (INIS)

    Blincoe, C.; Bohman, V.R.; Smith, D.D.

    1981-01-01

    The intake of plutonium and americium in the diet of cattle grazing on plutonium contaminated desert range was determined. Daily feed intake of the grazing animals was also determined so that the amount of nuclides ingested daily could be ascertained. Soil ingested by range cattle constituted the principal and possibly only source of ingested plutonium and americium and resulted in a daily intake of 3600-6600 pCi 238 Pu, 85,000-400,000 pCi 239 Pu, and 11,000-31,000 pCi 241 Am daily. Determining transuranic intake by direct measurement and from the composition and contamination of the diet gave identical results. (author)

  5. 1976 Hanford americium exposure incident: overview and perspective

    International Nuclear Information System (INIS)

    Thompson, R.C.

    1982-01-01

    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

  6. Determination of plutonium, americium and curium in the marine environment

    International Nuclear Information System (INIS)

    Grenaut, CLaude; Germain, Pierre; Miramand, Pierre.

    1982-01-01

    The method used in the Laboratory for plutonium, americium and curium determination in marine samples (water, sediments, animals, plants) is presented. It is a modification of a procedure based on adsorption on ion exchange resins developed by other authors. The preliminary preparation of the samples, the radiochemical procedures and electrodeposition are described so as to be used as a practical handbook [fr

  7. 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.

  8. Kinetics and mechanism of oxidation of americium(III) to americium(VI) in dilute phosphoric acid solutions

    International Nuclear Information System (INIS)

    Milyukova, M.S.; Litvina, M.N.; Myasoedov, B.F.

    1980-01-01

    The reaction between trivalent americium and a mixture of silver with ammonium persulfate in 0.1-3M H 3 PO 4 solutions was studied. Hexavalent americium was found to be the product of interaction under these conditions. Americium oxidation is described with a first order equation with rate constants k=18.7 hr -1 and k=8.74 hr -1 for 0.1-0.5M and 1M H 3 PO 4 , respectively. The activation energy calculated from the temperature dependence of the rate of americium oxidation by a mixture of Ag 3 PO 4 with (NH 4 ) 2 S 2 O 8 is 9.1 kcal/mole. The stability of Am(VI) in 0.1-1M H 3 PO 4 was studied. No reduction of Am(VI) over a period of 30-40 hrs was observed; after that the reduction of Am(VI) follows a zero order law with the apparent rate constant k=0.0036 hr -1 . The mechanism of Am(III) oxidation with a mixture of silver and ammonium persulfate is discussed. (author)

  9. Development of Halide and Oxy-Halides for Isotopic Separations

    Energy Technology Data Exchange (ETDEWEB)

    Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pfeiffer, Jana [Idaho National Lab. (INL), Idaho Falls, ID (United States); Finck, Martha R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  10. Organic halide electroreduction on silver

    Energy Technology Data Exchange (ETDEWEB)

    Fiori, G.; Mussini, P.; Rondinini, S.; Vertova, A. [Milan Univ., Milan (Italy). Dept. of Physical Chemistry and Electrochemistry

    2001-04-01

    Silver, whose extraordinary electrolytically properties for organic halide reduction have been recently evidenced, has been used as cathode material for systematic preparative electrolyses in membrane-divided cells. To better elucidate the substrate role on the remarkable positive shift of reduction potentials, and on the cage effect i. e. the promotion of intermolecular reaction on adsorbed intermediates, three halide substrate patterns are here compared in terms of both voltammetric characterization and preparative electroreduction products: aliphatic halides (adamantanes), aromatic halides (phenols) and anomeric glycosyl halides. The preparative electroreductions result mainly in dimerization in the case of glycosyl halides, in H {yields} Br substitution in the case of bromophenols, in dimerization + substitution in the case of haloadamantanes. The product analysis, both at the end of the reaction and at intermediate times, allows discussing the reaction pathways in terms of intermediate stability and of active surface accessibility. The possibility of complete dehalogenation on a wider substrate variety with remarkably lower energy consumption and almost quantitative current yields makes the process potentially very interesting for environmental purposes. [Italian] L'argento, di cui sono state recentemente evidenziate straordinarie proprieta' elettrocatalitiche per la riduzione degli alogenuri organici, e' stato utilizzato come materiale catodico per sistematiche elettrolisi preparative in celle a membrana. Per mettere in risalto il ruolo del substrato organico sul notevole anticipo del potenziale di riduzione e sull'effetto gabbia, ovvero la promozione di reazioni intermolecolari su intermedi adsorbiti, vengono qui confrontate, in termini sia di caratterizzazione voltammetrica sia di prodotti di elettroriduzioni preparative, tre tipologie di alogenuri: alifatici (adamantani), aromatici (fenoli) e glicosidici. Le elettroriduzioni preparative

  11. Americium extraction by alkylpyrocatechin from alkaline salt solutions

    International Nuclear Information System (INIS)

    Karalova, Z.K.; Rodionova, L.M.; Myasoedov, B.F.

    1984-01-01

    Effect of iron, aluminium, calcium, and sodium nitrates on americium extraction by 0.1 mol/l DOP solution [4-(α-α dioctylethyl) pyrocatechin] in toluene from a mixture of 2 mol/l NaOH with 0.1 mol/l EDTA has been investigated. It has been shown that americium extraction does not change essen-- tially in the presence of salts that permits to use DOP for Am extraction from alkaline solutions in the presence of outside salts. Verification of the above method of extraction of radioactive isotopes has been carried out. According to the data obtained double extraction provides a preparation of alkaline solutions practically free from radioactive isotopes. DOP application for Am extraction from alkaline salt solutions allows one to carry out repeated Am concentration and separation from accompanying elements. Conditions, under which Fe(3)-Am(3) pair separation coefficient achieves nx10 2 -10 4 , have been found out

  12. Contribution to the study of higher valency states of americium

    International Nuclear Information System (INIS)

    Langlet, Jean.

    1976-01-01

    Study of the chemistry of the higher valencies of americium in aqueous solutions and especially the autoreduction phenomenon. First a purification method of americium solutions is studied by precipitation, solvent extraction and ion exchange chromatography. Studies of higher valency states chemical properties are disturbed by the autoreduction phenomenon changing Am VI and Am V in Am III more stable. Stabilization of higher valency states, characterized by a steady concentration of Am VI in solution, can be done by complexation of Am VI and Am V ions or by a protecting effect of foreign ions. The original medium used has a complexing effect by SO 4 2- ions and a protecting effect by the system S 2 O 8 2- -Ag + consuming H 2 O 2 main reducing agent produced by water radiolysis. These effects are shown by the study of Am VI in acid and basic solutions. A mechanism of the stabilization effect is given [fr

  13. Method for removal of plutonium impurity from americium oxides and fluorides

    Science.gov (United States)

    FitzPatrick, J.R.; Dunn, J.G.; Avens, L.R.

    1987-02-13

    Method for removal of plutonium impurity from americium oxides and fluorides. AmF/sub 4/ is not further oxidized to AmF/sub 6/ by the application of O/sub 2/F at room temperature thereto, while plutonium compounds present in the americium sample are fluorinated to volatile PuF/sub 6/, which can readily be separated therefrom, leaving the purified americium oxides and/or fluorides as the solid tetrafluoride thereof.

  14. Research program on development of advanced treatment technology for americium-containing aqueous waste in NUCEF

    International Nuclear Information System (INIS)

    Mineo, Hideaki; Matsumura, Tatsuro; Tsubata, Yasuhiro

    1996-10-01

    A research program was prepared on the development of an advanced treatment process for the americium-containing concentrated aqueous waste in NUCEF, than allows americium recovery for the reuse and the reduction of TRU waste generation. A preliminary analysis was conducted on the separation requirements based on the components estimated for the waste. An R and D strategy was proposed from the view to reduce TRU waste generated in the processing that the highest priority is given on the control of TRU leakage such as americium into the effluent stream after americium recovery and the minimization of salt used in the separation over the decontamination of impurities from americium. The extraction chromatographic method was selected as a candidate technology for americium separation under the principle to use reagents that are functional in acidic conditions such as bidentate extractants of DHEDECMP, CMPO or diamides, considering the larger flexibilities in process modification and possible multi-component separation with compact equipment and the past achievements on the recovery of kg quantities of americium. Major R and D items extracted are screening and evaluation of extractants for americium and plutonium, optimization of separation conditions, selection of denitration method, equipment developments and development of solidification methods of discarded americium after reuse and of various kinds of separation residues. In order to cope these items, four steps of R and D program were proposed, i.e., fundamental experiment in beaker-scale on screening and evaluation of extractants, flowsheet study in bench-scale using simulated and small amount of americium aqueous waste solution to evaluate candidate process, americium recovery test in iron-shielded cell to be installed in NUCEF. It is objected to make recovery of 100g orders of americium used for research on fundamental TRU fuel properties. (J.P.N.)

  15. 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.

  16. 1976 Hanford americium-exposure incident: decontamination and treatment facility

    International Nuclear Information System (INIS)

    Berry, J.R.; McMurray, B.J.; Jech, J.J.; Breitenstein, B.D.; Quigley, E.J.

    1982-01-01

    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

  17. Americium-241: the most useful isotope of the actinide elements

    International Nuclear Information System (INIS)

    Navratil, J.D.

    1984-01-01

    Used extensively in nuclear gauges and in many other areas, this man-made element (Atomic Number 95) was first isolated in weighable amounts during World War II. Americium is now a very useful by-product of the nuclear industry and is produced in kilogram amounts by appropriate recovery, separation and purification processes. A review will be presented of its discovery, nuclear and chemical properties, and uses, with emphasis on its production process and separations chemistry

  18. Extraction separation of americium and curium. A review

    International Nuclear Information System (INIS)

    Petrzilova, H.

    1976-11-01

    A survey is given of extraction systems suitable for transplutonium element separation and preparation as well as for the practical application of their nuclear properties. Methods are discussed in detail of separating the actinide and the lanthanide fractions from fission and corrosion products and of separating americium from curium. The description is completed with flowsheets showing the separation of transplutonium elements from irradiated targets and waste solutions after spent fuel reprocessing. (L.K.)

  19. Ingestion Pathway Transfer Factors for Plutonium and Americium

    International Nuclear Information System (INIS)

    Blanchard, A.

    1999-01-01

    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

  20. On the structure of thorium and americium adenosine triphosphate complexes

    International Nuclear Information System (INIS)

    Mostapha, Sarah; Berton, Laurence; Boubals, Nathalie; Zorz, Nicole; Charbonnel, Marie-Christine; Fontaine-Vive, Fabien; Den Auwer, Christophe; Solari, Pier Lorenzo

    2014-01-01

    The actinides are chemical poisons and radiological hazards. One challenge to better appraise their toxicity and develop countermeasures in case of exposure of living organisms is to better assess pathways of contamination. Because of the high chemical affinity of those actinide elements for phosphate groups and the ubiquity of such chemical functions in biochemistry, nucleotides and in particular adenosine triphosphate nucleotide (ATP) may be considered critical target building blocks for actinides. Combinations of spectroscopic techniques (Fourier transformed Infra Red [FTIR], Electro-spray Ionization Mass Spectrometry [ESI-MS], and Extended X-ray Absorption Fine Structure [EXAFS]) with quantum chemical calculations have been implemented in order to assess the actinides coordination arrangement with ATP. We describe and compare herein the interaction of ATP with thorium and americium; thorium(IV) as a representative of actinide(IV) like plutonium(IV) and americium(III) as a representative of all heavier actinides. In the case of thorium, an insoluble complex is readily formed. In the case of americium, a behavior identical to that described previously for lutetium has been observed with insoluble and soluble complexes. The comparative study of ATP complexation with Th(IV) and Am(III) shows their ability to form insoluble complexes for which a structural model has been proposed by analogy with previously described Lu(III) complexes. (authors)

  1. On the structure of thorium and americium adenosine triphosphate complexes.

    Science.gov (United States)

    Mostapha, Sarah; Fontaine-Vive, Fabien; Berthon, Laurence; Boubals, Nathalie; Zorz, Nicole; Solari, Pier Lorenzo; Charbonnel, Marie Christine; Den Auwer, Christophe

    2014-11-01

    The actinides are chemical poisons and radiological hazards. One challenge to better appraise their toxicity and develop countermeasures in case of exposure of living organisms is to better assess pathways of contamination. Because of the high chemical affinity of those actinide elements for phosphate groups and the ubiquity of such chemical functions in biochemistry, nucleotides and in particular adenosine triphosphate nucleotide (ATP) may be considered critical target building blocks for actinides. Combinations of spectroscopic techniques (Fourier transformed Infra Red [FTIR], Electrospray Ionization Mass Spectrometry [ESI-MS], and Extended X-ray Absorption Fine Structure [EXAFS]) with quantum chemical calculations have been implemented in order to assess the actinides coordination arrangement with ATP. We describe and compare herein the interaction of ATP with thorium and americium; thorium(IV) as a representative of actinide(IV) like plutonium(IV) and americium(III) as a representative of all heavier actinides. In the case of thorium, an insoluble complex is readily formed. In the case of americium, a behavior identical to that described previously for lutetium has been observed with insoluble and soluble complexes. The comparative study of ATP complexation with Th(IV) and Am(III) shows their ability to form insoluble complexes for which a structural model has been proposed by analogy with previously described Lu(III) complexes.

  2. The EFTTRA-T4 experiment on americium transmutation

    CERN Document Server

    Konings, R J M; Dassel, G; Pijlgroms, B J; Somers, J; Toscano, E

    2000-01-01

    In the EFTTRA-T4 experiment the irradiation behaviour of a target containing americium dispersed in MgAl sub 2 O sub 4 was studied. Pellets containing 10-12 wt% sup 2 sup 4 sup 1 Am were fabricated by the infiltration method. However, it was found that the americium, intended to be present as AmO sub 2 sub - sub x , formed a compound, probably AmAlO sub 3 , during sintering. The T4 target was irradiated in the High Flux Reactor (HFR) Petten from August 1996 to January 1998 (358.4 fpd's). Post-test burn-up calculations indicated that the sup 2 sup 4 sup 1 Am concentration is reduced to 4% of the initial value at the end of the irradiation. The fraction of the initial americium atoms that were fissioned is 28%. Non-destructive and destructive examinations of the target indicated that swelling of the target pellets occurred. This is attributed to accumulation of helium, produced by alpha decay of sup 2 sup 4 sup 2 Cm that occurs in the transmutation scheme of sup 2 sup 4 sup 1 Am.

  3. Gut uptake factors for plutonium, americium and curium

    International Nuclear Information System (INIS)

    Harrison, J.D.

    1982-01-01

    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)

  4. Dehydrated rare earth halides and production process

    International Nuclear Information System (INIS)

    Picard, F.

    1990-01-01

    Rare earth chlorides, bromides or iodides containing less than 1 wt% water and less than 3 wt% oxyhalide are dehydrated by a gas flow of hydrogen halide through the halide bed. Structural water can interfer in some applications for instance metal preparation by chemical or electrochemical reduction [fr

  5. Hygroscopicity Evaluation of Halide Scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Zhuravleva, M [The University of Tennessee; Stand, L [The University of Tennessee; Wei, H [The University of Tennessee; Hobbs, C. L. [University of Tennessee, Knoxville (UTK); Boatner, Lynn A [ORNL; Ramey, Joanne Oxendine [ORNL; Burger, Arnold [Fisk University, Nashville; Rowe, E [Fisk University, Nashville; Bhattacharya, P. [Fisk University, Nashville; Tupitsyn, E [Fisk University, Nashville; Melcher, Charles L [University of Tennessee, Knoxville (UTK)

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  6. Quaternary system of cesium halides

    International Nuclear Information System (INIS)

    Bukhalova, G.A.; Shegurova, G.A.; Yagub'yan, E.S.; Zaporozhets, E.G.

    1977-01-01

    The state diagram of the quaternary system consisting of fluorides, chlorides, bromides, and iodides of cesium has been studied by visual-polythermal, partially X-ray phase and thermographical analyses. The crystallization volume of the quaternary system involves the crystallization volume of cesium fluoride and the crystallization volume of the ternary solid solutions of the rest cesium halides. A quaternary nonvariant point corresponding to melting point 360 deg C appears on the crystallization surface which separates the cesium fluoride volume from the volume of the ternary solid solutions

  7. Extraction of pentavalent americium by di(2-ethylhexyl)phosphoric acid

    International Nuclear Information System (INIS)

    Molochnikova, N.P.; Myasoedov, B.F.; Frenkel, V.Ya.

    1983-01-01

    Conditions have been found for the extraction of americium(V) by HDEHP in octane from acetate buffer solutions at pH 4.5-5.0 in the presence of ammonium persulphate which was necessary to stabilize oxidized americium under these conditions. The effect of the nature of a solvent on the extraction coefficient of americium(V) was studied. Macroamounts of americium(V) were extracted by 0.5M HDEHP in octane. The absorption spectrum of americium(V) in the extract has been recorded. The stability of americium(V) in the organic phase was evaluated. The absence of interfering influence of the anions of phosphotungstic acids on the extraction of americium(V) by 0.5M HDEHP in octane makes it possible to separate americium(V) from trivalent actinides during one extraction from acetate solutions at pH 4.5-5.0 in the presence of 10 -3 M potassium phosphotungstate; the separation factor is about 10 3 . (author)

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

    International Nuclear Information System (INIS)

    Sehmel, G.A.

    1978-01-01

    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

  9. Robotic sample preparation for radiochemical plutonium and americium analyses

    International Nuclear Information System (INIS)

    Stalnaker, N.; Beugelsdijk, T.; Thurston, A.; Quintana, J.

    1985-01-01

    A Zymate robotic system has been assembled and programmed to prepare samples for plutonium and americium analyses by radioactivity counting. The system performs two procedures: a simple dilution procedure and a TTA (xylene) extraction of plutonium. To perform the procedures, the robotic system executes 11 unit operations such as weighing, pipetting, mixing, etc. Approximately 150 programs, which require 64 kilobytes of memory, control the system. The system is now being tested with high-purity plutonium metal and plutonium oxide samples. Our studies indicate that the system can give results that agree within 5% at the 95% confidence level with determinations performed manually. 1 ref., 1 fig., 1 tab

  10. Implications of plutonium and americium recycling on MOX fuel fabrication

    International Nuclear Information System (INIS)

    Renard, A.; Pilate, S.; Maldague, Th.; La Fuente, A.; Evrard, G.

    1995-01-01

    The impact of the multiple recycling of plutonium in power reactors on the radiation dose rates is analyzed for the most critical stage in a MOX fuel fabrication plant. The limitation of the number of Pu recycling in light water reactors would rather stem from reactor core physics features. The case of recovering americium with plutonium is also considered and the necessary additions of shielding are evaluated. A comparison between the recycling of Pu in fast reactors and in light water reactors is presented. (author)

  11. Effect of 241-americium on bone marrow stroma

    International Nuclear Information System (INIS)

    Heuvel, R. van den

    1990-01-01

    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)

  12. Solubility of americium-241 in in vitro bovine ruminal-gastrointestinal fluids and predicted tissue retention and milk secretion of field-ingested americium-241

    International Nuclear Information System (INIS)

    Barth, J.

    1978-01-01

    The alimentary solubility and behavior of americium-241 were studied in an artificial rumen and simulated bovine gastrointestinal fluids. Rumen juice was augmented with americium-241 nitrate solution and incubated for 24 hours. This juice was successively converted by the addition of bile and enzymes and adjustment of the pH to simulate the digestive stages of the abomasum, duodenum, jejunum, and lower small intestine. Fluid samples were collected from each of these digestive stages and radioanalyzed for soluble americium-241. Shortly after the addition of americium-241 to rumen juice, an average of 15.3% remained soluble while 7.2% remained soluble following the incubation period. The solubility decreased to 5.3% following the abomasal period and increased to 11.6% and 20.0% when maintained at pH 4.0 and 5.0, respectively, in the duodenal phase. The solubility increased to 52% during the jejunal incubation period and was reduced to 44.8% during the lower intestinal incubation period. The sharp rise in americium-241 solubility during the jejunal incubation perid was found to be due mainly to the action of bile. Predictions of tissue retention and milk secretion of americium-241 ingested by grazing cattle at Area 13 of the Nevada Test Site are included

  13. Structure of polyvalent metal halide melts

    International Nuclear Information System (INIS)

    Tosi, M.P.

    1990-12-01

    A short review is given of recent progress in determining and understanding the structure of molten halide salts involving polyvalent metal ions. It covers the following three main topics: (i) melting mechanisms and types of liquid structure for pure polyvalent-metal chlorides; (ii) geometry and stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides; and (iii) structure breaking and electron localization on addition of metal to the melt. (author). 28 refs, 3 figs, 1 tab

  14. Analysis of americium, plutonium and technetium solubility in groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Seiji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1999-08-01

    Safety assessments for geologic disposal of radioactive waste generally use solubilities of radioactive elements as the parameter restricting the dissolution of the elements from a waste matrix. This study evaluated americium, plutonium and technetium solubilities under a variety of geochemical conditions using the geochemical model EQ3/6. Thermodynamic data of elements used in the analysis were provided in the JAERI-data base. Chemical properties of both natural groundwater and interstitial water in buffer materials (bentonite and concrete) were investigated to determine the variations in Eh, pH and ligand concentrations (CO{sub 3}{sup 2-}, F{sup -}, PO{sub 4}{sup 3-}, SO{sub 4}{sup 2-}, NO{sub 3}{sup -} and NH{sub 4}{sup +}). These properties can play an important role in the complexation of radioactive elements. Effect of the groundwater chemical properties on the solubility and formation of chemical species for americium, plutonium and technetium was predicted based on the solubility analyses under a variety of geochemical conditions. The solubility and speciation of the radioactive elements were estimated, taking into account the possible range of chemical compositions determined from the groundwater investigation. (author)

  15. Plutonium and americium in the foodchain lichen-reindeer-man

    International Nuclear Information System (INIS)

    Jaakkola, T.; Hakanen, M.; Keinonen, M.; Mussalo, H.; Miettinen, J.K.

    1977-01-01

    The atmospheric nuclear tests have produced a worldwide fallout of transuranium elements. In addition to plutonium measurable concentrations of americium are to be found in terrestrial and aquatic environments. The metabolism of plutonium in reindeer was investigated by analyzing plutonium in liver, bone, and lung collected during 1963-1976. To determine the distribution of plutonium in reindeer all tissues of four animals of different ages were analyzed. To estimate the uptake of plutonium from the gastrointestinal tract in reindeer, the tissue samples of elk were also analyzed. Elk which is of the same genus as reindeer does not feed on lichen but mainly on deciduous plants, buds, young twigs, and leaves of trees and bushes. The composition of its feed corresponds fairly well to that of reindeer during the summer. Studies on behaviour of americium along the foodchain lichen-reindeer-man were started by determining the Am-241 concentrations in lichen and reindeer liver. The Am-241 results were compared with those of Pu-239,240. The plutonium contents of the southern Finns, whose diet does not contain reindeer tissues, were determined by analyzing autopsy tissue samples (liver, lung, and bone). The southern Finns form a control group to the Lapps consuming reindeer tissues. Plutonium analyses of the placenta, blood, and tooth samples of the Lapps were performed

  16. Uptake and recovery of americium and uranium by Anacystis biomass

    International Nuclear Information System (INIS)

    Liu, H.H.; Jiunntzong Wu

    1993-01-01

    The optimum conditions for the uptake of americium and uranium from wastewater solutions by Anacystis nidulans cells, and the recovery of these radionuclides were studied. The optimum pH range for both actinides was in the acidic region between 3.0 and 5.0. In a pH 3.5 solution with an algal biomass of 70 μg/mL, up to 95% of the Am and U were taken up by the cells. However, the uptake levels were lowered considerably when ethylene dinitrilotetraacetic acid (EDTA) or iron or calcium ions were present in the solutions. Most of the radionuclides taken up by the cells could also be desorbed by washing with salt solutions. Of nine salt solutions tested, ammonium carbonate was the most effective. Our experiments using algal biomass to remove radionuclides from wastewater showed that about 92% of americium and 85% of uranium in wastewater could be taken up by algal biomass, from which about 46% of the Am and 82% of the U originally present in the wastewater could be recovered by elution with a salt solution. 17 refs., 7 figs., 2 tabs

  17. Fullerenes doped with metal halides

    International Nuclear Information System (INIS)

    Martin, T.P.; Heinebrodt, M.; Naeher, U.; Goehlich, H.; Lange, T.; Schaber, H.

    1993-01-01

    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 C 60 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

  18. Extraction of americium of different oxidation states in two-phase aqueous system based on polyethylene glycol

    International Nuclear Information System (INIS)

    Molochnikova, N.P.; Frenkel', V.Ya.; Myasoedov, B.F.; Shkinev, V.M.; Spivakov, B.Ya.; Zolotov, Yu.A.

    1987-01-01

    Americium extraction in different oxidation states in two-phase aqueous system based on polyethylene glycol is investigated. Conditions for quantitative extraction of americium (3) and americium (5) from ammonium sulfate solutions within pH=3-5 interval in the presence of arsenazo 3 are found. Composition of the produced americium complexes with reagent is determined; americium (3) interacts with arsenazo 3 in ammonium sulfate solutions with the formation of MeR and Me 2 R composition complexes. Absorption spectrum characteristics of americium (3) and- (5) complexes with arsenazo 3 in ammonium sulfate solutions and extracts based polyethylene glycol aqueous solutions are given. Molar extinction coefficients of americium complexes with arsenazo (3) in these solutions are determined

  19. Rare earth elements during diagenesis of abyssal sediments: analogies with a transuranic element americium

    International Nuclear Information System (INIS)

    Boust, D.

    1987-03-01

    One of the possibilities for the storage of high-level radioactive wastes consists in burying them into abyssal sediments, the sediments being supposed to barrier out radionuclides migration. The objective of the work was to estimate the efficiency of sediment barrier with respect to americium. As there is no americium in abyssal sediments, an indirect approach was used: the behaviour of the rare earth elements, the best natural analogs of americium. They were analysed in a 15 m long core, from the Cap Verde abyssal plateau. The terrigenous phase derived from the African continent was modified by short-term processes (1-1000 years); the intermediate rare earth elements were dissolved. Mineral coatings, enriched in rare earth appeared. After burial, the evolution continued at a much slower rate (10 5 - 10 6 years). The rare elements of the mineral coatings derived from the dissolution of the terrigenous phase and from an additional source, deeper in the sediment column. The fluxes of rare earth elements from sediment to water column were estimated. In suboxic sediments, the dissolved particulate equilibrium was related to redox conditions. The short-term reactivity of americium was studied in laboratory experiments. Simple americium migration models showed that the sediments barrier was totally efficient with respect to americium. In the conditions, neptunium 237 a daughter product of americium 241 could induce fluxes of 10 16 atoms per year per ton of stored waste (10 -8 Ci y-1), during millions years, towards the water column [fr

  20. Methods for producing single crystal mixed halide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Kai; Zhao, Yixin

    2017-07-11

    An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

  1. Analysis of biological samples for americium and curium

    International Nuclear Information System (INIS)

    Miglio, J.J.

    1976-01-01

    A method of analyzing biological materials by liquid scintillation counting for americium and curium which greatly reduces the contribution from 40 K is described. The method employs an extractant liquid scintillation cocktail using N,N,N-trioctyl-N-methyl-ammonium chloride as the extractant. Instrument as well as tissue backgrounds are reduced. The lowered backgrounds allow picocurie level samples to be analyzed by liquid scintillation counting instead of alpha pulse height analysis. The samples are reduced to a carbon-free ash and then dissolved in 8M LiNo 3 which is also 10 -2 M in HNO 3 . An aliquot is placed in a liquid scintillation vial along with the extractant-scintillator, shaken and counted

  2. Pretreatment of americium/curium solutions for vitrification

    International Nuclear Information System (INIS)

    Rudisill, T.S.

    1996-01-01

    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

  3. Determination of the oxygen-metal-ratio of uranium-americium mixed oxides

    International Nuclear Information System (INIS)

    Bartscher, W.

    1982-01-01

    During the dissolution of uranium-americium mixed oxides in phosphoric acid under nitrogen tetravalent uranium is oxidized by tetravalent americium. The obtained hexavalent uranium is determined by constant potential coulometry. The coulombs measured are equivalent to the oxygen in excess of the minimum composition of UO 2 x AmO 1 . 5 . The total uranium content of the sample is determined in a subsequent coulometric titration. The oxygen-metal ratio of the sample can be calculated for a given uranium-americium ratio. An excess of uranium dioxide is necessary in order to suppress the oxidation of water by tetravalent americium. The standard deviation of the method is 0.0017 O/M units. (orig.) [de

  4. In-line measurement of plutonium and americium in mixed solutions

    International Nuclear Information System (INIS)

    Li, T.K.

    1981-01-01

    A solution assay instrument (SAI) has been developed at the Los Alamos National Laboratory and installed in the plutonium purification and americium recovery process area in the Los Alamos Plutonium Processing Facility. The instrument is designed for accurate, timely, and simultaneous nondestructive analysis of plutonium and americium in process solutions that have a wide range of concentrations and Am/Pu ratios. For a 25-mL sample, the assay precision is 5 g/L within a 2000-s count time

  5. Biochemical fractionation and cellular distribution of americium and plutonium in the biomass of freshwater macrophytes

    International Nuclear Information System (INIS)

    Zotina, T.A.; Kalacheva, G.S.; Bolsunovsky, A.Ya.

    2011-01-01

    Accumulation of americium ( 241 Am) and plutonium ( 238,242 Pu) and their distribution in cell compartments and biochemical components of the biomass of freshwater aquatic plants Elodea canadensis, Ceratophyllum demersum and Myrioplyllum spicatum and aquatic moss Fontinalis antipyretica have been investigated in laboratory experiments. Americium and plutonium taken up from water by Elodea canadensis apical shoots were mainly absorbed by structural components of plant cells (90% for 241 Am; 89% for 238 Pu and 82-87% for 242 Pu). About 10-18% of isotope activity was recorded in the cytosol fraction. The major concentration (76-92%) of americium was bound to cell wall cellulose-like polysaccharides of Elodea canadensis, Myriophyllum spicatum, Ceratophyllum demersum and Fontinalis antipyretica, 8-24% of americium activity was registered in the fraction of proteins and carbohydrates, and just a minor concentration (<1%) in the lipid fraction. The distribution of plutonium in the biomass fractions of Elodea was similar to that of americium. Hence, americium and plutonium had the highest affinity to cellulose-like polysaccharides of cell walls of freshwater submerged macrophytes. (author)

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

    International Nuclear Information System (INIS)

    Zotina, T.A.; Kalacheva, G.S.; Bolsunovsky, A.YA.

    2010-01-01

    Accumulation of uranium ( 238 U), americium ( 241 Am) and plutonium ( 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)

  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. Recent advances in technetium halide chemistry.

    Science.gov (United States)

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  9. Selective dissolution of americium by ferricyanide ions in basic aqueous solutions

    International Nuclear Information System (INIS)

    Meyer, D.; Fouchard, S.; Simoni, E.

    2000-01-01

    Americium exhibits a soluble form in aqueous alkaline media under oxidizing conditions which is not the case for the other Transplutonium Elements (TPE). This property can be exploited for High Level Liquid Waste (HLLW) treatment to extract Am, one of the main radionuclides responsible for the long term radiotoxicity of nuclear waste. The Soluble Am compound can be obtained by adding a concentrated basic solution of ferricyanide ions (Fe(CN) 6 3- ) to a trivalent americium hydroxide precipitate. The method allows complete and rapid extraction of americium via its soluble form in alkaline solutions. Under these conditions, other TPE and lanthanides remain in the solid state as precipitates of highly insoluble trivalent hydroxides. In the case of dissolution involving large amounts of americium, the formation of the soluble americium species is followed by the appearance of a reddish precipitate in the basic solution. Dissolution of the reddish solid in NaOH or NaOH/Fe(CN) 6 3- media demonstrated the existence of a media dependent solubility of the precipitate, and therefore the existence of at least two forms of soluble Am. Spectroscopic studies (UV-visible, EXAFS-XANES) of this reddish solid led to the determination of an Am oxidation state (pentavalent americium) and its possible formula (Na 2 AmVO 2 (OH) 3 .nH 2 O). Electrochemical studies show that the only possible oxidation reaction of trivalent americium in the working media yields the pentavalent form, and that the hexavalent state is unattainable. Stoichiometric and spectroscopic studies show that not all the ferricyanide ions required for complete dissolution of Am remain in the free Fe(CN) 6 3- form. This observation supports the view that this dissolution of Am(III) solid compound is much more complex than a simple oxidation by the ferricyanide ions. The existence of a molecular interaction between Am(V)O 2 + and ferricyanide ions is highly probable. This work demonstrates that the selective dissolution

  10. 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.

  11. Americium/Curium Melter 2A Pilot Tests

    International Nuclear Information System (INIS)

    Smith, M.E.; Fellinger, A.P.; Jones, T.M.; Miller, C.B.; Miller, D.H.; Snyder, T.K.; Stone, M.E.; Witt, D.C.

    1998-05-01

    Isotopes of americium (Am) and curium (Cm) were produced in the past at the Savannah River Site (SRS) for research, medical, and radiological applications. These highly radioactive and valuable isotopes have been stored in an SRS reprocessing facility for a number of years. Vitrification of this solution will allow the material to be more safely stored until it is transported to the DOE Oak Ridge Reservation for use in research and medical applications. To this end, the Am/Cm Melter 2A pilot system, a full-scale non- radioactive pilot plant of the system to be installed at the reprocessing facility, was designed, constructed and tested. The full- scale pilot system has a frit and aqueous feed delivery system, a dual zone bushing melter, and an off-gas treatment system. The main items which were tested included the dual zone bushing melter, the drain tube with dual heating and cooling zones, glass compositions, and the off-gas system which used for the first time a film cooler/lower melter plenum. Most of the process and equipment were proven to function properly, but several problems were found which will need further work. A system description and a discussion of test results will be given

  12. Density of simulated americium/curium melter feed solution

    Energy Technology Data Exchange (ETDEWEB)

    Rudisill, T.S.

    1997-09-22

    Vitrification will be used to stabilize an americium/curium (Am/Cm) solution presently stored in F-Canyon for eventual transport to Oak Ridge National Laboratory and use in heavy isotope production programs. Prior to vitrification, a series of in-tank oxalate precipitation and nitric/oxalic 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. Following nitric acid dissolution and oxalate destruction, the solution will be denitrated and evaporated to a dissolved solids concentration of approximately 100 g/l (on an oxide basis). During the Am/Cm vitrification, an airlift will be used to supply the concentrated feed solution to a constant head tank which drains through a filter and an in-line orifice to the melter. Since the delivery system is sensitive to the physical properties of the feed, a simulated solution was prepared and used to measure the density as a function of temperature between 20 to 70{degrees} C. The measured density decreased linearly at a rate of 0.0007 g/cm3/{degree} C from an average value of 1.2326 g/cm{sup 3} at 20{degrees} C to an average value of 1.1973g/cm{sup 3} at 70{degrees} C.

  13. Density of simulated americium/curium melter feed solution

    International Nuclear Information System (INIS)

    Rudisill, T.S.

    1997-01-01

    Vitrification will be used to stabilize an americium/curium (Am/Cm) solution presently stored in F-Canyon for eventual transport to Oak Ridge National Laboratory and use in heavy isotope production programs. Prior to vitrification, a series of in-tank oxalate precipitation and nitric/oxalic 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. Following nitric acid dissolution and oxalate destruction, the solution will be denitrated and evaporated to a dissolved solids concentration of approximately 100 g/l (on an oxide basis). During the Am/Cm vitrification, an airlift will be used to supply the concentrated feed solution to a constant head tank which drains through a filter and an in-line orifice to the melter. Since the delivery system is sensitive to the physical properties of the feed, a simulated solution was prepared and used to measure the density as a function of temperature between 20 to 70 degrees C. The measured density decreased linearly at a rate of 0.0007 g/cm3/degree C from an average value of 1.2326 g/cm 3 at 20 degrees C to an average value of 1.1973g/cm 3 at 70 degrees C

  14. Americium adsorption on the surface of macrophytic algae

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, F.P.; Fowler, S.W.

    1985-01-01

    Data are presented on the rates at which americium (Am) deposits upon blade surfaces of three benthic algal species (Ulva rigida, Fucus vesiculosus and Gigartina stellata) following short-term exposures (1-6 h). Am is taken up in direct proportion to the ambient radionuclide concentration in sea water. Uptake by the green alga was 3 to 5 times greater than that for the brown and red species. Experimental evidence indicated that Am accumulation is a passive process and that adsorption takes place mainly on the thin outer organic coating of the seaweed. The Am transport coefficients are quite similar to that previously found for the naturally occurring ..cap alpha..-emitter /sup 210/Po, but are an order of magnitude lower than a plutonium transport coefficient reported in the literature. Release of labelled extracellular products associated with the algal surface coating is considered to be responsible for the rapid loss of Am observed previously in macroalgae and may in fact serve as a mechanism for transferring Am to filter feeding zooplankton. (author).

  15. Americium adsorption on the surface of macrophytic algae

    International Nuclear Information System (INIS)

    Carvalho, F.P.; Fowler, S.W.

    1985-01-01

    Data are presented on the rates at which americium (Am) deposits upon blade surfaces of three benthic algal species (Ulva rigida, Fucus vesiculosus and Gigartina stellata) following short-term exposures (1-6 h). Am is taken up in direct proportion to the ambient radionuclide concentration in sea water. Uptake by the green alga was 3 to 5 times greater than that for the brown and red species. Experimental evidence indicated that Am accumulation is a passive process and that adsorption takes place mainly on the thin outer organic coating of the seaweed. The Am transport coefficients are quite similar to that previously found for the naturally occurring α-emitter 210 Po, but are an order of magnitude lower than a plutonium transport coefficient reported in the literature. Release of labelled extracellular products associated with the algal surface coating is considered to be responsible for the rapid loss of Am observed previously in macroalgae and may in fact serve as a mechanism for transferring Am to filter feeding zooplankton. (author)

  16. Harmonic dynamical behaviour of thallous halides

    Indian Academy of Sciences (India)

    2015-11-27

    Nov 27, 2015 ... 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 ...

  17. Unraveling halide hydration: A high dilution approach

    Science.gov (United States)

    Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

    2014-07-01

    The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (Δ G^{ominus }_{hyd}[H^+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a Δ G^{ominus }_{hyd}[H^+] value of -1100 kJ mol-1 [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl-, Br-, and I- ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F- ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl-, Br-, and I- ions does not extend beyond the ion first hydration shell, and the structure of water in the F- second shell is also substantially unaffected by the ion.

  18. Monocrystalline halide perovskite nanostructures : For optoelectronic applications

    NARCIS (Netherlands)

    Khoram, P.

    2018-01-01

    Halide perovskites are a promising class of materials for incorporation in optoelectronics with higher efficiency and lower cost. The solution processability of these materials provides unique opportunities for simple nanostructure fabrication. In the first half of the thesis (chapter 2 and 3) we

  19. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

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

    2013-01-01

    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. In total...

  20. luminescence in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    irradiated alkali halide crystals are similar to the luminescence excited by high energy radiation. Ueta et al [11] ... emission, a correlation between the deformation bleaching and mechanoluminescence of coloured alkali ..... [32] V P Zakrevskii, T S Orlova and A V Shuldiner, J. Solid State 37, 675 (1995). [33] C D Clark and ...

  1. luminescence in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    Abstract. The present paper reports the correlation between deformation bleaching of coloration and mechanoluminescence (ML) in coloured alkali halide crystals. When the F-centre electrons captured by moving dislocations are picked up by holes, deep traps and other compatible traps, then deformation bleaching occurs.

  2. Formation of structured nanophases in halide crystals

    Czech Academy of Sciences Publication Activity Database

    Kulveit, Jan; Demo, Pavel; Polák, Karel; Sveshnikov, Alexey; Kožíšek, Zdeněk

    2013-01-01

    Roč. 5, č. 6 (2013), s. 561-564 ISSN 2164-6627 R&D Projects: GA ČR GAP108/12/0891 Institutional support: RVO:68378271 Keywords : halide crystals * nucleation Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.aspbs.com/asem.html#v5n6

  3. The rapid determination of americium curium, and uranium in urine by ultrafiltration

    International Nuclear Information System (INIS)

    Stradling, G.N.; Popplewell, D.S.; Ham, G.J.; Griffin, R.

    1975-01-01

    The rapid ultrafiltration method developed for the assay of plutonium has been extended to the determination of americium, curium and uranium in urine. The limits of detection for americium and curium, and uranium are 0.09 and 0.12 dm -1 l -1 respectively, and the analysis time excluding counting less than 2 hours. The method can therefor be effectively used as a rapid screening procedure. When the reference level for plutonium is exceeded, the α activity may require to be characterised. The single ultrafiltration technique must be modified for turbid urine samples. The method is inappropriate, except for uranium, when the urine contains DTPA. (author)

  4. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

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

    the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally......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 of natural...

  5. Physicochemical properties of mixed phosphorus halides

    International Nuclear Information System (INIS)

    Sladkov, I.B.; Tugarinova, N.S.

    1996-01-01

    Certain physicochemical properties (thermodynamic characteristics at boiling point, critical constants, density of liquid on the saturation line) of mixed phosphorus halides (PI 3 , PI 2 F, PIF 2 , PI 2 Cl, PICl 2 , PI 1 Br, PIBr 2 , PIClF, PIBrCl, etc.) are determined by means of approximate methods. Reliability of the results obtained is confirmed by comparison of calculated and experimental data for phosphorus compounds of the same type. 7 refs., 3 figs., 4 tabs

  6. Thermomechanical measurements of lead halide single crystals

    Czech Academy of Sciences Publication Activity Database

    Nitsch, Karel; Rodová, Miroslava

    2002-01-01

    Roč. 234, č. 2 (2002), s. 701-709 ISSN 0370-1972 R&D Projects: GA AV ČR IAA2010926 Institutional research plan: CEZ:AV0Z1010914 Keywords : PbX 2 (X=Cl, Br, I) * coefficients of linear thermal expansion * polymorphism in lead halides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.930, year: 2002

  7. Electrochemistry of plutonium in molten halides

    International Nuclear Information System (INIS)

    McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

    1987-01-01

    The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

  8. 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.

  9. Medical management after contamination and incorporation of americium in occupational exposure. Medizinische Massnahmen nach Kontamination und Inkorporation von Americium bei beruflicher Strahlenexposition

    Energy Technology Data Exchange (ETDEWEB)

    Gensicke, F.; Stopp, G.; Scheler, R.; Klucke, H.; Czarwinski, R.; Naumann, M.; Hoelzer, F.; Ott, R.; Schmidt, I. (Staatliches Amt fuer Atomsicherheit und Strahlenschutz, Berlin (Germany, F.R.). Abt. Strahlenschutzmedizin)

    1990-10-01

    In handling with an ampule of {sup 241}Am-nitrate solution one person received an contamination of the body surface, especially the face and the hairs, and an internal contamination of americium. The paper presents the results obtained in medical management to reduced the contamination of the skin and of the incorporated radionuclide. The radioactivity of the body surface could be reduced up to small local areas. After treatment with DTPA (Ditripentat) the internal exposure decrease about 83%. (orig.).

  10. 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)

    Murray, C.N.; Fukai, R.

    1975-01-01

    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 237 Pu 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)

  11. 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.

  12. Investigation of surface halide modification of nitrile butadiene rubber

    Science.gov (United States)

    Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

    2017-12-01

    The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

  13. 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

  14. Total and Compound Formation Cross Sections for Americium Nuclei: Recommendations for Coupled-Channels Calculations

    Energy Technology Data Exchange (ETDEWEB)

    Escher, J. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-04-11

    Calculations for total cross sections and compound-nucleus (CN) formation cross sections for americium isotopes are described, for use in the 2017 NA-22 evaluation effort. The code ECIS 2006 was used in conjunction with Frank Dietrich's wrapper `runtemplate'.

  15. 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...

  16. Migration ability of plutonium and americium in the soils of Polessie State Radiation-Ecological Reserve

    International Nuclear Information System (INIS)

    Svetlana Ovsiannikova; Maryna Papenia; Katsiaryna Voinikava; Galina Sokolik; Sergey Svirschevsky; Justin Brown; Lindys Skipperud

    2010-01-01

    The physicochemical forms of radionuclides in soils determine the processes of their entry into the soil solutions, redistribution in the soil profile, soil-plant and soil-ground or surface waters transfer as well as spreading outside the contaminated area. The vertical distribution of plutonium and americium and their physicochemical forms in soils of Polessie State Radiation-Ecological Reserve (PSRER) were studied with the aim of establishing the potential for radionuclide migration. Samples of alluvial soddy-podzolic and peaty soils with a low (1-3%) and relatively high (∼80% of dry sample mass) content of organic matter have been selected for investigation. A method employing sequential selective extraction has been used for analysis of radionuclide physicochemical forms in the soils. Activity concentrations of 238 Pu, 239,240 Pu and 241 Am in the samples were determined via radiochemical analysis with alpha-spectrometric identification of radionuclides. The results indicate that the main proportion of plutonium and americium remains in the 0-20 cm soil layer. The inventories of mobile and biologically available forms of plutonium and americium, expressed as a percentage of the total radionuclide content in soil, lie in the ranges of 1.1-9.4 and 2.7-29% respectively. Greater proportions of mobile and biologically available forms of radionuclides appear to be associated with mineral soil as compared to organic soil. In both mineral and organic soils, the portion of mobile americium is higher than plutonium. The inventories of mobile forms of plutonium and americium increase with the depth of soils. (author)

  17. Metal halide reduction with molten sodium/potassium alloy

    International Nuclear Information System (INIS)

    Martin, W.

    1986-01-01

    A method of obtaining a desired metal, selected from the group consisting of titanium, aluminium, iron, manganese, hafnium, zirconium, tantalum, vanadium, uranium and tungsten, which comprises reacting a halide of the desired metal with an alkali metal reducing agent at temperature at which the reducing agent is molten, in order to produce the desired metal and halide of the metal reducing agent

  18. Dislocation unpinning model of acoustic emission from alkali halide ...

    Indian Academy of Sciences (India)

    theoretical and experimental results related to the AE from alkali halide crystals. Keywords. Acoustic emission; dislocation; alkali halide crystals; plastic deformation. PACS Nos 43.40.Le; 62.20.Fe; 61.72.Hh. 1. Introduction. Discrete acoustic wave packets are generated in solids during their mechanical de- formation.

  19. Radiation damage in the alkali halide crystals

    International Nuclear Information System (INIS)

    Diller, K.M.

    1975-10-01

    A general review is given of the experimental data on radiation damage in the alkali halide crystals. A report is presented of an experimental investigation of irradiation produced interstitial dislocation loops in NaCl. These loops are found to exhibit the usual growth and coarsening behaviour during thermal annealing which operates by a glide and self-climb mechanism. It is shown that the recombination of defects in these crystals is a two stage process, and that the loss of interstitials stabilized at the loops is caused by extrinsic vacancies. The theoretical techniques used in simulating point defects in ionic crystals are described. Shell model potentials are derived for all the alkali halide crystals by fitting to bulk crystal data. The fitting is supplemented by calculations of the repulsive second neighbour interactions using methods based on the simple electron gas model. The properties of intrinsic and substitutional impurity defects are calculated. The HADES computer program is used in all the defect calculations. Finally the report returns to the problems of irradiation produced interstitial defects. The properties of H centres are discussed; their structure, formation energies, trapping at impurities and dimerization. The structure, formation energies and mobility of the intermediate and final molecular defects are then discussed. The thermodynamics of interstitial loop formation is considered for all the alklai halide crystals. The nucleation of interstitial loops in NaCl and NaBr is discussed, and the recombination of interstitial and vacancy defects. The models are found to account for all the main features of the experimental data. (author)

  20. 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

  1. Exciton-relaxation dynamics in lead halides

    International Nuclear Information System (INIS)

    Iwanaga, Masanobu; Hayashi, Tetsusuke

    2003-01-01

    We survey recent comprehensive studies of exciton relaxation in the crystals of lead halides. The luminescence and electron-spin-resonance studies have revealed that excitons in lead bromide spontaneously dissociate and both electrons and holes get self-trapped individually. Similar relaxation has been also clarified in lead chloride. The electron-hole separation is ascribed to repulsive correlation via acoustic phonons. Besides, on the basis of the temperature profiles of self-trapped states, we discuss the origin of luminescence components which are mainly induced under one-photon excitation into the exciton band in lead fluoride, lead chloride, and lead bromide

  2. Research Update: Luminescence in lead halide perovskites

    Directory of Open Access Journals (Sweden)

    Ajay Ram Srimath Kandada

    2016-09-01

    Full Text Available Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  3. Research Update: Luminescence in lead halide perovskites

    Science.gov (United States)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-09-01

    Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  4. Feature issue introduction: halide perovskites for optoelectronics.

    Science.gov (United States)

    White, Thomas P; Deleporte, Emmanuelle; Sum, Tze-Chien

    2018-01-22

    This joint Optics Express and Optical Materials Express feature issue presents a collection of nine papers on the topic of halide perovskites for optoelectronics. Perovskite materials have attracted significant attention over the past four years, initially for their outstanding performance in thin film solar cells, but more recently for applications in light-emitting devices (LEDs and lasers), photodetectors and nonlinear optics. At the same time, there is still much more to learn about the fundamental properties of these materials, and how these depend on composition, processing, and exposure to the environment. This feature issue provides a snapshot of some of the latest research in this rapidly-evolving multidisciplinary field.

  5. Large polarons in lead halide perovskites

    OpenAIRE

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3 ? framewor...

  6. Development of novel growth methods for halide single crystals

    Science.gov (United States)

    Yokota, Yuui; Kurosawa, Shunsuke; Shoji, Yasuhiro; Ohashi, Yuji; Kamada, Kei; Yoshikawa, Akira

    2017-03-01

    We developed novel growth methods for halide scintillator single crystals with hygroscopic nature, Halide micro-pulling-down [H-μ-PD] method and Halide Vertical Bridgman [H-VB] method. The H-μ-PD method with a removable chamber system can grow a single crystal of halide scintillator material with hygroscopicity at faster growth rate than the conventional methods. On the other hand, the H-VB method can grow a large bulk single crystal of halide scintillator without a quartz ampule. CeCl3, LaBr3, Ce:LaBr3 and Eu:SrI2 fiber single crystals could be grown by the H-μ-PD method and Eu:SrI2 bulk single crystals of 1 and 1.5 inch in diameter could be grown by the H-VB method. The grown fiber and bulk single crystals showed comparable scintillation properties to the previous reports using the conventional methods.

  7. The alkali halide disk technique in infra-red spectrometry : Anomalous behaviour of some samples dispersed in alkali halide disks

    NARCIS (Netherlands)

    Tolk, A.

    1961-01-01

    Some difficulties encountered in the application of the alkali halide disk technique in infra-red spectrometry are discussed. Complications due to interaction of the sample with the alkali halide have been studied experimentally. It was found that the anomalous behaviour of benzoic acid, succinic

  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. Local polar fluctuations in lead halide perovskites

    Science.gov (United States)

    Tan, Liang; Yaffe, Omer; Guo, Yinsheng; Brus, Louis; Rappe, Andrew; Egger, David; Kronik, Leeor

    The lead halide perovskites have recently attracted much attention because of their large and growing photovoltaic power conversion efficiencies. However, questions remain regarding the temporal and spatial correlations of the structural fluctuations, their atomistic nature, and how they affect electronic and photovoltaic properties. To address these questions, we have performed a combined ab initio molecular dynamics (MD) and density functional theory (DFT) study on CsPbBr3. We have observed prevalent anharmonic motion in our MD trajectories, with local polar fluctuations involving head-to-head motion of A-site Cs cations coupled with Br window opening. We calculate Raman spectra from the polarizability auto-correlation functions obtained from these trajectories and show that anharmonic A-site cation motion manifests as a broad central peak in the Raman spectrum, which increases in intensity with temperature. A comparison of the experimental Raman spectrum of hybrid organometallic MAPbBr3 and fully inorganic CsPbBr3 suggests that structural fluctuations in lead-halide perovskites is more general than rotation of polar organic cations and is intimately coupled to the inorganic framework.

  10. Large polarons in lead halide perovskites

    Science.gov (United States)

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3− frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]− sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility. PMID:28819647

  11. Structural characterisations and mechanistic investigations of the selective dissolution of americium by the ferricyanide ions in alkaline media. Application for the partitioning americium curium

    International Nuclear Information System (INIS)

    Fouchard, Sebastien

    2000-01-01

    Americium exhibits a high solubility form in basic media under oxidant conditions, unlike the other Transplutonium elements (TPE). This property can be used in the frame of High Level Liquid Waste (HLLW) treatment in order to extract preferentially the americium element, the main responsible of the long term radiotoxicity of the nuclear waste. This soluble compound can be obtained by addition of a concentrated basic solution of Fe(CN) 6 3- ions on Am(OH) 3 precipitates. This technique enables a rapid extraction of Am by the synthesis of this soluble form in alkaline solutions. Under these conditions, the other TPE remain in the solid state as trivalent hydroxide solids, strongly insoluble. In the case of dissolutions involving large amounts of Am(OH) 3 , the formation of the soluble complex is concomitant with the appearance of a reddish precipitate in the basic solution. Dissolution experiments which were carried out on this solid in NaOH/Fe(CN) 6 3- have demonstrated the dependency of the solubility equilibria with the media. Spectroscopic studies (UV Visible, XAS) on the precipitate have enabled the determination of the chemical structure and the oxidation state of the americium in the solid: Na 2 Am(V)O 2 (OH) 3 ,nH 2 O. Electrochemical studies on the americium solution have confirmed that the oxidation of Am(OH) 3 by the Fe(CN) 6 3- ions in basic media could only lead to the pentavalent form. A stoichiometric study carries out between a AmO 2 + ion and one Fe(CN) 6 3- ion and the spectroscopic characterisation of this reaction have demonstrated that the Fe(CN) 6 3- ion didn't remain as an un-complexed form in solution after the alkaline mixing. These results tend to prove that this dissolution of Am(OH) 3 is much more complex than a simple oxidation by the Fe(CN) 6 3- ions. The existence of molecular interactions between AmO 2 + and Fe(CN) 6 3- has been postulated and a mechanistic scheme has been proposed in order to explain the appearance of the soluble

  12. 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

    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.......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 65°N, 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...

  13. Biochemical behaviour of plutonium and americium and geochemical modelling of the soil solution

    International Nuclear Information System (INIS)

    Bryan, N.D.; Livens, F.R.; Horrill, A.D.

    1994-01-01

    Field observations suggest that plutonium and americium in the environment are present in very different chemical forms in the interstitial waters of an intertidal sediment. Thermodynamic modelling using the PHREEQE code predicts that plutonium is present entirely in oxidation state (V) as the PuO 2 CO 3 - ion, whereas americium is present entirely in oxidation state (III), largely as the uncharged Am(OH)CO 3 species, but with significant concentrations of the Am 3+ and the AmSO 4 + ions. There are, however, differences between these predictions and others published for a very similar system which apparently arise from uncertainties in the thermodynamic data. Field data cannot resolve these differences unambiguously. (author) 29 refs.; 3 tabs

  14. High-purity germanium detection system for the in vivo measurement of americium and plutonium

    International Nuclear Information System (INIS)

    Tyree, W.H.; Falk, R.B.; Wood, C.B.; Liskey, R.W.

    1976-01-01

    A high-purity germanium (HPGe) array, photon-counting system has been developed for the Rocky Flats Plant Body-Counter Medical Facility. The newly improved system provides exceptional resolutions of low-energy X-ray and gamma-ray spectra associated with the in vivo deposition of plutonium and americium. Described are the operational parameters of the system and some qualitative results illustrating detector performance for the photon emissions produced from the decay of plutonium and americium between energy ranges from 10 to 100 kiloelectron volts. Since large amounts of data are easily generated with the system, data storage, analysis, and computer software developments continue to be an essential ingredient for processing spectral data obtained from the detectors. Absence of quantitative data is intentional. The primary concern of the study was to evaluate the effects of the various physical and electronic operational parameters before adding those related entirely to a human subject

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

    International Nuclear Information System (INIS)

    Laplace, A.; Lacquement, J.; Maillard, C.; Donner, L.

    2004-01-01

    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 AmO 2 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-AmCl 3 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)

  16. Metal halide-group III halide gas complexes with emphasis on aluminum chloride

    International Nuclear Information System (INIS)

    Oeye, H.A.; Gruen, D.M.

    1978-01-01

    The thermodynamics of the presently known gas complexation reactions between metal halides and group III halides are treated in a self-consistent manner. By focusing on aluminum chloride as a complexing agent, certain systematic trends are revealed. The partial pressures of the gaseous complexes display shallow minima near 800 0 K whenever the complex molecules involve more than one molecule of AlCl 3 . Increasing the aluminum chloride pressure from 1 atm. to 10 3 atm. decreases somewhat the differences in the partial pressures among the various gaseous complexes which span two to three orders of magnitude. The methods developed for characterizing the complexes, and their structures as well as some applications of gas complexation are discussed

  17. Determination of americium and plutonium in autopsy tissue: methods and problems

    International Nuclear Information System (INIS)

    Boyd, H.A.; Eutsler, B.C.; McInroy, J.F.

    1979-01-01

    The current methods used by the tissue analysis program at LASL for the determination of americium and plutonium in autopsy tissue are described. Problems affecting radiochemical yield are discussed. Included are problems associated with sample preparation, separation of plutonium from large amounts of bone ash, and reagent contamination. The average 242 Pu tracer yield for 1800 Pu determinations is 78 +- 12%. The average 242 Am tracer yield is 85 +- 7% for 40 determinations

  18. 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.

  19. Quantitative determination of americium and curium in solutions using potassium tungstophosphate

    International Nuclear Information System (INIS)

    Chistyakov, V.M.; Baranov, A.A.; Erin, E.A.; Timoaeev, G.A.

    1990-01-01

    Two methods of americium (4) and curium (4) titration-replacement and redox ones - have been considered. According to the replacement method thorium nitrate solution was used as a titrant and the final point of titration was determined spectophotometrically. Using the method developed, on the basis of experimental data, the composition of thorium (4) complex with potassium tungstophosphate was determined. In case of the redox titration sodium nitrite was used, and the final titration point was indicated either spectrophotometrically or potentiometrically

  20. Medical management after contamination and incorporation of americium in occupational exposure

    International Nuclear Information System (INIS)

    Gensicke, F.; Stopp, G.; Scheler, R.; Klucke, H.; Czarwinski, R.; Naumann, M.; Hoelzer, F.; Ott, R.; Schmidt, I.

    1990-01-01

    In handling with an ampule of 241 Am-nitrate solution one person received an contamination of the body surface, especially the face and the hairs, and an internal contamination of americium. The paper presents the results obtained in medical management to reduced the contamination of the skin and of the incorporated radionuclide. The radioactivity of the body surface could be reduced up to small local areas. After treatment with DTPA (Ditripentat) the internal exposure decrease about 83%. (orig.) [de

  1. Experimental studies to validate model calculations and maximum solubility limits for Plutonium and Americium

    International Nuclear Information System (INIS)

    2017-01-01

    This report focuses on studies of KIT-INE to derive a significantly improved description of the chemical behaviour of Americium and Plutonium in saline NaCl, MgCl 2 and CaCl 2 brine systems. The studies are based on new experimental data and aim at deriving reliable Am and Pu solubility limits for the investigated systems as well as deriving comprehensive thermodynamic model descriptions. Both aspects are of high relevance in the context of potential source term estimations for Americium and Plutonium in aqueous brine systems and related scenarios. Americium and Plutonium are long-lived alpha emitting radionuclides which due to their high radiotoxicity need to be accounted for in a reliable and traceable way. The hydrolysis of trivalent actinides and the effect of highly alkaline pH conditions on the solubility of trivalent actinides in calcium chloride rich brine solutions were investigated and a thermodynamic model derived. The solubility of Plutonium in saline brine systems was studied under reducing and non-reducing conditions and is described within a new thermodynamic model. The influence of dissolved carbonate on Americium and Plutonium solubility in MgCl 2 solutions was investigated and quantitative information on Am and Pu solubility limits in these systems derived. Thermodynamic constants and model parameter derived in this work are implemented in the Thermodynamic Reference Database THEREDA owned by BfS. According to the quality assurance approach in THEREDA, is was necessary to publish parts of this work in peer-reviewed scientific journals. The publications are focused on solubility experiments, spectroscopy of aquatic and solid species and thermodynamic data. (Neck et al., Pure Appl. Chem., Vol. 81, (2009), pp. 1555-1568., Altmaier et al., Radiochimica Acta, 97, (2009), pp. 187-192., Altmaier et al., Actinide Research Quarterly, No 2., (2011), pp. 29-32.).

  2. Synthesis, Reactivity and Stability of Aryl Halide Protecting Groups towards Di-Substituted Pyridines

    Directory of Open Access Journals (Sweden)

    Ptoton Mnangat Brian

    2016-03-01

    Full Text Available This paper reports the synthesis and reactivity of different Benzyl derivative protecting groups. The synthesis and stability of Benzyl halides, 4-methoxybenzyl halides, 3,5-dimethoxybenzyl halides, 3,4-dimethoxybenzyl halides, 3,4,5-trimethoxybenzyl halide protecting groups and their reactivity towards nitrogen atom of a di-substituted pyridine ring in formation of pyridinium salts is also reported.

  3. The creation of defects in ammonium halides by excitons

    International Nuclear Information System (INIS)

    Kim, L.M.

    2002-01-01

    The ammonium halides crystals and alkali halides crystals are analogous by kind chemical bonds and crystalline lattices. The anionic sublattice is identical in this crystals. It is known the main mechanism of defect creation by irradiation is radiationless decay of excitons in alkali halides crystals. The F-, H-centers are formation in this processes. However, F, H-centres are not detected in ammonium halides. The goal of this work is investigation the creation of defects in ammonium halides by excitons. We established that excitons in ammonium chlorides and bromides are similar to excitons in alkali halides. It is known excitons are self-trapped and have identical parameters of the exciton-phonon interaction in both kind crystals. It is supposed, that processes of radiationless disintegration of excitons are identical in ammonium and alkali halides. It is necessary to understand why F-, H-centers are absent in ammonium halides. V k -centres are created by the excitation of the ammonium halides crystals in the absorption band of excitons. It was established by thermoluminescence and spectrums of absorption. The V k -centers begin to migrate at 110-120 K in ammonium chlorides and bromides. The curve of thermoluminescence have peak with maximum at this temperatures. It is known V k -centers in ammonium chlorides have the absorption band at 380 nm. We discovered this absorption band after irradiation of crystals by ultra-violet. In alkali halides F-center is anionic vacancy with electron. The wave function of electron are spread ed at the cations around anionic vacancy. We established the cation NH 4 + in ammonium halides can to capture electron. The ion NH 4 2+ is unsteady. It is disintegrated to NH 3 + and H + . We suppose that excitons in ammonium and alkali halides are disintegrated identically. When cation NH 4 + capture electron, in the anionic sublattice the configuration are created in a direction (100) The indicated configuration is unsteady in relation to a

  4. Alkali metal and alkali earth metal gadolinium halide scintillators

    Science.gov (United States)

    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.

  5. Adsorption-Desorption Characteristics of Plutonium and Americium with Sediment Particles in the Estuarine Environment

    International Nuclear Information System (INIS)

    Murray, C.N.; Fukai, R.

    1976-01-01

    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 237 Pu was in particulate form, larger than 0.45pm, 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)

  6. Bis(2-ethylhexyl)sulfoxide as an extractant for americium(III) from aqueous nitrate media

    International Nuclear Information System (INIS)

    Shukla, J.P.; Kedari, C.S.

    1992-01-01

    Solvent extraction separation of Am(III) from dilute aqueous nitrate media into n-dodecane by bis(2-ethylhexyl)sulfoxide (BESO) has been investigated over a wide range of experimental conditions. Very poor extractability of Am(III) necessitated the use of calcium nitrate as the salting-out agent. Effects of certain variables such as acidity, extractant concentration, salting-out agent concentration, organic diluents on the metal extraction by BESO have been examined in detail. By increasing the concentration of BESO in organic phase or calcium nitrate in aqueous phase, nearly quantitative extraction of americium even from moderate acidity is accomplished. Slope analyses applied to Am(III) distribution experiments from acidic nitrate solutions indicate predominant formation of the trisolvated organic phase complex, Am(NO 3 ) 3 *3BESO for which equilibrium constant is found to be, log K x = 1.99. Extraction behavior of Am(III) has also been evaluated in the presence of several water-miscible polar organic solvents to study their possible synergistic effects on its extraction. Extractability of americium increased 5 to 10-fold with increasing concentration of some of these additives, with maximum enhancement being observed in the presence of acetone or acetonitrile. Recovery of BESO from loaded americium is easily obtained using dilute nitric acid as the strippant. (author) 30 refs.; 2 figs.; 5 tabs

  7. Fabrication of uranium-americium mixed oxide pellet from microsphere precursors: Application of CRMP process

    Science.gov (United States)

    Remy, E.; Picart, S.; Delahaye, T.; Jobelin, I.; Lebreton, F.; Horlait, D.; Bisel, I.; Blanchart, P.; Ayral, A.

    2014-10-01

    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.

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

    International Nuclear Information System (INIS)

    Boggs, S. Jr.; Seitz, M.G.

    1984-01-01

    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 22 0 C, 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 90 0 C 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 22 0 C 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

  9. Novel Silver Cobaltacarborane Complexes with a Linearly Bridging Halide

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyun Seo; Bae, Hye Jin; Do, Youngkyu [KAIST, Daejeon (Korea, Republic of); Park, Youngwhan [LG Chem/Research Park, Daejeon (Korea, Republic of); Go, Min Jeong; Lee, Junseong [Chonnam National Univ., Gwangju (Korea, Republic of)

    2013-10-15

    The structural versatility of halides mainly originates from their coordinating abilities of adopting a bridging bond between two or more metal atoms, as well as a terminal bond. Moreover, a halide bridging bond angle is so flexible that thermodynamic stability can be endowed with proper geometry, which conceptually varies from acute to right, obtuse, and linear. In spite of innumerable reports on molecular metal halides, examples of the linearly bridging fashion are very scarce. The reason for the rarity of the linear M. X. M arrangement can be easily explained by the VSEPR (Valence Shell Electron Pair Repulsion) concept. The linear M. X. M formation has only been achieved by adopting a macrocyclic chelate ligand, which is structurally demanding, so that the VSEPR repulsions among lone-pair electrons on the halide atom could be overcome.

  10. Dislocation unpinning model of acoustic emission from alkali halide ...

    Indian Academy of Sciences (India)

    AE) from alkali halide crystals. ... School of Studies in Physics, Pt. Ravi Shankar Shukia University, Raipur 492 010, India; Department of Electronics and Telecommunication, Raipur Institute of Technology, Raipur 492 101, India; Department of ...

  11. Systemic analysis of thermodynamic properties of lanthanide halides

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  12. Genetic control of methyl halide production in Arabidopsis.

    Science.gov (United States)

    Rhew, Robert C; Østergaard, Lars; Saltzman, Eric S; Yanofsky, Martin F

    2003-10-14

    Methyl chloride (CH(3)Cl) and methyl bromide (CH(3)Br) are the primary carriers of natural chlorine and bromine, respectively, to the stratosphere, where they catalyze the destruction of ozone, whereas methyl iodide (CH(3)I) influences aerosol formation and ozone loss in the boundary layer. CH(3)Br is also an agricultural pesticide whose use is regulated by international agreement. Despite the economic and environmental importance of these methyl halides, their natural sources and biological production mechanisms are poorly understood. Besides CH(3)Br fumigation, important sources include oceans, biomass burning, tropical plants, salt marshes, and certain crops and fungi. Here, we demonstrate that the model plant Arabidopsis thaliana produces and emits methyl halides and that the enzyme primarily responsible for the production is encoded by the HARMLESS TO OZONE LAYER (HOL) gene. The encoded protein belongs to a group of methyltransferases capable of catalyzing the S-adenosyl-L-methionine (SAM)-dependent methylation of chloride (Cl(-)), bromide (Br(-)), and iodide (I(-)) to produce methyl halides. In mutant plants with the HOL gene disrupted, methyl halide production is largely eliminated. A phylogenetic analysis with the HOL gene suggests that the ability to produce methyl halides is widespread among vascular plants. This approach provides a genetic basis for understanding and predicting patterns of methyl halide production by plants.

  13. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    International Nuclear Information System (INIS)

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-01-01

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10 25 /m 3 . The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics

  14. Structured alkali halides for medical applications

    International Nuclear Information System (INIS)

    Schmitt, B.; Fuchs, M.; Hell, E.; Knuepfer, W.; Hackenschmied, P.; Winnacker, A.

    2002-01-01

    Image plates based on storage phosphors are a major application of radiation defects in insulators. Storage phosphors absorb X-ray quanta creating trapped electron-hole pairs in the material. Optical stimulation of the electron causes recombination leading to light emission. Application of image plates requires an optimal compromise between resolution (represented by the modulation transfer function (MTF)) and sensitivity. In our paper we present a new solution of the problem of combining a high MTF with a high sensitivity by structuring the image plates in form of thin needles acting as light guides. This suppresses the lateral spread of light which is detrimental to resolution. As doped CsBr, e.g. CsBr:Ga [Physica Medica XV (1999) 301], can pose a good storage phosphor evaporated layers are of interest in computed radiography. Needle structured CsI:Tl is used as scintillator in direct radiography [IEEE Trans. Nucl. Sci. 45 (3) (1998)]. CsBr layers have been produced by evaporation in vacuum and in inert gas atmosphere varying pressure and temperature. The resulting structures are of fibrous or columnar nature being in good agreement with the zone model of Thornton [Ann. Rev. Mater. Sci. 7 (1977) 239]. A zone model for CsBr has been developed. Measurements on doped alkali halide image plates having needle structure show good MTF at high sensitivity making a significant progress in image plate technology

  15. Physics of plutonium and americium recycling in PWR using advanced fuel concepts

    International Nuclear Information System (INIS)

    Hourcade, E.

    2004-01-01

    PWR waste inventory management is considered in many countries including Frances as one of the main current issues. Pu and Am are the 2 main contents both in term of volume and long term radio-toxicity. Waiting for the Generation IV systems implementation (2035-2050), one of the mid-term solutions for their transmutation involves the use of advanced fuels in Pressurized Water Reactors (PWR). These have to require as little modification as possible of the core internals, the cooling system and fuel cycle facilities (fabrication and reprocessing). The first part of this paper deals with some neutronic characteristics of Pu and/or Am recycling. In a second part, 2 technical solutions MOX-HMR and APA-DUPLEX-84 are presented and the third part is devoted to the study of a few global strategies. The main neutronic parameters to be considered for Pu and Am recycling in PWR are void coefficient, Doppler coefficient, fraction of delayed neutrons and power distribution (especially for heterogeneous configurations). The modification of the moderation ratio, the opportunity to use inert matrices (targets), the optimisation of Uranium, Plutonium and Americium contents are the key parameters to play with. One of the solutions (APA-DUPLEX-84) presented here is a heterogeneous assembly with regular moderation ratio composed with both target fuel rods (Pu and Am embedded in an inert matrix) and standard UO 2 fuel rods. An EPR (European Pressurised Reactor) type reactor, loaded only with assemblies containing 84 peripheral targets, can reach an Americium consumption rate of (4.4; 23 kg/TWh) depending on the assembly concept. For Pu and Am inventories stabilisation, the theoretical fraction of reactors loaded with Pu + Am or Pu assemblies is about 60%. For Americium inventory stabilisation, the fraction decreases down to 16%, but Pu is produced at a rate of 18.5 Kg/TWh (-25% compared to one through UOX cycle)

  16. Accumulation of americium-241 in the biomass of aquatic plants of the Yenisei river: experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Zotina, T.A.; Bolsunovsky, A.Y.A.; Bondareva, L.G. [Institute of Biophysics SB RAS, Akademgorodok, Krasnoyarsk (Russian Federation)

    2004-07-01

    Due to the operation of the Mining-and-Chemical Combine (Krasnoyarsk-26), which has been manufacturing weapons-grade plutonium for several decades, the Yenisei River is contaminated with transuranic elements (including {sup 241}Am). {sup 241}Am was found in the riverside soil, sediment and in the biomass of aquatic plants (Bolsunovsky et al., 1999, 2002). Aquatic plants are an important link in the migration of radionuclides in an aquatic ecosystem. In laboratory experiments, we investigated accumulation of {sup 241}Am by the submerged macrophyte from the Yenisei River: the pond weed (Elodea canadensis) and the aquatic moss (Fontinalis antipyretica), and release of {sup 241}Am from the biomass. The content of {sup 241}Am was measured on a Canberra (USA) gamma-spectrometer. The experiments showed that specific accumulation and concentration factors of {sup 241}Am in the plants were in inverse proportion to their biomass. We obtained new data on release of {sup 241}Am from the biomass of macrophyte. Americium-241 was more firmly fixed in the biomass of the aquatic moss. In 12 months, the biomass of the aquatic moss released about 30% of the initial americium activity into the water. To compare, the biomass of the pond weed released into the water medium up to 64% of the initial {sup 241}Am activity in 1.5 4 months. The release rate was dependent on the decomposition rate of the plant biomass. The experiments showed that submerged macrophyte of the Yenisei River can accumulate considerable activities of {sup 241}Am and retain americium for long periods of time in biomass. (author)

  17. 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

  18. Uptake of plutonium and americium by barley from two contaminated Nevada Test Site soils

    International Nuclear Information System (INIS)

    Schulz, R.K.; Tompkins, G.A.; Leventhal, L.; Babcock, K.L.

    1976-01-01

    Barley (Hordeum vulgare, Var. Atlas 68) plant uptake of Pu 239 , Pu 240 , and Am 241 was studied using two soil samples collected from widely separated areas of the Nevada Test Site. Each area had been previously contaminated with plutonium and americium as a result of a separate high explosive (nonnuclear) detonation of a device containing plutonium. The plants were grown on 3-kg soil samples in a controlled environment chamber. The plutonium concentration ratio (plutonium concentration in dry plant tissue/plutonium concentration in dry soil) was in the order of 10 -5 for plant vegetative material. The plutonium concentration ratio for the grain was 20 to 100 times lower than that in the vegetative material. Concentration ratios for americium were in the order of 10 -4 for vegetative growth and 25 to 75 times lower for the grain. These results imply that americium is more available to plants than plutonium. Plutonium-bearing particles were identified in a soil sample using an autoradiographic technique and then separated from the soil samples. The Pu 239 oxide equivalent diameters of plutonium-bearing particles could be described by a log-normal distribution function in the range of 0.2 to 0.7 μm. The actual diameters of the particles were 2 to 3 times the PuO 2 equivalent diameter. Microprobe analyses of the surface region of particles greater than 2 μm showed the following order of abundance: U, Pu is greater than O is greater than Al is greater than Si is greater than Fe is greater than Mg. Photographs obtained with a scanning electron microscope revealed that some of the particles are quite irregular and have large specific surface areas which might enhance solubility and plant uptake

  19. 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.

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

    International Nuclear Information System (INIS)

    Cruz, W.H.

    2013-01-01

    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 ( 241 Am), fewer and Radium 226 ( 226 Ra) 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 241 Am radioactive lightning rods using the conventional chemical treatment method using agents and acids to break down the slides. The 241 Am recovered was as excitation source and alpha particle generator for analysing samples by X Ray Fluorescence, for fixing the stainless steel 241 Am technique was used electrodeposition. (author)

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

    International Nuclear Information System (INIS)

    Smith, L.L.; Markun, F.; TenKate, T.

    1992-06-01

    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

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

    International Nuclear Information System (INIS)

    Baumann, Nils; Zirnstein, Isabel; Arnold, Thuro

    2015-01-01

    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).

  3. Rad Calc III: Radioanalysis calculation program for plutonium and americium determination

    International Nuclear Information System (INIS)

    Blackadar, J.M.; Wong, A.S.; Stalnaker, N.D.; Willerton, J.R.

    2000-01-01

    The radiochemistry team of the Analytical Chemistry Group has supported nuclear materials production and management programs at Los Alamos National Laboratory since the 1940s. Routinely, plutonium and americium contents in various matrices (such as metals, oxides, process solutions, and waste streams) are determined by direct alpha and gamma analyses. Over the years, analysts have written a number of computer programs to calculate analytical results. In 1999, the program was enhanced and upgraded to produce Rad Calc III. The new program, written in Visual Basic 4.0, corrects limitations of previous versions, offers enhanced features, and incorporates user suggestions to customize the program and make it more user friendly

  4. Recovery of americium from slag and crucible wastes and its purification

    International Nuclear Information System (INIS)

    Michael, K.M.; Dabholkar, G.M.; Vijayan, K.; Ramamoorthy, N.; Narayanan, C.V.; Jambunathan, U.; Kapoor, S.C.

    1990-01-01

    A method of recovery and purification of americium-241 from slag waste streams is described. Extraction of Am from slag solution of 0.16 M HNO 3 was carried out by tri-n-butyl phosphate. After stripping with acetic acid, Am was precipitated at pH 1. This was followed by metathesis to remove Ca. Final separation of Pu from Am solution was achieved by anion exchange method using Dowex 1x4 anion exchange resin. Details of large scale recovery of Am from slag are also described. (author). 12 refs., 11 tabs., 1 fig

  5. Distribution coefficients for plutonium and americium on particulates in aquatic environments

    International Nuclear Information System (INIS)

    Sanchez, A.L.; Schell, W.R.; Sibley, T.H.

    1982-01-01

    The distribution coefficients of two transuranic elements, plutonium and americium, were measured experimentally in laboratory systems of selected freshwater, estuarine, and marine environments. Gamma-ray emitting isotopes of these radionuclides, 237 Pu and 241 Am, were significantly greater than the sorption Ksub(d) values, suggesting some irreversibility in the sorption of these radionuclides onto sediments. The effects of pH and of sediment concentration on the distribution coefficients were also investigated. There were significant changes in the Ksub(d) values as these parameters were varied. Experiments using sterilized and nonsterilized samples for some of the sediment/water systems indicate possible bacterial effects on Ksub(d) values. (author)

  6. 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

    collected from the Irish coast in 1983. Fallout is found to dominate as a source of 239+240Pu north of latitude 65°N, 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...... 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....

  7. 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

  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)

    Guillou, P.

    1990-12-01

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

    Energy Technology Data Exchange (ETDEWEB)

    Raison, P.E. [CEA Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. d' Etudes des Combustibles; Haire, R.G. [Oak Ridge National Lab., TN (United States)

    2001-07-01

    Presented are studies involving the incorporation of americium and curium in zirconia-based materials. First explored was the pseudo ternary system AmO{sub 2}-ZrO{sub 2}-Y{sub 2}O{sub 3}. 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 AmO{sub 2} content. The Cm{sub 2}O{sub 3}-ZrO{sub 2} system was also investigated. It was found that at 25 mol% of CmO{sub 1.5}, 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 CmO{sub 1.5}, a pyrochlore oxide - Cm{sub 2}Zr{sub 2}O{sub 7} - is formed (a = 10.63 {+-}0.02 Angstrom). (author)

  10. Fuel cycle covariance of plutonium and americium separations to repository capacity using information theoretic measures

    International Nuclear Information System (INIS)

    Scopatz, Anthony; Schneider, Erich; Li, Jun; Yim, Man-Sung

    2011-01-01

    A light water reactor, fast reactor symbiotic fuel cycle scenario was modeled and parameterized based on thirty independent inputs. Simultaneously and stochastically choosing different values for each of these inputs and performing the associated fuel cycle mass-balance calculation, the fuel cycle itself underwent Monte Carlo simulation. A novel information theoretic metric is postulated as a measure of system-wide covariance. This metric is the coefficient of variation of the set of uncertainty coefficients generated from 2D slices of a 3D contingency table. It is then applied to the fuel cycle, taking fast reactor used fuel plutonium and americium separations as independent variables and the capacity of a fully-loaded tuff repository as the response. This set of parameters is known from prior studies to have a strong covariance. When measured with all 435 other input parameters possible, the fast reactor plutonium and americium separations pair was found to be ranked the second most covariant. This verifies that the coefficient of variation metric captures the desired sensitivity of sensitivity effects in the nuclear fuel cycle. (author)

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

    International Nuclear Information System (INIS)

    Robouch, P.

    1989-01-01

    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 (CO 3 ) 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-CO 3 complexes are not needed). No evidence of Am(CO 3 ) 4 5- 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 PuO 2 (CO 3 ) is measured in bicarbonate media at high ionic strength, to obtain the solubility product and formation constants of the PuO 2 (CO 3 ) i 2-2i complexes [fr

  12. Production of a square geometry Americium standard source for use with photodiodes

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Priscila; Geraldo, Bianca; Raele, Marcus P.; Marumo, Júlio T.; Vicente, Roberto; Zahn, Guilherme S.; Genezini, Frederico A., E-mail: priscila3.costa@usp.br, E-mail: fredzini@ipen.br [Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil)

    2017-07-01

    In the development of a thermal neutron detector using a square photodiode and a thin boron film, a radioactive calibration source with the same geometry was needed. An americium-243 standard source was produced by electrodeposition aiming at the calibration of a PIN-type silicon photodiode with a detection area of 10 x 10 mm{sup 2}. To produce the samples two tests were performed. In the first test, a square stainless steel plate (10 x 10 mm{sup 2}) was fixed on the surface of the conventional plate, which was removed after deposition. To reduce the loss of activity of the source, in the second test nail polish was applied on the silver plate leaving only an area of 10 x 10 mm{sup 2} without varnish coating. Once the electrodeposition process was completed, the activity concentration measurement was performed by alpha particle spectrometry. The first method presented a lower activity when compared to the total activity of Am-243 added initially. For the second method, the total activity was concentrate in the exposed square region (without nail polish). The results showed that it is possible to obtain a square geometry source; furthermore, the surrounding nail polish was not contaminated by {sup 243}Am. The comparison of these two approaches indicated that the second method was more efficient as it was possible to concentrate all the americium activity in the delimited square area. (author)

  13. Comparison of Americium-Beryllium neutron spectrum obtained using activation foil detectors and NE-213 spectrometer

    International Nuclear Information System (INIS)

    Sunny, Sunil; Subbaiah, K.V.; Selvakumaran, T.S.

    1999-01-01

    Neutron spectrum of Americium - Beryllium (α,n) source is measured with two different spectrometers vis-a-vis activation foils (foil detectors) and NE-213 organic scintillator. Activity induced in the foils is measured with 4π-β-γ sodium iodide detector by integrating counts under photo peak and the saturation activity is found by correcting to elapsed time before counting. The data on calculated activity is fed into the unfolding code, SAND-II to obtain neutron spectrum. In the case of organic scintillator, the pulse height spectrum is obtained using MCA and this is processed with unfolding code DUST in order to get neutron spectrum. The Americium - Beryllium (α,n) neutron spectrum thus obtained by two different methods is compared. It is inferred that the NE-213 scintillator spectrum is in excellent agreement with the values beyond 1MeV. Neutron spectrum obtained by activation foils depends on initial guess spectrum and is found to be in reasonable agreement with NE-213 spectrum. (author)

  14. Local polar fluctuations in lead halide perovskite crystals

    International Nuclear Information System (INIS)

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor

    2017-01-01

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH 3 NH 3 PbBr 3 ) and all-inorganic (CsPbBr 3 ) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. Furthermore, MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr 3 .

  15. Local Polar Fluctuations in Lead Halide Perovskite Crystals

    Science.gov (United States)

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

    2017-03-01

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3 NH3 PbBr3 ) and all-inorganic (CsPbBr3 ) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3 .

  16. 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...

  17. Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2017-03-02

    Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making organometallic halide perovskite monocrystalline film, and the like.

  18. 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.

  19. Local coordination of polyvalent metal ions in molten halide mixtures

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1989-07-01

    Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

  20. Halide Edib Adıvar and University Education

    OpenAIRE

    Erdal, Kelime

    2008-01-01

    As a writer worked at a university, Halide Edib Adıvar points out the problems of the university students and the people work there. The students studying abroad with many difficulties, can’t find an appropriate occupation related with the subject they have studied. Carefully choosing students who will be sent to abroad and their education in the light of our country’s needs is very important. In this article, Halide Edib’s ideas about financial problems of university members, students not wo...

  1. Single Crystals of Organolead Halide Perovskites: Growth, Characterization, and Applications

    KAUST Repository

    Peng, Wei

    2017-04-01

    With the soaring advancement of organolead halide perovskite solar cells rising from a power conversion efficiency of merely 3% to more than 22% shortly in five years, researchers’ interests on this big material family have been greatly spurred. So far, both in-depth studies on the fundamental properties of organolead halide perovskites and their extended applications such as photodetectors, light emitting diodes, and lasing have been intensively reported. The great successes have been ascribed to various superior properties of organolead halide hybrid perovskites such as long carrier lifetimes, high carrier mobility, and solution-processable high quality thin films, as will be discussed in Chapter 1. Notably, most of these studies have been limited to their polycrystalline thin films. Single crystals, as a counter form of polycrystals, have no grain boundaries and higher crystallinity, and thus less defects. These characteristics gift single crystals with superior optical, electrical, and mechanical properties, which will be discussed in Chapter 2. For example, organolead halide perovskite single crystals have been reported with much longer carrier lifetimes and higher carrier mobilities, which are especially intriguing for optoelectronic applications. Besides their superior optoelectronic properties, organolead halide perovskites have shown large composition versatility, especially their organic components, which can be controlled to effectively adjust their crystal structures and further fundamental properties. Single crystals are an ideal platform for such composition-structure-property study since a uniform structure with homogeneous compositions and without distraction from grain boundaries as well as excess defects can provide unambiguously information of material properties. As a major part of work of this dissertation, explorative work on the composition-structure-property study of organic-cation-alloyed organolead halide perovskites using their single

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

    International Nuclear Information System (INIS)

    Rodwell, P.; Stather, J.W.

    1978-01-01

    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.)

  3. Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative to Hybrid Lead Halide Perovskites.

    Science.gov (United States)

    Turkevych, Ivan; Kazaoui, Said; Ito, Eisuke; Urano, Toshiyuki; Yamada, Koji; Tomiyasu, Hiroshi; Yamagishi, Hideo; Kondo, Michio; Aramaki, Shinji

    2017-10-09

    Hybrid CPbX 3 (C: Cs, CH 3 NH 3 ; X: Br, I) perovskites possess excellent photovoltaic properties but are highly toxic, which hinders their practical application. Unfortunately, all Pb-free alternatives based on Sn and Ge are extremely unstable. Although stable and non-toxic C 2 ABX 6 double perovskites based on alternating corner-shared AX 6 and BX 6 octahedra (A=Ag, Cu; B=Bi, Sb) are possible, they have indirect and wide band gaps of over 2 eV. However, is it necessary to keep the corner-shared perovskite structure to retain good photovoltaic properties? Here, we demonstrate another family of photovoltaic halides based on edge-shared AX 6 and BX 6 octahedra with the general formula A a B b X x (x=a+3 b) such as Ag 3 BiI 6 , Ag 2 BiI 5 , AgBiI 4 , AgBi 2 I 7 . As perovskites were named after their prototype oxide CaTiO 3 discovered by Lev Perovski, we propose to name these new ABX halides as rudorffites after Walter Rüdorff, who discovered their prototype oxide NaVO 2 . We studied structural and optoelectronic properties of several highly stable and promising Ag-Bi-I photovoltaic rudorffites that feature direct band gaps in the range of 1.79-1.83 eV and demonstrated a proof-of-concept FTO/c-m-TiO 2 /Ag 3 BiI 6 /PTAA/Au (FTO: fluorine-doped tin oxide, PTAA: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], c: compact, m: mesoporous) solar cell with photoconversion efficiency of 4.3 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Worldwide bioassay data resources for plutonium/americium internal dosimetry studies

    International Nuclear Information System (INIS)

    Miller, G.; Bertelli, L.; Little, T.; Guilmette, R.; Riddell, T.; Filipy, R.

    2005-01-01

    Full text: Biokinetic models are the scientific underpinning of internal dosimetry. These models describe how materials of interest taken into the body by various routes (for example inhalation) are transported through the body, allowing the modelling of bioassay measurements and the estimation of radiation dose. The International Commission on Radiation Protection (ICRP) publishes biokinetic models for use in internal dosimetry. These models represent the consensus judgement of a committee of experts, based on human and animal data. Nonetheless, it is important to validate biokinetic models using directly applicable data, in a scientifically transparent manner, especially for internal dosimetry research purposes (as opposed to radiation protection), as in epidemiology studies. Two major goals would be to determine individual variations of model parameters for the purpose of assessing this source of uncertainty in internal dose calculations, and to determine values of workplace specific parameters (such as particle solubility in lung fluids) for different representative workplaces. Furthermore, data on the observed frequency of intakes under various conditions can be used in the interpretation of bioassay data. All of the above may be couched in the terminology of Bayesian statistical analysis and amount to the determination of the Bayesian prior probability distributions needed in a Bayesian interpretation of bioassay data. The authors have direct knowledge of several significant databases of plutonium/americium bioassay data (including autopsy data). The purpose of this paper is to acquaint the worldwide community with these resources and to invite others who may know of other such databases to participate with us in a publication that would document the content, form, and the procedures for seeking access to these databases. These databases represent a tremendous scientific resource in this field. Examples of databases known to the authors include: the

  5. Efficient and convenient oxidation of benzyl halides to carbonyl ...

    African Journals Online (AJOL)

    ketones in good to high yields by phase transfer catalysis combined with sodium nitrate and acetic acid at reflux. As a result, a simple and high yield procedure has been developed. KEY WORDS: Oxidation, Benzyl halides, Phase transfer catalyst, ...

  6. THERMODYNAMICS OF MICELLE FORMATION BY 1-METHYL-4-ALKYLPYRIDINIUM HALIDES

    NARCIS (Netherlands)

    BIJMA, K; ENGBERTS, JBFN; HAANDRIKMAN, G; VANOS, NM; BLANDAMER, MJ; BUTT, MD; CULLIS, PM

    This paper reports enthalpies of micellization for a series of 1-methyl-4-alkylpyridinium halide surfactants at 303.2 K with different lengths and degrees of branching of the 4-alkyl chain and different sizes of counterions using two microcalorimeters (LKB 2277 and Omega Microcal). The standard

  7. Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

    NARCIS (Netherlands)

    Brenes, Roberto; Guo, D.; Osherov, Anna; Noel, Nakita K.; Eames, Christopher; Hutter, E.M.; Pathak, Sandeep K.; Niroui, Farnaz; Friend, Richard H.; Islam, M. Saiful; Snaith, Henry J.; Bulović, Vladimir; Savenije, T.J.; Stranks, Samuel D.

    2017-01-01

    Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum

  8. 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…

  9. Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

    Science.gov (United States)

    Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

    2017-06-21

    Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

  10. Empirical formula for the parameters of metallic monovalent halides ...

    African Journals Online (AJOL)

    By collating the data on melting properties and transport coefficients obtained from various experiments and theories for certain halides of monovalent metals, allinclusive linear relationship has been fashioned out. This expression holds between the change in entropy and volume on melting; it is approximately obeyed by ...

  11. Crystal growth, structure and phase studies on gold halides

    NARCIS (Netherlands)

    Janssen, Eugenius Maria Wilhelmus Janssen

    1977-01-01

    Only very corrosive substances attack gold, the most noble metal. In this study the reactivity and the phase diagrams of gold with the halogens chlorine, bromine and iodine have been investigated. owing to the noble behaviour of gold, its halides are sensitive to heat; on heating they decompose into

  12. Methyl halide emission estimates from domestic biomass burning in Africa

    Science.gov (United States)

    Mead, M. I.; Khan, M. A. H.; White, I. R.; Nickless, G.; Shallcross, D. E.

    Inventories of methyl halide emissions from domestic burning of biomass in Africa, from 1950 to the present day and projected to 2030, have been constructed. By combining emission factors from Andreae and Merlet [2001. Emission of trace gases and aerosols from biomass burning. Global Biogeochemical Cycles 15, 955-966], the biomass burning estimates from Yevich and Logan [2003. An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochemical Cycles 17(4), 1095, doi:10.1029/2002GB001952] and the population data from the UN population division, the emission of methyl halides from domestic biomass usage in Africa has been estimated. Data from this study suggest that methyl halide emissions from domestic biomass burning have increased by a factor of 4-5 from 1950 to 2005 and based on the expected population growth could double over the next 25 years. This estimated change has a non-negligible impact on the atmospheric budgets of methyl halides.

  13. On the interpretation of luminescence of lead halide crystals

    Czech Academy of Sciences Publication Activity Database

    Babin, V.; Krasnikov, A.; Nikl, Martin; Stolovits, A.; Zazubovich, S.

    2002-01-01

    Roč. 229, č. 3 (2002), s. 1295-1304 ISSN 0370-1972 Institutional research plan: CEZ:AV0Z1010914 Keywords : luminescence * lead halide * exciton Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.930, year: 2002

  14. International Symposium on Halide Glasses (2nd) (Extended Abstracts).

    Science.gov (United States)

    1983-08-05

    Glasses In the CuCI -CsBr-PbBr, System" T. Yamagishi, J. Nishii and Y. Kaite, Nippon Sheet Glass Co., Itami City, Japan The glass forming ability of...PbBr2 melts which contained various other halides have been investigated. Among the systems studied, the ternary system CuCI -CsBr-PbBr2 showed a

  15. Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors

    NARCIS (Netherlands)

    Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar; Robles, Roberto; Fang, Hong-Hua; Loi, Maria Antonietta; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda; Tretiak, Sergei; Mohite, Aditya D.; Katan, Claudine; Even, Jacky; Kepenekian, Mikael

    2016-01-01

    Layered halide hybrid organic inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells

  16. Strong Carrier-Phonon Coupling in Lead Halide Perovskite Nanocrystals

    NARCIS (Netherlands)

    Iaru, Claudiu M; Geuchies, Jaco J|info:eu-repo/dai/nl/370526090; Koenraad, Paul M; Vanmaekelbergh, Daniël|info:eu-repo/dai/nl/304829137; Silov, Andrei Yu

    2017-01-01

    We highlight the importance of carrier-phonon coupling in inorganic lead halide perovskite nanocrystals. The low-temperature photoluminescence (PL) spectrum of CsPbBr3 has been investigated under a nonresonant and a nonstandard, quasi-resonant excitation scheme, and phonon replicas of the main PL

  17. Dislocation unpinning model of acoustic emission from alkali halide ...

    Indian Academy of Sciences (India)

    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 ...

  18. Analysis and modeling of alkali halide aqueous solutions

    DEFF Research Database (Denmark)

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

    2016-01-01

    on 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...

  19. 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…

  20. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

    Science.gov (United States)

    Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M.; Alsari, Mejd; Booker, Edward P.; Hutter, Eline M.; Pearson, Andrew J.; Lilliu, Samuele; Savenije, Tom J.; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H.; Stranks, Samuel D.

    2018-03-01

    Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can

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

    International Nuclear Information System (INIS)

    Melanie Mueller; Margret Acker; Steffen Taut; Gert Bernhard; Forschungszentrum Dresden-Rossendorf, Dresden

    2010-01-01

    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 NaClO 4 , 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 β 110 = 2.56 ± 0.08 and log β 120 = 3.93 ± 0.19. (author)

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

    International Nuclear Information System (INIS)

    Testa, C.; Desideri, D.; Meli, M.A.; Guerra, F.; Degetto, S.; Jia, G.; Gerdol, R.

    1998-01-01

    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 210 Pb method. A typical peak for 239,240 Pu and 241 Am 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 239,240 Pu and 238 Pu. (author)

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

    International Nuclear Information System (INIS)

    Popplewell, D.S.; Ham, G.J.; Johnson, T.E.

    1984-01-01

    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.)

  4. Separation of trivalent americium and europium by purified Cyanex 301 immobilized in macro porous polymer

    International Nuclear Information System (INIS)

    Jing Chen; Veltkamp, A.C.; Booij, A.S.

    2002-01-01

    High separation ability of purified Cyanex 301 towards trivalent americium over europium in liquid-liquid extraction is confirmed. Solvent 2-nitrophenyl octyl ether (NPOE) lowered the partitioning of Am 3+ but remained the separation ability over europium. Solvent toluene and 3-octanone lowered the separation factor to ∼ 1000. It is feasible to separate Am 3+ from Eu 3+ by Cyanex 301 which was immobilized in the macro porous polymer (MPP). 3-Octanone is a suitable solvent for dissolving NH 4 OH-saponified Cyanex 301 and MPP is a suitable solid supported material for column operation. A five-step column experiment demonstrated the feasibility to separate Am 3+ from Eu 3+ in column which was packed with Cyanex 301-impregnated MPP. (author)

  5. Spectral properties of americium(III) in silicate matrices. Concentration-dependent up-conversion emission

    International Nuclear Information System (INIS)

    Assefa, Zerihun; Haire, R.G.; Stump, N.

    2002-01-01

    We have been pursuing the spectroscopic properties of actinide ions in silicate matrices. One facet of these studies involves the behavior of Stokes and anti-Stokes emissions exhibited by Am 3+ in these hosts. Several attributes have been found to influence the spectral profile, which include excitation wavelength, laser power, and dopant-concentration. Excitation with the 514.5 nm (19435 cm -1 ) line of argon laser provides anti-Stokes emissions at 21100 and ∼19920 cm -1 in the borosilicate matrices. This up-conversion was found to proceed through a multi-photon scheme, and the efficiency increases with increased dopant concentration. Based on our concentration-dependent studies, the up-conversion is suggested to involve a cross-relaxation process [( 5 D 1' , 7 F 0' ) ( 7 F 6' , 7 F 2' )] between neighboring americium ions. (author)

  6. 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.

  7. Magnesium ionophore II as an extraction agent for trivalent europium and americium

    Energy Technology Data Exchange (ETDEWEB)

    Makrlik, Emanuel [Czech Univ. of Life Sciences, Prague (Czech Republic). Faculty of Environmental Sciences; Vanura, Petr [Univ. of Chemistry and Technology, Prague (Czech Republic). Dept. of Analytical Chemistry

    2016-11-01

    Solvent extraction of microamounts of trivalent europium and americium into nitrobenzene by using a mixture of hydrogen dicarbollylcobaltate (H{sup +}B{sup -}) and magnesium ionophore II (L) was studied. The equilibrium data were explained assuming that the species HL{sup +}, HL{sup +}{sub 2}, ML{sup 3+}{sub 2}, and ML{sup 3+}{sub 3} (M{sup 3+} = Eu{sup 3+}, Am{sup 3+}; L=magnesium, ionophore II) are extracted into the nitrobenzene phase. Extraction and stability constants of the cationic complex species in nitrobenzene saturated with water were determined and discussed. From the experimental results it is evident that this effective magnesium ionophore II receptor for the Eu{sup 3+} and Am{sup 3+} cations could be considered as a potential extraction agent for nuclear waste treatment.

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

    Energy Technology Data Exchange (ETDEWEB)

    Burns, J.D.; Clearfield, A. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemistry; Borkowski, M.; Reed, D.T. [Los Alamos National Laboratory, Carlsbad, NM (United States). Earth and Environmental Sciences Div.

    2012-07-01

    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 K{sub d} values ca. 6 x 10{sup 5} mL/g, while the K{sub d} values for Am(V) were much lower. A new method of synthesizing and stabilizing AmO{sub 2}{sup +} to yield a lifetime of at least 24 h in acidic media using a combination of sodium persulfate and calcium hypochlorite will be described.

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

    International Nuclear Information System (INIS)

    Burns, J.D.; Clearfield, A.; Borkowski, M.; Reed, D.T.

    2012-01-01

    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 K d values ca. 6 x 10 5 mL/g, while the K d values for Am(V) were much lower. A new method of synthesizing and stabilizing AmO 2 + to yield a lifetime of at least 24 h in acidic media using a combination of sodium persulfate and calcium hypochlorite will be described.

  10. Heterofacial alkylation of alkylenediamines by higher alkyl halides

    International Nuclear Information System (INIS)

    Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

    1985-01-01

    A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

  11. Double Charged Surface Layers in Lead Halide Perovskite Crystals

    KAUST Repository

    Sarmah, Smritakshi P.

    2017-02-01

    Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

  12. Halide Re-Shelled Quantum Dot Inks for Infrared Photovoltaics.

    Science.gov (United States)

    Fan, James Z; Liu, Mengxia; Voznyy, Oleksandr; Sun, Bin; Levina, Larissa; Quintero-Bermudez, Rafael; Liu, Min; Ouellette, Olivier; García de Arquer, F Pelayo; Hoogland, Sjoerd; Sargent, Edward H

    2017-11-01

    Colloidal quantum dots are promising materials for tandem solar cells that complement silicon and perovskites. These devices are fabricated from solution phase; however, existing methods for making infrared-bandgap CQD inks suffer agglomeration and fusion during solution exchange. Here we develop a ligand exchange that provides robust surface protection and thereby avoids aggregation. First, we exchanged long oleic acid ligands to a mixed system comprising medium-chain ammonium and anionic chloride ligands; we then reshelled the surface using short halides and pseudohalide ligands that enabled transfer to a polar solvent. Absorbance and photoluminescence measurements reveal the retention of exciton sharpness, whereas X-ray photoelectron spectroscopy indicates halide capping. The best power conversion efficiency of these devices is 0.76 power points after filtering through silicon, which is 1.9× higher than previous single-step solution-processed IR-CQD solar cells.

  13. Laser Direct Write Synthesis of Lead Halide Perovskites.

    Science.gov (United States)

    Chou, Stanley S; Swartzentruber, Brian S; Janish, Matthew T; Meyer, Kristin C; Biedermann, Laura B; Okur, Serdal; Burckel, D Bruce; Carter, C Barry; Kaehr, Bryan

    2016-10-06

    Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. Here we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We demonstrate arbitrary pattern formation of crystalline CH 3 NH 3 PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetector using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.

  14. Local Polar Fluctuations in Lead Halide Perovskite Crystals

    Energy Technology Data Exchange (ETDEWEB)

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

    2017-03-01

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3NH3PbBr3) and all-inorganic (CsPbBr3) leadhalide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-tohead Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.

  15. 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.

  16. Phase holograms formed by silver halide (sensitized) gelatin processing.

    Science.gov (United States)

    Graver, W R; Gladden, J W; Eastes, J W

    1980-05-01

    A novel recording process for the formation of phase volume holograms at up to 1500 cycles/mm is described. The term silver halide (sensitized) gelatin or SHG denotes an all-gelatin phase material, which records the initial image information through photon absorption by the silver halide. Our process uses a reversal bleach that dissolves the developed silver image and cross-links the gelatin molecules in the vicinity of the developed image. Experiments have determined the stored image as refractive-index differences within the remaining gelatin. The major attributes of SHG holograms are (1) panchromatic response, (2) 100:1 greater light sensitivity than dichromate (sensitized) gelatin, and (3) elimination of darkening (printout) effects.

  17. Upper limits to americium concentration in large sized sodium-cooled fast reactors loaded with metallic fuel

    International Nuclear Information System (INIS)

    Zhang, Youpeng; Wallenius, Janne

    2014-01-01

    Highlights: • The americium transmutation capability of Integral Fast Reactor was investigated. • The impact from americium introduction was parameterized by applying SERPENT Monte Carlo calculations. • Higher americium content in metallic fuel leads to a power penalty, preserving consistent safety margins. - Abstract: Transient analysis of a large sized sodium-cooled reactor loaded with metallic fuel modified by different fractions of americium have been performed. Unprotected loss-of-offsite power, unprotected loss-of-flow and unprotected transient-over-power accidents were simulated with the SAS4A/SASSYS code based on the geometrical model of an IFR with power rating of 2500 MW th , using safety parameters obtained with the SERPENT Monte Carlo code. The Ti-modified austenitic D9 steel, having higher creep rupture strength, was considered as the cladding and structural material apart from the ferritic/martensitic HT9 steel. For the reference case of U–12Pu–1Am–10Zr fuel at EOEC, the margin to fuel melt during a design basis condition UTOP is about 50 K for a maximum linear rating of 30 kW/m. In order to maintain a margin of 50 K to fuel failure, the linear power rating has to be reduced by ∼3% and 6% for 2 wt.% and 3 wt.% Am introduction into the fuel respectively. Hence, an Am concentration of 2–3 wt.% in the fuel would lead to a power penalty of 3–6%, permitting a consumption rate of 3.0–5.1 kg Am/TW h th . This consumption rate is significantly higher than the one previously obtained for oxide fuelled SFRs

  18. 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.

  19. 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

  20. Development and melt growth of novel scintillating halide crystals

    Czech Academy of Sciences Publication Activity Database

    Yoshikawa, A.; Yokota, Y.; Shoji, Y.; Král, Robert; Kamada, K.; Kurosawa, S.; Ohashi, Y.; Arakawa, M.; Chani, V.I.; Kochurikhin, V.V.; Yamaji, A.; Medvedev, A.; Nikl, Martin

    2017-01-01

    Roč. 74, Dec (2017), s. 109-119 ISSN 0925- 3467 Institutional support: RVO:68378271 Keywords : scintillator * halide * crystal growth from the melt * Bridgman method * Czochralski method * edge-defined film-fed method * micro-pulling-down method Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.238, year: 2016

  1. Methyl halide emissions from greenhouse-grown mangroves

    Science.gov (United States)

    Manley, Steven L.; Wang, Nun-Yii; Walser, Maggie L.; Cicerone, Ralph J.

    2007-01-01

    Two mangrove species, Avicennia germinans and Rhizophora mangle, were greenhouse grown for nearly 1.5 years from saplings. A single individual of each species was monitored for the emission of methyl halides from aerial tissue. During the first 240 days, salinity was incrementally increased with the addition of seawater, and was maintained between 18 and 28‰ for the duration of the study. Exponential growth occurred after 180 days. Methyl halide emissions normalized to leaf area were measured throughout the study and varied dramatically. Emission rates normalized to land area (mg m-2 y-1), assuming a LAI = 5, yielded 82 and 29 for CH3Cl, 10 and 1.6 for CH3Br, and 26 and 11 for CH3I, for A. germinans and R. mangle, respectively. From these preliminary determinations, only CH3I emissions emerge as being of possible global atmospheric significance. This study emphasizes the need for field studies of methyl halide emissions from mangrove forests.

  2. Lasing in robust cesium lead halide perovskite nanowires

    Science.gov (United States)

    Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

    2016-01-01

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

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

    Science.gov (United States)

    Gupta, A; Maynes, M; Silver, S

    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+ 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+.

  4. High Pressure phase transition in some alkali halides using interatomic potential model

    International Nuclear Information System (INIS)

    Yazar, H.R.

    2002-01-01

    We have predicted the phase transition pressure in some alkali halides using an interatomic potential approach based on rigid ion model.The phase transition pressures(28.69 and 2.4 GPa) obtained by us for two alkali halides (NaCl and KCl ) are in closer agreement with their corresponding experimental data(29.0 and 2.0 GPa).This potential is promising with respect to prediction of the phase transition pressure of other alkali halides as well

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

    International Nuclear Information System (INIS)

    Rashydov, N.M.

    2002-01-01

    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 241 Am 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 241 Am and 137 Cs was at the level of 660 and 27 MBq/m 2 , respectively. Gamma spectroscopy and radiochemical methods were used to estimate the activity concentration of 137 Cs, 90 Sr, 238 Pu, 239+240 Pu, 241 Am. 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 137 Cs was (5.8±1,5)x10 6 , (7.4±1.1)x10 5 , and (2.6±0.2)x10 6 Bq/kg dry mass, respectively, and contamination by 241 Am was 47±5, 45±3 and 3.2±0.2 Bq/kg, respectively. The soil-to-plant transfer ratio for 137 Cs ranged lay within the interval of 0.2 to 0.03 Bq/kg : Bq/m 2 , the the transfer ratio for 241 Am did not exceed 7x10 -5 Bq/kg : Bq/m 2 . The coefficient of the relative contents of the 241 Am/ 239+240 Pu radionuclides in the various plant samples varied from 3.2 to 8.3, while for soil from

  6. Contrasts between the marine and freshwater biological interactions of plutonium and americium

    International Nuclear Information System (INIS)

    Livingston, H.D.; Bowen, V.T.

    1975-01-01

    Whether in lakes or the oceans the transuranic elements plutonium and americium are taken up by marine organisms, with concentration factors that would class them as nice, typical heavy metals. There is no evidence for strong, widespread discrimination against the transuranics by either plant or animal absorptive surfaces. In both freshwater and marine situations the major reservoir of Pu and Am soon becomes the sediments, and organisms are more exposed to uptake of these nuclides the closer is their ecological involvement with the sediments. Although there is little evidence that this can be an ionic strength effect, it does appear that Pu may be somewhat more available, biologically, in marine environments, and Am, conversely, in fresh water. We incline to the belief that details of these behaviors are usually controlled by local availability of organic complexers. No compelling evidence exists of increase in Pu concentration at higher levels of food chains; in marine situations this appears true of Am as well, but a few data suggest that in fresh water fish there is a progressive increase, in higher trophic levels, in the ratio Am to Pu. Although marine and fresh water biogeochemistries of transuranics are much more similar than we had expected, it will generally be dangerous to extrapolate from one to the other. In both systems there appears to us no question that we are observing real element biogeochemistry, not the redistribution of inert, labelled, fallout fragments

  7. Multicompartment kinetic models for the metabolism of americium, plutonium and uranium in rats

    International Nuclear Information System (INIS)

    Sontag, W.

    1986-01-01

    To examine the kinetic behaviour of americium, plutonium and uranium in male and female rats, an extended mammillary model has been developed, composed of 10 compartments connected with 17 linear transfer coefficients. The 10 compartments describe the behaviour of the three nuclides in the blood, skeleton, liver and kidney; the remaining activity is assigned to one residual organ. Each organ is divided into two compartments, short- and long-term. In the skeleton the short-term compartment has been assumed to be the bone surface and marrow, and the long-term compartment the deep bone; in the liver, evidence suggests that the short-term compartment is physiologically associated with lysosomes and the long-term compartment identical with telolysosomes. Influence of age, sex and different nuclides on the transfer coefficients and the absorbed radiation dose are discussed. By using the transfer coefficients calculated for intravenous injection, the behaviour of the nuclides in skeleton and liver during continuous intake has been calculated. The behaviour of the three nuclides in skeleton and liver after intravenous injection has also been calculated with the additional assumption that from the fifth day the animals were treated continuously with a chelating agent. (UK)

  8. 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.

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

    International Nuclear Information System (INIS)

    Bierkens, J.

    1986-01-01

    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 241 Am in the freshwater environment aim to establish a relation between the behavior of 241 Am 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 241 Am with humic acids and competition with trivalent cations such as A1 and Fe, were proven to be significant on the speciation of 241 Am. Based on the registration of the 241 Am uptake by a large number of freshwater organisms, the crayfish Astacus leptodactylus Eschscholtz was chosen to study the whole-body uptake of 241 Am, 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 241 Am in the hemolymph and the hepatopancreas, and its subcellular distribution in the digestive gland. Finally, by comparing the physiology of 241 Am with some other metals ( 240 Pu, 64 Cu, 198 Au) with analogous or contradictional properties, we tried to find out whether the behavior of 241 Am in organisms can be explained from its chemical characteristics

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

    Energy Technology Data Exchange (ETDEWEB)

    Nielsen, Reinald Dreas [Oregon State Univ., Corvallis, OR (United States)

    1982-06-01

    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.

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

    International Nuclear Information System (INIS)

    Nielsen, R.D.

    1982-06-01

    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

  12. 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.

  13. Removal of plutonium and Americium from hydrochloric acid waste streams using extraction chromatography

    International Nuclear Information System (INIS)

    Schulte, L.D.; FitzPatrick, J.R.; Salazar, R.R.; Schake, B.S.; Martinez, B.T.

    1995-01-01

    Extraction chromatography is under development as a method to lower actinide activity levels in hydrochloric acid (HCl) effluent streams. Successful application of this technique for radioactive liquid waste treatment would provide a low activity feedstream for HCl recycle, reduce the loss of radioactivity to the environment in aqueous effluents, and lower the quantity and improve the form of solid waste generated. The extraction of plutonium and americium from HCl solutions was examined for several commercial and laboratory-produced sorbed resin materials. Polymer beads were coated with n-octyl(phenyl)-N,N-diisobutylcarbamoyl- methylphosphine oxide (CMPO) and either tributyl phosphate (TBP), or diamyl amylphosphonate (DAAP). Distribution coefficients for Pu and Am were measured by contact studies in 1-10 M HCl, while varying REDOX conditions, actinide loading levels, and resin formulations. Flow experiments were run to evaluate actinide loading and elution under varied conditions. Significant differences in the actinide distribution coefficients in contact experiments, and in actinide retention in flow experiments were observed as a function of resin formulation

  14. Cleanex process: a versatile solvent extraction process for recovery and purification of lanthanides, americium, and curium

    International Nuclear Information System (INIS)

    Bigelow, J.E.; Collins, E.D.; King, L.J.

    1979-01-01

    At a concentration of 1 M in straight-chain hydrocarbon diluent, HDEHP will extract americium, curium, and other trivalent actinide and lanthanide elements from dilute acid or salt solutions. The solute is back-extracted with more concentrated acid, either nitric or hydrochloric. The process has been used in the continuous, countercurrent mode, but its greatest advantage arises in batch extractions where the excess acid can be titrated with NaOH to produce a final acidity of about 0.03 M. Under these conditions, 99% recovery can be achieved, usually in one stage. Cleanex was used on the 50-liter scale at the Transuranium Processing Plant at Oak Ridge for 12 years to provide a broad spectrum cleanup to transuranium elements before applying more sophisticated techniques for separating individual products. The process is also used routinely to recover excessive losses of curium and/or californium from plant waste streams. The solvent system is relatively resistant to radiation damage, being usable up to 200 W-h/liter

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

    International Nuclear Information System (INIS)

    O'Donnell, F.R.; Etnier, E.L.; Holton, G.A.; Travis, C.C.

    1981-10-01

    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

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

    International Nuclear Information System (INIS)

    Borba, Tania Regina de

    2010-01-01

    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)

  17. 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

    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...

  18. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Science.gov (United States)

    2010-01-01

    ... lamp, and the capacitor when the capacitor is provided, shall constitute a nominal system in accordance... designed to be operated with a metal halide lamp and a ballast for a metal halide lamp. Probe-start metal... discharge and then power to sustain the discharge through the glow-to-arc transition. Test Procedures ...

  19. Broadly tunable metal halide perovskites for solid-state light-emission applications

    NARCIS (Netherlands)

    Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

    2017-01-01

    The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as

  20. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    Science.gov (United States)

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  1. Calcium phosphate cements with strontium halides as radiopacifiers.

    Science.gov (United States)

    López, Alejandro; Montazerolghaem, Maryam; Engqvist, Håkan; Ott, Marjam Karlsson; Persson, Cecilia

    2014-02-01

    High radiopacity is required to monitor the delivery and positioning of injectable implants. Inorganic nonsoluble radiopacifiers are typically used in nondegradable bone cements; however, their usefulness in resorbable cements is limited due to their low solubility. Strontium halides, except strontium fluoride, are ionic water-soluble compounds that possess potential as radiopacifiers. In this study, we compare the radiopacity, mechanical properties, composition, and cytotoxicity of radiopaque brushite cements prepared with strontium fluoride (SrF2 ), strontium chloride (SrCl2 ·6H2 O), strontium bromide (SrBr2 ), or strontium iodide (SrI2 ). Brushite cements containing 10 wt % SrCl2 ·6H2 O, SrBr2 , or SrI2 exhibited equal to or higher radiopacity than commercial radiopaque cements. Furthermore, the brushite crystal lattice in cements that contained the ionic radiopacifiers was larger than in unmodified cements and in cements that contained SrF2 , indicating strontium substitution. Despite the fact that the strontium halides increased the solubility of the cements and affected their mechanical properties, calcium phosphate cements containing SrCl2 ·6H2 O, SrBr2 , and SrI2 showed no significant differences in Saos-2 cell viability and proliferation with respect to the control. Strontium halides: SrCl2 ·6H2 O, SrBr2 , and SrI2 may be potential candidates as radiopacifiers in resorbable biomaterials although their in vivo biocompatibility, when incorporated into injectable implants, is yet to be assessed. Copyright © 2013 Wiley Periodicals, Inc.

  2. 10 CFR 431.324 - Uniform test method for the measurement of energy efficiency of metal halide ballasts.

    Science.gov (United States)

    2010-01-01

    ... energy efficiency of metal halide ballasts. (b) Testing and Calculations. [Reserved] Energy Conservation... 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 and...

  3. Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

    Science.gov (United States)

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

  4. Transport phenomena of aluminium oxide in metal halide lamps

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, S; Markus, T [Institute for Energy Research, Forschungszentrum Juelich GmbH, D-52425 Juelich (Germany); Niemann, U [Philips GmbH, Research Laboratories, PO Box 500145, Aachen, D-52085 (Germany)], E-mail: s.fischer@fz-juelich.de

    2008-07-21

    A better understanding of the transport phenomena observed in metal halide lamps can be achieved using computer-based model calculations. The chemical transport of aluminium oxide in advanced high-pressure discharge vessels was calculated as a function of temperature and composition of the salt mixture relevant to the lamp. Below 1773 K chemical transport is the prevailing process; above this temperature the vaporization and condensation of the envelope material-aluminium oxide-become more important. The results of the calculations show that the amount of transported alumina increases linearly with the number of iteration cycles and exponentially with the temperature gradient.

  5. Status quo of ceramic material for metal halide discharge lamps

    International Nuclear Information System (INIS)

    Kappen, Theo G M M

    2005-01-01

    Polycrystalline alumina is an excellent ceramic material for use as the envelope for metal halide discharge lamps. Although this material was introduced in the mid-1960s, and is thus already known for several decades, recent years have seen considerable effort aimed at further development of these ceramic envelope materials. Developments are not only in the field of ceramic shaping technologies, but are also concentrated on the material properties of the ceramic material itself. Optical, mechanical as well as the chemical properties of the ceramic envelope are strongly controlled by the shape as well as the microstructure of the ceramics used

  6. Evaluation of field test equipment for halide and DOP testing

    International Nuclear Information System (INIS)

    Schreiber, K.L.; Kovach, J.L.

    1975-01-01

    The Nucon Testing Services Department, field testing at power reactor sites, has performed tests using R-11, R-12, and R-112 in conjunction with gas chromatographs and direct reading halide detectors. The field operational experience with these detector systems, thus sensitivity, precision, and manner of field calibration, are presented. Laboratory experiments regarding 3 H-tagged methyl iodide for in place leak testing of adsorber systems indicate a low hazard, high reliability process for leak testing in facilities where atmospheric cross contamination occurs. (U.S.)

  7. Synthesis of halide- and solvent free metal borohydrides

    DEFF Research Database (Denmark)

    Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

    have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

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

    Directory of Open Access Journals (Sweden)

    David T. Moore

    2014-08-01

    Full Text Available 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.

  9. 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).

  10. Separation of neptunium, plutonium, americium and curium from uranium with di-(2-ethylhexyl)-phosphoric acid (HDEHP) for radiometric and ICP-MS analysis

    International Nuclear Information System (INIS)

    Ramebaeck, H.; Skaalberg, M.

    1998-01-01

    The possibility of using di-(2-ethylhexyl)-phosphoric acid (HDEHP) in solvent extraction for the separation of neptunium, plutonium, americium and curium from large amounts of uranium was studied. Neptunium, plutonium, americium and curium (as well as uranium) were extracted from HNO 3 , whereafter americium and curium were back-extracted with 5M HNO 3 . Thereafter was neptunium back-extracted in 1M HNO 3 containing hydroxylamine hydronitrate. Finally, plutonium was back-extracted in 3M HCl containing Ti(III). The method separates 238 Pu from 241 Am for α-spectroscopy. For ICP-MS analysis, the interferences from 238 U are eliminated: tailing from 238 U, for analysis of 237 Np, and the interference of 238 UH + for analysis of 239 Pu. The method has been used for the analysis of actinides in samples from a spent nuclear fuel leaching and radionuclide transport experiment. (author)

  11. 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)

    Saiki, M.; Lima, F.W. de

    1986-01-01

    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 239 Np and 2 4 1 Am 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) [pt

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

    International Nuclear Information System (INIS)

    Pimpl, M.; Schuettelkopf, H.

    1979-12-01

    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.) [de

  13. Experiments comparing the uptake of americium from chloride media using extraction chromatography

    International Nuclear Information System (INIS)

    FitzPatrick, J.R.; Schake, B.S.; Schulte, L.D.; Martinez, B.T.; Salazar, R.R.

    1995-01-01

    Clean-up of actinide effluent waste steams is of increasing importance at the Los Alamos Plutonium Facility, TA-55, and removing the actinide elements to very low levels allows less radioactivity to go the Los Alamos National Laboratory Water Treatment Facility, TA-50, thus reducing the number of drums of TRU waste. Americium (Am) is a difficult element to remove from chloride media because the +3 state is difficult to oxidize and chelating resins work better with elements such as plutonium which are more readily oxidized to the +4 and/or +6 state. Currently in hydrochloric acid (HC1) media, the acidic liquid waste is neutralized with potassium hydroxide to precipitate the metal hydroxides, before disposal to TA-50. This process is not very efficient. The removal of Am from chloride media was compared using a series of resins, some commercial and some made in our laboratory, using different percentages by weight of octyl(phenyl)-N,N-diiso- butylcarbamoyl-methylphosphine oxide (CMPO ) along with diamyl amylphosphonate (DAAP) or tributyl phosphate (TBP) as diluents. Resins were also made with no added diluent. Early comparisons using small-scale contact studies with 0.5 grams of resin in 0.1M-12M HC1, and subsequent small-scale flow experiments show a trend in which Am uptake is proportional to the amount of CMPO on the resins and the diluent plays a minor role in the uptake of Am from these solutions. Redox chemistry effects were also investigated. From these studies, it is possible to determine the best conditions for the removal of Am from HC1 media thus reducing the gross alpha content of the waste stream by a factor of 10-100 which reduces the number of barrels of waste produced at the Water Treatment Facility

  14. Concentration and vertical distribution of plutonium and americium in Italian mosses and lichens

    International Nuclear Information System (INIS)

    Jia, G.; Desideri, D.; Guerra, F.; Meli, M.A.; Testa, C.

    1997-01-01

    The plutonium and americium concentration and vertical distribution in some Italian mosses and lichens have been determined. The 239,240 Pu, 238 Pu and 241 Am concentration ranges in tree trunk lichens 0.83-1.87, 0.052-0.154 and 0.180-0.770 Bq/kg, respectively. The corresponding values in tree mosses are higher and more scattered ranging from 0.321 to 4.96, from 0.029 to 0.171 and from 0.200 to 1.93 Bq/kg. The mean 238 Pu/ 239,240 Pu and 241 Am/ 239,240 Pu ratios are 0.088±0.037 and 0.38 ± 0.13 in lichens and 0.091±0.072 and 0.54±0.16 in tree mosses. The Pu and Am concentrations are relatively low in terrestrial mosses. The 239,240 Pu, 238 Pu and 241 Am vertical distributions in a terrestrial moss core (Neckera Crispa) collected near Urbino (central Italy) show an exponential decrease with the height. On the contrary the 241 Am vertical distribution in another terrestrial moss core (Sphagnum Compactum) collected in the Alps (northern Italy) shows an interesting peak at 16 cm which corresponds to the deposition of fallout from the nuclear weapon tests in 1960's. The 241 Am movement upward and downward in the moss core is also studied. The results show once again that both mosses and lichens are very effective accumulators of Pu and Am and that they can be used as good biological indicators of the radionuclide airborne pollution from nuclear facilities and nuclear weapon tests. They can play a very important role in cycling naturally or artificially enhanced radionuclides in the atmosphere over long time scales. (author)

  15. Americium/Lanthanide Separations in Alkaline Solutions for Advanced Nuclear Fuel Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Goff, George S. [Los Alamos National Laboratory; Long, Kristy Marie [Los Alamos National Laboratory; Reilly, Sean D. [Los Alamos National Laboratory; Jarvinen, Gordon D. [Los Alamos National Laboratory; Runde, Wolfgang H. [Los Alamos National Laboratory

    2012-06-11

    Project goals: Can used nuclear fuel be partitioned by dissolution in alkaline aqueous solution to give a solution of uranium, neptunium, plutonium, americium and curium and a filterable solid containing nearly all of the lanthanide fission products and certain other fission products? What is the chemistry of Am/Cm/Ln in oxidative carbonate solutions? Can higher oxidation states of Am be stabilized and exploited? Conclusions: Am(VI) is kinetically stable in 0.5-2.0 M carbonate solutions for hours. Aliquat 336 in toluene has been successfully shown to extract U(VI) and Pu(VI) from carbonate solutions. (Stepanov et al 2011). Higher carbonate concentration gives lower D, SF{sub U/Eu} for = 4 in 1 M K{sub 2}CO{sub 3}. Experiments with Am(VI) were unsuccessful due to reduction by the organics. Multiple sources of reducing organics...more optimization. Reduction experiments of Am(VI) in dodecane/octanol/Aliquat 336 show that after 5 minutes of contact, only 30-40% of the Am(VI) has been reduced. Long enough to perform an extraction. Shorter contact times, lower T, and lower Aliquat 336 concentration still did not result in any significant extraction of Am. Anion exchange experiments using a strong base anion exchanger show uptake of U(VI) with minimal uptake of Nd(III). Experiments with Am(VI) indicate Am sorption with a Kd of 9 (10 minute contact) but sorption mechanism is not yet understood. SF{sub U/Nd} for = 7 and SF{sub U/Eu} for = 19 after 24 hours in 1 M K{sub 2}CO{sub 3}.

  16. Determination of americium and curium using ion-exchange in the nitric-acid-methanol medium for environmental analysis

    International Nuclear Information System (INIS)

    Holm, E.; Fukai, R.

    1976-01-01

    While transplutonic elements are only slightly sorbed to anion exchangers from hydrochloric or nitric acid media, the presence of alcohol enhances the anionic exchange of these elements, especially in nitric and sulfuric solutions. In the present work a method has been developed for determining americium and curium in environmental samples, on the basis of the difference between the sorption characteristics to anion exchangers in the acid-methanol system of these transplutonic elements and those of plutonium, polonium and thorium. The method also permits us to perform sequential determination of plutonium, when necessary

  17. A vibrational model of F centres in alkali halides

    Energy Technology Data Exchange (ETDEWEB)

    Salis, M. [Universita di Cagliari, Dipt. di Fisica, Istituto Nazionale di Fisica della Materia, Monserrato, CA (Italy)

    2003-07-01

    Halide vacancies in ionic crystals originate localized positive extra-charges which can trap electrons when crystals are excited by ionizing radiations. A model of F-centres in alkali halides, which relates absorption energies in F-bands to the dynamic parameters of host lattices, is proposed. According to this model, the electrons trapped in F-centres are treated as classical particles with a proper mass, m{sup *} = m*{epsilon}{sub loc}{sup 4} / {epsilon}{sub {infinity}}{sup 2}, m standing for the actual electron mass, and {epsilon}{sub loc} and {epsilon}{sub {infinity}} for local high frequency and optical dielectric constants, respectively. Hence, by considering the trapped electrons as substitutional impurities of small mass, the dynamics of the lattice is investigated by means of the theory of local modes with the assumption of isotopy. A simple equation allowing calculation of the local mode frequencies is obtained. Knowledge of the Debye frequency and of transverse and longitudinal mode frequencies at the long wavelength limit is required. With this model, F-band absorption energy is reasonably well accounted for. (author)

  18. Low -Dimensional Halide Perovskites and Their Advanced Optoelectronic Applications

    Science.gov (United States)

    Zhang, Jian; Yang, Xiaokun; Deng, Hui; Qiao, Keke; Farooq, Umar; Ishaq, Muhammad; Yi, Fei; Liu, Huan; Tang, Jiang; Song, Haisheng

    2017-07-01

    Metal halide perovskites are crystalline materials originally developed out of scientific curiosity. They have shown great potential as active materials in optoelectronic applications. In the last 6 years, their certified photovoltaic efficiencies have reached 22.1%. Compared to bulk halide perovskites, low-dimensional ones exhibited novel physical properties. The photoluminescence quantum yields of perovskite quantum dots are close to 100%. The external quantum efficiencies and current efficiencies of perovskite quantum dot light-emitting diodes have reached 8% and 43 cd A-1, respectively, and their nanowire lasers show ultralow-threshold room-temperature lasing with emission tunability and ease of synthesis. Perovskite nanowire photodetectors reached a responsivity of 10 A W-1 and a specific normalized detectivity of the order of 1012 Jones. Different from most reported reviews focusing on photovoltaic applications, we summarize the rapid progress in the study of low-dimensional perovskite materials, as well as their promising applications in optoelectronic devices. In particular, we review the wide tunability of fabrication methods and the state-of-the-art research outputs of low-dimensional perovskite optoelectronic devices. Finally, the anticipated challenges and potential for this exciting research are proposed.

  19. Subsurface Ectomycorrhizal Fungi: A New Source of Atmospheric Methyl Halides?

    Science.gov (United States)

    Treseder, K. K.; Redeker, K. R.; Allen, M. F.

    2001-12-01

    Incomplete source budgets for methyl halides---compounds that release inorganic halogen radicals which, in turn, catalyze atmospheric ozone depletion---limit our abilities to predict the fate of the stratospheric ozone layer. We tested the ability ectomycorrhizal fungi to produce methyl bromide and methyl iodide. These fungi are abundant in temperate forests, where they colonize tree roots and provide nutrients to their symbiotic plants in exchange for carbon compounds. The observed range of emissions from seven different species in culture is 0.001- to 100-μ g g-1 fungi d-1 for methyl bromide, and 0.5- to 500-μ g g-1 fungi d-1 for methyl iodide. While methyl chloride was not specifically tested, large emissions were observed from several species with little to no emissions observed from others. Further analyses of the effects of substrate concentration, headspace concentration, and temperature were performed on the species Cenococcum geophilum, one of the most abundant ectomycorrhizal fungi. Our results suggest that subsurface fungal emissions may be a significant global source of methyl halides.

  20. Cation Dynamics Governed Thermal Properties of Lead Halide Perovskite Nanowires.

    Science.gov (United States)

    Wang, Yuxi; Lin, Renxing; Zhu, Pengchen; Zheng, Qinghui; Wang, Qianjin; Li, Deyu; Zhu, Jia

    2018-04-09

    Metal halide perovskite (MHP) nanowires such as hybrid organic-inorganic CH 3 NH 3 PbX 3 (X = Cl, Br, I) have drawn significant attention as promising building blocks for high-performance solar cells, light-emitting devices, and semiconductor lasers. However, the physics of thermal transport in MHP nanowires is still elusive even though it is highly relevant to the device thermal stability and optoelectronic performance. Through combined experimental measurements and theoretical analyses, here we disclose the underlying mechanisms governing thermal transport in three different kinds of lead halide perovskite nanowires (CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr 3 and CsPbBr 3 ). It is shown that the thermal conductivity of CH 3 NH 3 PbBr 3 nanowires is significantly suppressed as compared to that of CsPbBr 3 nanowires, which is attributed to the cation dynamic disorder. Furthermore, we observed different temperature-dependent thermal conductivities of hybrid perovskites CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 , which can be attributed to accelerated cation dynamics in CH 3 NH 3 PbBr 3 at low temperature and the combined effects of lower phonon group velocity and higher Umklapp scattering rate in CH 3 NH 3 PbI 3 at high temperature. These data and understanding should shed light on the design of high-performance MHP based thermal and optoelectronic devices.

  1. Ultralow thermal conductivity in all-inorganic halide perovskites.

    Science.gov (United States)

    Lee, Woochul; Li, Huashan; Wong, Andrew B; Zhang, Dandan; Lai, Minliang; Yu, Yi; Kong, Qiao; Lin, Elbert; Urban, Jeffrey J; Grossman, Jeffrey C; Yang, Peidong

    2017-08-15

    Controlling the flow of thermal energy is crucial to numerous applications ranging from microelectronic devices to energy storage and energy conversion devices. Here, we report ultralow lattice thermal conductivities of solution-synthesized, single-crystalline all-inorganic halide perovskite nanowires composed of CsPbI 3 (0.45 ± 0.05 W·m -1 ·K -1 ), CsPbBr 3 (0.42 ± 0.04 W·m -1 ·K -1 ), and CsSnI 3 (0.38 ± 0.04 W·m -1 ·K -1 ). We attribute this ultralow thermal conductivity to the cluster rattling mechanism, wherein strong optical-acoustic phonon scatterings are driven by a mixture of 0D/1D/2D collective motions. Remarkably, CsSnI 3 possesses a rare combination of ultralow thermal conductivity, high electrical conductivity (282 S·cm -1 ), and high hole mobility (394 cm 2 ·V -1 ·s -1 ). The unique thermal transport properties in all-inorganic halide perovskites hold promise for diverse applications such as phononic and thermoelectric devices. Furthermore, the insights obtained from this work suggest an opportunity to discover low thermal conductivity materials among unexplored inorganic crystals beyond caged and layered structures.

  2. Sodium-metal halide and sodium-air batteries.

    Science.gov (United States)

    Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

    2014-07-21

    Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Kim, Jong Sung; Shea, Patrick J.; Yang, Jae E.; Kim, Jang-Eok

    2007-01-01

    Zerovalent iron (Fe 0 , 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 Fe 0 (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

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

    International Nuclear Information System (INIS)

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

    2008-01-01

    In this study a total of 186 complex halide systems were collected; the formabilities of ABX 3 (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-MnF 2 ) without perovskite structure and six systems (RbF-PbF 2 , CsF- BeF 2 , KCl-FeCl 2 , TlI-MnI 2 , RbI-SnI 2 , TlI-PbI 2 ) 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 ABX 3 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 ABO 3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. (orig.)

  5. Refined global methyl halide budgets with respect to rapeseed (Brassica napus) by life-cycle measurements

    Science.gov (United States)

    Jiao, Y.; Acdan, J.; Xu, R.; Deventer, M. J.; Rhew, R. C.

    2017-12-01

    A precise quantification of global methyl halide budgets is needed to evaluate the ozone depletion potential of these compounds and to predict future changes of stratospheric ozone. However, the global budgets of methyl halides are not balanced between currently identified and quantified sources and sinks. Our study re-evaluated the methyl bromide budget from global cultivated rapeseed (Brassica napus) through life-cycle flux measurements both in the greenhouse and in the field, yielding a methyl bromide emission rate that scales globally to 1.0 - 1.2 Gg yr-1. While this indicates a globally significant source, it is much smaller than the previously widely cited value of 5 - 6 Gg yr-1(Mead et al., 2008), even taking into account the near tripling of annual global yield of rapeseed since the previous evaluation was conducted. Our study also evaluated the methyl chloride and methyl iodide emission levels from rapeseed, yielding emission rates that scale to 5.4 Gg yr-1 for methyl chloride and 1.8 Gg yr-1 of methyl iodide. The concentrations of the methyl donor SAM (S-adenosyl methionine) and the resultant product SAH (S-Adenosyl-L-homocysteine) were also analyzed to explore their role in biogenic methyl halide formation. Halide gradient incubations showed that the magnitude of methyl halide emissions from rapeseed is highly correlated to soil halide levels, thus raising the concern that the heterogeneity of soil halide contents geographically should be considered when extrapolating to global budget.

  6. Temperature and concentration dependences of the electrical resistivity for alloys of plutonium with americium under normal conditions

    Science.gov (United States)

    Tsiovkin, Yu. Yu.; Povzner, A. A.; Tsiovkina, L. Yu.; Dremov, V. V.; Kabirova, L. R.; Dyachenko, A. A.; Bystrushkin, V. B.; Ryabukhina, M. V.; Lukoyanov, A. V.; Shorikov, A. O.

    2010-01-01

    The temperature and concentration dependences of the electrical resistivity for alloys of americium with plutonium are analyzed in terms of the multiband conductivity model for binary disordered substitution-type alloys. For the case of high temperatures ( T > ΘD, ΘD is the Debye temperature), a system of self-consistent equations of the coherent potential approximation has been derived for the scattering of conduction electrons by impurities and phonons without any constraints on the interaction intensity. The definitions of the shift and broadening operator for a single-electron level are used to show qualitatively and quantitatively that the pattern of the temperature dependence of the electrical resistivity for alloys is determined by the balance between the coherent and incoherent contributions to the electron-phonon scattering and that the interference conduction electron scattering mechanism can be the main cause of the negative temperature coefficient of resistivity observed in some alloys involving actinides. It is shown that the great values of the observed resistivity may be attributable to interband transitions of charge carriers and renormalization of their effective mass through strong s-d band hybridization. The concentration and temperature dependences of the resistivity for alloys of plutonium and americium calculated in terms of the derived conductivity model are compared with the available experimental data.

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

    International Nuclear Information System (INIS)

    Taylor, D.M.

    1988-01-01

    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

  8. 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.

  9. Electrochemical mechanism of silver nanoprisms transformation in aqueous solutions containing the halide ions

    Science.gov (United States)

    Abkhalimov, E. V.; Timofeev, A. A.; Ershov, B. G.

    2018-02-01

    The transformation process of 20-50 nm silver nanoprisms in the presence of Cl-, Br-, and I- ions was studied. The threshold concentrations of halide ions that initiate the transformation do not depend on the size of nanoprisms. It was shown that the structure change is caused by the formation of poorly soluble silver complexes on nanoprisms and occurs by an electrochemical mechanism. The induction period preceding the onset of shape transformation is related to the formation of silver halide nanoelectrodes. The electrochemical reactions involving silver and silver halide nanoelectrodes induce restructuring of silver particles the efficiency of which is determined by electrode potentials. [Figure not available: see fulltext.

  10. 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).

  11. Feshbach resonances associated with Rydberg states of the hydrogen halides

    International Nuclear Information System (INIS)

    Spence, D.; Noguchi, T.

    1975-01-01

    Using an electron transmission spectrometer we locate Feshbach resonances in the hydrogen halides HF, HCl, HBr, and HI. These resonances consist of two Rydberg electrons bound to a positive ion core grandparent state. By analysis of previously published data, we determine the electron configurations of resonances observed in the isoelectronic rare gases and hence deduce the electron configurations of the resonances observed in HCl, HBr, and HI. We find that most of the observed resonances whose grandparent positive ion states have term value X 2 Pi are associated with Rydberg parent states of symmetry X 2 Pinssigma, X 2 Pinpsigma, and X 2 Pindlambda. In HF, only one resonance series, associated with the X 2 Pi3ssigma 1 , 3 Pi Rydberg state is observed

  12. The Effect of Radiation "Memory" in Alkali-Halide Crystals

    Science.gov (United States)

    Korovkin, M. V.; Sal'nikov, V. N.

    2017-01-01

    The exposure of the alkali-halide crystals to ionizing radiation leads to the destruction of their structure, the emergence of radiation defects, and the formation of the electron and hole color centers. Destruction of the color centers upon heating is accompanied by the crystal bleaching, luminescence, and radio-frequency electromagnetic emission (REME). After complete thermal bleaching of the crystal, radiation defects are not completely annealed, as the electrons and holes released from the color centers by heating leave charged and locally uncompensated defects. Clusters of these "pre centers" lead to electric microheterogeneity of the crystal, the formation of a quasi-electret state, and the emergence of micro-discharges accompanied by radio emission. The generation of REME associated with residual defectiveness, is a manifestation of the effect of radiation "memory" in dielectrics.

  13. Charged-soft-sphere potentials for trivalent metal halides

    International Nuclear Information System (INIS)

    Erbolukbas, A.; Akdeniz, Z.; Tosi, M.P.

    1991-09-01

    Octahedral-type coordination by halogens in the liquid state has been reported for a number of trivalent metal ions from diffraction and Raman scattering experiments on their molten trihalides and from Raman scattering spectroscopy of liquid mixtures of trihalides with alkali halides. We analyze the available data on bond lengths and Raman frequencies by treating an isolated (MX 6 ) 3- species within a model which adopts charged-soft-sphere interionic potentials supplemented by an account of ionic polarization. The trivalent metal ions that we consider are M = La, Ce, Pr, Nd, Sm, Gd, Dy and Y for X = Cl and M = Al for X = F. The main result of the analysis is the prediction of trends in the soft-sphere repulsive parameters for the trivalent metal ions, leading to estimates of all the vibrational frequencies and the binding energy of such octahedral species. (author). 26 refs, 1 fig., 4 tabs

  14. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals

    Science.gov (United States)

    Kovalenko, Maksym V.; Protesescu, Loredana; Bodnarchuk, Maryna I.

    2017-11-01

    Semiconducting lead halide perovskites (LHPs) have not only become prominent thin-film absorber materials in photovoltaics but have also proven to be disruptive in the field of colloidal semiconductor nanocrystals (NCs). The most important feature of LHP NCs is their so-called defect-tolerance—the apparently benign nature of structural defects, highly abundant in these compounds, with respect to optical and electronic properties. Here, we review the important differences that exist in the chemistry and physics of LHP NCs as compared with more conventional, tetrahedrally bonded, elemental, and binary semiconductor NCs (such as silicon, germanium, cadmium selenide, gallium arsenide, and indium phosphide). We survey the prospects of LHP NCs for optoelectronic applications such as in television displays, light-emitting devices, and solar cells, emphasizing the practical hurdles that remain to be overcome.

  15. White-Light Emission from Layered Halide Perovskites.

    Science.gov (United States)

    Smith, Matthew D; Karunadasa, Hemamala I

    2018-03-20

    With nearly 20% of global electricity consumed by lighting, more efficient illumination sources can enable massive energy savings. However, effectively creating the high-quality white light required for indoor illumination remains a challenge. To accurately represent color, the illumination source must provide photons with all the energies visible to our eye. Such a broad emission is difficult to achieve from a single material. In commercial white-light sources, one or more light-emitting diodes, coated by one or more phosphors, yield a combined emission that appears white. However, combining emitters leads to changes in the emission color over time due to the unequal degradation rates of the emitters and efficiency losses due to overlapping absorption and emission energies of the different components. A single material that emits broadband white light (a continuous emission spanning 400-700 nm) would obviate these problems. In 2014, we described broadband white-light emission upon near-UV excitation from three new layered perovskites. To date, nine white-light-emitting perovskites have been reported by us and others, making this a burgeoning field of study. This Account outlines our work on understanding how a bulk material, with no obvious emissive sites, can emit every color of the visible spectrum. Although the initial discoveries were fortuitous, our understanding of the emission mechanism and identification of structural parameters that correlate with the broad emission have now positioned us to design white-light emitters. Layered hybrid halide perovskites feature anionic layers of corner-sharing metal-halide octahedra partitioned by organic cations. The narrow, room-temperature photoluminescence of lead-halide perovskites has been studied for several decades, and attributed to the radiative recombination of free excitons (excited electron-hole pairs). We proposed that the broad white emission we observed primarily stems from exciton self-trapping. Here, the

  16. Recent progress in efficient hybrid lead halide perovskite solar cells.

    Science.gov (United States)

    Cui, Jin; Yuan, Huailiang; Li, Junpeng; Xu, Xiaobao; Shen, Yan; Lin, Hong; Wang, Mingkui

    2015-06-01

    The efficiency of perovskite solar cells (PSCs) has been improved from 9.7 to 19.3%, with the highest value of 20.1% achieved in 2014. Such a high photovoltaic performance can be attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths of the hybrid lead halide perovskite materials. In this review, some fundamental details of hybrid lead iodide perovskite materials, various fabrication techniques and device structures are described, aiming for a better understanding of these materials and thus highly efficient PSC devices. In addition, some advantages and open issues are discussed here to outline the prospects and challenges of using perovskites in commercial photovoltaic devices.

  17. Water-Induced Dimensionality Reduction in Metal-Halide Perovskites

    KAUST Repository

    Turedi, Bekir

    2018-03-30

    Metal-halide perovskite materials are highly attractive materials for optoelectronic applications. However, the instability of perovskite materials caused by moisture and heat-induced degradation impairs future prospects of using these materials. Here we employ water to directly transform films of the three-dimensional (3D) perovskite CsPbBr3 to stable two-dimensional (2D) perovskite-related CsPb2Br5. A sequential dissolution-recrystallization process governs this water induced transformation under PbBr2 rich condition. We find that these post-synthesized 2D perovskite-related material films exhibit excellent stability against humidity and high photoluminescence quantum yield. We believe that our results provide a new synthetic method to generate stable 2D perovskite-related materials that could be applicable for light emitting device applications.

  18. Vacuum-Deposited Organometallic Halide Perovskite Light-Emitting Devices.

    Science.gov (United States)

    Chiang, Kai-Ming; Hsu, Bo-Wei; Chang, Yi-An; Yang, Lin; Tsai, Wei-Lun; Lin, Hao-Wu

    2017-11-22

    In this work, a sequential vacuum deposition process of bright, highly crystalline, and smooth methylammonium lead bromide and phenethylammonium lead bromide perovskite thin films are investigated and the first vacuum-deposited organometallic halide perovskite light-emitting devices (PeLEDs) are demonstrated. Exceptionally low refractive indices and extinction coefficients in the emission wavelength range are obtained for these films, which contributed to a high light out-coupling efficiency of the PeLEDs. By utilizing these perovskite thin films as emission layers, the vacuum-deposited PeLEDs exhibit a very narrow saturated green electroluminescence at 531 nm, with a spectral full width at half-maximum bandwidth of 18.6 nm, a promising brightness of up to 6200 cd/m 2 , a current efficiency of 1.3 cd/A, and an external quantum efficiency of 0.36%.

  19. The photoluminescence of crystallophosphors on the base of NaBi(WO4)2 activated by americium, plutonium and neptunium

    International Nuclear Information System (INIS)

    Gliva, V.R.; Novikov, Yu.P.; Myasoedov, B.F.

    1989-01-01

    The luminescence properties of crystallophosphors based on NaBi(WO 4 ) 2 activated by americium, plutonium and neptunium were studied. The synthesis of crystallophosphors is described. Crystallophosphors luminesce in the near infrared region. The excitation and luminescence spectra of crystallophosphors are considered. The dependence of luminescence yield is linear in the wide interval of activator concentration. (author) 3 refs.; 4 figs

  20. 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.

  1. 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.

  2. Lightweight and Flexible Metal Halide Perovskite Thin Films for High Temperature Solar Cells

    Data.gov (United States)

    National Aeronautics and Space Administration — The goal of this project is to develop metal halide perovskites (MHPs) based solar cells for high temperature operation. MHPs have been recently discovered as high...

  3. Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

    Energy Technology Data Exchange (ETDEWEB)

    Martinson, Alex B.; Kim, In Soo

    2017-09-26

    A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film. The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.

  4. Growth and Characterization of PDMS-Stamped Halide Perovskite Single Microcrystals

    NARCIS (Netherlands)

    Khoram, P.; Brittman, S.; Dzik, W.I.; Reek, J.N.H.; Garneett, E.C.

    2016-01-01

    Recently, halide perovskites have attracted considerable attention for optoelectronic applications, but further progress in this field requires a thorough understanding of the fundamental properties of these materials. Studying perovskites in their single-crystalline form provides a model system for

  5. Peculiar Behavior of (U,Am)O(2-δ) Compounds for High Americium Contents Evidenced by XRD, XAS, and Raman Spectroscopy.

    Science.gov (United States)

    Lebreton, Florent; Horlait, Denis; Caraballo, Richard; Martin, Philippe M; Scheinost, Andreas C; Rossberg, Andre; Jégou, Christophe; Delahaye, Thibaud

    2015-10-19

    In U(1-x)Am(x)O(2±δ) compounds with low americium content (x ≤ 20 atom %) and oxygen-to-metal (O/M) ratios close to 2.0, Am(III+) cations are charge-balanced by an equivalent amount of U(V+) cations while the fluorite structure of pure U(IV+)O2 is maintained. Up to now, it is unknown whether this observation also holds for higher americium contents. In this study, we combined X-ray diffraction with Raman and X-ray absorption spectroscopies to investigate a U(0.5)Am(0.5)O(2±δ) compound. Our results indicate that americium is again only present as Am(III+), while U(V+) remains below the amount required for charge balance. Unlike lower americium contents, this leads to an overall oxygen hypostoichiometry with an average O/M ratio of 1.92(2). The cationic sublattice is only slightly affected by the coexistence of large amounts of reduced (Am(III+)) and oxidized (U(V+)) cations, whereas significant deviations from the fluorite structure are evidenced by both extended X-ray absorption fine structure and Raman spectroscopies in the oxygen sublattice, with the observation of both vacancies and interstitials, the latter being apparently consistent with the insertion of U6O12 cuboctahedral-type clusters (as observed in the U4O9 or U3O7 phases). These results thus highlight the specificities of uranium-americium mixed oxides, which behave more like trivalent lanthanide-doped UO2 than U(1-x)Pu(x)O(2±δ) MOX fuels.

  6. On-line separation of volatile fission products by thermochromatography: Comparison of halide systems

    International Nuclear Information System (INIS)

    Hickmann, U.; Greulich, N.; Trautmann, N.; Herrmann, G.

    1993-01-01

    The volatilization and deposition of fission product fluorides, bromides, iodides and of complexes with aluminum trichloride were investigated with an on-line system. The activity was transported by a gas jet from the target area to a quartz-powder column. Volatile halides were generated with various reagents at the entrance into the column and deposited along the column in a descending temperature gradient. Adsorption enthalpies for some fission product halides on quartz surfaces were derived. (orig.)

  7. Electro-optic response of metal halide : A first-principles study

    Indian Academy of Sciences (India)

    Amreen Bano

    2017-07-08

    Jul 8, 2017 ... A theoretical study of electronic and optical properties of metal-halide cubic perovskite, CsPbI3, ... In the case of conductors, the ... To the best of our knowledge, no attempts have been made to study the optical properties of cubic CsPbI3. In this paper, we assess the properties of halide perovskite CsPbI3 ...

  8. 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.

  9. 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

  10. Mechanistic Aspects of Aryl-Halide Oxidative Addition, Coordination Chemistry, and Ring-Walking by Palladium.

    Science.gov (United States)

    Zenkina, Olena V; Gidron, Ori; Shimon, Linda J W; Iron, Mark A; van der Boom, Milko E

    2015-11-02

    This contribution describes the reactivity of a zero-valent palladium phosphine complex with substrates that contain both an aryl halide moiety and an unsaturated carbon-carbon bond. Although η(2) -coordination of the metal center to a C=C or C≡C unit is kinetically favored, aryl halide bond activation is favored thermodynamically. These quantitative transformations proceed under mild reaction conditions in solution or in the solid state. Kinetic measurements indicate that formation of η(2) -coordination complexes are not nonproductive side-equilibria, but observable (and in several cases even isolated) intermediates en route to aryl halide bond cleavage. At the same time, DFT calculations show that the reaction with palladium may proceed through a dissociation-oxidative addition mechanism rather than through a haptotropic intramolecular process (i.e., ring walking). Furthermore, the transition state involves coordination of a third phosphine to the palladium center, which is lost during the oxidative addition as the C-halide bond is being broken. Interestingly, selective activation of aryl halides has been demonstrated by adding reactive aryl halides to the η(2) -coordination complexes. The product distribution can be controlled by the concentration of the reactants and/or the presence of excess phosphine. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Self-Organized Superlattice and Phase Coexistence inside Thin Film Organometal Halide Perovskite.

    Science.gov (United States)

    Kim, Tae Woong; Uchida, Satoshi; Matsushita, Tomonori; Cojocaru, Ludmila; Jono, Ryota; Kimura, Kohei; Matsubara, Daiki; Shirai, Manabu; Ito, Katsuji; Matsumoto, Hiroaki; Kondo, Takashi; Segawa, Hiroshi

    2018-02-01

    Organometal halide perovskites have attracted widespread attention as the most favorable prospective material for photovoltaic technology because of their high photoinduced charge separation and carrier transport performance. However, the microstructural aspects within the organometal halide perovskite are still unknown, even though it belongs to a crystal system. Here direct observation of the microstructure of the thin film organometal halide perovskite using transmission electron microscopy is reported. Unlike previous reports claiming each phase of the organometal halide perovskite solely exists at a given temperature range, it is identified that the tetragonal and cubic phases coexist at room temperature, and it is confirmed that superlattices composed of a mixture of tetragonal and cubic phases are self-organized without a compositional change. The organometal halide perovskite self-adjusts the configuration of phases and automatically organizes a buffer layer at boundaries by introducing a superlattice. This report shows the fundamental crystallographic information for the organometal halide perovskite and demonstrates new possibilities as promising materials for various applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Determination of halide impurities in ionic liquids by total reflection X-ray fluorescence spectrometry.

    Science.gov (United States)

    Vander Hoogerstraete, Tom; Jamar, Steven; Wellens, Sil; Binnemans, Koen

    2014-04-15

    The determination and quantification of halide impurities in ionic liquids is highly important because halide ions can significantly influence the chemical and physical properties of ionic liquids. The use of impure ionic liquids in fundamental studies on solvent extraction or catalytic reactions can lead to incorrect experimental data. The detection of halide ions in solution by total reflection X-ray fluorescence (TXRF) has been problematic because volatile hydrogen halide (HX) compounds are formed when the sample is mixed with the acidic metal standard solution. The loss of HX during the drying step of the sample preparation procedure gives imprecise and inaccurate results. A new method based on an alkaline copper standard Cu(NH3)4(NO3)2 is presented for the determination of chloride, bromide, and iodide impurities in ionic liquids. The 1-butyl-3-methylimidazolium ([C4mim]) ionic liquids with the anions acetate ([C4mim][OAc]), nitrate ([C4mim][NO3]), trifluoromethanesulfonate ([C4mim][OTf]), and bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]) were synthesized via a halide-free route and contaminated on purpose with known amounts of [C4mim]Cl, [C4mim]Br, [C4mim]I, or potassium halide salts in order to validate the new method and standard.

  13. Sequential separation method for the determination of Plutonium and Americium in fecal samples

    International Nuclear Information System (INIS)

    Raveendran, Nanda; Rao, D.D.; Yadav, J.R.; Baburajan, A.

    2014-01-01

    The estimation of internal contamination due to Plutonium and Americium of radiation workers of Advanced Fuel Fabrication Facility (AFFF) at Tarapur was carried out by the bioassay (Fecal sample) of the workers. Conventionally the separation of 'Pu' and 'Am' was carried out by alkali fusion followed by the anion exchange separation for Pu and cation exchange separation for Am. This paper deals with an alternative method in which initially the entire ash of the sample added with 236 Pu tracer (3-11 mBq) and 243 Am tracer (2.8-14.5 mBq) was acid leached and Pu was separated by anion exchange as per standard analytical procedure and Am by using TRU resin. In this work the extraction chromatography method using TRU resin procured from Eichrom,U.K. which contains N-N-di isobutyl carbanoyl methyl phosphine oxide (CMPO) as extractant, tri-n-butyl phosphate (TBP) as diluent absorbed on inert polymeric support has been used for the separation of Am from fecal sample. The 8N HNO 3 effluent from Pu separation step was dried and the residue was dissolved in 10 ml 1M Al(NO 3 ) 3 in 3M HNO 3 and pinch of Ascorbic acid was added and loaded on a TRU resin column (dia ∼ 4 mm and height 60 mm) preconditioned with 30 ml 1M Al(NO 3 ) 3 in 3 MHNO 3 . The column was washed with 5 ml 3M HNO 3 and 5 ml 2M HNO 3 . The nitrate concentration was lowered using addition of 10 ml 0.05 M HNO 3 . Am was eluted with 3 ml 9M HCl and 20 ml 2M HCl. The elute was dried and electrodeposited on a SS planchet in NH 4 (SO 4 ) 2 solution at pH 2.2 for two hours. Pu and Am activity estimated by counting in passivated ion implanted planner Silicon detector (PIPS) coupled to 8K channel alpha spectrometer. The sample was counted for duration of 3-4 lacs of seconds. In this study the numbers of samples analyzed are 25. The paper gives detail of analytical recoveries of Pu tracer varies from 55-90 % with a mean of 70% and std. deviation 9.9%. The Am tracer recovery was in the range of 20-89.3% with a mean of

  14. Crystallographic and Spectroscopic Characterization of Americium Complexes Containing the Bis[(phosphino)methyl]pyridine-1-oxide (NOPOPO) Ligand Platform

    Energy Technology Data Exchange (ETDEWEB)

    Corbey, Jordan F. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Rapko, Brian M. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Wang, Zheming [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; McNamara, Bruce K. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Surbella, Robert G. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Pellegrini, Kristi L. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Schwantes, Jon M. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States

    2018-02-06

    Abstract The crystal structures of americium species containing a common multi-functional phosphine oxide ligand, reported for its ability to extract f elements from acidic solutions, namely 2,6-[Ph2P(O)CH2]2C5H3-NO, L, have finally been determined after over three decades of separations studies involving these species and their surrogates. The molecular compounds Am(L)(NO3)3, Am 1:1, and [Am(L)2(NO3)][NO3]2, Am 2:1, along with their neodymium and europium analogs were synthesized and characterized using single-crystal X-ray crystallography, attenuated total reflectance Fourier transform infrared (ATR) spectroscopy and luminescence spectroscopy to provide a comprehensive comparison with new and known analogous complexes.

  15. Moessbauer spectroscopy of 237Np created by α-decay of 241Am in some compounds of americium

    International Nuclear Information System (INIS)

    Rebizant, Jean.

    1977-01-01

    The Moessbauer emission spectra of 237 Np impurities fed by α decay of 241 Am were measured in the following compounds: Am metal, AmPtsub(x) (x=1, 3, 5), AmAs, AmBi, Am 2 O 3 , AmO 2 , Lisub(x)AmOsub(x+1) (x=1, 2, 3, 4) and Li 6 AmO 6 . The studies concerned the consequences of the recoil and ionization effects, associated with the α-decay of 241 Am in the solid phase; these are analysed in situ and on a time scale of about 100 ns after the α emission; the dependence of these effects on the physico-chemical nature of the host and on the temperature; information about the electronic, magnetic and structural properties and, also, about the vibrational properties of the Np impurity in the investigated solid matrice as far as the previous effects do not hamper such conclusions. The existence itself of the Moessbauer effect shows that the Np ions are stabilized in well-defined lattice locations at the time of emission of the 59.5keV γ quanta (approximately 100ns), once this level is reached after the 241 Am decay. In Am metal and AmPtsub(x) alloys, the observation of a single charge state for neptunium indicates that the electronic effects associated with the α-decay are recovered in less than 100ns. In the americium oxide compounds and the monopnictides AmAs and AmBi, several charge states of neptunium recoil ions are observed; this shows unambiguously the importance of the ionization effects caused by the α-decay. Some informations about magnetic and electronic properties of the americium host matrices were obtained. The vibration modes of 237 Np impurities in the lattice of Am metal are described by means of the Debye model with a characteristic temperature thetasub(D)=115K [fr

  16. Separation of americium by liquid-liquid extraction using diglycol-amides water-soluble complexing agents

    Energy Technology Data Exchange (ETDEWEB)

    Chapron, S.; Marie, C.; Pacary, V.; Duchesne, M.T.; Miguirditchian, M. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Processses Departement, 30207 Bagnols-sur-Ceze (France); Arrachart, G.; Pellet-Rostaing, S. [Institut de Chimie Separative de Marcoule, LTSM, Bat 426, F-30207 Bagnols-sur- Ceze (France)

    2016-07-01

    Recycling americium (Am) alone from spent nuclear fuels is an important option studied for the future nuclear cycle (Generation IV systems) since Am belongs to the main contributors of the long-term radiotoxicity and heat power of final waste. Since 2008, a liquid-liquid extraction process called EXAm has been developed by the CEA to allow the recovery of Am alone from a PUREX raffinate (a dissolution solution already cleared from U, Np and Pu). A mixture of DMDOHEMA (N,N'-dimethyl-N,N'-dioctyl-2-(2-(hexyloxy)ethyl)-malonamide) and HDEHP (di-2-ethylhexylphosphoric acid) in TPH is used as the solvent and the Am/Cm selectivity is improved using TEDGA (N,N,N',N'-tetraethyl-diglycolamide) as a selective complexing agent to maintain Cm and heavier lanthanides in the acidic aqueous phase (5 M HNO{sub 3}). Americium is then stripped selectively from light lanthanides at low acidity (pH=3) with a poly-aminocarboxylic acid. The feasibility of sole Am recovery was already demonstrated during hot tests in ATALANTE facility and the EXAm process was adapted to a concentrated raffinate to optimize the process compactness. The speciation of TEDGA complexes formed in the aqueous phase with Am, Cm and lanthanides was studied to better understand and model the behavior of TEDGA in the process. Some Ln-TEDGA species are extracted into the organic phase and this specific chemistry might play a role in the Am/Cm selectivity improvement. Hence the hydrophilicity-lipophilicity balance of the complexing agent is an important parameter. In this comprehensive study, new analogues of TEDGA were synthesized and tested in the EXAm process conditions to understand the relationship between their structure and selectivity. New derivatives of TEDGA with different N-alkyl chain lengths and ramifications were synthesized. The impact of lipophilicity on ligand partitioning and Am/Cm selectivity was investigated. (authors)

  17. Magnetic properties of nickel halide hydrates including deuteration effects

    Energy Technology Data Exchange (ETDEWEB)

    DeFotis, G.C., E-mail: gxdefo@wm.edu [Chemistry Department, College of William & Mary, Williamsburg, VA, 23187 United States (United States); Van Dongen, M.J.; Hampton, A.S.; Komatsu, C.H.; Trowell, K.T.; Havas, K.C.; Davis, C.M.; DeSanto, C.L. [Chemistry Department, College of William & Mary, Williamsburg, VA, 23187 United States (United States); Hays, K.; Wagner, M.J. [Chemistry Department, George Washington University, Washington, DC, 20052 United States (United States)

    2017-01-01

    Magnetic measurements on variously hydrated nickel chlorides and bromides, including deuterated forms, are reported. Results include locations and sizes of susceptibility maxima, T{sub max} and χ{sub max}, ordering temperatures T{sub c}, Curie constants and Weiss theta in the paramagnetic regime, and primary and secondary exchange interactions from analysis of low temperature data. For the latter a 2D Heisenberg model augmented by interlayer exchange in a mean-field approximation is applied. Magnetization data to 16 kG as a function of temperature show curvature and hysteresis characteristics quite system dependent. For four materials high field magnetization data to 70 kG at 2.00 K are also obtained. Comparison is made with theoretical relations for spin-1 models. Trends are apparent, primarily that T{sub max} of each bromide hydrate is less than for the corresponding chloride, and that for a given halide nD{sub 2}O (n=1 or 2) deuterates exhibit lesser T{sub max} than do nH{sub 2}O hydrates. A monoclinic unit cell determined from powder X-ray diffraction data on NiBr{sub 2}·2D{sub 2}O is different from and slightly larger than that of NiBr{sub 2}·2H{sub 2}O. This provides some rationale for the difference in magnetic properties between these. - Highlights: • The magnetism of Ni(II) chloride and bromide dihydrates and monohydrates is studied. • Effects of replacing H{sub 2}O by D{sub 2}O are examined for both hydration states and both halides. • Exchange interactions in bromides are weaker than in corresponding chlorides. • Exchange interactions are weaker in D{sub 2}O than in corresponding H{sub 2}O containing systems. • The unit cell of NiBr{sub 2}·2D{sub 2}O is different from and slightly larger than that of NiBr{sub 2}·2H{sub 2}O.

  18. Isotope effects in aqueous solvation of simple halides

    Science.gov (United States)

    Videla, Pablo E.; Rossky, Peter J.; Laria, D.

    2018-03-01

    We present a path-integral-molecular-dynamics study of the thermodynamic stabilities of DOH⋯ X- and HOD⋯ X- (X = F, Cl, Br, I) coordination in aqueous solutions at ambient conditions. In agreement with experimental evidence, our results for the F- case reveal a clear stabilization of the latter motif, whereas, in the rest of the halogen series, the former articulation prevails. The DOH⋯ X- preference becomes more marked the larger the size of the ionic solute. A physical interpretation of these tendencies is provided in terms of an analysis of the global quantum kinetic energies of the light atoms and their geometrical decomposition. The stabilization of the alternative ionic coordination geometries is the result of a delicate balance arising from quantum spatial dispersions along parallel and perpendicular directions with respect to the relevant O-H⋯X- axis, as the strength of the water-halide H-bond varies. This interpretation is corroborated by a complementary analysis performed on the different spectroscopic signals of the corresponding IR spectra.

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

    International Nuclear Information System (INIS)

    Selles, O.

    2006-12-01

    This work is dedicated to two recently discovered scintillating crystals: cerium doped lanthanum halides (LaCl 3 :Ce 3+ and LaBr 3 :Ce 3+ ).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 Ce 3+ 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)

  20. Two dimensional condensation of argon adsorbed on lamellar halides

    International Nuclear Information System (INIS)

    Millot, Francis.

    1976-03-01

    Lamellar halides such as NiCl 2 , FeCl 2 , NiBr 2 , MnBr 2 , MgBr 2 , CdBr 2 , CoI 2 , FeI 2 , MnI 2 , CaI 2 and PbI 2 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 [fr

  1. Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites.

    Science.gov (United States)

    Rahimnejad, Sara; Kovalenko, Alexander; Forés, Sergio Martí; Aranda, Clara; Guerrero, Antonio

    2016-09-19

    We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS5 (+) , PbI2 S4, PbI3 S3 (-) , PbI4 S2 (2-) , PbI5 S2 (3-) , PbI6 (4-) and 1D (Pb2 I4 )n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI6 (-) . We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  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. Methyl Halide Emissions From Experimental Fires With Southern African Biofuels

    Science.gov (United States)

    Lobert, J. M.; Lobert, J. M.; Keene, W. C.; Crutzen, P. J.; Scharffe, D. H.; Maben, J. R.; Williams, J.

    2001-12-01

    Under the auspices of SAFARI 2000, biofuels (savanna grasses, shrubs, woody plants, litter, agricultural waste, and charcoal) were sampled in the savannah of Kruger National Park, the Kalahari of Etosha National Park and the Miombo woodlands in Zambia and Malawi. More than 50 sub-samples were burned in 60 experiments under semi-controlled conditions at the biomass burning facility of the Max Planck Institute for Chemistry in Mainz, Germany. Emissions were sampled with flasks and analyzed by GC-MS for gaseous CH3Br, CH3Cl, CH3I and other halogenated compounds. The elemental compositions of the fuel and ash from each burn were also measured. Molar emission ratios of these compounds relative to CO, CO2 and the elemental composition of the fuel as well as partial mass balances for carbon, nitrogen and halogens will be presented with emphasis on methyl halide emissions. These results will be compared to similar data in the literature and preliminary estimates for the impacts of biomass burning on regional and global budgets will be presented. Additional resources can be found at: http://jurgenlobert.org/projects/mpi_safari/ and http://safari.gecp.virginia.edu/

  4. Strong Carrier–Phonon Coupling in Lead Halide Perovskite Nanocrystals

    Science.gov (United States)

    2017-01-01

    We highlight the importance of carrier–phonon coupling in inorganic lead halide perovskite nanocrystals. The low-temperature photoluminescence (PL) spectrum of CsPbBr3 has been investigated under a nonresonant and a nonstandard, quasi-resonant excitation scheme, and phonon replicas of the main PL band have been identified as due to the Fröhlich interaction. The energy of longitudinal optical (LO) phonons has been determined from the separation of the zero phonon band and phonon replicas. We reason that the observed LO phonon coupling can only be related to an orthorhombically distorted crystal structure of the perovskite nanocrystals. Additionally, the strength of carrier–phonon coupling has been characterized using the ratio between the intensities of the first phonon replica and the zero-phonon band. PL emission from localized versus delocalized carriers has been identified as the source of the observed discrepancies between the LO phonon energy and phonon coupling strength under quasi-resonant and nonresonant excitation conditions, respectively. PMID:29019652

  5. Thermodynamic origin of instability in hybrid halide perovskites

    Science.gov (United States)

    Tenuta, E.; Zheng, C.; Rubel, O.

    2016-11-01

    Degradation of hybrid halide perovskites under the influence of environmental factors impairs future prospects of using these materials as absorbers in solar cells. First principle calculations can be used as a guideline in search of new materials, provided we can rely on their predictive capabilities. We show that the instability of perovskites can be captured using ab initio total energy calculations for reactants and products augmented with additional thermodynamic data to account for finite temperature effects. Calculations suggest that the instability of CH3NH3PbI3 in moist environment is linked to the aqueous solubility of the CH3NH3I salt, thus making other perovskite materials with soluble decomposition products prone to degradation. Properties of NH3OHPbI3, NH3NH2PbI3, PH4PbI3, SbH4PbI3, CsPbBr3, and a new hypothetical SF3PbI3 perovskite are studied in the search for alternative solar cell absorber materials with enhanced chemical stability.

  6. A new fundamental hydrogen defect in alkali halides

    International Nuclear Information System (INIS)

    Morato, S.P.; Luety, F.

    1978-01-01

    Atom hydrogen in neutral (H 0 ) and negative (H - ) form on substitutional and interstitial lattice sites gives rise to well characterized model defects in alkali-halides (U,U 1 ,U 2 ,U 3 centers), which have been extensively investigated in the past. When studying the photo-decomposition of OH - defects, a new configuration of atomic charged hidrogen was discovered, which can be produced in large quantities in the crystal and is apparently not connected to any other impurity. This new hidrogen defect does not show any pronounced electronic absorption, but displays a single sharp local mode band (at 1114cm -1 in KCl) with a perfect isotope shift. The defect can be produced by various UV or X-ray techniques in crystais doped with OH - , Sh - or H - defects. A detailed study of its formation kinetics at low temperature shows that it is primarily formed by the reaction of a mobile CI 2 - crowdion (H-center) with hidrogen defects [pt

  7. Exploring Anomalous Polarization Dynamics in Organometallic Halide Perovskites.

    Science.gov (United States)

    Ahmadi, Mahshid; Collins, Liam; Puretzky, Alexander; Zhang, Jia; Keum, Jong Kahk; Lu, Wei; Ivanov, Ilia; Kalinin, Sergei V; Hu, Bin

    2018-03-01

    Organometallic halide perovskites (OMHPs) have attracted broad attention as prospective materials for optoelectronic applications. Among the many anomalous properties of these materials, of special interest are the ferroelectric properties including both classical and relaxor-like components, as a potential origin of slow dynamics, field enhancement, and anomalous mobilities. Here, ferroelectric properties of the three representative OMHPs are explored, including FAPb x Sn 1- x I 3 (x = 0, x = 0.85) and FA 0.85 MA 0.15 PbI 3 using band excitation piezoresponse force microscopy and contact mode Kelvin probe force microscopy, providing insight into long- and short-range dipole and charge dynamics in these materials and probing ferroelectric density of states. Furthermore, second-harmonic generation in thin films of OMHPs is observed, providing a direct information on the noncentrosymmetric polarization in such materials. Overall, the data provide strong evidence for the presence of ferroelectric domains in these systems; however, the domain dynamics is suppressed by fast ion dynamics. These materials hence present the limit of ferroelectric materials with spontaneous polarization dynamically screened by ionic and electronic carriers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Inspection report of unauthorized possession and use of unsealed americium-241 and subsequent confiscation, J.C. Haynes Company, Newark, Ohio

    International Nuclear Information System (INIS)

    1985-11-01

    This US Nuclear Regulatory Commission report documents the circumstances surrounding the March 26, 1985, confiscation and subsequent decontamination activities related to the use of unauthorized quantities of americium-241 at the John C. Haynes Company (licensee) of Newark, Ohio. It focuses on the period from early February to July 26, 1985. The incident started when NRC Region III recieved information that John C. Haynes possessed unauthorized quantities of americium-241 and was conducting unauthorized activities (diamond irradiation). By July 26, 1985, the decontamination activities at the licensee's laboratory were concluded. The licensee's actions with diamond irradiation resulted in contamination in restricted and unrestricted areas of the facility. The confiscation and decontamination activities required the combined efforts of NRC, Federal Bureau of Investigation, US Department of Energy, Oak Ridge Associated Universities, the State of Ohio, and the US Environmental Protection Agency. The report describes the factual information and significant findings associated with the confiscation and decontamination activities

  9. Intrinsic Halide Segregation at Nanometer Scale Determines the High Efficiency of Mixed Cation/Mixed Halide Perovskite Solar Cells.

    Science.gov (United States)

    Gratia, Paul; Grancini, Giulia; Audinot, Jean-Nicolas; Jeanbourquin, Xavier; Mosconi, Edoardo; Zimmermann, Iwan; Dowsett, David; Lee, Yonghui; Grätzel, Michael; De Angelis, Filippo; Sivula, Kevin; Wirtz, Tom; Nazeeruddin, Mohammad Khaja

    2016-12-14

    Compositional engineering of a mixed cation/mixed halide perovskite in the form of (FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 is one of the most effective strategies to obtain record-efficiency perovskite solar cells. However, the perovskite self-organization upon crystallization and the final elemental distribution, which are paramount for device optimization, are still poorly understood. Here we map the nanoscale charge carrier and elemental distribution of mixed perovskite films yielding 20% efficient devices. Combining a novel in-house-developed high-resolution helium ion microscope coupled with a secondary ion mass spectrometer (HIM-SIMS) with Kelvin probe force microscopy (KPFM), we demonstrate that part of the mixed perovskite film intrinsically segregates into iodide-rich perovskite nanodomains on a length scale of up to a few hundred nanometers. Thus, the homogeneity of the film is disrupted, leading to a variation in the optical properties at the micrometer scale. Our results provide unprecedented understanding of the nanoscale perovskite composition.

  10. The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

    2017-01-05

    Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

  11. Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

    Science.gov (United States)

    Paula, S.; Volkov, A. G.; Deamer, D. W.

    1998-01-01

    Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

  12. Influence of Halide Solutions on Collagen Networks: Measurements of Physical Properties by Atomic Force Microscopy

    Science.gov (United States)

    Kempe, André; Lackner, Maximilian

    2016-01-01

    The influence of aqueous halide solutions on collagen coatings was tested. The effects on resistance against indentation/penetration on adhesion forces were measured by atomic force microscopy (AFM) and the change of Young's modulus of the coating was derived. Comparative measurements over time were conducted with halide solutions of various concentrations. Physical properties of the mesh-like coating generally showed large variability. Starting with a compact set of physical properties, data disperse after minutes. A trend of increase in elasticity and permeability was found for all halide solutions. These changes were largest in NaI, displaying a logical trend with ion size. However a correlation with concentration was not measured. Adhesion properties were found to be independent of mechanical properties. The paper also presents practical experience for AFM measurements of soft tissue under liquids, particularly related to data evaluation. The weakening in physical strength found after exposure to halide solutions may be interpreted as widening of the network structure or change in the chemical properties in part of the collagen fibres (swelling). In order to design customized surface coatings at optimized conditions also for medical applications, halide solutions might be used as agents with little impact on the safety of patients. PMID:27721994

  13. 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)

    Paquet, F.

    1991-12-01

    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

  14. 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)

    Paquet, F.

    1993-01-01

    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

  15. Bright triplet excitons in caesium lead halide perovskites

    Science.gov (United States)

    Becker, Michael A.; Vaxenburg, Roman; Nedelcu, Georgian; Sercel, Peter C.; Shabaev, Andrew; Mehl, Michael J.; Michopoulos, John G.; Lambrakos, Samuel G.; Bernstein, Noam; Lyons, John L.; Stöferle, Thilo; Mahrt, Rainer F.; Kovalenko, Maksym V.; Norris, David J.; Rainò, Gabriele; Efros, Alexander L.

    2018-01-01

    Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund’s rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the ‘dark exciton’. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX3, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin–orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX3 nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

  16. Origins and mechanisms of hysteresis in organometal halide perovskites

    Science.gov (United States)

    Li, Cheng; Guerrero, Antonio; Zhong, Yu; Huettner, Sven

    2017-05-01

    Inorganic-organic halide organometal perovskites, such as CH3NH3PbI3 and CsPbI3, etc, have been an unprecedented rising star in the field of photovoltaics since 2009, owing to their exceptionally high power conversion efficiency and simple fabrication processability. Despite its relatively short history of development, intensive investigations have been concentrating on this material; these have ranged from crystal structure analysis and photophysical characterization to performance optimization and device integration, etc. Yet, when applied in photovoltaic devices, this material suffers from hysteresis, that is, the difference of the current-voltage (I-V) curve during sweeping in two directions (from short-circuit towards open-circuit and vice versa). This behavior may significantly impede its large-scale commercial application. This Review will focus on the recent theoretical and experimental efforts to reveal the origin and mechanism of hysteresis. The proposed origins include (1) ferroelectric polarization, (2) charge trapping/detrapping, and (3) ion migration. Among them, recent evidence consistently supports the idea that ion migration plays a key role for the hysteretic behavior in perovskite solar cells (PSCs). Hence, this Review will summarize the recent results on ion migration such as the migrating ion species, activation energy measurement, capacitive characterization, and internal electrical field modulation, etc. In addition, this Review will also present the devices with alleviation/elimination of hysteresis by incorporating either large-size grains or phenyl-C61-butyric acid methyl ester molecules. In a different application, the hysteretic property has been utilized in photovoltaic and memristive switching devices. In sum, by examining these three possible mechanisms, it is concluded that the origin of hysteresis in PSCs is associated with a combination of effects, but mainly limited by ion/defect migration. This strong interaction between ion

  17. 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.

  18. 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

  19. Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

    DEFF Research Database (Denmark)

    Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

    2017-01-01

    The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group...... in the para position or a cyano group in the ortho position. A range of other substituents gave no conversion of the aryl halide or led to the formation of side products. A broader scope was observed for the Grignard reagents, where a variety of alkyl- and arylmagnesium chlorides participated in the coupling....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

  20. 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.

  1. The Mode of Action of Silver and Silver Halides Nanoparticles against Saccharomyces cerevisiae Cells

    Directory of Open Access Journals (Sweden)

    A. A. Kudrinskiy

    2014-01-01

    Full Text Available Silver and silver halides nanoparticles (NPs (Ag, AgCl, AgBr, and AgI capped with two different stabilizers (sodium citrate and nonionic surfactant Tween 80 were obtained via sodium borohydride reduction of silver nitrate in an aqueous solution. The effect of the biocidal action of as-prepared synthesized materials against yeast cells Saccharomyces cerevisiae was compared to the effect produced by silver nitrate and studied through the measurement of cell loss and kinetics of K+ efflux from the cells depending on concentration of silver. The results clearly indicate that the silver ions either remained in the dispersion of silver NPs and silver halides NPs after their synthesis or were generated afterwards by dissolving silver and silver halides particles playing a major part in the cytotoxic activity of NPs against yeast cells. It was also supposed that this activity most likely does not relate to the damage of cell membrane.

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

    International Nuclear Information System (INIS)

    Wang, Jun; Wang, Yafeng; Hu, Tao; Wu, Lin; Shen, Xuechu; Chen, Zhanghai; Cao, Runan; Xu, Fei; Da, Peimei; Zheng, Gengfeng; Lu, Jian

    2016-01-01

    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

  3. A study on the localized corrosion of cobalt in bicarbonate solutions containing halide ions

    Energy Technology Data Exchange (ETDEWEB)

    Gallant, Danick [Departement de Biologie, Chimie et Sciences de la Sante, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Que., G5L 3A1 (Canada); Departement de Chimie, Universite Laval, Quebec, Que., G1K 7P4 (Canada); Simard, Stephan [Departement de Biologie, Chimie et Sciences de la Sante, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Que., G5L 3A1 (Canada)]. E-mail: stephan_simard@uqar.qc.ca

    2005-07-01

    The localized attack of cobalt in bicarbonate aqueous solutions containing halide ions was investigated using electrochemical techniques, scanning electron microscopy, UV-visible and Raman spectroscopies. Rotating disc and rotating ring-disc electrodes were used to determine the effect of bicarbonate concentration, solution pH, nature and concentration of the halide ions, convection and potential sweep rate on the corrosion processes. These parameters were found to play a key role on the localized attack induced by halide ions by influencing the production of a Co(HCO{sub 3}){sub 2} precipitate on the pit surface. Potentiostatically generated cobalt oxide films (CoO and Co{sub 3}O{sub 4}) were found to be efficient to reduce pitting corrosion of cobalt.

  4. Preliminary results from uranium/americium affinity studies under experimental conditions for cesium removal from NPP ''Kozloduy'' simulated wastes solutions

    International Nuclear Information System (INIS)

    Nikiforova, A.; Kinova, L.; Peneva, C.; Taskaeva, I.; Petrova, P.

    2005-01-01

    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 K ozloduy . 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, H 2 C 2 O 4 , 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

  5. Structures of butyl ions formed by electron impact ionization of isomeric butyl halides and alkanes

    International Nuclear Information System (INIS)

    Shold, D.M.; Ausloos, P.

    1978-01-01

    Using a pulsed ion cyclotron resonance (ICR) spectrometer, it is demonstrated that at pressures of about 10 -6 Torr and at observation times ranging from 10 -3 to 0.5 s, isobutane, neopentane, 2,2-dimethylbutane, isobutyl halides, and tert-butyl halides form C 4 H 9 + ions having the tertiary structure. In n-alkanes, 2-methylbutane, 3-methylpentane, n-butyl halides, and sec-butyl halides, both sec-C 4 H 9 + and t-C 4 H 9 + ions are observed, the sec-C 4 H 9 + ions surviving without rearrangement for at least 0.1 s. However, in the case of the halides, a collision-induced isomerization of the sec-C 4 H 9 + to the t-C 4 H 9 + ions occurs. The efficiency of this process increases with the basicity of the alkyl halide. Radiolysis experiments carried out at atmospheric pressures indicate, in agreement with ICR and solution experiments, that at times as short as 10 -10 s the majority of the i-C 4 H 9 + ions from isobutyl bromide rearrange to the t-C 4 H 9 + structure. On the other hand, in the radiolysis of both n-hexane and 3-methylpentane, the abundance of t-C 4 H 9 + relative to sec-C 4 H 9 + is substantially smaller than that observed in the ICR experiments, and decreases with decreasing collision interval. It is suggested that about 90% of the i-C 4 H 9 + can rearrange to t-C 4 H 9 + by simple 1,2-hydride shift without involving secondary or protonated methylcyclopropane structures as intermediates. 4 figures, 2 tables

  6. 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.

  7. The electronic structure of the F-center in alkali-halides-The Bethe cluster - lattice

    International Nuclear Information System (INIS)

    Queiroz, S.L.A. de.

    1977-07-01

    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) [pt

  8. 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.

  9. A Cluster-Bethe lattice treatment for the F-center in alkali-halides

    International Nuclear Information System (INIS)

    Queiroz, S.L.A. de; Koiller, B.; Maffeo, B.; Brandi, H.S.

    1977-01-01

    The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Cluster-Bethe 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 [pt

  10. The Electrical and Optical Properties of Organometal Halide Perovskites Relevant to Optoelectronic Performance

    KAUST Repository

    Adinolfi, Valerio

    2017-10-12

    Organometal halide perovskites are under intense study for use in optoelectronics. Methylammonium and formamidinium lead iodide show impressive performance as photovoltaic materials; a premise that has spurred investigations into light-emitting devices and photodetectors. Herein, the optical and electrical material properties of organometal halide perovskites are reviewed. An overview is given on how the material composition and morphology are tied to these properties, and how these properties ultimately affect device performance. Material attributes and techniques used to estimate them are analyzed for different perovskite materials, with a particular focus on the bandgap, mobility, diffusion length, carrier lifetime, and trap-state density.

  11. Analytical utility of the M series x-ray emission lines applied to uranium, neptunium, plutonium, and americium

    International Nuclear Information System (INIS)

    Miller, A.G.

    1976-01-01

    Secondary emission x-ray analysis for actinide elements has usually meant utilizing the L series x-ray lines. The major disadvantage of these x-ray lines is that they fall in the region of high level Bremsstrahlung radiation, producing a high background and, subsequently, larger error and high detection limits. The utilization of the M series x-ray lines of actinide elements with wavelength dispersive x-ray spectrometers greatly minimizes these problems. Calibration curves for uranium, neptunium, plutonium, and americium were prepared by the ''coprex'' method, and the analytical characteristics of the L and M series compared. The Mα and β x-ray lines, under optimum conditions, are several times more sensitive than their L series counterparts. With the greater sensitivity in addition to the lower background, peak to background ratios for M lines up to 40 times greater than those for L lines were obtained. Detection limits can be lowered from about 0.7 μg using the Lα 1 line to 0.05 μg when M x-ray lines are used. The relative advantages and disadvantages of utilizing the L and M series x-ray lines for secondary emission x-ray analysis are discussed

  12. Use of radioanalytical methods for determination of uranium, neptunium, plutonium, americium and curium isotopes in radioactive wastes

    International Nuclear Information System (INIS)

    Geraldo, Bianca

    2012-01-01

    Activated charcoal is a common type of radioactive waste that contains high concentrations of fission and activation products. The management of this waste includes its characterization aiming the determination and quantification of the specific radionuclides including those known as Difficult-to-Measure Radionuclides (RDM). The analysis of the RDM's generally involves complex radiochemical analysis for purification and separation of the radionuclides, which are expensive and time-consuming. The objective of this work was to define a methodology for sequential analysis of the isotopes of uranium, neptunium, plutonium, americium and curium present in a type of radioactive waste, evaluating chemical yield, analysis of time spent, amount of secondary waste generated and cost. Three methodologies were compared and validated that employ ion exchange (TI + EC), extraction chromatography (EC) and extraction with polymers (ECP). The waste chosen was the activated charcoal from the purification system of primary circuit water cooling the reactor IEA-R1. The charcoal samples were dissolved by acid digestion followed by purification and separation of isotopes with ion exchange resins, extraction and chromatographic extraction polymers. Isotopes were analyzed on an alpha spectrometer, equipped with surface barrier detectors. The chemical yields were satisfactory for the methods TI + EC and EC. ECP method was comparable with those methods only for uranium. Statistical analysis as well the analysis of time spent, amount of secondary waste generated and cost revealed that EC method is the most effective for identifying and quantifying U, Np, Pu, Am and Cm present in charcoal. (author)

  13. Vertical transport of particulate-associated plutonium and americium in the upper water column of the Northeast Pacific

    International Nuclear Information System (INIS)

    Fowler, S.W.; Ballestra, S.; La Rosa, J.; Fukai, R.

    1983-01-01

    Concentrations of plutonium (Pu) and americium (Am) were determined in seawater, suspended particulate matter, sediment trap samples, and biogenic material collected at the VERTEX I site in the North Pacific off central California. From a vertical profile taken over the upper 1500 m, the presence of sub-surface maxima of sup(239+240)Pu and 241 Am were identified between 100 to 750 m and 250 to 750 m, respectively. A large fraction (32%) of the filterable sup(239+240)Pu in surface waters was associated with cells during a phytoplankton bloom; Pu:Am activity ratios in surface water and the suspended particles indicated that Pu was concentrated by the cells to a greater degree than Am. However, similar measurements beneath the surface layer showed an overall enrichment of Am over Pu on fine suspended particles with depth. Freshly produced zooplankton fecal pellets and large, fast sinking particles collected in PITS contained relatively high concentrations of Pu and Am. Both transuranic concentrations in trapped particles and transuranic flux tended to increase with depth down to 750 m, suggesting that their scavenging is in the upper water column. Am appeared to be scavenged by sinking biogenic particles to a greater extent than Pu. The results are discussed. (author)

  14. Resonance Raman spectra of metal halide vapor complexes

    International Nuclear Information System (INIS)

    Paptheodorou, G.N.

    1978-01-01

    Resonance Raman spectra of complex vapor phase compounds formed by reacting ''acidic'' gases (A 2 X 6 = Al 2 Cl 6 , Al 2 Br 6 , In 2 Cl 6 ) with metal halides have been measured. Spectra obtained from equilibrium vapor mixtures of A 2 X 6 over solid MX 2 (= PdCl 2 , PdBr 2 , CuCl 2 , CoBr 2 , TiCl 2 , FeCl 2 , NiCl 2 , PtCl 2 ) were a superposition of the A 2 X 6 -AX 3 bands and in few cases of new resonance-enhanced polarized bands due to MA 2 X 8 and/or MAX 5 complexes. At temperatures above 800 0 K, characteristic bands due to MX 2 (g) (M = Fe, Co, Ni, Cu, Zn) and M 2 X 4 (g) (M = Cu) were observed. The predominant features of the PdAl 2 Cl 8 , CuAl 2 Cl 8 , and PdAl 2 Br 6 spectra were three high-intensity, polarized bands which were attributed to the vibrational modes of the complex coupled to the electronic state of the central atom. The spectra of CuAlCl 5 (g), CuInCl 5 (g) and Cu 2 Cl 4 (g) species showed resonance enhancement of selective fundamentals which were attributed to vibrational modes of trigonally coordinated Cu(II). Resonance Raman spectra of U 2 Cl 10 (g) and UCl 5 .AlCl 3 (g) were characterized by the presence of a strong band attributed to the U-Cl/sub t/ stretching frequency. Raman band intensity measurements were carried out for the iron(III) chloride vapors and for the vapor complexes of CuAl 2 Cl 8 , CuInCl 5 and UCl 5 .AlCl 3 using different laser powers and frequencies. The measurements suggested increasing spectroscopic temperatures and decomposition of the vapor complexes. The data are discussed in terms of the distribution of vibrational modes and the structure of the vapor species. 22 figs

  15. 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.

  16. Nickel(II) complexes of N2S2 donor set ligand and halide ...

    Indian Academy of Sciences (India)

    Nickel(II) complexes of N2S2 donor set ligand and halide/pseudohalides: Synthesis, crystal structure, DNA and bovine/human serum albumin interaction. ANIMESH PATRAa ..... sitive to the length changes of nucleic acids, and so a classical intercalation mode should be indicated by a lengthening of the DNA double chain, ...

  17. A Solvent-Free Base Liberation of a Tertiary Aminoalkyl Halide by Flow Chemistry

    DEFF Research Database (Denmark)

    Pedersen, Michael Jønch; Skovby, Tommy; Mealy, Michael J.

    2016-01-01

    A flow setup for base liberation of 3-(N,N-dimethylamino)propyl chloride hydrochloride and solvent-free separation of the resulting free base has been developed. Production in flow profits from an on-demand approach, useful for labile aminoalkyl halides. The requirement for obtaining a dry product...

  18. 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...

  19. Amination of Aryl Halides and Esters Using Intensified Continuous Flow Processing.

    Science.gov (United States)

    Kohl, Thomas M; Hornung, Christian H; Tsanaktsidis, John

    2015-09-25

    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.

  20. Electro-optic response of metal halide : A first-principles study

    Indian Academy of Sciences (India)

    Amreen Bano

    2017-07-08

    Jul 8, 2017 ... the optical properties of cubic CsPbI3. In this paper, we assess the properties of halide perovskite CsPbI3 using density functional theory (DFT) for ground-state proper- ties like electronic band structure, and density functional perturbation theory (DFPT) for dielectric and optical response functions. We have ...

  1. Charge-charge liquid structure factor and the freezing of alkali halides

    International Nuclear Information System (INIS)

    March, N.H.; Tosi, M.P.

    1980-10-01

    The peak height of the charge-charge liquid structure factor Ssub(QQ) in molten alkali halides is proposed as a criterion for freezing. Available data on molten alkali chlorides, when extrapolated to the freezing point suggests Ssub(QQ)sup(max) approximately 5. (author)

  2. Synthesis and Spectroscopic studies on cadmium halide complexes of isonicotinic acid

    International Nuclear Information System (INIS)

    Bardak, F.

    2004-01-01

    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

  3. Shape evolution and single particle luminescence of organometal halide perovskite nanocrystals.

    Science.gov (United States)

    Zhu, Feng; Men, Long; Guo, Yijun; Zhu, Qiaochu; Bhattacharjee, Ujjal; Goodwin, Peter M; Petrich, Jacob W; Smith, Emily A; Vela, Javier

    2015-03-24

    Organometallic halide perovskites CH3NH3PbX3 (X = I, Br, Cl) have quickly become one of the most promising semiconductors for solar cells, with photovoltaics made of these materials reaching power conversion efficiencies of near 20%. Improving our ability to harness the full potential of organometal halide perovskites will require more controllable syntheses that permit a detailed understanding of their fundamental chemistry and photophysics. In this manuscript, we systematically synthesize CH3NH3PbX3 (X = I, Br) nanocrystals with different morphologies (dots, rods, plates or sheets) by using different solvents and capping ligands. CH3NH3PbX3 nanowires and nanorods capped with octylammonium halides show relatively higher photoluminescence (PL) quantum yields and long PL lifetimes. CH3NH3PbI3 nanowires monitored at the single particle level show shape-correlated PL emission across whole particles, with little photobleaching observed and very few off periods. This work highlights the potential of low-dimensional organometal halide perovskite semiconductors in constructing new porous and nanostructured solar cell architectures, as well as in applying these materials to other fields such as light-emitting devices and single particle imaging and tracking.

  4. Surface Termination, Morphology and Bright Photoluminescence of Cesium Lead Halide Perovskite Nanocrystals

    NARCIS (Netherlands)

    ten Brinck, Stephanie; Infante, Ivan

    2016-01-01

    Colloidal cesium lead halide perovskite nanocrystals (CsPbX3 PNC, X=Cl, Br, I) exhibit important optoelectronic properties that make them amenable for a plethora of applications. The origin of these properties, even for as-synthesized and unpurified PNCs, is however largely unknown. Electronic

  5. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    Science.gov (United States)

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-02

    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.

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

    Science.gov (United States)

    Cruz-Ramírez de Arellano, Daniel; Towns, Marcy H.

    2014-01-01

    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…

  7. Metal-halide systems: From molecular clusters to liquid-state structure

    Directory of Open Access Journals (Sweden)

    Mario P. Tosi

    2015-03-01

    Full Text Available I present a short review of the relationship between quantum-mechanical calculations on small molecular clusters of some metal-ion halides and studies of the microscopic structure in the condensed liquid phases of these compounds. The review is dedicated to the memory of Professor Vincenzo Grasso.

  8. Luminescent decay and spectra of impurity-activated alkali halides under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Klick, David Ira [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1977-01-01

    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.

  9. A method for de-halogenating a composition containing halides as impurities

    International Nuclear Information System (INIS)

    Grossman, L.N.; Brigham, D.A.

    1974-01-01

    A fast dehalogenation low-temperature method, consisting in heating the halide-containing composition up to a temperature of from 315 deg C to 870 deg C in a de-halogenating atmosphere containing a vaporized alcohol. That method can be applied to the generation of uranium dioxide [fr

  10. Can Ferroelectric Polarization Explain the High Performance of Hybrid Halide Perovskite Solar Cells?

    NARCIS (Netherlands)

    Sherkar, Tejas; Koster, L. Jan Anton

    The power conversion efficiency of photovoltaic cells based on the use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), now exceeds 20%. Recently, it was suggested that this high performance originates from the presence of ferroelectricity in the perovskite, which is hypothesized to lower

  11. Organic Cation Rotation and Immobilization in Pure and Mixed Methylammonium Lead-Halide Perovskites

    NARCIS (Netherlands)

    Selig, Oleg; Sadhanala, Aditya; Muller, Christian; Lovrincic, Robert; Chen, Zhuoying; Rezus, Yves L. A.; Frost, Jarvist M.; Jansen, Thomas L. C.; Bakulin, Artem A.

    2017-01-01

    Three-dimensional lead-halide perovskites have attracted a lot of attention due to their ability to combine solution processing with outstanding optoelectronic properties. Despite their soft ionic nature these materials demonstrate a surprisingly low level of electronic disorder resulting in sharp

  12. 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

  13. Determination of the structural phase and octahedral rotation angle in halide perovskites

    Science.gov (United States)

    dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

    2018-02-01

    A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

  14. Luminescent decay and spectra of impurity-activated alkali halides under high pressure

    International Nuclear Information System (INIS)

    Klick, D.I.

    1977-01-01

    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

  15. Electrochemical specific adsorption of halides on Cu 111, 100, and 211: A Density Functional Theory study

    International Nuclear Information System (INIS)

    McCrum, Ian T.; Akhade, Sneha A.; Janik, Michael J.

    2015-01-01

    The specific adsorption of ions onto electrode surfaces can affect electrocatalytic reactions. Density functional theory is used to investigate the specific adsorption of aqueous F − , Cl − , Br − , and I − onto Cu (111), (100), and (211) surfaces. The adsorption is increasingly favorable in the order of F − < Cl − < Br − < I − . The adsorption has a weak dependence on the surface facet, with adsorption most favorable on Cu (100) and least favorable on Cu (111). Potential ranges where specific adsorption would be expected on each facet are reported. The thermodynamics of bulk copper halide (CuX, CuX 2 ) formation are also investigated as a function of potential. CuX formation occurs at potentials slightly more positive of halide specific adsorption and of copper oxidation in aqueous electrolytes. Specifically adsorbed halides and bulk CuX may be present during a variety of electrochemical reactions carried out over a Cu electrode in halide containing electrolyte solutions

  16. 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...

  17. Thorium valency in molten alkali halides in equilibrium with metallic thorium

    International Nuclear Information System (INIS)

    Smirnov, M.V.; Kudyakov, V.Ya.

    1983-01-01

    Metallic thorium is shown to corrode in molten alkali halides even in the absence of external oxidizing agents, alkali cations acting as oxidizing agents. Its corrosion rate grows in the series of alkali chlorides from LiCl to CsCl at constant temperature. Substituting halide anions for one another exerts a smaller influence, the rate rising slightly in going from chlorides to bromides and iodides, having the same alkali cations. Thorium valency is determined coulometrically, the metal being dissolved anodically in molten alkali halides and their mixtures. In fluoride melts it is equal to 4 but in chloride, bromide and iodide ones, as a rule, it has non-integral values between 4 and 2 which diminish as the temperature is raised, as the thorium concentration is lowered, as the radii of alkali cations decrease and those of halide anions increase. The emf of cells Th/N ThHlsub(n) + (1-N) MHl/MHl/C, Hlsub(2(g)) where Hl is Cl, Br or I, M is Li, Na, K, Cs or Na + K, and N < 0.05, is measured as a function of concentration at several temperatures. Expressions are obtained for its concentration dependence. The emf grows in the series of alkali chlorides from LiCl to CsCl, other conditions being equal. (author)

  18. Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films

    KAUST Repository

    Bretschneider, Simon A.

    2017-05-08

    Photovoltaic devices that employ lead-halide perovskites as photoactive materials exhibit power conversion efficiencies of 22%. One of the potential routes to go beyond the current efficiencies is to extract charge carriers that carry excess energy, that is, nonrelaxed or

  19. Syntheses and characterization of two novel 1D Pb (II) Halide ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 7. Syntheses and characterization of two novel 1D Pb(II) Halide supramolecular polymers possessing incomplete Cubane subunit directed by -conjugated Dication templates. Chengjie Ma Mei Liu Wenli Zhang Haijuan Du Yao Li Chaohai Wang Yunyin ...

  20. Radiation chemistry of hydrocarbon and alkyl halide systems. Progress report, August 1, 1977--August 1, 1978

    International Nuclear Information System (INIS)

    Hanrahan, R.J.

    1978-01-01

    Progress of experimental work is reported on pulse radiolysis of simple alkyl halides in the gas phase, gas phase radiolysis of CHF 3 -CH 3 I mixtures, gamma radiolysis of the system CO/H 2 , and improvements in equipment and facilities

  1. Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning.

    Science.gov (United States)

    Jang, Dong Myung; Park, Kidong; Kim, Duk Hwan; Park, Jeunghee; Shojaei, Fazel; Kang, Hong Seok; Ahn, Jae-Pyung; Lee, Jong Woon; Song, Jae Kyu

    2015-08-12

    In recent years, methylammonium lead halide (MAPbX3, where X = Cl, Br, and I) perovskites have attracted tremendous interest caused by their outstanding photovoltaic performance. Mixed halides have been frequently used as the active layer of solar cells, as a result of their superior physical properties as compared to those of traditionally used pure iodide. Herein, we report a remarkable finding of reversible halide-exchange reactions of MAPbX3, which facilitates the synthesis of a series of mixed halide perovskites. We synthesized MAPbBr3 plate-type nanocrystals (NCs) as a starting material by a novel solution reaction using octylamine as the capping ligand. The synthesis of MAPbBr(3-x)Clx and MAPbBr(3-x)Ix NCs was achieved by the halide exchange reaction of MAPbBr3 with MACl and MAI, respectively, in an isopropyl alcohol solution, demonstrating full-range band gap tuning over a wide range (1.6-3 eV). Moreover, photodetectors were fabricated using these composition-tuned NCs; a strong correlation was observed between the photocurrent and photoluminescence decay time. Among the two mixed halide perovskite series, those with I-rich composition (x = 2), where a sole tetragonal phase exists without the incorporation of a cubic phase, exhibited the highest photoconversion efficiency. To understand the composition-dependent photoconversion efficiency, first-principles density-functional theory calculations were carried out, which predicted many plausible configurations for cubic and tetragonal phase mixed halides.

  2. Halide ordering in reduced mixed halides, chlorides/iodides, of zirconium: syntheses and structures of Cs2[(Zr6B)(Cl,I)15] cluster compounds.

    Science.gov (United States)

    Pigorsch, Arne; Köckerling, Martin

    2012-10-15

    A series of high-temperature solid state chemical reactions was carried out in the quasi-quarternary mixed-halide Cs-Zr-B-(Cl,I) system with stoichiometries aiming for zirconium cluster phases of the Cs(2)[(Zr(6)B)X(15)] type (X = mixture of Cl + I). In the phase range from ~ Cs(2)[(Zr(6)B)Cl(13)I(2)] to Cs(2)[(Zr(6)B)Cl(3)I(12)] the structures of the obtained cluster phases are derived from the orthorhombic CsK[(Zr(6)B)Cl(15)]. At a composition of Cs(2)[(Zr(6)B)Cl(~10) I(~4)] a lower symmetry, monoclinic derivative has been found. X-ray diffraction data of single crystals of three compounds of this phase system were collected, orthorhombic Cs(2)[(Zr(6)B)Cl(12.99(3))I(2.01)] (1), (Pmma, Z = 4, a = 19.304(4), b = 14.617(3), c = 9.921(2) Å, R1/wR2 = 0.0444/0.0886), monoclinic Cs(2)[(Zr(6)B)Cl(10.63(3))I(4.37)] (2), (P2/c, Z = 4, a = 14.9502(3), b = 10.0098(2), c = 19.8798(4) Å, β = 90.977(1) R1/wR2 = 0.0460/0.1182), and orthorhombic Cs(2)[(Zr(6)B)Cl(8.79(4))I(6.21)] (3) (Pmma, Z = 4, a = 20.0534(4), b = 15.1488(3), c = 10.1739(2) Å, R1/wR2 = 0.0494/0.1123). These compounds are obtained as single phase products. As in other known mixed-halide systems halide ordering is observed, such that the different halide sites have different amounts of Cl and I. With increasing amount of iodide, relative to Cl, the cluster-interconnecting halide sites are more and more occupied by I. For the first time it is observed for 3 that a halide site, which forms a linear bridge between two neighboring Zr(6)B cluster units (so far known examples are solely occupied by Cl), is statistically mixed occupied by Cl and I. Nevertheless, both halide types achieve acceptable bonding situations (bond lengths) because the I atoms are moved out of the linearly bridging position, thereby achieving longer Zr-X distances than the Cl atom, which remains linearly bridging. The generally interesting aspect of this paper is that in the very complex systems the atoms of the mixed occupied sites as well

  3. 2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

    Science.gov (United States)

    Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

    2017-09-01

    Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

  4. Molten salt extraction (MSE) of americium from plutonium metal in CaCl2-KCl-PuCl3 and CaCl2-PuCl3 salt systems

    International Nuclear Information System (INIS)

    Dodson, K.E.

    1992-01-01

    Molten salt extraction (MSE) of americium-241 from reactor-grade plutonium has been developed using plutonium trichloride salt in stationary furnaces. Batch runs with oxidized and oxide-free metal have been conducted at temperature ranges between 750 and 945C, and plutonium trichloride concentrations from one to one hundred mole percent. Salt-to-metal ratios of 0.10, 0.15, and 0 30 were examined. The solvent salt was either eutectic 74 mole percent CaCl 2 endash 26 mole percent KCl or pure CaCl 2 . Evidence of trivalent product americium, and effects of temperature, salt-to-metal ratio, and oxide contamination on the americium extraction efficiency are given. 24 refs, 20 figs, 13 tabs

  5. Observations on the redistribution of plutonium and americium in the Irish Sea sediments, 1978 to 1996: concentrations and inventories

    International Nuclear Information System (INIS)

    Kershaw, P.J.; Denoon, D.C.; Woodhead, D.S.

    1999-01-01

    The distribution of plutonium and americium in the sub-tidal sediments of the Irish Sea is described following major surveys in 1978, 1983, 1988 and 1995. Concentrations in surface sediments have declined near the source at Sellafield since 1988. Time-series of inter-tidal surface sediment concentrations are presented from 1977 onwards, revealing the importance of sediment reworking and transport in controlling the evolution of the environmental signal. The surface and near-surface sediments, in the eastern Irish Sea 'mud-patch', are generally well mixed with respect to Pu (α) and 241 Am distributions but show increasing variability with depth - up to 4 orders of magnitude in concentration. The inventories of 239,240 Pu and 241 Am in the sub-tidal sediments have been estimated and compared with the reported decay-corrected discharges. These amounted to 360 and 545 TBq respectively, in 1995, about 60% of the total decay-corrected discharge. Part of the unaccounted fraction may be due to unrepresentative sampling of the seabed. It is speculated that some tens of TBq of plutonium and 241 Am reside undetected in the large volumes of coarse-grained, sub-tidal and inter-tidal sediment which characterise much of the Irish Sea. This has been due to the inability of the available corers to penetrate to the base of contamination in these mobile sediments. Further observations are needed to verify and quantify the missing amount. A budget of plutonium-α and 241 Am has been estimated based on published observations in the three main compartments: water column, sub-tidal and inter-tidal sediments. This amounts to 460-540 TBq and 575-586 TBq respectively, or 64-75% and 60-61%, of the decay-corrected reported discharge. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  6. Picomolar traces of americium(III) introduce drastic changes in the structural chemistry of terbium(III). A break in the ''gadolinium break''

    Energy Technology Data Exchange (ETDEWEB)

    Welch, Jan M. [TU Wien, Atominstitut, Vienna (Austria); Mueller, Danny; Knoll, Christian; Wilkovitsch, Martin; Weinberger, Peter [TU Wien, Institute of Applied Synthetic Chemistry, Vienna (Austria); Giester, Gerald [University of Vienna, Institute of Mineralogy and Crystallography, Vienna (Austria); Ofner, Johannes; Lendl, Bernhard [TU Wien, Institute of Chemical Technologies and Analytics, Vienna (Austria); Steinhauser, Georg [Leibniz Universitaet Hannover, Institute of Radioecology and Radiation Protection (Germany)

    2017-10-16

    The crystallization of terbium 5,5{sup '}-azobis[1H-tetrazol-1-ide] (ZT) in the presence of trace amounts (ca. 50 Bq, ca. 1.6 pmol) of americium results in 1) the accumulation of the americium tracer in the crystalline solid and 2) a material that adopts a different crystal structure to that formed in the absence of americium. Americium-doped [Tb(Am)(H{sub 2}O){sub 7}ZT]{sub 2} ZT.10 H{sub 2}O is isostructural to light lanthanide (Ce-Gd) 5,5{sup '}-azobis[1H-tetrazol-1-ide] compounds, rather than to the heavy lanthanide (Tb-Lu) 5,5{sup '}-azobis[1H-tetrazol-1-ide] (e.g., [Tb(H{sub 2}O){sub 8}]{sub 2}ZT{sub 3}.6 H{sub 2}O) derivatives. Traces of Am seem to force the Tb compound into a structure normally preferred by the lighter lanthanides, despite a 10{sup 8}-fold Tb excess. The americium-doped material was studied by single-crystal X-ray diffraction, vibrational spectroscopy, radiochemical neutron activation analysis, and scanning electron microscopy. In addition, the inclusion properties of terbium 5,5{sup '}-azobis[1H-tetrazol-1-ide] towards americium were quantified, and a model for the crystallization process is proposed. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Measurement of total alpha activity of neptunium, plutonium, and americium in highly radioactive Hanford waste by iron hydroxide precipitation and 2-heptanone solvent extraction

    International Nuclear Information System (INIS)

    Maiti, T.C.; Kaye, J.H.

    1992-06-01

    An improved method has been developed to concentrate the major alpha-emitting actinide elements neptunium, plutonium, and americium from samples with high salt content such as those resulting from efforts to characterize Hanford storage tank waste. Actinide elements are concentrated by coprecipitation of their hydroxides using iron carrier. The iron is removed by extraction from 8M HCI with 2-heptanone. The actinide elements remain in the aqueous phase free from salts, iron, and long-lived fission products. Recoveries averaged 98 percent

  8. 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

    2016-07-14

    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.

  9. 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

  10. Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

    International Nuclear Information System (INIS)

    Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

    1988-01-01

    Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

  11. Synthesis of zirconia sol stabilized by trivalent cations (yttrium and neodymium or americium): a precursor for Am-bearing cubic stabilized zirconia.

    Science.gov (United States)

    Lemonnier, Stephane; Grandjean, Stephane; Robisson, Anne-Charlotte; Jolivet, Jean-Pierre

    2010-03-07

    Recent concepts for nuclear fuel and targets for transmuting long-lived radionuclides (minor actinides) and for the development of innovative Gen-IV nuclear fuel cycles imply fabricating host phases for actinide or mixed actinide compounds. Cubic stabilized zirconia (Zr, Y, Am)O(2-x) is one of the mixed phases tested in transmutation experiments. Wet chemical routes as an alternative to the powder metallurgy are being investigated to obtain the required phases while minimizing the handling of contaminating radioactive powder. Hydrolysis of zirconium, neodymium (a typical surrogate for americium) and yttrium in aqueous media in the presence of acetylacetone was firstly investigated. Progressive hydrolysis of zirconium acetylacetonate and sorption of trivalent cations and acacH on the zirconia particles led to a stable dispersion of nanoparticles (5-7 nm) in the 6-7 pH range. This sol gels with time or with temperature. The application to americium-containing solutions was then successfully tested: a stable sol was synthesized, characterized and used to prepare cubic stabilized zirconia (Zr, Y, Am)O(2-x).

  12. Determining the americium transmutation rate and fission rate by post-irradiation examination within the scope of the ECRIX-H experiment

    Energy Technology Data Exchange (ETDEWEB)

    Lamontagne, J., E-mail: jerome.lamontagne@cea.fr [Commissariat à l’énergie atomique et aux énergies alternatives (CEA), DEN, DEC, Cadarache, F-13108 St. Paul Lez Durance (France); Pontillon, Y. [Commissariat à l’énergie atomique et aux énergies alternatives (CEA), DEN, DEC, Cadarache, F-13108 St. Paul Lez Durance (France); Esbelin, E. [CEA, DEN, DRCP, Marcoule, F-30207 Bagnols-sur-Cèze (France); Béjaoui, S.; Pasquet, B. [Commissariat à l’énergie atomique et aux énergies alternatives (CEA), DEN, DEC, Cadarache, F-13108 St. Paul Lez Durance (France); Bourdot, P. [CEA, DEN, DER, Cadarache, F-13108 St. Paul Lez Durance (France); Bonnerot, J.M. [Commissariat à l’énergie atomique et aux énergies alternatives (CEA), DEN, DEC, Cadarache, F-13108 St. Paul Lez Durance (France)

    2013-09-15

    The ECRIX-H experiment aims to assess the feasibility of transmuting americium micro-dispersed in an inert magnesia matrix under a locally moderated neutron flux in the Phénix reactor. A first set of examinations demonstrated that pellet behaviour was satisfactory with moderate swelling at the end of the irradiation. Additional post-irradiation examinations needed to be conducted to confirm the high transmutation rate so as to definitively conclude on the success of the ECRIX-H experiment. This article presents and discusses the results of these new examinations. They confirm the satisfactory behaviour of the MgO matrix not only during the basic irradiation but also during post-irradiation thermal transients. These examinations also provide additional information on the behaviour of fission products both in the americium-based particles and in the MgO matrix. These results particularly validate the transmutation rate predicted by the calculation codes using several different analytical techniques. The fission rate is also determined.

  13. Analytical performance of radiochemical method for americium determination in urine; Desempenho analitico do metodo radioquimico para determinacao de americio em urina

    Energy Technology Data Exchange (ETDEWEB)

    Barreto, Juliana Ferreira; Carneiro, Janete C.G. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)]. E-mail: ju_barreto@terra.com.br

    2005-07-01

    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 {sup 243}Am 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{sup -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)

  14. 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.

  15. [BMIM][PF(6)] promotes the synthesis of halohydrin esters from diols using potassium halides.

    Science.gov (United States)

    Oromí-Farrús, Mireia; Eras, Jordi; Villorbina, Gemma; Torres, Mercè; Llopis-Mestre, Veronica; Welton, Tom; Canela, Ramon

    2008-10-01

    Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF(6)] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF(6)] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

  16. 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.

  17. Energetics and dynamics in organic-inorganic halide perovskite photovoltaics and light emitters

    Science.gov (United States)

    Chien Sum, Tze; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-08-01

    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.

  18. Oxygen- and Water-induced Energetics Degradation in Organometal Halide Perovskites.

    Science.gov (United States)

    Yang, Jianming; Yuan, Zhongcheng; Liu, Xianjie; Braun, Slawomir; Li, Yanqing; Tang, Jian-Xin; Gao, Feng; Duan, Chun-Gang; Fahlman, Mats; Bao, Qinye

    2018-04-13

    Organometal halide perovskites are under rapid development and significant focus has been placed on their stability that currently presents a major obstacle for practical application. The energetics play a vital role in charge injection/extraction and transport properties in devices. Here, we in-situ investigate oxygen and water-induced energetic degradation in organometal halide perovskite films. Oxygen gas induces an upwards shift of the vacuum level of the perovskite films due to the formation of an oxygen-induced surface dipole and water vapor causes vacuum level significant downshift as well as the valence band binding energy referenced to Fermi level simultaneously increase so as to keep the ionization potential of the perovskite films unchanged. Moreover, the chemical compositions, crystalline structures, surface morphologies and dynamical properties also are monitored and analyzed in detail. These results are indispensable to understand the degradation mechanisms and to in future perform the optimizations of the sable materials and devices.

  19. 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)

  20. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Energy Technology Data Exchange (ETDEWEB)

    Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

    2012-02-15

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

  1. Energetics and dynamics in organic–inorganic halide perovskite photovoltaics and light emitters

    International Nuclear Information System (INIS)

    Sum, Tze Chien; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-01-01

    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. (topical review)

  2. Energy distributions of atoms sputtered from alkali halides by 540 eV electrons, Ch.1

    International Nuclear Information System (INIS)

    Overeijnder, H.; Szymonski, M.; Haring, A.; Vries, A.E. de

    1978-01-01

    The emission of halogen and alkali atoms, occurring under bombardment of alkali halides with electrons has been investigated. The electron energy was 540 eV and the temperature of the target was varied between room temperature and 400 0 C. The energy distribution of the emitted neutral particles was measured with a time of flight method. It was found that either diffusing interstitial halogen atoms or moving holes dominate the sputtering process above 200 0 C. Below 150 0 C alkali halides with lattice parameters s/d >= 0.33 show emission of non-thermal halogen atoms. s is the interionic space between two halogen ions in a direction and d is the diameter of a halogen atom. In general the energy distribution of the alkali and halogen atoms is thermal above 200 0 C, but not Maxwellian. (Auth.)

  3. Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals.

    Science.gov (United States)

    Chen, Lan; Li, Bin; Zhang, Chunfeng; Huang, Xinyu; Wang, Xiaoyong; Xiao, Min

    2018-02-23

    Perovskite semiconductor nanocrystals with different compositions have shown promise for applications in light-emitting devices. Dark excitonic states may suppress light emission from such nanocrystals by providing an additional nonradiative recombination channel. Here, we study the composition dependence of dark exciton dynamics in nanocrystals of lead halides by time-resolved photoluminescence spectroscopy at cryogenic temperatures. The presence of a spin-related dark state is revealed by magneto-optical spectroscopy. The energy splitting between bright and dark states is found to be highly sensitive to both halide elements and organic cations, which is explained by considering the effects of size confinement and charge screening, respectively, on the exchange interaction. These findings suggest the possibility of manipulating dark exciton dynamics in perovskite semiconductor nanocrystals by composition engineering, which will be instrumental in the design of highly efficient light-emitting devices.

  4. Development of alkali halide-optics for high power-IR laser

    International Nuclear Information System (INIS)

    Pohl, L.

    1989-01-01

    In this work 'Development of Alkali Halide-Optics for High Power-IR Laser' we investigated the purification of sodiumchloride-, potassiumchloride- and potassiumbromide-raw materials. We succeeded to reduce the content of impurities like Cu, Pb, V, Cr, Mn, Fe, Co and Ni in these raw materials to the lower of ppb's by a Complex-Adsorption-Method (CAM). Crystals were grown from purified substances by 'Kyropoulos' method'. Windows were cur thereof, polished and measured by FTIR-spectroscopy. Analytical data showed, that the resulting crystals were of lower quality than the raw materials. Because of this fact crystal-growing-conditions have to undergo a special improvement. Alkali halide windows from other sources on the market had been tested. (orig.) [de

  5. Determination of halide ions in solution by Total Reflection X-ray Fluorescence (TXRF) spectrometry.

    Science.gov (United States)

    Vander Hoogerstraete, Tom; Jamar, Steven; Wellens, Sil; Binnemans, Koen

    2014-02-04

    An accurate quantitative determination of halide ions X (X = Cl, Br, I) in aqueous solution by total reflection X-ray fluorescence (TXRF) is not possible using the traditional acidic internal standards. In general, the standard solutions are highly acidic (e.g., Ga(NO3)3 in HNO3) to avoid precipitation of hydroxides of the standard element and to obtain a stable and reliable standard. In acidic solutions, dissolved halide salts can exchange their cation for a proton. The resulting volatile HX compounds can evaporate during the drying procedure of the TXRF sample preparation. In this technical note, we show that an alkaline Cu(NH3)4(NO3)2 standard can be used for the determination of chlorine, bromine and iodine without facing problems of HX evaporation.

  6. The nature of dynamic disorder in lead halide perovskite crystals (Conference Presentation)

    Science.gov (United States)

    Yaffe, Omer; Guo, Yinsheng; Hull, Trevor; Stoumpos, Costas; Tan, Liang Z.; Egger, David A.; Zheng, Fan; Szpak, Guilherme; Semonin, Octavi E.; Beecher, Alexander N.; Heinz, Tony F.; Kronik, Leeor; Rappe, Andrew M.; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Pimenta, Marcos A.; Brus, Louis E.

    2016-09-01

    We combine low frequency Raman scattering measurements with first-principles molecular dynamics (MD) to study the nature of dynamic disorder in hybrid lead-halide perovskite crystals. We conduct a comparative study between a hybrid (CH3NH3PbBr3) and an all-inorganic lead-halide perovskite (CsPbBr3). Both are of the general ABX3 perovskite formula, and have a similar band gap and structural phase sequence, orthorhombic at low temperature, changing first to tetragonal and then to cubic symmetry as temperature increases. In the high temperature phases, we find that both compounds show a pronounced Raman quasi-elastic central peak, indicating that both are dynamically disordered.

  7. Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries

    Science.gov (United States)

    Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina; Hall, Alex T.; Alves, Thomaz C.; Adelstein, Nicole

    2018-04-01

    Alloying of anions is a promising engineering strategy for tuning ionic conductivity in halide-based inorganic solid electrolytes. We explain the alloying effects in Li3InBr6-xClx, in terms of strain, chemistry, and microstructure, using first-principles molecular dynamics simulations and electronic structure analysis. We find that strain and bond chemistry can be tuned through alloying and affect the activation energy and maximum diffusivity coefficient. The similar conductivities of the x = 3 and x = 6 compositions can be understood by assuming that the alloy separates into Br-rich and Cl-rich regions. Phase-separation increases diffusivity at the interface and in the expanded Cl-region, suggesting microstructure effects are critical. Similarities with other halide superionic conductors are highlighted.

  8. 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.

  9. Amination of Aryl Halides and Esters Using Intensified Continuous Flow Processing

    Directory of Open Access Journals (Sweden)

    Thomas M. Kohl

    2015-09-01

    Full Text Available 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.

  10. 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...

  11. Merging Photoredox and Nickel Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Vinyl Halides

    Science.gov (United States)

    2015-01-01

    Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions. PMID:25521443

  12. The Barbier-Grignard-type carbonyl alkylation using unactivated alkyl halides in water.

    Science.gov (United States)

    Keh, Charlene C K; Wei, Chunmei; Li, Chao-Jun

    2003-04-09

    The aqueous Barbier-Grignard-type alkylation of aldehydes with unactivated alkyl iodides and bromides was developed. By using a combination of zinc and cuprous iodide, catalyzed by indium(I) chloride, we successfully added tertiary, secondary, and primary alkyl halides to various aromatic aldehydes in 0.07 M aqueous Na2C2O4. A mechanistic rationale for the success of the reaction has been proposed.

  13. Solution structure and behavior of dimeric uranium(III) metallocene halides

    Energy Technology Data Exchange (ETDEWEB)

    Lukens, W.W. Jr.; Beshouri, S.M.; Stuart, A.L.; Andersen, R.A. [Lawrence Berkeley Lab., CA (United States)

    1999-03-29

    The variable-temperature {sup 1}H NMR behavior of the uranium(III) dimers [Cp{double_prime}{sub 2}UX]{sub 2} and [Cp{sup {double_dagger}}{sub 2}UX]{sub 2}, where X is F, Cl, Br, or I, Cp{double_prime} is 1,3-(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}, and Cp{sup {double_dagger}} is 1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}, has been examined. At low temperature, the number of inequivalent CMe{sub 3} or SiMe{sub 3} groups implies that the solution structure is the same as the solid-state structure in all of these complexes. The barriers to ring rotation in the Cp{double_prime} series are strongly dependent upon the U-X distance, but all of the barriers to ring rotation in the Cp{sup {double_dagger}} series are the same. The trends in ring rotation barriers are explained by the different conformations of the Cp ligands in the dimers. In addition to the homo-halide dimers, the variable-temperature NMR behavior of the hetero-halide dimers Cp{prime}{sub 4}({mu}-X)({mu}-Y), where Cp{prime} is Cp{double_prime} or Cp{sup {double_dagger}} and X and Y are halides where X {ne} Y, was examined. Above room temperature, the halide atoms exchange sites rapidly on the NMR time scale.

  14. 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 - others: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

  15. Allylmagnesium Halides Do Not React Chemoselectively Because Reaction Rates Approach the Diffusion Limit.

    Science.gov (United States)

    Read, Jacquelyne A; Woerpel, K A

    2017-02-17

    Competition experiments demonstrate that additions of allylmagnesium halides to carbonyl compounds, unlike additions of other organomagnesium reagents, occur at rates approaching the diffusion rate limit. Whereas alkylmagnesium and alkyllithium reagents could differentiate between electronically or sterically different carbonyl compounds, allylmagnesium reagents reacted with most carbonyl compounds at similar rates. Even additions to esters occurred at rates competitive with additions to aldehydes. Only in the case of particularly sterically hindered substrates, such as those bearing tertiary alkyl groups, were additions slower.

  16. Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability.

    Science.gov (United States)

    Fu, Yongping; Zhu, Haiming; Schrader, Alex W; Liang, Dong; Ding, Qi; Joshi, Prakriti; Hwang, Leekyoung; Zhu, X-Y; Jin, Song

    2016-02-10

    The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500-2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼10(8) shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼10(7) laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers.

  17. Mild copper-catalyzed N-arylation of azaheterocycles with aryl halides

    NARCIS (Netherlands)

    Kuil, M.; Bekedam, E.K.; Visser, G.M.; Hoogenband, van den A.; Terpstra, J.W.; Kamer, P.C.J.; Leeuwen, P.W.N.M.; Strijdonck, G.P.F.

    2005-01-01

    A highly efficient copper(I)-catalyzed N-arylation of azaheterocycles with various aryl halides is reported. The N-arylation reaction can be carried out using as low as 0.5 mol % of (Cu(I)OTf)2¿PhH and 1.0 mol % of 4,7-dichloro-1,10-phenanthroline as the ligand. Furthermore, cheap and stable copper

  18. Radiophotoluminescence of alkali-halide crystals stimulated by Bessel laser beam

    CERN Document Server

    Lyakh, V V; Kochubey, D I; Gyunsburg, K E; Zvezdova, N P; Kochubey, D I; Sedova, Y G; Koronkevich, V P; Poleschuk, A G; Sedukhin, A G

    2000-01-01

    A new approach to realization of optimal high-resolution reading of deep X-ray images in X-ray-sensitive materials on the base of alkali-halide crystals modified with admixtures has been suggested and investigated experimentally. A possibility to use diffraction axicons with ring aperture for forming micron bright light beams (spatially truncated Bessel beams) which can efficiently de-excite radiophotoluminescence centers lying at large depth in crystals is also presented.

  19. Growth of the high reflectivity Bi 2O 3 glass films by atmospheric pressure halide CVD

    Science.gov (United States)

    Takeyama, T.; Takahashi, N.; Nakamura, T.; Ito, S.

    2004-09-01

    We reported the results of an investigation into the preparation of amorphous Bi 2O 3 onto borosilicate glass substrate by means of atmospheric pressure halide chemical vapor deposition using BiI 3 and oxygen as a source materials. Obtained thin films lower than 475 °C was amorphous and it was almost transparent in infrared region. But the amorphous films are iodine-containing Bi 2O 3, as results of analysis by XRD and XPS.

  20. Preparation of gold microparticles using halide ions in bulk block copolymer phases via photoreduction

    International Nuclear Information System (INIS)

    Cha, Sang-Ho; Kim, Ki-Hyun; Lee, Won-Ki; Lee, Jong-Chan

    2009-01-01

    Gold microparticles were prepared from the gold salt in the solid bulk phase of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer via a photoreduction process in the presence of halide ions. The shapes and sizes of the gold microparticles were found to be dependent on the types and amount of halide ions as well as the types of cations used due to the combined effects of the adsorption power and oxidative dissolution ability of the additives on gold surfaces. Gold nanorods were obtained when poly(ethylene oxide) was used instead of the block copolymer. This suggests that the poly(propylene oxide) (PPO) parts in the block copolymer are essential for the formation of gold microparticles, even though the degree of the direct interaction between the PPO blocks and gold salt is not significant. - Graphical abstract: Gold microparticles were successfully prepared using halide ions as additives in the polymeric bulk phase via photoreduction with the glow lamp irradiation.

  1. First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

    Science.gov (United States)

    Bechtel, Jonathon S.; Van der Ven, Anton

    2018-04-01

    Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

  2. The Lewis Pair Polymerization of Lactones Using Metal Halides and N-Heterocyclic Olefins: Theoretical Insights

    Directory of Open Access Journals (Sweden)

    Jan Meisner

    2018-02-01

    Full Text Available Lewis pair polymerization employing N-Heterocyclic olefins (NHOs and simple metal halides as co-catalysts has emerged as a useful tool to polymerize diverse lactones. To elucidate some of the mechanistic aspects that remain unclear to date and to better understand the impact of the metal species, computational methods have been applied. Several key aspects have been considered: (1 the formation of NHO-metal halide adducts has been evaluated for eight different NHOs and three different Lewis acids, (2 the coordination of four lactones to MgCl2 was studied and (3 the deprotonation of an initiator (butanol was investigated in the presence and absence of metal halide for one specific Lewis pair. It was found that the propensity for adduct formation can be influenced, perhaps even designed, by varying both organic and metallic components. Apart from the NHO backbone, the substituents on the exocyclic, olefinic carbon have emerged as interesting tuning site. The tendency to form adducts is ZnCl2 > MgCl2 > LiCl. If lactones coordinate to MgCl2, the most likely binding mode is via the carbonyl oxygen. A chelating coordination cannot be ruled out and seems to gain importance upon increasing ring-size of the lactone. For a representative NHO, it is demonstrated that in a metal-free setting an initiating alcohol cannot be deprotonated, while in the presence of MgCl2 the same process is exothermic with a low barrier.

  3. ICES studies on 99mTc-halide complexes: formation, hydrolysis and ligand exchange

    International Nuclear Information System (INIS)

    Fiser, M.; Brabec, V.; Dragoun, O.; Kovalik, A.; Rysavy, M.; Dragounova, N.

    1988-01-01

    The Internal Conversion Electron Spectroscopy (ICES) method was employed to study the products of reduction of no-carrier-added [ 99m Tc]pertechnetate by concentrated hydrochloric, hydrobromic and hydroiodic acids. The reductions were carried out in vacuum with subbsequent evaporation of the solution to dryness. In the solid deposits, containing ∼ 10 -9 g Tc, chemical shifts of 99m Tc electron binding energies were measured and the results were compared with known data of x-ray photoelectron spectroscopy for defined technetium compounds. It was evidenced that all reduction/evaporation procedures yielded 99m Tc(IV)-halide complexes. Another technique of reduction by vapours of halogen acids was proposed to prepare thin radioactive sources for physics studies. The reduction power of alkali halides in absence of acids was examined and a partial reduction of pertechnetate by iodide was found. The product was a hydrolysed species. The hydrolysis of halide complexes yielded the same product. In the absence of acids, dissolved species were partly oxidised to Tc(VII) by air. Oxidation was most apparent for the chloride and negligible for the iodide system. Ligand exchange of chloro and bromo complexes to chelate with DTPA at pH 3 was found to be uncomplete. Tc(IV) hydrolysed species, Tc(IV)DTPA and Tc(VII) were evidenced. Tc(V)DTPA was also observed which arises from partially oxidised products. (author)

  4. On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites

    Science.gov (United States)

    Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea; Gigli, Guido; Latini, Alessandro

    2016-08-01

    The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices.

  5. Quantum confinement effect of two-dimensional all-inorganic halide perovskites

    KAUST Repository

    Cai, Bo

    2017-09-07

    Quantum confinement effect (QCE), an essential physical phenomenon of semiconductors when the size becomes comparable to the exciton Bohr radius, typically results in quite different physical properties of low-dimensional materials from their bulk counterparts and can be exploited to enhance the device performance in various optoelectronic applications. Here, taking CsPbBr3 as an example, we reported QCE in all-inorganic halide perovskite in two-dimensional (2D) nanoplates. Blue shifts in optical absorption and photoluminescence spectra were found to be stronger in thinner nanoplates than that in thicker nanoplates, whose thickness lowered below ∼7 nm. The exciton binding energy results showed similar trend as that obtained for the optical absorption and photoluminescence. Meanwile, the function of integrated intensity and full width at half maximum and temperature also showed similar results, further supporting our conclusions. The results displayed the QCE in all-inorganic halide perovskite nanoplates and helped to design the all-inorganic halide perovskites with desired optical properties.

  6. Strain-induced improper ferroelectricity in Ruddlesden-Popper perovskite halides

    Science.gov (United States)

    Zhang, Yajun; Sahoo, M. P. K.; Shimada, Takahiro; Kitamura, Takayuki; Wang, Jie

    2017-10-01

    Activating multiple symmetry modes and promoting a strong coupling between different modes by strain are indispensable to stabilize a polar ferroelectric (FE) phase from a nonpolar perovskite. Herein, through first-principles calculations, we propose an undiscovered and general avenue to engineering ferroelectricity in photovoltaic perovskites with a Ruddlesden-Popper (RP) structure. It is demonstrated that an experimentally accessible compressive strain can induce an in-plane polarization in RP perovskite halides thin films, resulting in an unusual paraelectric to FE phase transition. The detailed analysis on structure and energy reveals that the unusual FE phase transition in the perovskite halides stems from the strong coupling between strain and antiferrodistortive (AFD) mode. Further calculations show that the strain-AFD coupling-induced ferroelectricity is not only exhibited by perovskite halides but also observed in perovskite sulfides such as Ba3Zr2S7 . Moreover, it is found that the strained FE thin film possesses a suitable band gap of 1.6 eV for photovoltaic application. These findings not only unfold a general way to engineering nonpolar-to-polar transition, but also open an avenue to design optimal FE semiconductors for solar cell applications.

  7. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

    2016-06-14

    Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  8. First-principles study of γ-ray detector materials in perovskite halides

    Science.gov (United States)

    Im, Jino; Jin, Hosub; Stoumpos, Constantinos; Chung, Duck; Liu, Zhifu; Peters, John; Wessels, Bruce; Kanatzidis, Mercouri; Freeman, Arthur

    2013-03-01

    In an effort to search for good γ-ray detector materials, perovskite halide compounds containing heavy elements were investigated. Despite the three-dimensional network of the corner shared octahedra and the extended nature of the outermost shell, its strong ionic character leads to a large band gap, which is one of the essential criteria for γ-ray detector materials. Thus, considering high density and high atomic number, these pervoskite halides are possible candidate for γ-ray detector materials. We performed first-principles calculations to investigate electronic structures and thermodynamic properties of intrinsic defects in the selected perovskite halide, CsPbBr3. The screened-exchange local density approximation scheme was employed to correct the underestimation of the band gap in the LDA method. As a result, the calculated band gap of CsPbBr3 is found to be suitable for γ-ray detection. Furthermore, defect formation energy calculations allow us to predict thermodynamic and electronic properties of possible intrinsic defects, which affect detector efficiency and energy resolution. Supported by the office of Nonproliferation and Verification R &D under Contract No. DE-AC02-06CH11357

  9. Lead Halide Perovskite Nanocrystals in the Research Spotlight: Stability and Defect Tolerance

    Science.gov (United States)

    2017-01-01

    This Perspective outlines basic structural and optical properties of lead halide perovskite colloidal nanocrystals, highlighting differences and similarities between them and conventional II–VI and III–V semiconductor quantum dots. A detailed insight into two important issues inherent to lead halide perovskite nanocrystals then follows, namely, the advantages of defect tolerance and the necessity to improve their stability in environmental conditions. The defect tolerance of lead halide perovskites offers an impetus to search for similar attributes in other related heavy metal-free compounds. We discuss the origins of the significantly blue-shifted emission from CsPbBr3 nanocrystals and the synthetic strategies toward fabrication of stable perovskite nanocrystal materials with emission in the red and infrared parts of the optical spectrum, which are related to fabrication of mixed cation compounds guided by Goldschmidt tolerance factor considerations. We conclude with the view on perspectives of use of the colloidal perovskite nanocrystals for applications in backlighting of liquid-crystal TV displays. PMID:28920080

  10. Vibrational spectra of discrete UO22+ halide complexes in the gas phase

    International Nuclear Information System (INIS)

    Groenewold, Gary S.; van Stipdonk, Michael J.; de Jong, Wibe A.; Oomens, Jos; Gresham, Garold L.

    2010-01-01

    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

  11. Inhaled americium dioxide

    International Nuclear Information System (INIS)

    Park, J.F.

    1982-01-01

    This project includes experiments to determine the effects of Zn-DTPA therapy on the retention, translocation and biological effects of inhaled 241 AmO 2 . Beagle dogs that received inhalation exposure to 241 AmO 2 developed leukopenia, clincial chemistry changes associated with hepatocellular damage, and were euthanized due to respiratory insufficiency caused by radiation pneumonitis 120 to 131 days after pulmonary deposition of 22 to 65 μCi 241 Am. Another group of dogs that received inhalation exposure to 241 AmO 2 and were treated daily with Zn-DTPA had initial pulmonary deposition of 19 to 26 μCi 241 Am. These dogs did not develop respiratory insufficiency, and hematologic and clinical chemistry changes were less severe than in the non-DTPA-treated dogs

  12. Artificial radionuclides in the Northern European Marine Environment. Distribution of radiocaesium, plutonium and americium in sea water and sediments in 1995

    International Nuclear Information System (INIS)

    Groettheim, Siri

    2000-01-01

    This study considers the distribution of radiocaesium, plutonium and americium in the northern marine environment. The highest radiocaesium activity in sea water was observed in Skagerrak, 26 Bq/m 3 , and in surface sediments in the Norwegian Sea, 60 Bq/kg. These enhanced levels were related to Chernobyl. The highest 239,240Pu activity in surface water was measured in the western North Sea, 66 mBq/m 3 . In sea water, sub-surface maxima were observed at several locations with an 239,240Pu activity up to 160 mBq/m 3 , and were related to Sellafield. With the exception to the North Sea, surface sediments reflected Pu from global fallout from weapons tests only. (author)

  13. Recovery of Americium-241 from lightning rod by the method of chemical treatment; Recuperacion del Americio-241 provenientes de los pararrayos por el metodo de tratamiento quimico

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, W.H., E-mail: wcruz@ipen.gob.pe [Instituto Peruano de Energia Nuclear (GRRA/IPEN), Lima (Peru). Division de Gestion de Residuos Radiactivos

    2013-07-01

    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 ({sup 241}Am), fewer and Radium 226 ({sup 226}Ra) 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 {sup 241}Am radioactive lightning rods using the conventional chemical treatment method using agents and acids to break down the slides. The {sup 241}Am recovered was as excitation source and alpha particle generator for analysing samples by X Ray Fluorescence, for fixing the stainless steel {sup 241}Am technique was used electrodeposition. (author)

  14. Artificial radionuclides in the Northern European Marine Environment. Distribution of radiocaesium, plutonium and americium in sea water and sediments in 1995

    Energy Technology Data Exchange (ETDEWEB)

    Groettheim, Siri

    2000-07-01

    This study considers the distribution of radiocaesium, plutonium and americium in the northern marine environment. The highest radiocaesium activity in sea water was observed in Skagerrak, 26 Bq/m{sub 3}, and in surface sediments in the Norwegian Sea, 60 Bq/kg. These enhanced levels were related to Chernobyl. The highest 239,240Pu activity in surface water was measured in the western North Sea, 66 mBq/m{sub 3}. In sea water, sub-surface maxima were observed at several locations with an 239,240Pu activity up to 160 mBq/m{sub 3}, and were related to Sellafield. With the exception to the North Sea, surface sediments reflected Pu from global fallout from weapons tests only. (author)

  15. Safe handling of kilogram amounts of fuel-grade plutonium and of gram amounts of plutonium-238, americium-241 and curium-244

    International Nuclear Information System (INIS)

    Louwrier, K.P.; Richter, K.

    1976-01-01

    During the past 10 years about 600 glove-boxes have been installed at the Institute for Transuranium Elements at Karlsruhe. About 80% of these glove-boxes have been designed and equipped for handling 100-g to 1-kg amounts of 239 Pu containing 8-12% 240 Pu (low-exposure plutonium). A small proportion of the glove-boxes is equipped with additional shielding in the form of lead sheet or lead glass for work with recycled plutonium. In these glove-boxes gram-amounts of 241 Am have also been handled for preparation of Al-Am targets using tongs and additional shielding inside the glove-boxes themselves. Water- and lead-shielded glove-boxes equipped with telemanipulators have been installed for routine work with gram-amounts of 241 Am, 243 Am and 244 Cm. A prediction of the expected radiation dose for the personnel is difficult and only valid for a preparation procedure with well-defined preparation steps, owing to the fact that gamma dose-rates depend strongly upon proximity and source seize. Gamma radiation dose measurements during non-routine work for 241 Am target preparation showed that handling of gram amounts leads to a rather high irradiation dose for the personnel, despite lead or steel glove-box shielding and shielding within the glove-boxes. A direct glove-hand to americium contact must be avoided. For all glove-handling of materials with gamma radiation an irradiation control of the forearms of the personnel by, for example, thermoluminescence dosimeters is necessary. Routine handling of americium and curium should be executed with master-slave equipment behind neutron and gamma shielding. (author)

  16. Preliminary application of 241-Americium calcaneus bone mineral density measurement in osteoporosis. Comparison with double X-ray densitometry of the lumber spine

    International Nuclear Information System (INIS)

    Guan Liang; Zhu Chengmo; Li Peiyong; Wang Hui; Pu Mingfang; Qiu Jigao

    2001-01-01

    Bone mineral density (BMD) of calcaneus in 54 normals, 45 Osteoporosis, 25 suspected osteoporosis and 16 other non-osteoporosis patients, a total of 140 cases were measured by HUAKE (HK-1) 241-Americium BMD absorpmetry, among them 43 were compared with that of lumber spine (L2 - L4) measured by Lunar Corporation's Expert-XL absorpmeter. BMD of normal group of calcaneus was (409.8 +- 79.4) mg/cm 2 . The BMD were decreased slowly with the increasing age. The BMD of osteoporosis, suspected osteoporosis and non-osteoporosis group were 230.3 +- 62.3, 395.7 +- 57.4 and 363.3 +- 51.9 mg/cm 2 respectively. The BMD of osteoporosis group was much lower than that of normal group, and also lower than that of the other two groups, among 26 patients (57.78%) had bone fracture, all was in accordance with the clinical diagnosis of osteoporosis. The BMD of suspected osteoporosis and non-osteoporosis had no significant difference with normal group. The coefficient variation (CV) of BMD in repeated measurement in calcaneus of 4 participants was less than 1.2%. The correlative coefficient (r) between BMD of calcaneus and lumber spine (L2 - L4) group was 0.6824. The correlative coefficient of normal young adult-matched percentage and T value in 2 groups were 0.6863 and 0.6755 respectively, whereas aged-matched percentage, Z value were 0.4614 and 0.5009 respectively. In conclusion 241-Americium calcaneus BMD absorpmetry has the advantage of low price, easy to operate, reliable and valuable in diagnosis osteoporosis. The correlations of calcaneus and lumber spine BMD, normal young adult-matched percentage and T value were rather good

  17. Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution

    Science.gov (United States)

    Koolyk, Miriam; Amgar, Daniel; Aharon, Sigalit; Etgar, Lioz

    2016-03-01

    In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking

  18. A review on bis-hydrazonoyl halides: Recent advances in their synthesis and their diverse synthetic applications leading to bis-heterocycles of biological interest

    Directory of Open Access Journals (Sweden)

    Ahmad Sami Shawali

    2016-11-01

    Full Text Available This review covers a summary of the literature data published on the chemistry of bis-hydrazonoyl halides over the last four decades. The biological activities of some of the bis-heterocyclic compounds obtained from these bis-hydrazonoyl halides are also reviewed and discussed.

  19. Correction factor K calculation for Americium-Beryllium neutron sources measured in a manganese sulfate bath; Calculo do fator de correcao K para fontes de neutrons de Americio-Berilio medida no banho de sulfato de manganes do LNMRI/IRD

    Energy Technology Data Exchange (ETDEWEB)

    Leite, Sandro P.; Fonseca, Evaldo S. da; Patrao, Karla C.S.; Goncalves, Marcello G. [Instituto de Radioprotecao e Dosimetria (IRD/CNEN-RJ), Rio de Janeiro, RJ (Brazil). Lab. de Neutrons; Pereira, Walsan W. [Instituto de Radioprotecao e Dosimetria (IRD/CNEN-RJ), Rio de Janeiro, RJ (Brazil). Lab. Nacional de Metrologia das Radiacoes Ionizantes (LNMRI)

    2005-03-15

    This paper simulates a manganese sulfate bath at the Ionizing Radiation Metrology National Laboratory for the calculation of K correction factor for the neutro emission ratio in some Americium-Beryllium sources.

  20. Monitoring of heavy/toxic metals and halides in surface/ground water (abstract)

    International Nuclear Information System (INIS)

    Viqar-un-Nisa; Ahmed, R.; Husain, M.

    1999-01-01

    Water is essential for maintaining physical and social life. Human and animal consumption is perhaps the most evident essential use of water. Water quality and quantity have become critical issues, affecting all life. The importance of water in our lives, combined with the threats, make water resources use a global problem. Among the different pollutants toxic metals, metalloids and halides have special significance. Industrial effluents and municipal wastewater are normally drained into water streams, rivers and other reservoirs thus polluting these significantly. Quality of our water resources especially is an issue, which continues to arouse the attention of concerned scientists, legislators and the general public. Among various pollutant chemicals, the heavy metals and metalloids are present at trace levels in various compartments of the environment. Some metals become toxic even at trace levels because of the important features that distinguishes metals from other pollutants is that they are not biodegradable. The halides like Cl, Br, and I from different sources can enter easily into water systems and then they make their way directly into the human body. The intake of toxic as wells as essential elements through water and other food items like vegetables, milk wheat flour etc. is significant. The abundance or deficiency of these meals as well as halides results in abnormal metabolic functions. Due to excessive demand for trace analysis in water and other materials a variety of techniques and instrumentation has been developed. Determination of heavy metals ions is of the highest interest in environmental analysis. Among the food materials water is most important because of their large consumption by man. Also toxic metals in water may be in dissolved ionic form, which directly go into human metabolism and start their toxic action. Presence of even small amounts of toxic metals in drinking water can produce serious health hazards. (author)

  1. Concentration Effects and Ion Properties Controlling the Fractionation of Halides in Sea Spray

    Science.gov (United States)

    Guzman, M. I.; Pillar, E. A.

    2013-12-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (fX-) and their correlation with ion properties. Although no correlation exists between fX- and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions, dehydration free-energy, and polarizability α, is larger for the reciprocal square of anion size. The same pure physical process is observed in H2O and D2O. The factor fX- does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol- and ethanol-water mixtures (0 ≤ xwater ≤ 1). Polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I- on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I- layer due to concentration effects in sea spray aerosol formation. Experiments reporting the products for the ozonolysis of halides in microdroplets at typical ozone concentrations of ~ 50 ppbv display the formation or reactive halogen species that contribute to the destruction of ozone over the open ocean.

  2. Thermal neutron detection using alkali halide scintillators with Li-6 and pulse shape discrimination

    Energy Technology Data Exchange (ETDEWEB)

    Brubaker, Erik [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Dibble, Dean C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Mengesha, Wondwosen [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Yang, Pin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2013-09-01

    An ideal 3He detector replacement for the near- to medium-term future will use materials that are easy to produce and well understood, while maintaining thermal neutron detection efficiency and gamma rejection close to the 3He standard. Toward this end, we investigated the use of standard alkali halide scintillators interfaced with 6Li and read out with photomultiplier tubes (PMTs). Thermal neutrons are captured on 6Li with high efficiency, emitting high-energy and triton (3H) reaction products. These particles deposit energy in the scintillator, providing a thermal neutron signal; discrimination against gamma interactions is possible via pulse shape discrimination (PSD), since heavy particles produce faster pulses in alkali halide crystals. We constructed and tested two classes of detectors based on this concept. In one case 6Li is used as a dopant in polycrystalline NaI; in the other case a thin Li foil is used as a conversion layer. In the configurations studied here, these systems are sensitive to both gamma and neutron radiation, with discrimination between the two and good energy resolution for gamma spectroscopy. We present results from our investigations, including measurements of the neutron efficiency and gamma rejection for the two detector types. We also show a comparison with Cs2LiYCl6:Ce (CLYC), which is emerging as the standard scintillator for simultaneous gamma and thermal neutron detection, and also allows PSD. We conclude that 6Li foil with CsI scintillating crystals has near-term promise as a thermal neutron detector in applications previously dominated by 3He detectors. The other approach, 6Li-doped alkali halides, has some potential, but require more work to understand material properties and improve fabrication processes.

  3. Metallaphotoredox-catalysed sp3-sp3 cross-coupling of carboxylic acids with alkyl halides

    Science.gov (United States)

    Johnston, Craig P.; Smith, Russell T.; Allmendinger, Simon; MacMillan, David W. C.

    2016-08-01

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp3-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3-sp3 bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp3-sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp3-sp3 coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3-sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for

  4. Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

    Energy Technology Data Exchange (ETDEWEB)

    Selling, J.

    2007-07-01

    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 BaCl{sub 2} 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 BaI{sub 2} 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 Eu{sup 2+}/Eu{sup 3+} ratio in the glass ceramics should be determined and optimize favor of the Eu{sup 2+}. We also want to distinguish between Eu{sup 2+} in the glass matrix and Eu{sup 2+} in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a

  5. Band Gap Tuning and Defect Tolerance of Atomically Thin Two- Dimensional Organic-Inorganic Halide Perovskites

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

    2016-01-01

    report first-principles calculations for isolated monolayers of the organometallic halide perovskites (C4H9NH3)2MX2Y2, where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC functional are found to be in excellent agreement with experimental photoluminescence data...... for the already synthesized perovskites. Finally, we study the effect of different defects on the band structure. We find that the most common defects only introduce shallow or no states in the band gap, indicating that these atomically thin 2D perovskites are likely to be defect tolerant....

  6. Measurements of prompt fission gamma-rays and neutrons with lanthanide halide scintillation detectors

    CERN Document Server

    Oberstedt, A; Billnert, R; Borcea, R; Brys, T; Chaves, C; Gamboni, T; Geerts, W; Göök, A; Guerrero, C; Hambsch, F-J; Kis, Z; Martinez, T; Oberstedt, S; Szentmiklosi, L; Takács, K; Vivaldi, M

    2014-01-01

    Photons have been measured with lanthanide halide scintillation detectors in coincidence with fission fragments. Using the time-of-flight information, reactions from γ-rays and neutrons could easily be distinguished. In several experiments on $^{252}$Cf(sf), $^{235}$U(n$_{th}$,f) and $^{241}$Pu(n$_{th}$,f) prompt fission γ-ray spectra characteristics were determined with high precision and the results are presented here. Moreover, a measured prompt fission neutron spectrum for $^{235}$U(n$_{th}$,f) is shown in order to demonstrate a new detection technique.

  7. Structural, optical, and electronic studies of wide-bandgap lead halide perovskites

    KAUST Repository

    Comin, Riccardo

    2015-01-01

    © The Royal Society of Chemistry 2015. We investigate the family of mixed Br/Cl organolead halide perovskites which enable light emission in the blue-violet region of the visible spectrum. We report the structural, optical and electronic properties of this air-stable family of perovskites, demonstrating full bandgap tunability in the 400-550 nm range and enhanced exciton strength upon Cl substitution. We complement this study by tracking the evolution of the band levels across the gap, thereby providing a foundational framework for future optoelectronic applications of these materials.

  8. All-Inorganic Colloidal Quantum Dot Photovoltaics Employing Solution-Phase Halide Passivation

    KAUST Repository

    Ning, Zhijun

    2012-09-12

    A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis, radiochemical labeling, and properties of some aryl- and alkylstibines and their halide derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Benmalek, M.; Chermette, H.; Martelet, C.; Sandino, D.; Tousset, J.

    1973-07-01

    The condensation of aryl or alkyl magnesium halides on radiochemically labeled (/sup 124/Sb) antimony trichloride enables labeled triaryl or trialkyl stibines to be obtained. Triaryl and trialkyl antimony difluorides can be obtained with excellent yields using solvent extraction from the corresponding dichloride, dibromide, or di-iodide, these substances being obtained by condensation of the halogen on stibine. Radiochemical labeling enabled the values of the partition coefficients to be obtained for some of the derivatives, and also the hydrolysis of these compounds to be examined. (FR)

  10. All-inorganic colloidal quantum dot photovoltaics employing solution-phase halide passivation

    Energy Technology Data Exchange (ETDEWEB)

    Ning, Zhijun; Ren, Yuan; Hoogland, Sjoerd; Voznyy, Oleksandr; Levina, Larissa; Stadler, Philipp; Lan, Xinzheng; Zhitomirsky, David; Sargent, Edward H. [Department of Electrical and Computer Engineering, University of Toronto, 10 King' s College Road, Toronto, Ontario, M5S 3G4 (Canada)

    2012-12-11

    A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Solvated Positron Chemistry - Positron Reactions with Pseudo-Halide Ions in Water

    DEFF Research Database (Denmark)

    Mogensen, O. E.; Pedersen, Niels Jørgen; Andersen, Jan Rud

    1982-01-01

    The hydrated positron e+aq reactions with SCN−, OCN−, CN−, S2− were studied by means of the angular correlation technique. The positron forms bound states with SCN−, CN−, and S2− but not with OCN−. Apparently, the e+aq reaction with SH− results in a positron bound state with S2−. It was difficult...... to determine the shapes of the bound-state angular correlation curves. Only in the SCN− case could a very rough estimate of the rate constant be obtained. Estimates of the binding energies relative to those of the corresponding halide ion states could be determined for SCN− and S2−....

  12. High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

    OpenAIRE

    Carolin M. Sutter-Fella Yanbo Li Matin Amani Joel W. Ager III Francesca M. Toma; Eli Yablonovitch Ian D. Sharp and Ali Javey

    2016-01-01

    Hybrid organic–inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low cost solution processability. Here we present a two step low pressure vapor assisted solution process to grow high quality homogeneous CH3NH3PbI3–xBrx perovskite films over the full band gap range of 1.6–2.3 eV. Photoluminescence light in versus light out charac...

  13. Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water.

    Science.gov (United States)

    Wang, Shaoyan; Zhang, Zhiqiang; Hu, Zhizhi; Wang, Yue; Lei, Peng; Chi, Haijun

    2009-01-01

    An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl boronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated.

  14. Refined potentials for rare gas atom adsorption on rare gas and alkali-halide surfaces

    Science.gov (United States)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1985-01-01

    The utilization of models of interatomic potential for physical interaction to estimate the long range attractive potential for rare gases and ions is discussed. The long range attractive force is calculated in terms of the atomic dispersion properties. A data base of atomic dispersion parameters for rare gas atoms, alkali ion, and halogen ions is applied to the study of the repulsive core; the procedure for evaluating the repulsive core of ion interactions is described. The interaction of rare gas atoms on ideal rare gas solid and alkali-halide surfaces is analyzed; zero coverage absorption potentials are derived.

  15. Research Update: Challenges for high-efficiency hybrid lead-halide perovskite LEDs and the path towards electrically pumped lasing

    Directory of Open Access Journals (Sweden)

    Guangru Li

    2016-09-01

    Full Text Available Hybrid lead-halide perovskites have emerged as promising solution-processed semiconductor materials for thin-film optoelectronics. In this review, we discuss current challenges in perovskite LED performance, using thin-film and nano-crystalline perovskite as emitter layers, and look at device performance and stability. Fabrication of electrically pumped, optical-feedback devices with hybrid lead halide perovskites as gain medium is a future challenge, initiated by the demonstration of optically pumped lasing structures with low gain thresholds. We explain the material parameters affecting optical gain in perovskites and discuss the challenges towards electrically pumped perovskite lasers.

  16. Possible configuration of two-knot auto-localized exciton in strainless and deformed alkali halide crystals

    International Nuclear Information System (INIS)

    Dzhumanov, S.; Tulepbergenov, S.K.; Shunkeev, K.Sh.

    2002-01-01

    In the paper molecular component of two-knot auto-localized exciton (TALE) occupying centrosymmetric state in alkali halide crystal cubic lattice with local D 2h symmetry is considered. In is suggested that the symmetry lowering of forming small radius auto-localized exciton (ALE) is realizing in order configuration transformation by the scenario: multi-knot continual ALE (with O h symmetry)→six-halide ALE (with O h symmetry)→TALE (with O h symmetry) or by the scenario O h →D 2h . Then for TALE with local D 2h symmetry normal molecular ion shifts are considered as well

  17. Sequential One-Pot Ruthenium-Catalyzed Azide−Alkyne Cycloaddition from Primary Alkyl Halides and Sodium Azide

    KAUST Repository

    Johansson, Johan R.

    2011-04-01

    An experimentally simple sequential one-pot RuAAC reaction, affording 1,5-disubstituted 1H-1,2,3-triazoles in good to excellent yields starting from an alkyl halide, sodium azide, and an alkyne, is reported. The organic azide is formed in situ by treating the primary alkyl halide with sodium azide in DMA under microwave heating. Subsequent addition of [RuClCp*(PPh 3) 2] and the alkyne yielded the desired cycloaddition product after further microwave irradiation. © 2011 American Chemical Society.

  18. Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy

    OpenAIRE

    Kawashima, Kazuhiro; Okamoto, Yuji; Annayev, Orazmuhammet; Toyokura, Nobuo; Takahashi, Ryota; Lippmaa, Mikk; Itaka, Kenji; Suzuki, Yoshikazu; Matsuki, Nobuyuki; Koinuma, Hideomi

    2017-01-01

    Abstract As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic?inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thic...

  19. Fabrication of ultra-fine-grain silver halide recording material for color holography

    Science.gov (United States)

    Bjelkhagen, H. I.; Crosby, P. G.; Green, D. P. M.; Mirlis, E.; Phillips, N. J.

    2008-02-01

    Color holography is the most accurate imaging technology known to science. It is possible to produce holographic images that are almost identical to the original scene. Color holograms and holographic optical elements (HOEs) are becoming increasingly attractive. Since the 1990s the developments in other technology areas have created many potential new applications for color holograms and HOEs but again these new market areas are unexploited due to the lack of a suitable color holographic recording material. This restricts the commercial and technical development and exploitation of holographic-based industries, applications, techniques and processes. There is not a sufficient, commercial recording material for color holograms and HOEs. Most of the materials that are in use at present have relative poor performance and many manufacture methods of the materials are limited to laboratory scale. This paper presents fabrication details of ultra-fine grain (5 -10 nm), high sensitivity (less than 2.0 mJcm -2), low light-scattering, panchromatic silver halide emulsions. Such materials can be used for high-quality 3-D imaging recording techniques, including color holograms and HOEs. A comprehensive approach regarding all aspects of the emulsion preparation, from the precipitation of the silver halide crystals to sensitization and coating is provided. There are also recommendations regarding the processing of the material in order to achieve optimum performance.

  20. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

    KAUST Repository

    Samu, Gergely F.

    2017-12-06

    The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and to assemble their hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic-inorganic MaPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. We believe that the presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that easier comparisons can be made.

  1. Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

    Directory of Open Access Journals (Sweden)

    Azzedine Bouleghlimat

    2017-09-01

    Full Text Available In this communication, we present studies of the oxidative homocoupling of arylboronic acids catalyzed by immobilised palladium nanoparticles in aqueous solution. This reaction is of significant interest because it shares a key transmetallation step with the well-known Suzuki-Miyaura cross-coupling reaction. Additives can have significant effects on catalysis, both in terms of reaction mechanism and recovery of catalytic species, and our aim was to study the effect of added halides on catalytic efficiency and catalyst recovery. Using kinetic studies, we have shown that added halides (added as NaCl and NaBr can increase the catalytic activity of the palladium nanoparticles more than 10-fold, allowing reactions to be completed in less than half a day at 30 °C. However, this increased activity comes at the expense of catalyst recovery. The results are in agreement with a reaction mechanism in which, under conditions involving high concentrations of chloride or bromide, palladium leaching plays an important role. Considering the evidence for analogous reactions occurring on the surface of palladium nanoparticles under different reaction conditions, we conclude that additives can exert a significant effect on the mechanism of reactions catalyzed by nanoparticles, including switching from a surface reaction to a solution reaction. The possibility of this switch in mechanism may also be the cause for the disagreement on this topic in the literature.

  2. Superior Self-Powered Room-Temperature Chemical Sensing with Light-Activated Inorganic Halides Perovskites.

    Science.gov (United States)

    Chen, Hongjun; Zhang, Meng; Bo, Renheng; Barugkin, Chog; Zheng, Jianghui; Ma, Qingshan; Huang, Shujuan; Ho-Baillie, Anita W Y; Catchpole, Kylie R; Tricoli, Antonio

    2018-02-01

    Hybrid halide perovskite is one of the promising light absorber and is intensively investigated for many optoelectronic applications. Here, the first prototype of a self-powered inorganic halides perovskite for chemical gas sensing at room temperature under visible-light irradiation is presented. These devices consist of porous network of CsPbBr 3 (CPB) and can generate an open-circuit voltage of 0.87 V under visible-light irradiation, which can be used to detect various concentrations of O 2 and parts per million concentrations of medically relevant volatile organic compounds such as acetone and ethanol with very quick response and recovery time. It is observed that O 2 gas can passivate the surface trap sites in CPB and the ambipolar charge transport in the perovskite layer results in a distinct sensing mechanism compared with established semiconductors with symmetric electrical response to both oxidizing and reducing gases. The platform of CPB-based gas sensor provides new insights for the emerging area of wearable sensors for personalized and preventive medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Dielectric relaxation of alkyl chains in graphite oxide and n-alkylammonium halides

    Energy Technology Data Exchange (ETDEWEB)

    Ai, Xiaoqian; Tian, Yuchen; Gu, Min, E-mail: mgu@nju.edu.cn; Yu, Ji [National Laboratory of Solid State Microstructures and Department of Physics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); Tang, Tong B. [Department of Physics, Hong Kong Baptist University, Kowloon, Hong Kong (China)

    2016-05-15

    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 parallel to GO layers, and with cations of headgroups bonded ionically to C-O{sup -} groups of GO; backbones of the confined molecules remain free. All halides and intercalation compounds suffer dielectric loss at low temperature. Arrhenius plots of the thermal dependence of the loss peaks, which are asymmetric, produce apparent activation energies that rise with increasing n. Ngai’s correlated-state model helps to correct for effects of dipole-dipole interaction, leading to virtually identical values for actual activation energy of 110 meV ± 5%; the values are also almost the same as the barrier energy for internal rotation in the alkyl macromolecule. We conclude that the relaxation of the alkylammonium cations arises not from C{sub 3} reorientation of the CH{sub 3} at its headgroup, but from small-angle wobbling around its major axis, an intrinsic motion.

  4. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

    Science.gov (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

    2016-03-01

    Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules.

  5. Intrinsic Defect Physics in Indium-based Lead-free Halide Double Perovskites.

    Science.gov (United States)

    Xu, Jian; Liu, Jian-Bo; Liu, Bai-Xin; Huang, Bing

    2017-09-21

    Lead-free halide double perovskites (HDPs) are expected to be promising photovoltaic (PV) materials beyond organic-inorganic halide perovskite, which is hindered by its structural instability and toxicity. The defect- and stability-related properties of HDPs are critical for the use of HDPs as important PV absorbers, yet their reliability is still unclear. Taking Cs 2 AgInBr 6 as a representative, we have systemically investigated the defect properties of HDPs by theoretical calculations. First, we have determined the stable chemical potential regions to grow stoichiometric Cs 2 AgInBr 6 without structural decomposition. Second, we reveal that Ag-rich and Br-poor are the ideal chemical potential conditions to grow n-type Cs 2 AgInBr 6 with shallow defect levels. Third, we find the conductivity of Cs 2 AgInBr 6 can change from good n-type, to poorer n-type, to intrinsic semiconducting depending on the growth conditions. Our studies provided important guidance for experiments to fabricate Pb-free perovskite-based solar cell devices with superior PV performances.

  6. Absorption of NO and NO2in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids.

    Science.gov (United States)

    Duan, Erhong; Guo, Bin; Zhang, Dandan; Shi, Long; Sun, Hua; Wang, Yanan

    2011-12-01

    To explore environmentally benign solvents for the absorption of NO and NO 2 , a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO 2 was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO 2 in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO 2 decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO 2 was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO 2 . [Box: see text].

  7. Structural and Chemical Analysis of Gadolinium Halides Encapsulated within WS 2 Nanotubes

    KAUST Repository

    Anumol, E A

    2016-05-18

    The hollow cavities of nanotubes could serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of inorganic nanotubes of WS2 by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is a non-trivial matter due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

  8. Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency

    KAUST Repository

    Qin, Peng

    2014-05-12

    Organo-lead halide perovskites have attracted much attention for solar cell applications due to their unique optical and electrical properties. With either low-temperature solution processing or vacuum evaporation, the overall conversion efficiencies of perovskite solar cells with organic hole-transporting material were quickly improved to over 15% during the last 2 years. However, the organic hole-transporting materials used are normally quite expensive due to complicated synthetic procedure or high-purity requirement. Here, we demonstrate the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices. With low-temperature solution-process deposition method, a power conversion efficiency of 12.4% was achieved under full sun illumination. This work represents a well-defined cell configuration with optimized perovskite morphology by two times of lead iodide deposition, and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application. © 2014 Macmillan Publishers Limited.

  9. Evaluation of quaternary ammonium halides for removal of methyl iodide from flowing air streams

    International Nuclear Information System (INIS)

    Freeman, W.P.; Mohacsi, T.G.; Kovach, J.L.

    1985-01-01

    The quaternary ammonium halides of several tertiary amines were used as impregnants on activated carbon and were tested for methyl iodide penetration in accordance with test Method A, ASTM D3803, 1979, ''Standard Test Methods for Radio-iodine Testing of Nuclear Grade Gas Phase Adsorbents''. The results suggest that the primary removal mechanism for methyl iodide-131 is isotopic exchange with the quaternary ammonium halide. For example, a 5 wt% impregnation of each of the tetramethyl, tetraethyl, tetrapropyl and tetrabutyl ammonium iodides on activated carbon yielded percent penetrations of 0.47, 0.53, 0.78, and 0.08 respectively when tested according to Method A of ASTM D3803. A sample impregnated with 5% tetramethyl ammonium hydroxide gave a methyl iodide penetration of 64.87%, thus supporting the isotopic exchange mechanism for removal. It has been a generally held belief that the success of tertiary amines as impregnants for radioiodine removal is a result of their ability to complex with the methyl iodide. The results of the work indicates that the superiority of the tertiary amines similar to triethylene diamine and quinuclidine, when compared to their straight chain analogs, is a result of their ease in reacting with methyl iodide-127 to form the quaternary ammonium iodide followed by isotopic exchange

  10. Extended Photo-Conversion Spectrum in Low-Toxic Bismuth Halide Perovskite Solar Cells.

    Science.gov (United States)

    Johansson, Malin B; Zhu, Huimin; Johansson, Erik M J

    2016-09-01

    Lead-based perovskites show very promising properties for use in solar cells; however, the toxicity of lead is a potential inhibitor for large-scale application of these solar cells. Here, a low-toxic bismuth halide, CsBi3I10, is synthesized from solution and the optical properties and crystal structure are compared with previously reported Cs3Bi2I9 perovskite, and the photovoltaic properties are also investigated. The XRD pattern suggests that the CsBi3I10 film has a layered structure with a different dominating crystal growth direction than the Cs3Bi2I9 perovskite. A band gap of 1.77 eV is obtained for the CsBi3I10 film, which is smaller than the band gap of Cs3Bi2I9 at 2.03 eV, and an extended visible light absorption spectrum is therefore obtained. The solar cell device with CsBi3I10 shows a photocurrent up to 700 nm, and this work shows therefore the possibility for increased light absorption and higher photocurrents in solar cells based on bismuth halide perovskites.

  11. TG-FTIR, DSC and quantum chemical studies of the thermal decomposition of quaternary methylammonium halides

    International Nuclear Information System (INIS)

    Sawicka, Marlena; Storoniak, Piotr; Skurski, Piotr; Blazejowski, Jerzy; Rak, Janusz

    2006-01-01

    The thermal decomposition of quaternary methylammonium halides was studied using thermogravimetry coupled to FTIR (TG-FTIR) and differential scanning calorimetry (DSC) as well as the DFT, MP2 and G2 quantum chemical methods. There is almost perfect agreement between the experimental IR spectra and those predicted at the B3LYP/6-311G(d,p) level: this has demonstrated for the first time that an equimolar mixture of trimethylamine and a methyl halide is produced as a result of decomposition. The experimental enthalpies of dissociation are 153.4, 171.2, and 186.7 kJ/mol for chloride, bromide and iodide, respectively, values that correlate well with the calculated enthalpies of dissociation based on crystal lattice energies and quantum chemical thermodynamic barriers. The experimental activation barriers estimated from the least-squares fit of the F1 kinetic model (first-order process) to thermogravimetric traces - 283, 244 and 204 kJ/mol for chloride, bromide and iodide, respectively - agree very well with theoretically calculated values. The theoretical approach assumed in this work has been shown capable of predicting the relevant characteristics of the thermal decomposition of solids with experimental accuracy

  12. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

    Science.gov (United States)

    2017-01-01

    The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and for assembling them into hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic–inorganic MAPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. The presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that comparisons can more easily be made. PMID:29503507

  13. Time Domain View of Liquid-like Screening and Large Polaron Formation in Lead Halide Perovskites

    Science.gov (United States)

    Joshi, Prakriti Pradhan; Miyata, Kiyoshi; Trinh, M. Tuan; Zhu, Xiaoyang

    The structural softness and dynamic disorder of lead halide perovskites contributes to their remarkable optoelectronic properties through efficient charge screening and large polaron formation. Here we provide a direct time-domain view of the liquid-like structural dynamics and polaron formation in single crystal CH3NH3PbBr3 and CsPbBr3 using femtosecond optical Kerr effect spectroscopy in conjunction with transient reflectance spectroscopy. We investigate structural dynamics as function of pump energy, which enables us to examine the dynamics in the absence and presence of charge carriers. In the absence of charge carriers, structural dynamics are dominated by over-damped picosecond motions of the inorganic PbBr3- sub-lattice and these motions are strongly coupled to band-gap electronic transitions. Carrier injection from across-gap optical excitation triggers additional 0.26 ps dynamics in CH3NH3PbBr3 that can be attributed to the formation of large polarons. In comparison, large polaron formation is slower in CsPbBr3 with a time constant of 0.6 ps. We discuss how such dynamic screening protects charge carriers in lead halide perovskites. US Department of Energy, Office of Science - Basic Energy Sciences.

  14. An objective protocol for comparing the noise performance of silver halide film and digital sensor

    Science.gov (United States)

    Cao, Frédéric; Guichard, Frédéric; Hornung, Hervé; Tessière, Régis

    2012-01-01

    Digital sensors have obviously invaded the photography mass market. However, some photographers with very high expectancy still use silver halide film. Are they only nostalgic reluctant to technology or is there more than meets the eye? The answer is not so easy if we remark that, at the end of the golden age, films were actually scanned before development. Nowadays film users have adopted digital technology and scan their film to take advantage from digital processing afterwards. Therefore, it is legitimate to evaluate silver halide film "with a digital eye", with the assumption that processing can be applied as for a digital camera. The article will describe in details the operations we need to consider the film as a RAW digital sensor. In particular, we have to account for the film characteristic curve, the autocorrelation of the noise (related to film grain) and the sampling of the digital sensor (related to Bayer filter array). We also describe the protocol that was set, from shooting to scanning. We then present and interpret the results of sensor response, signal to noise ratio and dynamic range.

  15. Linear chrono-amperometry using re-dissolution: application to halides

    International Nuclear Information System (INIS)

    Perchard, J.-P.; Buvet, M.; Molina, R.

    1966-06-01

    The possibility of applying linear chrono-amperometry to analysis was studied using a falling-drop mercury electrode. Measurements of the cations were carried out by direct reduction or by prior formation of an amalgam, which is then oxidized. Using the first technique, the minimum concentration that can be attained is about 10 -6 M and the reproducibility of the results is of the order of 2%. With the second method the sensitivity is much improved: in the concentration range of 10 -7 to 10 -8 M, the scatter of the results is less than 10% if the agitation and temperature conditions are kept constant. The halides are determined by re-dissolving the mercurous halide deposit formed by electrolysis. From the analytical point of view, the sensitivity is limited in the domain where the phenomena can be interpreted and used. In the case of the chloride ion the lower limit of this zone is close to 10 -5 M; it is 10 -6 M for the bromide and less than 10 -7 M for the iodide. For lower concentrations, simple laws that might be applied in analysis are no longer valid. However, the splitting of the peak observed during the reduction of the mercurous iodide deposit was interpreted as showing that the mono-molecular Hg 2 I 2 layer formed on the drop has particular electrochemical properties. (authors) [fr

  16. Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

    Science.gov (United States)

    Manser, Joseph S.

    The burgeoning class of metal halide perovskites constitutes a paradigm shift in the study and application of solution-processed semiconductors. Advancements in thin film processing and our understanding of the underlying structural, photophysical, and electronic properties of these materials over the past five years have led to development of perovskite solar cells with power conversion efficiencies that rival much more mature first and second-generation commercial technologies. It seems only a matter of time before the real-world impact of these compounds is put to the test. Like oxide perovskites, metal halide perovskites have ABX3 stoichiometry, where typically A is a monovalent cation, B a bivalent post-transition metal, and X a halide anion. Characterizing the behavior of photogenerated charges in metal halide perovskites is integral for understanding the operating principles and fundamental limitations of perovskite optoelectronics. The majority of studies outlined in this dissertation involve fundamental study of the prototypical organic-inorganic compound methylammonium lead iodide (CH3NH3PbI 3). Time-resolved pump-probe spectroscopy serves as a principle tool in these investigations. Excitation of a semiconductor can lead to formation of a number different excited state species and electronic complexes. Through analysis of excited state decay kinetics and optical nonlinearities in perovskite thin films, we identify spontaneous formation of a large fraction of free electrons and holes, whose presence is requisite for efficient photovoltaic operation. Following photogeneration of charge carriers in a semiconductor absorber, these species must travel large distances across the thickness of the material to realize large external quantum efficiencies and efficient carrier extraction. Using a powerful technique known as transient absorption microscopy, we directly image long-range carrier diffusion in a CH3NH3PbI 3 thin film. Charges are unambiguously shown to

  17. Variable Charge and Electrical Double Layer of Mineral-Water Interfaces: Silver Halides versus Metal (Hydr)Oxides

    NARCIS (Netherlands)

    Hiemstra, T.

    2012-01-01

    Classically, silver (Ag) halides have been used to understand thermodynamic principles of the charging process and the corresponding development of the electrical double layer (EDL). A mechanistic approach to the processes on the molecular level has not yet been carried out using advanced surface

  18. Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

    Czech Academy of Sciences Publication Activity Database

    Ivanova, Z.G.; Zavadil, Jiří; Kostka, P.; Djouama, T.; Reinfelde, M.

    2017-01-01

    Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985882 Keywords : caesium halides * chalcohalide glass es * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

  19. Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

    Czech Academy of Sciences Publication Activity Database

    Ivanova, Z.G.; Zavadil, Jiří; Kostka, P.; Djouama, T.; Reinfelde, M.

    2017-01-01

    Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985882 Keywords : caesium halides * chalcohalide glasses * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics , Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

  20. Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

    Czech Academy of Sciences Publication Activity Database

    Ivanova, Z.G.; Zavadil, Jiří; Kostka, Petr; Djouama, T.; Reinfelde, M.

    2017-01-01

    Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985891 Keywords : caesium halides * chalcohalide glasses * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

  1. Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

    Science.gov (United States)

    Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

    2016-03-07

    Innovative americium-bearing uranium-plutonium mixed oxides U1-yPuyO2-x are envisioned as nuclear fuel for sodium-cooled fast neutron reactors (SFRs). The oxygen-to-metal (O/M) ratio, directly related to the oxidation state of cations, affects many of the fuel properties. Thus, a thorough knowledge of its variation with the sintering conditions is essential. The aim of this work is to follow the oxidation state of uranium, plutonium, and americium, and so the O/M ratio, in U0.750Pu0.246Am0.004O2-x samples sintered for 4 h at 2023 K in various Ar + 5% H2 + z vpm H2O (z = ∼ 15, ∼ 90, and ∼ 200) gas mixtures. The O/M ratios were determined by gravimetry, XAS, and XRD and evidenced a partial oxidation of the samples at room temperature. Finally, by comparing XANES and EXAFS results to that of a previous study, we demonstrate that the presence of uranium does not influence the interactions between americium and plutonium and that the differences in the O/M ratio between the investigated conditions is controlled by the reduction of plutonium. We also discuss the role of the homogeneity of cation distribution, as determined by EPMA, on the mechanisms involved in the reduction process.

  2. Analisa Teknis Pemakaian Kombinasi Lampu Metal Halide Dan Led Sebagai Pemikat Ikan Pada Kapal Pukat Cincin (Purse Seine Dan Pengaruhnya Terhadap Konsumsi Bahan Bakar Genset

    Directory of Open Access Journals (Sweden)

    Septian Ragil Wibisono

    2017-01-01

    Full Text Available Saat ini lampu Metal Halide dipakai sebagai pemikat ikan  oleh nelayan Purse Seine. Peggunaan lampu tersebut memerlukan daya Genset yang besar karena satu lampu Metal Halide berdaya 1500 Watt. Semakin banyak lampu Metal Halide yang digunakan semakin besar pula konsumsi bahan bakar Genset. Dalam upaya penghematan energi bahan bakar maka digunakan lampu LED sebagai alternatif pemikat ikan. Lampu LED dikenal sebagai lampu yang hemat energi. Penelitian ini ditujukan untuk mengetahui dan membandingkan konsumsi bahan bakar Genset saat menggunakan kombinasi lampu Metal Halide dan LED. Penelitian ini dilakukan dengan mengambil data konsumsi bahan bakar Genset untuk menyalakan sejumlah lampu Metal Halide dan lampu LED, kemudian dilakukan analisa regresi untuk mendapatkan model persaamaan konsumsi bahan bakar Genset. Selanjutnya dilakukan ekstrapolasi untuk memprediksi konsumsi bahan bakar saat Genset dengan jumlah lampu tertentu. Hasilnya dengan besar fluks cahaya yang hampir sama, saat penggunaan 6 lampu Metal Halide konsumsi bahan bakar sebesar 13.606,03 liter, dan saat menggunakan kombinasi lampu 1 Metal Halide dan 25 lampu LED konsumsi bahan bakar sebesar 13.255,63 liter, yang artinya terjadi penghematan bahan bakar sebesar 2,58%.

  3. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    Science.gov (United States)

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas.

  4. Americium, plutonium and uranium contamination and speciation in well waters, streams and atomic lakes in the Sarzhal region of the Semipalatinsk Nuclear Test Site, Kazakhstan.

    Science.gov (United States)

    León Vintró, L; Mitchell, P I; Omarova, A; Burkitbayev, M; Jiménez Nápoles, H; Priest, N D

    2009-04-01

    New data are reported on the concentrations, isotopic composition and speciation of americium, plutonium and uranium in surface and ground waters in the Sarzhal region of the Semipalatinsk Test Site, and an adjacent area including the settlement of Sarzhal. The data relate to filtered water and suspended particulate from (a) streams originating in the Degelen Mountains, (b) the Tel'kem 1 and Tel'kem 2 atomic craters, and (c) wells on farms located within the study area and at Sarzhal. The measurements show that (241)Am, (239,240)Pu and (238)U concentrations in well waters within the study area are in the range 0.04-87mBq dm(-3), 0.7-99mBq dm(-3), and 74-213mBq dm(-3), respectively, and for (241)Am and (239,240)Pu are elevated above the levels expected solely on the basis of global fallout. Concentrations in streams sourced in the Degelen Mountains are similar, while concentrations in the two water-filled atomic craters are somewhat higher. Suspended particulate concentrations in well waters vary considerably, though median values are very low, at 0.01mBq dm(-3), 0.08mBq dm(-3) and 0.32mBq dm(-3) for (241)Am, (239,240)Pu and (238)U, respectively. The (235)U/(238)U isotopic ratio in almost all well and stream waters is slightly elevated above the 'best estimate' value for natural uranium worldwide, suggesting that some of the uranium in these waters is of test-site provenance. Redox analysis shows that on average most of the plutonium present in the microfiltered fraction of these waters is in a chemically reduced form (mean 69%; 95% confidence interval 53-85%). In the case of the atomic craters, the proportion is even higher. As expected, all of the americium present appears to be in a reduced form. Calculations suggest that annual committed effective doses to individual adults arising from the daily ingestion of these well waters are in the range 11-42microSv (mean 21microSv). Presently, the ground water feeding these wells would not appear to be contaminated with

  5. Americium, plutonium and uranium contamination and speciation in well waters, streams and atomic lakes in the Sarzhal region of the Semipalatinsk Nuclear Test Site, Kazakhstan

    Energy Technology Data Exchange (ETDEWEB)

    Leon Vintro, L. [School of Physics, University College Dublin, Belfield, Dublin 4 (Ireland)], E-mail: luis.leon@ucd.ie; Mitchell, P.I.; Omarova, A. [School of Physics, University College Dublin, Belfield, Dublin 4 (Ireland); Burkitbayev, M. [Department of Inorganic Chemistry, Al-Faraby Kazakh National University, Almaty (Kazakhstan); Jimenez Napoles, H. [School of Physics, University College Dublin, Belfield, Dublin 4 (Ireland); Priest, N.D. [School of Health and Social Sciences, Middlesex University, Enfield, EN3 4SA (United Kingdom)

    2009-04-15

    New data are reported on the concentrations, isotopic composition and speciation of americium, plutonium and uranium in surface and ground waters in the Sarzhal region of the Semipalatinsk Test Site, and an adjacent area including the settlement of Sarzhal. The data relate to filtered water and suspended particulate from (a) streams originating in the Degelen Mountains, (b) the Tel'kem 1 and Tel'kem 2 atomic craters, and (c) wells on farms located within the study area and at Sarzhal. The measurements show that {sup 241}Am, {sup 239,240}Pu and {sup 238}U concentrations in well waters within the study area are in the range 0.04-87 mBq dm{sup -3}, 0.7-99 mBq dm{sup -3}, and 74-213 mBq dm{sup -3}, respectively, and for {sup 241}Am and {sup 239,240}Pu are elevated above the levels expected solely on the basis of global fallout. Concentrations in streams sourced in the Degelen Mountains are similar, while concentrations in the two water-filled atomic craters are somewhat higher. Suspended particulate concentrations in well waters vary considerably, though median values are very low, at 0.01 mBq dm{sup -3}, 0.08 mBq dm{sup -3} and 0.32 mBq dm{sup -3} for {sup 241}Am, {sup 239,240}Pu and {sup 238}U, respectively. The {sup 235}U/{sup 238}U isotopic ratio in almost all well and stream waters is slightly elevated above the 'best estimate' value for natural uranium worldwide, suggesting that some of the uranium in these waters is of test-site provenance. Redox analysis shows that on average most of the plutonium present in the microfiltered fraction of these waters is in a chemically reduced form (mean 69%; 95% confidence interval 53-85%). In the case of the atomic craters, the proportion is even higher. As expected, all of the americium present appears to be in a reduced form. Calculations suggest that annual committed effective doses to individual adults arising from the daily ingestion of these well waters are in the range 11-42 {mu}Sv (mean 21 {mu

  6. Theoretical and experimental study of the bio-geochemical behaviour of americium 241 in simplified rhizosphere conditions. Application to a calcareous agricultural soil; Etude theorique et experimentale du comportement biogeochimique de l'americium-241 en conditions rhizospheriques simplifiees. Application dans un sol agricole calcaire

    Energy Technology Data Exchange (ETDEWEB)

    Perrier, T

    2004-06-01

    Americium 241, is one of the most radio-toxic contaminant produced during the nuclear fuel cycle. It can be found in all environmental compartments, in particular the soils. The main goals of this study are to identify, quantify and model the effect of the main factors controlling the mobility of {sup 241}Am in the rhizosphere and the agricultural soils. The physico-chemical parameters of the soil and of the soil solution, the potential role of microorganisms on the sorption-desorption processes, and the speciation of americium in solution have been more particularly studied. {sup 241}Am remobilization has been studied at the laboratory using leaching experiments performed in controlled conditions on reworked calcareous soils artificially contaminated with {sup 241}Am. The soil samples have been washed out in different hydrodynamic conditions by solutions with various compositions. The eluted solution has been analyzed (pH, conductivity, ionic composition, Fe{sub tot}, organic acids, {sup 241}Am) and its bacterial biomass content too. The overall results indicate that {sup 241}Am remobilization is contrasted and strongly linked with the condition under study (pH, ionic strength, glucose and/or citrate concentration). Therefore, a solution in equilibrium with the soil or containing small exudate concentrations (10{sup -4} M) re-mobilizes only a very small part of the americium fixed on the solid phase. The desorption of {sup 241}Am corresponds to a solid/liquid coefficient of partition (K{sub d}) of about 10{sup 5} L.kg{sup -1}. A significant addition of glucose induces an important dissolution of soil carbonates by the indirect action of microorganisms, but does not significantly favor the {sup 241}Am remobilization. On the other hand, the presence of strong citrate concentrations ({>=} 10{sup -2} M) allows 300 to 10000 time greater re-mobilizations by the complexing of {sup 241}Am released after the dissolution of the carrying phases. Finally, the colloidal

  7. Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

    Science.gov (United States)

    Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

    2016-03-09

    Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance.

  8. Ground-state properties and optical excitations of a solvated electron in molten alkali halides

    International Nuclear Information System (INIS)

    Roman, E.; Senatore, G.; Tosi, M.P.; Trieste Univ.

    1983-09-01

    Properties of solvated electrons at high dilution in four molten alkali halides are investigated theoretically. A self-consistent evaluation of the bound ground state of the electron and of the surrounding liquid structure, already developed in a previous paper, is compared with the results of NMR hyperfine shifts and magnetic susceptibility measurements. The absorption bands associated with Franck-Condon 1s→2p and 1s→3p transitions are calculated and compared with the available data of optical absorption, with special emphasis on the detailed analysis by Yuh and Nachtrieb for molten CsCl. An instability of the excited states against ionic relaxation and the origin of a finite lifetime for the ground state are also discussed. Finally, the perturbation induced by the solvated electron in the fundamental absorption of the molten salt is estimated. (author)

  9. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica

    Science.gov (United States)

    Olguin, Gianni; Yacou, Christelle; Smart, Simon; Diniz da Costa, João C.

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications. PMID:24022785

  10. Far IR spectra of Th(IV) halide complexes of some heterocyclic bases

    International Nuclear Information System (INIS)

    Srivastava, A.K.; Agarwal, R.K.; Srivastava, M.; Kapoor, V.; Srivastava, T.N.

    1981-01-01

    The synthesis and IR spectra of Th(IV) perchlorato, nitrato and thiocyanato complexes of some heterocyclic bases have been reported. Halogens are common ligands in coordination chemistry forming coordinate bonds with metals readily. Metal halogen (M-X) stretching bands show a strong absorption in the far-IR region. Very little information is available on Th-X stretching frequencies. In the present communication, adducts of Th(IV) halide with certain nitrogen heterocyclic bases such as pyridine, α-picoline, 2-amino pyridine, 2:4-lutidine, 2:6-lutidine, quinoline, 2,2'-bipyridine and 1,10-phenanthroline were synthesised and characterised. Experimental details are given. Results are presented and discussed. (author)

  11. Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

    Science.gov (United States)

    Cressault, Yann; Teulet, Philippe; Zissis, Georges

    2016-07-01

    The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

  12. Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin-Orbitronics.

    Science.gov (United States)

    Kepenekian, Mikaël; Even, Jacky

    2017-07-20

    In halide hybrid organic-inorganic perovskites (HOPs), spin-orbit coupling (SOC) presents a well-documented large influence on band structure. However, SOC may also present more exotic effects, such as Rashba and Dresselhaus couplings. In this Perspective, we start by recalling the main features of this effect and what makes HOP materials ideal candidates for the generation and tuning of spin-states. Then, we detail the main spectroscopy techniques able to characterize these effects and their application to HOPs. Finally, we discuss potential applications in spintronics and in spin-orbitronics in those nonmagnetic systems, which would complete the skill set of HOPs and perpetuate their ride on the crest of the wave of popularity started with optoelectronics and photovoltaics.

  13. Research progress on organic-inorganic halide perovskite materials and solar cells

    Science.gov (United States)

    Ono, Luis K.; Qi, Yabing

    2018-03-01

    Owing to the intensive research efforts across the world since 2009, perovskite solar cell power conversion efficiencies (PCEs) are now comparable or even better than several other photovoltaic (PV) technologies. In this topical review article, we review recent progress in the field of organic-inorganic halide perovskite materials and solar cells. We associate these achievements with the fundamental knowledge gained in the perovskite research. The major recent advances in the fundamental perovskite material and solar cell research are highlighted, including the current efforts in visualizing the dynamical processes (in operando) taking place within a perovskite solar cell under operating conditions. We also discuss the existing technological challenges. Based on a survey of recently published works, we point out that to move the perovskite PV technology forward towards the next step of commercialization, what perovskite PV technology need the most in the coming next few years is not only further PCE enhancements, but also up-scaling, stability, and lead-toxicity.

  14. Measurements of spin-lattice relaxation time in mixed alkali halide crystals

    International Nuclear Information System (INIS)

    Tannus, A.

    1983-01-01

    Using magneto-optic techniques the ground state spin-lattice relaxation times (T1) of 'F' centers in mixed Alkali Halide cristals (KCl-KBr), was studied. A computer assisted system to optically measure short relaxation times (approx. = 1mS), was described. The technique is based on the measurement of the Magnetic Circular Dicroism (MCD) presented by F centers. The T1 magnetic field dependency at 2 K (up to 65 KGauss), was obtained as well as the MCD spectra for different relative concentration at the mixed matrices. The theory developed by Panepucci and Mollenauer for F centers spin-lattice relaxation in pure matrices was modified to explain the behaviour of T1 in mixed cristals. The Direct Process results (T approx. = 2.0 K) compared against that theory shows that the main relaxation mecanism, up to 25 KGauss, continues to be phonon modulation of the hiperfine iteraction between F electrons and surrounding nuclei. (Author) [pt

  15. Lattice dynamics and the nature of structural transitions in organolead halide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.; Herron, Norman; Guise, William E.; Wang, Xiaoping; Whitfield, Pamela S.; Jain, Ankit; Gong, Xiwen; McGaughey, Alan J. H.; Sargent, Edward H.

    2016-09-09

    Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remarkable optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic x-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our findings confirm the displacive nature of the cubic-to-tetragonal phase transition, which is further shown, using neutron and x-ray diffraction, to be close to a tricritical point. Lastly, we detect quasistatic symmetry-breaking nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These findings reveal key structural properties of these materials, and also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.

  16. Three- and Two-Dimensional Tin and Lead Halide Perovskite Semiconductors: Synthesis and Application in Photovoltaics

    Science.gov (United States)

    Cao, Duyen Hanh

    Halide perovskites, AMX3 (A = monocation, B = Ge, Sn, or Pb, and X = halogen), present a versatile class of solution-processable semiconductors made from earth abundant materials with outstanding electrical and optical properties. Their solar cell efficiencies have dramatically increased from 9% to 22% in less than five years since 2012, a rate that has never been seen before in photovoltaic research. Critical to the final goal of commercializing perovskite solar cell technology is achieving device long-term stability and eliminating toxic elements in device components. This thesis uses 3D AMX 3 perovskites as a stand-in to develop a new class of lead-free, moisture stable, functional and highly tunable 2D Ruddlesden-Popper (BA) 2(MA)n-1SnnI3n+1 (n is an integer) perovskite semiconductors. Synthesis, thin film fabrication, extensive characterization, and solar cell device structure-performance relationships are presented throughout the entire thesis.

  17. Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer

    Directory of Open Access Journals (Sweden)

    Ulli Englert

    2011-07-01

    Full Text Available The chain polymer [{Cd(μ-X2py2}1∞] (X = Cl, Br; py = pyridine undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples.

  18. Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites.

    Science.gov (United States)

    Coll, Mariona; Gomez, Andrés; Mas-Marza, Elena; Almora, Osbel; Garcia-Belmonte, Germà; Campoy-Quiles, Mariano; Bisquert, Juan

    2015-04-16

    We investigate the ferroelectric properties of photovoltaic methylammonium lead halide CH3NH3PbI3 perovskite using piezoelectric force microscopy (PFM) and macroscopic polarization methods. The electric polarization is clearly observed by amplitude and phase hysteresis loops. However, the polarization loop decreases as the frequency is lowered, persisting for a short time only, in the one second regime, indicating that CH3NH3PbI3 does not exhibit permanent polarization at room temperature. This result is confirmed by macroscopic polarization measurement based on a standard capacitive method. We have observed a strong increase of piezoelectric response under illumination, consistent with the previously reported giant photoinduced dielectric constant at low frequencies. We speculate that an intrinsic charge transfer photoinduced dipole in the perovskite cage may lie at the origin of this effect.

  19. Comparison of boron halide, decaborane and B implants in Si from Molecular Dynamics simulations

    International Nuclear Information System (INIS)

    Webb, R.P.; Winston, S.H.; Gwilliam, R.M.; Sealy, B.J.; Boudreault, G.; Jeynes, C.; Kirkby, K.J.

    2003-01-01

    Ultra shallow junctions (depths 2 + , have been used to transport low velocity boron at higher energies, enabling the use of conventional implanters in the production of shallow junctions. However, with ever shrinking scales the energies required even for BF 2 are becoming too low. The investigation here is to look at the alternative heavier halides and decaborane as possible alternatives to allow continued use of conventional ion implanters. We use a molecular dynamics simulation to see if we can find any evidence of non-linear behaviour from the use of such molecular species for implantation, thereby making the modelling and simulation of such implants more complex than more conventional implantation. The simulation results presented suggest that there is no evidence of non-linear behaviour and all the standard parameters of implantation - ion ranges and displacements of silicon atoms - change in a well predicted manner

  20. Shape-controlled synthesis of organolead halide perovskite nanocrystals and their tunable optical absorption

    International Nuclear Information System (INIS)

    Chen, Zhenhua; Tang, Yongbing; Huang, Xing; Lee, Chun-Sing; Li, Hui; Ho, Derek

    2014-01-01

    Hybrid organolead halide perovskites (CH 3 NH 3 PbI 3 ) with polymorphic structures have been successfully synthesized by controlling their solubility in solvents with different polarities. Crystal formation stages of the perovskites have been demonstrated for the first time. Shape changes of such perovskites are accompanied by transition in their crystal structures and variation of optical properties. Herein, a new trigonal phase for CH 3 NH 3 PbI 3 has been observed with a rod-like morphology. Photoemission study indicates a significant red shift in the perovskite nanoparticles, compared to that of the rod-like nanocrystals. This solvent-controlled formation of polymorphic phases provide an additional approach for controlling the optical properties of CH 3 NH 3 PbI 3 for various optoelectronic applications. (papers)

  1. The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

    KAUST Repository

    Zhumekenov, Ayan A.

    2017-07-06

    The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current bottlenecks retarding the shift towards single crystal-based optoelectronics. Here we theoretically and experimentally elucidate the role of surface tension in the rapid synthesis of perovskite single crystals by inverse temperature crystallization (ITC). Understanding the nucleation and growth mechanisms enabled us to exploit surface tension to direct the growth of monocrystalline films of perovskites (AMX3, where A = CH3NH3+ or MA; M = Pb2+, Sn2+; X = Br-, I-) on the solution surface. We achieve up to 1 cm2-sized monocrystalline films with thickness on the order of the charge carrier diffusion length (~5-10 µm). Our work paves the way to control the crystallization process of perovskites, including thin film deposition, which is essential to advance the performance benchmarks of perovskite optoelectronics.

  2. Concentration Effects of Silver Ions on Ionic Conductivities of Molten Silver Halides

    Directory of Open Access Journals (Sweden)

    Okada T.

    2011-05-01

    Full Text Available Ionic conductivities of molten (RbXc(AgX1-c (X = Cl and I mixtures were measured to clarify the concentration effects of silver ions on ionic conductivities of molten silver halides. It is found that the addition of RbX to molten AgX rapidly reduces the ionic conductivity with 0 ≤ c ≤ 0.4. It suggests that strong Ag-Ag correlation is necessary to fast conduction of Ag ions in molten state. The absolute values of ionic conductivity for (RbClc(AgCl1-c are larger than those for (RbIc(AgI1-c mixtures at all compositions. These differences might relate to difference of diffusion constant between Cl- and I- and difference of effective charge carried by an ion between molten AgCl and AgI

  3. Energy and geometry of boron compounds. Halides BHHal2, BHal3 and their disproportionation

    International Nuclear Information System (INIS)

    Ionov, S.P.; Kuznetsov, N.T.

    1998-01-01

    Analysis of structural and thermodynamic parameters of boron halogen derivatives was conducted on the basis of structural-thermochemical (ST) model. Equilibrium interatomic B-H distances were specified for gaseous BHF 2 , BHCl 2 and BHBr 2 molecules. They were equal to 1.199±0.002, 1.175±0.003 and 1.79±0.01 A respectively. Formation heat was determined for BHI 2 : Δ f H 298 (BHI 2 (hg) = 72±5 kJ/mol. Qualitative analysis of thermodynamics of reactions of boron halide disproportionation was performed in the framework of ST-model: BHal 3 + 4BHal 3 . It was shown that halogen atoms weakened B-H-H bridges, halogens formed weak bridges in intermediate nonstable dimers

  4. Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Dou, Benjia [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Wheeler, Lance M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christians, Jeffrey A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Moore, David [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Harvey, Steven P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berry, Joseph J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Van Hest, Marinus F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Barnes, Frank S. [University of Colorado; Shaheen, Sean E. [University of Colorado

    2018-03-02

    Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporates into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.

  5. Temperature-dependent excitonic photoluminescence of hybrid organometal halide perovskite films

    KAUST Repository

    Wu, Kewei

    2014-01-01

    Organometal halide perovskites have recently attracted tremendous attention due to their potential for photovoltaic applications, and they are also considered as promising materials in light emitting and lasing devices. In this work, we investigated in detail the cryogenic steady state photoluminescence properties of a prototypical hybrid perovskite CH3NH3PbI3-xClx. The evolution of the characteristics of two excitonic peaks coincides with the structural phase transition around 160 K. Our results further revealed an exciton binding energy of 62.3 ± 8.9 meV and an optical phonon energy of 25.3 ± 5.2 meV, along with an abnormal blue-shift of the band gap in the high-temperature tetragonal phase. This journal is

  6. 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......, J–V performance. A perovskite solar cell converted from PbI2 with a dense bottom layer and porous top layer achieved higher device performance than those of analogue cells with a dense PbI2 top layer. This work demonstrates a facile way to control PbI2 film configuration and morphology simply...

  7. Fabrication and characterization of rubidium/formamidinium-incorporated methylammonium-lead-halide perovskite solar cells

    Science.gov (United States)

    Kato, Masataka; Suzuki, Atsushi; Ohishi, Yuya; Tanaka, Hiroki; Oku, Takeo

    2018-01-01

    Fabrication and characterization of perovskite solar cells using mesoporous TiO2 as an electron transporting layer and 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene as a hole-transporting layer were performed for improving the photovoltaic performance. Additive effects of formamidinium (FA), rubidium (Rb), chlorine (Cl) and bromine (Br) into the methylammonium-lead-halide perovskite crystal on the photovoltaic properties and microstructures were investigated. The photovoltaic parameters of short-circuit current density, conversion efficiency, the surface morphology and domain in the perovskite crystal were characterized. The slight addition of FACl and RbBr to the CH3NH3PbI3 crystal provided homogeneous microstructures with the dispersed crystal domains, which improved the photovoltaic performance. The excess addition of Cl to the perovskite crystal caused nanorod-like crystals, which degraded the photovoltaic performance.

  8. Structure and bonding in metal-rich compounds: pnictides, chalcides and halides

    International Nuclear Information System (INIS)

    Franzen, H.F.

    1978-01-01

    The subject is reviewed under the following headings: introduction (compounds included in the review; purpose of the review); MX compounds with M = transition metal and X = O,N,S or P; sulfides and selenides of the transition metals; transition-metal phosphides; alkali oxides; transition-metal oxides and nitrides with X/M < 1; metal-rich halides; conclusion. The references number 238. Compounds of the following principal elements of nuclear interest are included in the tables and text: Am, Ce, Cs, Eu, Gd, Hf, La, Mo, Np, Nb, Pu, Pr, Pa, Re, Ru, Sc, Ta, Tb, Th, W, U, V, Y, Zr. The information in the tables is presented under: structure type, space group, lattice parameters and remarks. (U.K.)

  9. High-Purity Hybrid Organolead Halide Perovskite Nanoparticles Obtained by Pulsed-Laser Irradiation in Liquid

    KAUST Repository

    Amendola, Vincenzo

    2016-11-17

    Nanoparticles of hybrid organic-inorganic perovskites have attracted a great deal of attention due to their variety of optoelectronic properties, their low cost, and their easier integration into devices with complex geometry, compared with microcrystalline, thin-film, or bulk metal halides. Here we present a novel one-step synthesis of organolead bromide perovskite nanocrystals based on pulsed-laser irradiation in a liquid environment (PLIL). Starting from a bulk CHNHPbBr crystal, our PLIL procedure does not involve the use of high-boiling-point polar solvents or templating agents, and runs at room temperature. The resulting nanoparticles are characterized by high crystallinity and are completely free of any microscopic product or organic coating layer. We also demonstrate the straightforward inclusion of laser-generated perovskite nanocrystals in a polymeric matrix to form a nanocomposite with single- and two-photon luminescence properties.

  10. Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

    KAUST Repository

    Zernickel, Anna

    2018-01-09

    A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

  11. Experimental and theoretical studies of thermodynamics of lithium halide solutions - ethanol mixtures

    International Nuclear Information System (INIS)

    Nasehzadeh, Asadollah; Noroozian, Ebrahim; Omrani, Hengameh

    2004-01-01

    The vapor pressures of lithium halide solutions in ethanol have been determined in the range of concentration from (0.01 to 2.0) mol · kg -1 at 298.15 K. The activity of solvent was obtained directly and the osmotic coefficients of solutions were then calculated. An accurate reference osmotic coefficient (phi 0 ) was obtained in a more diluted solution at a reference molality, m 0 (=10 -3 kg · mol -1 ). The ionic activity coefficient, the excess, and the change in partial molal free energy of solutions were calculated by using Gibbs-Duhem equation. The values of osmotic coefficient that obtained in this work were fitted to MSA-NRTL and Pitzer's models and the values of characteristic adjustable parameters were calculated. It is shown that the goodness and the overall quality of the fit for both models are excellent

  12. High Defect Tolerance in Lead Halide Perovskite CsPbBr3.

    Science.gov (United States)

    Kang, Jun; Wang, Lin-Wang

    2017-01-19

    The formation energies and charge-transition levels of intrinsic point defects in lead halide perovskite CsPbBr 3 are studied from first-principles calculations. It is shown that the formation energy of dominant defect under Br-rich growth condition is much lower than that under moderate or Br-poor conditions. Thus avoiding the Br-rich condition can help to reduce the defect concentration. Interestingly, CsPbBr 3 is found to be highly defect-tolerant in terms of its electronic structure. Most of the intrinsic defects induce shallow transition levels. Only a few defects with high formation energies can create deep transition levels. Therefore, CsPbBr 3 can maintain its good electronic quality despite the presence of defects. Such defect tolerance feature can be attributed to the lacking of bonding-antibonding interaction between the conduction bands and valence bands.

  13. Heavy metal ternary halides for room-temperature x-ray and gamma-ray detection

    Science.gov (United States)

    Liu, Zhifu; Peters, John A.; Stoumpos, Constantinos C.; Sebastian, Maria; Wessels, Bruce W.; Im, Jino; Freeman, Arthur J.; Kanatzidis, Mercouri G.

    2013-09-01

    We report our recent progress on wide bandgap ternary halide compounds CsPbBr3 and CsPbCl3 for room temperature x-ray and gamma-ray detectors. Their bandgaps are measured to be 2.24 eV and 2.86 eV, respectively. The measured mobility-lifetime products of CsPbBr3 are 1.7×10-3, 1.3×10-3 cm2/V, for electron and hole carriers, respectively, comparable to those of CdTe. We measured the room temperature spectral response of CsPbBr3 sample to Ag x-ray radiation. It has a well-resolved spectral response to the 22.4 keV Kα radiation peak and detector efficiency comparable to that of CdZnTe detector at 295 K.

  14. Ion Segregation and Deliquescence of Alkali Halide Nanocrystals on SiO2

    Energy Technology Data Exchange (ETDEWEB)

    Arima, Kenta; Jiang, Peng; Lin, Deng-Sung; Verdaguer, Albert; Salmeron, Miquel

    2009-08-11

    The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO{sub 2} and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

  15. EPR Study of Hole-Trapping at Cation Vacancies in Silver-Halides

    Science.gov (United States)

    Kao, Chien-Teh

    The hole-trapping at cation vacancies in silver halides is studied by means of electron paramagnetic resonance (EPR). The studied silver halide crystals were doped with trivalent Fe, and also with one of the divalent ions Ca, Cd, or Zn. The former dopant is to serve as a hole source upon sub-band-gap irradiation, while the latter increases the concentration of silver vacancies in the crystal. In AgCl, the photo-hole is observed to become self-trapped at a silver ion at a regular lattice site near a cation vacancy. The thermal stability of the resulting vacancy-perturbed self-trapped hole (STH) is found to be substantially enhanced by the presence of the nearby vacancy. Due to the close similarity of the EPR spectrum of the new centers to that of the normal STH, the existence of the vacancy-perturbed STH centers is further confirmed by isochronal annealing experiments. By comparing the intensities of the 20K STH spectra after annealing at successively higher temperatures, it is demonstrated that, in fact, there exist two types of vacancy-perturbed STH centers, one of which decays at 70K and the other survives up to a higher temperature (110K). In addition, by computer simulation, the position of the perturbing vacancy is determined to be located at the next-nearest-neighbor position for the less stable perturbed STH. On the other hand, in AgBr, no corresponding effects have been seen here. This result is in contrast to what is expected from Kanzaki's optical absorption experiments, in which an absorption line was assigned to a hole trapped near a cation vacancy in AgBr. The metastable nature of the self-trapped hole state in AgBr might probably provide explanation for the absence of such a resonance, even with the stabilizing effect of a nearby silver vacancy.

  16. Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

    Science.gov (United States)

    Guzman, Marcelo I.; Athalye, Richa R.; Rodriguez, Jose M.

    2012-01-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ?Gdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp -2)) > (R(sub x-)(exp -1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol - and ethanol-water mixtures (0 concentration effects in sea spray aerosol formation.

  17. The Importance of Moisture in Hybrid Lead Halide Perovskite Thin Film Fabrication.

    Science.gov (United States)

    Eperon, Giles E; Habisreutinger, Severin N; Leijtens, Tomas; Bruijnaers, Bardo J; van Franeker, Jacobus J; deQuilettes, Dane W; Pathak, Sandeep; Sutton, Rebecca J; Grancini, Giulia; Ginger, David S; Janssen, Rene A J; Petrozza, Annamaria; Snaith, Henry J

    2015-09-22

    Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood and neither has the impact of moisture on the physical properties of resultant films. Herein, we carry out a comprehensive and well-controlled study of the effect of moisture exposure on methylammonium lead halide perovskite film formation and properties. We find that films formed in higher humidity atmospheres have a less continuous morphology but significantly improved photoluminescence, and that film formation is faster. In photovoltaic devices, we find that exposure to moisture, either in the precursor solution or in the atmosphere during formation, results in significantly improved open-circuit voltages and hence overall device performance. We then find that by post-treating dry films with moisture exposure, we can enhance photovoltaic performance and photoluminescence in a similar way. The enhanced photoluminescence and open-circuit voltage imply that the material quality is improved in films that have been exposed to moisture. We determine that this improvement stems from a reduction in trap density in the films, which we postulate to be due to the partial solvation of the methylammonium component and "self-healing" of the perovskite lattice. This work highlights the importance of controlled moisture exposure when fabricating high-performance perovskite devices and provides guidelines for the optimum environment for fabrication. Moreover, we note that often an unintentional water exposure is likely responsible for the high performance of solar cells produced in some laboratories, whereas careful synthesis and fabrication in a dry environment will lead to lower-performing devices.

  18. The effect of illumination on the formation of metal halide perovskite films

    Science.gov (United States)

    Ummadisingu, Amita; Steier, Ludmilla; Seo, Ji-Youn; Matsui, Taisuke; Abate, Antonio; Tress, Wolfgang; Grätzel, Michael

    2017-04-01

    Optimizing the morphology of metal halide perovskite films is an important way to improve the performance of solar cells when these materials are used as light harvesters, because film homogeneity is correlated with photovoltaic performance. Many device architectures and processing techniques have been explored with the aim of achieving high-performance devices, including single-step deposition, sequential deposition and anti-solvent methods. Earlier studies have looked at the influence of reaction conditions on film quality, such as the concentration of the reactants and the reaction temperature. However, the precise mechanism of the reaction and the main factors that govern it are poorly understood. The consequent lack of control is the main reason for the large variability observed in perovskite morphology and the related solar-cell performance. Here we show that light has a strong influence on the rate of perovskite formation and on film morphology in both of the main deposition methods currently used: sequential deposition and the anti-solvent method. We study the reaction of a metal halide (lead iodide) with an organic compound (methylammonium iodide) using confocal laser scanning fluorescence microscopy and scanning electron microscopy. The lead iodide crystallizes before the intercalation of methylammonium iodide commences, producing the methylammonium lead iodide perovskite. We find that the formation of perovskite via such a sequential deposition is much accelerated by light. The influence of light on morphology is reflected in a doubling of solar-cell efficiency. Conversely, using the anti-solvent method to form methyl ammonium lead iodide perovskite in a single step from the same starting materials, we find that the best photovoltaic performance is obtained when films are produced in the dark. The discovery of light-activated crystallization not only identifies a previously unknown source of variability in opto-electronic properties, but also opens up

  19. Crystal structures of model lithium halides in bulk phase and in clusters

    Science.gov (United States)

    Lanaro, G.; Patey, G. N.

    2017-04-01

    We employ lattice energy calculations and molecular dynamics simulations to compare the stability of wurtzite and rock salt crystal structures of four lithium halides (LiF, LiCl, LiBr, and LiI) modeled using the Tosi-Fumi and Joung-Cheatham potentials, which are models frequently used in simulation studies. Both infinite crystals and finite clusters are considered. For the Tosi-Fumi model, we find that all four salts prefer the wurtzite structure both at 0 K and at finite temperatures, in disagreement with experiments, where rock salt is the stable structure and wurtzite exists as a metastable state. For Joung-Cheatham potentials, rock salt is more stable for LiF and LiCl, but the wurtzite structure is preferred by LiBr and LiI. It is clear that the available lithium halide force fields need improvement to bring them into better accord with the experiment. Finite-size clusters that are more stable as rock salt in the bulk phase tend to solidify as small rock salt crystals. However, small clusters of salts that prefer the wurtzite structure as bulk crystals tend to form structures that have hexagonal motifs, but are not finite-size wurtzite crystals. We show that small wurtzite structures are unstable due to the presence of a dipole and rearrange into more stable, size-dependent structures. We also show that entropic contributions can act in favor of the wurtzite structure at higher temperatures. The possible relevance of our results for simulation studies of crystal nucleation from melts and/or aqueous solutions is discussed.

  20. Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

    Science.gov (United States)

    Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae; Cho, Himchan; Kwon, Woosung; Do, Sungan; Sadhanala, Aditya; Park, Chan Gyung; Rhee, Shi-Woo; Im, Sang Hyuk; Friend, Richard H; Lee, Tae-Woo

    2017-07-25

    Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > D B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.