WorldWideScience

Sample records for americium halides

  1. Americium recovery from reduction residues

    Science.gov (United States)

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

    1973-12-25

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

  2. Determination of americium in urine

    International Nuclear Information System (INIS)

    Shvydko, N.S.; Mikhajlova, O.A.; Popov, D.K.

    1988-01-01

    A technique has been developed for the determination of americium 241 in urine by a raiochemical purification of the nuclide from uranium (upon co-precipitation of americium 241 with calcium and lanthanum), plutonium, thorum, and polonium 210 (upon co-precipitation of these radionuclides with zirconium iodate). α-Radioactivity was measured either in a thick layer of the americium 241 precipitate with a nonisotope carrier or in thin-layer preparations after electrolytic precipitation of americium 241 on a cathode

  3. Contributions to the preparation of 241americium metal and a few 241americium silicides

    International Nuclear Information System (INIS)

    Wittmann, F.D.

    1980-01-01

    In order to take a closer look at the americium-silicon system, three further silicides of americium: Am 5 Si 3 , Am 2 Si 3 and AmSi 2 were prepared in addition to the already known americium monosilicide and starting from the knowledge gained from the latters preparation. Radiographic investigations were carried out into the temperature region of 900 0 C. They showed no change of structure in the three compounds. It was possible to prepare residue-free americium metal by reducing AmF 3 with Si, whereby the SiF 4 formed can be easily separated off as volatile compound, and the Am metal is brought into a very pure form by sublimation suitable for spectrochemical investigations. Attempts to prepare binary germanides and gallides of 241 americium were unsuccessful. (RB) [de

  4. Americium in the Finnish environment

    Energy Technology Data Exchange (ETDEWEB)

    Lehto, J. (Helsinki Univ., Lab. of Radiochemistry (Finland))

    2009-07-01

    This paper reviews studies on environmental americium,241 Am, in Finland. There are two sources of americium in the Finnish environment: fallouts from nuclear weapons tests in the 1950s and 1960s and from the Chernobyl accident in 1986, the former constituting around 98% of the total environmental load. The weapons test fallout was distributed more or less uniformly over Finland, while the Chernobyl fallout was deposited on a sector from southwestern coast to northeast. The total deposition of 241 Am in Finland is approximately 20 Bq m-2 and the amount is still somewhat increasing due to decay of 241 Pu. In this paper, the distribution and migration of americium in forest and aquatic environments is described. Americium concentrations in natural waters, sediments, soils, vegetation and fishes are given. In addition, the behaviour of americium in the food chain from lichen via reindeer into man is discussed. Radiation doses to humans due to the environmental americium in Finland are of no practical importance (orig.)

  5. Accidental exposure to americium

    International Nuclear Information System (INIS)

    Heid, K.R.

    1985-04-01

    This report desribes an accident in which a 64-year old Hanford nuclear worker was exposed to high levels of americium while working in an americium recovery facility in 1976. As a result of the accident, he was heavily externally contaminated with americium, sustained with 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 immediate and longer-term treatment given the patient, including the decontamination efforts and clinical laboratory studies, are discussed. Special in-vivo equipment and techniques were used to measure the americium deposited in the patient. These and subsequent 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. The 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 as a result of the accident. A total of 1100 μCi was excreted in urine and feces during the first 2 years following the accident. The long-term use of diethylenetriaminepentaacetic acid (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 was given approximately 560 g of DTPA. 6 refs

  6. On the americium oxalate solubility

    International Nuclear Information System (INIS)

    Zakolupin, S.A.; Korablin, Eh.V.

    1977-01-01

    The americium oxalate solubility at different nitric (0.0-1 M) and oxalic (0.0-0.4 M) acid concentrations was investigated in the temperature range from 14 to 60 deg C. The dependence of americium oxalate solubility on the oxalic acid concentration was determined. Increasing oxalic acid concentration was found to reduce the americium oxalate solubility. The dependence of americium oxalate solubility on the oxalic acid concentration was noted to be a minimum at low acidity (0.1-0.3 M nitric acid). This is most likely due to Am(C 2 O 4 ) + , Am(C 2 O 4 ) 2 - and Am(C 2 O 4 ) 3 3- complex ion formation which have different unstability constants. On the basis of the data obtained, a preliminary estimate was carried out for the product of americium oxalate solubility in nitric acid medium (10 -29 -10 -31 ) and of the one in water (6.4x10 -20 )

  7. Isolation of high purity americium metal via distillation

    Science.gov (United States)

    Squires, Leah N.; King, James A.; Fielding, Randall S.; Lessing, Paul

    2018-03-01

    Pure americium metal is a crucial component for the fabrication of transmutation fuels. Unfortunately, americium in pure metal form is not available; however, a number of mixed metals and mixed oxides that include americium are available. In this manuscript a method is described to obtain high purity americium metal from a mixture of americium and neptunium metals with lead impurity via distillation.

  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. 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.

    1978-01-01

    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-hour collection period, and the americium concentrations were determined by gamma counting. Gastrointestinal uptake of americium by cows and goats was estimated to be 0.014 and 0.016% of the oral dose, respectively. 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 5.6 x 10 -4 and 1.2 x 10 -3 , respectively, for goats. 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 hours after injection. All animals were sacrificed 8 to 9 days after dosing. Bovine bone retained the greatest fraction of the administered dose followed by liver and kidney. 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

  10. 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%

  11. Redox chemistry of americium in nitric acid media

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-07-01

    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)

  12. 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)

  13. 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.)

  14. 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

  15. 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

  16. Analysis of Americium in Transplutonium Process Solutions

    International Nuclear Information System (INIS)

    Ferguson, R.B.

    2001-01-01

    One of the more difficult analyses in the transplutonium field is the determination of americium at trace levels in a complex matrix such as a process dissolver solution. Because of these conditions a highly selective separation must precede the measurement of americium. The separation technique should be mechanically simple to permit remote operation with master-slave manipulators. For subsequent americium measurement by the mass spectroscopic isotopic-dilution technique, plutonium and curium interferences must also have been removed

  17. 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...

  18. Americium thermodynamic data for the EQ3/6 database

    International Nuclear Information System (INIS)

    Kerrisk, J.F.

    1984-07-01

    Existing thermodynamic data for aqueous and solid species of americium have been reviewed and collected in a form that can be used with the EQ3/6 database. Data that are important in solubility calculations for americium at a proposed Yucca Mountain nuclear waste repository were emphasized. Conflicting data exist for americium complexes with carbonates. Essentially no data are available for americium solids or complexes at temperatures greater than 25 0 C. 17 references, 4 figures

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

    International Nuclear Information System (INIS)

    Knighton, J.B.; Hagan, P.G.; Navratil, J.D.; Thompson, G.H.

    1981-01-01

    This paper is presented in two parts: Part I, Molten Salt Extraction of Americium from Molten Plutonium Metal, and Part II, Aqueous Recovery of Americium from Extraction Salts. The Rocky Flats recovery process used for waste salts includes (1) dilute hydrochloric acid dissolution of residues; (2) cation exchange to convert from the chloride to the nitrate system and to remove gross amounts of monovalent impurities; (3) anion exchange separation of plutonium; (4) oxalate precipitation of americium; and (5) calcination of the oxalate at 600 0 C to yield americium oxide. The aqueous process portion describes attempts to improve the recovery of americium. The first part deals with modifications to the cation exchange step; the second describes development of a solvent extractions process that will recovery americium from residues containing aluminium as well as other common impurities. Results of laboratory work are described. 3 figures, 6 tables. (DP)

  20. Americium removal from nitric acid waste streams

    International Nuclear Information System (INIS)

    Muscatello, A.C.; Navratil, J.D.

    1986-01-01

    Separations research at the Rocky Flats Plant (RFP) has found ways to significantly improve americium removal from nitric acid (7M) waste streams generated by plutonium purification operations. Partial neutralization of the acid waste followed by solid supported liquid membranes (SLM) are useful in transferring and concentrating americium from nitrate solutions. Specifically, DHDECMP (dihexyl-N,N-diethylcarbamoylmethylphosphonate) supported on Accurel polypropylene hollow fibers assembled in modular form transfers >95% of the americium from high nitrate (6.9M), low acid (0.1M) feeds into 0.25M oxalic acid stripping solution. Maximum permeabilities were observed to be 0.001 cm/sec, consistent with typical values for other systems. The feed:strip volume ratio shows an inverse relationship to the fraction of metal ion transferred. Cation exchangers may be used to concentrate americium from the strip solution. Furthermore, O0D (iB)CMPO (or CMPO) (octylphenyl-N-N-diisobutylcarbamoylmethylphosphine oxide) has been tested in an extraction chromatography mode. Preliminary results show CMPO to be effective in removing americium if the feed is neutralized to 1.0M acidity and iron(III) is complexed with 0.20M oxalic acid. 3 figs

  1. 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.

  2. 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)

  3. 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

  4. Americium product solidification and disposal

    International Nuclear Information System (INIS)

    Mailen, J.C.; Campbell, D.O.; Bell, J.T.; Collins, E.D.

    1987-01-01

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

  5. Uptake of americium-241 by algae and bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Geisy, J P; Paine, D

    1978-01-01

    Algae and bacteria are important factors in the transport and mobilization of elements in the biosphere. These factors may be involved in trophic biomagnification, resulting in a potential human hazard or environmental degradation. Although americium, one of the most toxic elements known, is not required for plant growth, it may be concentrated by algae and bacteria. Therefore, the availability of americium-241 to algae and bacteria was studied to determine their role in the ultimate fate of this element released into the environment. Both algae and bacteria concentrated americium-241 to a high degree, making them important parts of the biomagnification process. The ability to concentrate americium-241 makes algae and bacteria potentially significant factors in cycling this element in the water column. (4 graphs, numerous references, 3 tables)

  6. 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

  7. Recovery and purification of americium from molten salt extraction residues

    International Nuclear Information System (INIS)

    Navratil, J.D.; Martella, L.L.; Thompson, G.H.

    1980-01-01

    Americium recovery and purification development at Rocky Flats involves the testing of a combined anion exchange - bidentate organophosphorus liquid - liquid extraction or extraction chromatography process for separating americium from molten salt extraction residues. Laboratory-scale and preliminary pilot-plant results have shown that americium can be effectively recovered and purified from impurity elements such as aluminum, calcium, magnesium, plutonium, potassium, sodium, and zinc. The purified americium oxide product from the liquid - liquid extraction process contained greater than 95% AmO 2 with less than 1% of any individual impurity element

  8. 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

  9. 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

  10. 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

  11. 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)

  12. Comparative behavior of americium and plutonium in wastewater

    International Nuclear Information System (INIS)

    Tsvetaeva, N.E.; Filin, V.M.; Ragimov, T.K.; Rudaya, L.Y.; Shapiro, K.Y.; Shcherbakov, B.Y.

    1986-01-01

    This paper studies the behavior of trace americium and plutoniumin wastewater fed into purification systems. Activities of the elements were determined on a semiconductive alpha-ray spectrometer. the distributio nonuniformity, or heterogeneity, of americium and plutonium per unit volume of wastewater was determined quantitatively before and after passage through filter papers. The two elements were found to be in a colloidal or pseudocolloidal state in the original wastewater sample at pH 6. On acidifying the wastewater from pH 4 to 1 M nitric acid the americium passed quantitatively into the water phase but the most plutonium remained in the colloidal or pseudocolloidal state. the plutonium also passed quantitatively into the water phase in wastewater at a 1 M nitric acid acidity but only after a prolonged (12-day) hold. A knowledge of the heterogeneity of plutonium and americium in wastewaters made it possible to quickly distinguish their state, i.e., colloidal, pseudocolloidal, or in true solution

  13. 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)

  14. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

    Cantrell, Kirk J.; Felmy, Andrew R.

    2012-08-23

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

  16. Investigation of factors affecting the quality of americium electroplating

    International Nuclear Information System (INIS)

    Trdin, M.; Benedik, L.; Samardžija, Z.; Pihlar, B.

    2012-01-01

    Four different electrolyte solutions were used in the electrodeposition of americium and their influences on the quality of the thin layer of deposited americium isotopes in combination with three different cathode disc materials were investigated. The relations between alpha spectral resolution and disc surface properties were established. - Highlights: ► Compared alpha spectra of americium radioisotopes obtained by electrodeposition. ► Various cathode materials and electrolyte solutions were used. ► Homogeneity and peak area resolution were investigated. ► Electron microscope images show surface structure of electrodeposited material.

  17. Measurement of plutonium and americium in molten salt residues

    International Nuclear Information System (INIS)

    Haas, F.X.; Lawless, J.L.; Herren, W.E.; Hughes, M.E.

    1979-01-01

    The measurement of plutonium and americium in molten salt residues using a segmented gamma-ray scanning device is described. This system was calibrated using artificially fabricated as well as process generated samples. All samples were calorimetered and the americium to plutonium content of the samples determined by gamma-ray spectroscopy. For the nine samples calorimetered thus far, no significant biases are present in the comparison of the segmented gamma-ray assay and the calorimetric assay. Estimated errors are of the order of 10 percent and is dependent on the americium to plutonium ratio determination

  18. Americium separations from high salt solutions

    International Nuclear Information System (INIS)

    Barr, Mary E.; Jarvinen, Gordon D.; Schulte, Louis D.; Stark, Peter C.; Chamberlin, Rebecca M.; Abney, Kent D.; Ricketts, Thomas E.; Valdez, Yvette E.; Bartsch, Richard A.

    2000-01-01

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

  19. Transmutation of americium in critical reactors

    International Nuclear Information System (INIS)

    Wallenius, J.

    2005-01-01

    Already in 1974, a Los Alamos report suggested that the recycling of higher actinides would be detrimental for the safety of critical reactors. Later investigations confirmed this understanding, and stringent limits on the fraction of minor actinides allowed to be present in the fuel of fast neutron reactors were established. In recent years, and in particular in connection with the generation IV initiative, it has been advocated that recycling of americium in critical reactors is not only feasible, but also a recommendable approach. In the present contribution, it is shown, to the contrary, that introduction of americium into reactors with uranium based fuels deteriorates the safety margin of these reactors to a degree that will not allow consumption of the americium sources present in any economically competitive nuclear fuel cycle. Further, it is shown that uranium and thorium free cores with plutonium based fuels may be designed, that features excellent safety characteristics, as long as americium is not present in the feed. Hence, a closed fuel cycle is suggested, that consists of commercial power production in light water reactors, plutonium burning in uranium and thorium free fast neutron critical reactors, and higher actinide consumption in accelerator driven systems with inert matrix fuel. It is argued that such a fuel cycle (being a refinement of the Double Strata fuel cycle proposed by JAERI and further developed by M. Salvatores) provides a minimum cost penalty for implementing P and T under realistic boundary conditions. (author)

  20. Sorption of americium and neptunium by deep-sea sediments

    International Nuclear Information System (INIS)

    Higgo, J.J.W.; Rees, L.V.C.; Cronan, D.S.

    1983-01-01

    The sorption and desorption of americium and neptunium by a wide range of deep-sea sediments from natural sea water at 4 0 C has been studied using a carefully controlled batch technique. All the sediments studied should form an excellent barrier to the migration of americium since distribution coefficients were uniformly greater than 10 5 and the sorption-desorption reaction may not be reversible. The sorption of neptunium was reversible and, except for one red clay, the distribution coefficients were greater than 10 3 for all the sediments investigated. Nevertheless the migration of neptunium should also be effectively retarded by most deep-sea sediments even under relatively oxidizing conditions. The neptunium in solution remained in the V oxidation state throughout the experiments. Under the experimental conditions used colloidal americium was trapped by the sediment and solubility did not seem to be the controlling factor in the desorption of americium. (Auth.)

  1. Supported extractant membranes for americium and plutonium recovery

    International Nuclear Information System (INIS)

    Muscatello, A.C.; Navratil, J.D.; Killion, M.E.; Price, M.Y.

    1987-01-01

    Solid supported liquid membranes(SLM) are useful in transferring and concentrating americium and plutonium from nitrate solutions. Specifically, DHDECMP(dihexyl-N,N-diethylcarbamoylmethylphosphonate) supported on Accurel or Celgard polypropylene hollow fibers assembled in modular form transfers >95% of the americium and >70% of the plutonium from high nitrate (6.9 M), low acid (0.1 M) feeds into 0.25 M oxalic acid stripping solution. Membranes supporting TBP (tri-n-butylphosphate) also transfer these metal ions. Maximum permeabilities were observed to be 1 x 10 -3 cm sec -1 , similar to the values for other systems. The feed:strip volume ratio shows an inverse relationship to the fraction of metal ion transferred. Cation exchangers may be used to concentrate americium from the strip solution

  2. Recovery of americium-241 from aged plutonium metal

    International Nuclear Information System (INIS)

    Gray, L.W.; Burney, G.A.; Reilly, T.A.; Wilson, T.W.; McKibben, J.M.

    1980-12-01

    About 5 kg of ingrown 241 Am was recovered from 850 kg of aged plutonium using a process developed specifically for Savannah River Plant application. The aged plutonium metal was first dissolved in sulfamic acid. Sodium nitrite was added to oxidize the plutonium to Pu(IV) and the residual sulfamate ion was oxidized to nitrogen gas and sulfate. The plutonium and americium were separated by one cycle of solvent extraction. The recovered products were subsequently purified by cation exchange chromatography, precipitated as oxalates, and calcined to the oxides. Plutonium processng was routine. Before cation exchange purification, the aqueous americium solution from solvent extraction was concentrated and stripped of nitric acid. More than 98% of the 241 Am was then recovered from the cation exchange column where it was effectively decontaminated from all major impurities except nickel and chromium. This partially purified product solution was concentrated further by evaporation and then denitrated by reaction with formic acid. Individual batches of americium oxalate were then precipitated, filtered, washed, and calcined. About 98.5% of the americium was recovered. The final product purity averaged 98% 241 AmO 2 ; residual impurities were primarily lead and nickel

  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. 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

  5. Investigation of factors affecting the quality of americium electroplating.

    Science.gov (United States)

    Trdin, M; Benedik, L; Samardžija, Z; Pihlar, B

    2012-09-01

    Four different electrolyte solutions were used in the electrodeposition of americium and their influences on the quality of the thin layer of deposited americium isotopes in combination with three different cathode disc materials were investigated. The relations between alpha spectral resolution and disc surface properties were established. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Method of isolation of traces of americium by using the +6 oxidation state properties

    International Nuclear Information System (INIS)

    Kwinta, Jean; Michel, Jean-Jacques

    1969-05-01

    The authors present a method to separate traces of americium from a solution containing fission products and actinides. This method comprises the following steps: firstly, the oxidation of americium at the +6 state by ammonium persulfate and carrying over of actinides and III and IV lanthanides by lanthanum fluoride; secondly, the reduction by hydrazine of the oxidized americium and carrying over of the reduced americium by lutetium fluoride; and thirdly, the americium-lutetium separation by selective extractions either with di 2 ethyl hexyl phosphoric acid, or by fractionated elution on an anionic resin column by a mixture of nitric acid and methanol [fr

  7. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

    Mineo, Hideaki; Matsumura, Tatsuro; Tsubata, Yasuhiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    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.)

  9. Decontaminaion of metals containing plutonium and americium

    International Nuclear Information System (INIS)

    Seitz, M.G.; Gerding, T.J.; Steindler, M.J.

    1979-06-01

    Melt-slagging (melt-refining) techniques were evaluated as a decontamination and consolidation step for metals contaminated with oxides of plutonium and americium. Experiments were performed in which mild steel, stainless steel, and nickel contaminated with oxides of plutonium and americium were melted in the presence of silicate slags of various compositions. The metal products were low in contamination, with the plutonium and americium strongly fractionated to the slags. Partition coefficients (plutonium in slag/plutonium in steel) of 7 x 10 6 were measured with boro-silicate slag and of 3 x 10 6 with calcium, magnesium silicate slag. Decontamination of metals containing as much as 14,000 ppM plutonium appears to be as efficient as for metals with plutonium levels of 400 ppM. Staged extraction, that is, a remelting of processed metal with clean slag, results in further decontamination of the metal. The second extraction is effective with either resistance-furnace melting or electric-arc melting. Slag adhering to the metal ingots and in defects within the ingots is in the important contributors to plutonium retained in processed metals. If these sources of plutonium are controlled, the melt-refining process can be used on a large scale to convert highly contaminated metals to homogeneous and compact forms with very low concentrations of plutonium and americium. A conceptual design of a melt-refining process to decontaminate plutonium- and americium-contaminated metals is described. The process includes single-stage refining of contaminated metals to produce a metal product which would have less than 10 nCi/g of TRU-element contamination. Two plant sizes were considered. The smaller conceptual plant processes 77 kg of metal per 8-h period and may be portable.The larger one processes 140 kg of metal per 8-h period, is stationary, and may be near te maximum size that is practical for a metal decontamination process

  10. 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)

  11. 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)

  12. Analytical separation of americium and curium, using high performance liquid chromatography

    International Nuclear Information System (INIS)

    Billon, A.

    1978-01-01

    Americium and curium are separated on a column of cation exchange resin (Aminex) using hydroxyisobutyric acid (α HIBA) as eluent, at a temperature of 80 0 C. Americium and curium were detected in line using their α emission: the separation was performed in a shielded glove box whose setting-up is given. Finally, the time necessary for a separation is comprised between 30 min and 1 hr. The purity of separated fractions was assayed by mass-spectrometry. An application in the determination of isotopic composition of americium and curium in fuels is described

  13. 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

  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. Separation of Americium from plutonium, Annex 3; Prilog 3: Odvajanje amercijuma od plutonijuma

    Energy Technology Data Exchange (ETDEWEB)

    Cvjeticanin, D; Milic, N; Janicijevic, P; Ratkovic, S [Institute of Nuclear Sciences Boris Kidric, Laboratorija za visoku aktivnost, Vinca, Beograd (Serbia and Montenegro)

    1963-12-15

    Since there was the possibility of working with plutonium milligram quantities, it was possible to study plutonium with contents of americium, which was expected in the about two years old plutonium solutions. Method for separation of the micro quantities of americium and plutonium was needed as well as a multichannel alpha-pulse analyzer. Method for separation of americium from plutonium by thenol trifluoro-acetone (TTA) and anion exchange was adopted.

  16. Extraction of americium from acid aqueous solutions by diethyl-2-hexyl-pyro-phosphoric acid

    International Nuclear Information System (INIS)

    Guillaume, Bernard

    1971-02-01

    After having outlined the interesting properties of americium and the difficulties of its recovery, the author reports the study of the mechanism of extraction of americium from acid aqueous solutions by using the diethyl-2hexyl-pyro-phosphoric acid. Several aspects are thus discussed: influence of concentration of H 2 DEHPP, influence of the acidity of the aqueous phase, saturation of extracting agent, influence of the diluting agent, complexing of americium, influence of other cations. In a second part, the author reports the application to the recovery of americium from effluents, and discusses the obtained results

  17. Environmental impact of a teratogenic actinide: a case study of americium-241

    Energy Technology Data Exchange (ETDEWEB)

    Wang, J.; Yang, J.Y.

    1985-10-16

    Americium-241 is widely used as a radiation source, but it also has some potential risk if taken into the body. Although the radiotoxicity of americium-241 is small compared to other transuranic actinides, its effects on the reproductive system and on development of the placenta are more damaging than the effects of plutonium-239. A previous report based on a worst-case scenario involving a hypothetical fire accident in a contaminated facility indicated that there could have been a significant impact on nearby residents from a unit release of americium-241 via atmospheric dispersion. However, because the facility is located in a rural region where most drinking water supplies are drawn from private wells, it is believed that deposition of americium-241 from the atmosphere might also have impacts via the groundwater pathway by infiltration of rainwater. In this analysis, a three-dimensional analytical mathematical model is used to assess several aspects of americium-241 contamination of groundwater, including radioactive transformation, advection, dispersion, and soil sorption. Simulation results indicate that no significant radiological impacts would occur to the nearby residents via the groundwater pathway. 15 refs., 2 figs., 2 tabs.

  18. Environmental impact of a teratogenic actinide: a case study of americium-241

    International Nuclear Information System (INIS)

    Wang, J.; Yang, J.Y.

    1985-01-01

    Americium-241 is widely used as a radiation source, but it also has some potential risk if taken into the body. Although the radiotoxicity of americium-241 is small compared to other transuranic actinides, its effects on the reproductive system and on development of the placenta are more damaging than the effects of plutonium-239. A previous report based on a worst-case scenario involving a hypothetical fire accident in a contaminated facility indicated that there could have been a significant impact on nearby residents from a unit release of americium-241 via atmospheric dispersion. However, because the facility is located in a rural region where most drinking water supplies are drawn from private wells, it is believed that deposition of americium-241 from the atmosphere might also have impacts via the groundwater pathway by infiltration of rainwater. In this analysis, a three-dimensional analytical mathematical model is used to assess several aspects of americium-241 contamination of groundwater, including radioactive transformation, advection, dispersion, and soil sorption. Simulation results indicate that no significant radiological impacts would occur to the nearby residents via the groundwater pathway. 15 refs., 2 figs., 2 tabs

  19. Modelling of curium and americium behaviour during separation with displacing complexing chromatography

    International Nuclear Information System (INIS)

    Chuveleva, Eh.A.; Kharitonov, O.V.; Firsova, L.A.

    1994-01-01

    Certain heavy rare earths, curium and americium were separated by the method of displacement complexing chromatography using DTPA solutions and solutions containing DTPA and citric acid as eluents. Separation factors of rare earths and curium (americium) were calculated. Imitators for curium and americium separation were suggested: thulium for curium elution using 0.025 mol/l DTPA, holmium-for curium elution using 0.025 mol/l DTPA in the presence of 0.025 mol/l citric acid; terbium can serve as the imitator in both cases. 5 refs., 5 figs

  20. 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

  1. 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)

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

    International Nuclear Information System (INIS)

    Fife, K.W.; West, M.H.

    1987-05-01

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

  3. Supercritical Fluid Extraction of Plutonium and Americium from Soil

    International Nuclear Information System (INIS)

    Fox, R.V.; Mincher, B.J.

    2002-01-01

    Supercritical fluid extraction (SFE) of plutonium and americium from soil was successfully demonstrated using supercritical fluid carbon dioxide solvent augmented with organophosphorus and beta-diketone complexants. Spiked Idaho soils were chemically and radiologically characterized, then extracted with supercritical fluid carbon dioxide at 2,900 psi and 65 C containing varying concentrations of tributyl phosphate (TBP) and thenoyltrifluoroacetone (TTA). A single 45 minute SFE with 2.7 mol% TBP and 3.2 mol% TTA provided as much as 88% ± 6.0 extraction of americium and 69% ± 5.0 extraction of plutonium. Use of 5.3 mol% TBP with 6.8 mol% of the more acidic beta-diketone hexafluoroacetylacetone (HFA) provided 95% ± 3.0 extraction of americium and 83% ± 5.0 extraction of plutonium in a single 45 minute SFE at 3,750 psi and 95 C. Sequential chemical extraction techniques were used to chemically characterize soil partitioning of plutonium and americium in pre-SFE soil samples. Sequential chemical extraction techniques demonstrated that spiked plutonium resides primarily (76.6%) in the sesquioxide fraction with minor amounts being absorbed by the oxidizable fraction (10.6%) and residual fractions (12.8%). Post-SFE soils subjected to sequential chemical extraction characterization demonstrated that 97% of the oxidizable, 78% of the sesquioxide and 80% of the residual plutonium could be removed using SFE. These preliminary results show that SFE may be an effective solvent extraction technique for removal of actinide contaminants from soil

  4. 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)

  5. Uptake of americium-241 by algae and bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Giesy, Jr, J P; Paine, D [Savannah River Ecology Lab., Aiken, S.C. (USA)

    1978-01-01

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

  6. Methods for producing single crystal mixed halide perovskites

    Science.gov (United States)

    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.

  7. 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.)

  8. 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.

  9. 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.)

  10. Americium Separations from High-Salt Solutions Using Anion Exchange

    International Nuclear Information System (INIS)

    Barr, Mary E.; Jarvinen, Gordon D.; Stark, Peter C.; Chamberlin, Rebecca M.; Bartsch, Richard A.; Zhang, Z.Y.; Zhao, W.

    2001-01-01

    The aging of the US nuclear stockpile presents a number of challenges, including the increasing radioactivity of plutonium residues due to the ingrowth of 241 Am from the β-decay of 241 Pu. We investigated parameters that affect the sorption of Am onto anion-exchange resins from concentrated effluents derived from nitric acid processing of plutonium residues. These postevaporator wastes are nearly saturated solutions of acidic nitrate salts, and americium removal is complicated by physical factors, such as solution viscosity and particulates, as well as by the presence of large quantities of competing metals and acid. Single- and double-contact batch distribution coefficients for americium and neodymium from simple and complex surrogate solutions are presented. Varied parameters include the nitrate salt concentration and composition and the nitric acid concentration. We find that under these extremely concentrated conditions, Am(III) removal efficiencies can surpass 50% per contact. Distribution coefficients for both neodymium and americium are insensitive to solution acidity and appear to be driven primarily by low water activities of the solutions

  11. Organic components and plutonium and americium state in soils and soil solutions

    International Nuclear Information System (INIS)

    Sokolik, G.A.; Ovsyannikova, S.V.; Kimlenko, I.M.

    2002-01-01

    The fraction composition of humus substances of different type soils and soil solutions have been studied. A distribution of Pu 239, 240 and Am 241 between humus substances fractions of different dispersity and mobility in soil-vegetation cover has been established. It was shown that humus of organic soils fixes plutonium and americium in soil medium in greater extent than humus of mineral soils. That leads to lower migration ability of radionuclides in organic soils. The lower ability of americium to form difficultly soluble organic and organic-mineral complexes and predomination of its anion complexes in soil solutions may be a reason of higher mobility and biological availability of americium in comparison to plutonium during soil-plant transfer (authors)

  12. 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

  13. 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)

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

    International Nuclear Information System (INIS)

    Cole, T.G.; Higgo, J.J.W.; Cronan, D.S.; Rees, L.V.C.

    1984-07-01

    A series of selective leaching experiments were undertaken to investigate the solid phase speciation and distribution of americium, neptunium and plutonium which had been experimentally loaded onto different marine sediment types. The chemical leaches employed showed rather poor selectivity but certain trends were evident. Adsorption was not by ion exchange. Americium showed a preferential affinity for carbonate and plutonium for organic matter. Neptunium appeared to have no preferential affinities. Americium was sorbed by acetic acid residues (CaCO 3 removed) and by unleached carbonate-rich sediments with equal efficiency. This indicates that it is able to diversify its solid phase affinity/distribution depending upon which solid phases are available. (author)

  15. On the role of different biocomponents of bile and excretions in the elimination of plutonium and americium from the body

    International Nuclear Information System (INIS)

    Shvydko, N.S.

    1986-01-01

    A study was made of the role of biocomponents of bile, urine and feces in the elimination of plutonium and americium from the organism. Plutonium 239 and americium 241 were separated in bile due to higher tropism of plutonium to low molecular weight addends, and of americium, to a protein-containing fraction. The status of plutonium excreted in feces was the same as the physicochemical status of americium. Plutonium 239 and americium 241 eliminated in urine were in a completely ultrafiltered state

  16. Mobility of plutonium and americium through a shallow aquifer in a semiarid region

    International Nuclear Information System (INIS)

    Penrose, W.R.; Polzer, W.L.; Essington, E.H.; Nelson, D.M.; Orlandini, K.A.

    1990-01-01

    Treated liquid wastes containing traces of plutonium and americium are released into Mortandad Canyon, within the site of Los Alamos National Laboratory, NM. The wastes infiltrate a small aquifer within the canyon. Although laboratory studies have predicted that the movement of actinides in subsurface environments will be limited to less than a few meters, both plutonium and americium are detectable in monitoring wells as far as 3,390 m downgradient from the discharge. Between the first and last monitoring wells (1.8 and 3.4 km from the discharge), plutonium concentrations decreased exponentially from 1,400 to 0.55 mBq/L. Americium concentrations ranged between 94 and 1,240 mBq/L, but did not appear to vary in a systematic way with distance. Investigation of the properties of the mobile actinides indicates that the plutonium and part of the americium are tightly or irreversibly associated with colloidal material between 25 and 450 nm in size. The colloidally bound actinides are removed only gradually from the groundwater. The fraction of the americium not associated with colloids exists in a low molecular weight form (diameter, ≤ 2 nm) and appears to be a stable, anionic complex of unknown composition. The mobile forms of these actinides defeat the forces that normally act to retard their movement through groundwater systems

  17. Americium-241 and -243 as an ion-engine propellant

    International Nuclear Information System (INIS)

    Schachter, M.M.

    1994-01-01

    Commercially available americium-241 and -243 can be obtained as the mixture of the two isotopes in 100-gram quantities--a product of reprocessing spent nuclear powerplant fuel elements along with plutonium. The half-lives of the isotopes are 450 years for the -241 and 8,000 years for the -243 (the plutonium half-life isotope so obtained is 24,000 years). Americium rolled out in thin foil sheets emits alpha-rays (helium-4 ions) and beta-rays--2 valence electrons for each helium ion. Electrons are also considered as ions. As a foil, the americium radiates only a minimal amount of gamma-rays via the Curie effect. With appropriately designed permanent magnet rings insulated with Wood's alloy, the + and - ions can be accelerated from their already 5.5 million electron-Volts to billion and even trillions of electron-Volts by electronic control grids powered by the magnetohydrodynamic effect of electrons and helium ions streaming at the post-rocket nozzle of the ion engine. Protocol for the estimated thrust of this ion rocket engine is more than ten kilograms continuously sustainable for several thousand years

  18. 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)

  19. 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

  20. The availability of plutonium and americium in Irish Sea sediments for re-dissolution

    International Nuclear Information System (INIS)

    McDonald, P.; Vives i Batlle, J.; Bousher, A.; Whittall, A.; Chambers, N.

    2001-01-01

    The availability of plutonium and americium, for re-dissolution from offshore sediments into Irish Sea water, has been examined. Sediments collected from the mud-patch near the Cumbrian coast were characterized in terms of spatial location, particle size, partitioning of radionuclides with respect to physico-chemical bonds and availability of actinides for release into seawater. Sequential extraction investigations revealed that plutonium was predominantly associated with strongly bound sesquioxide and organic complex fractions. Americium was associated mainly with the organic complex fraction, but a significant fraction was in carbonate form. Sediment/water re-dissolution experiments with and without stirring were compared to simulate the effect of disturbing bed sediment. After 1 week, neither set of re-dissolution data provided significant trends between dissolved activity and time. Stirred systems appeared to release 2.5 times more plutonium and americium into seawater than unstirred systems. Measured 239,240Pu and 241Am distribution coefficients (K d values) were both typically approximately 10 5 l kg -1 . 241Am K d values are an order of magnitude lower than previously reported for the north-eastern Irish Sea, but similar to western Irish Sea values. Overall, the fractions of plutonium and americium available for re-dissolution from bed sediment are very low at <0.1%, with proportionally more plutonium being released than americium. These findings lend further support for the extrapolation of laboratory-derived information to environmental conditions

  1. 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

  2. Biokinetic study of plutonium and americium associated to the particulates of soil

    International Nuclear Information System (INIS)

    Espinosa, A.; Aragon, A.; Martinez, J.; Iranzo, C.E.

    1996-01-01

    The object of this study is to determine the biokinetic parameters of different Plutonium isotopes and Americium inhaled in the state in which they are found in the environment as a result of their deposition in the soil, from an aviation accident that generated different plutonium oxides. to achieve this objective, two lines of work planned. One was the determination of the mineralogical composition and associations that plutonium and americium present in that soil 22 years after the nuclear accident. Other studies were directed to determine the biokinetic of the plutonium isotopes and americium (contained in the dust) deposited tracheally and inhaled by laboratory animals (rats) and in vitro experiments by pulmonary leaching simulation. The in vivo tests have been developed in NRPB (U.K.) and the in vitro experiment, geochemical associations studies, assessment of internal doses to humans resulting from intake of plutonium and americium bearing dusts present in the contaminated area and establishment of ALIs for inhalation, were carried out in CIEMAT (Spain). In this work only determinations and experiments carried out by CIEMAT are includes as a part of the EU Project ''INHALATION AND INGESTION OF RADIONUCLIDES'' contract: FI3P-CT920064a. (Author) 10 refs

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

    International Nuclear Information System (INIS)

    Trebunova, T.

    1999-01-01

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

  4. 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

  5. Influence of organic components on plutonium and americium speciation in soils and soil solutions

    International Nuclear Information System (INIS)

    Sokolik, G.A.; Ovsyannikova, S.V.; Kimlenko, I.M.

    2003-01-01

    Group composition of humic substances of organic and mineral soils sampled in the 30-km zone of the Chernobyl accident was analyzed for studying influence of organic components on migration properties of plutonium and americium in soils and soil solutions by the method of gel-chromatography and chemical fractionation. It was ascertained that humus of organic soils binds plutonium and americium stronger than humus of mineral soils. Elevated mobility of americium compared to plutonium one stems from lower ability of the latter to from hard to solve organic and organomineral complexes, as well as from its ability to form anionic complexes in soil solutions [ru

  6. Halide-Dependent Electronic Structure of Organolead Perovskite Materials

    KAUST Repository

    Buin, Andrei; Comin, Riccardo; Xu, Jixian; Ip, Alexander H.; Sargent, Edward H.

    2015-01-01

    -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

  7. 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.

  8. Carbamoyl methylphosphine oxide derivatives of adamantane as americium and europium extractants

    International Nuclear Information System (INIS)

    Babain, V.A.; Alyapyshev, M.Yu.; Novakov, I.A.; Orlinson, B.S.; Savel'ev, E.N.; Shokova, Eh.A.; Serebrayannikova, A.E.; Kovalev, V.V.

    2007-01-01

    Adamantane di-1,3-carbamoyl methylphosphine oxide (CMPO) derivatives, where CMPO-groups connect with 1,3-positions of rigid adamantane platform by methylene and ethylene bridges, are synthesized, and their efficiency as extractants of americium(III) and europium(III) from nitric acid solutions is demonstrated. Distribution function of Am 3+ and Eu + during extraction from 3M HNO 3 are measured in the investigation of extraction properties. It is noted that first synthesized adamantane CMPO derivatives are more effective for the extraction of americium(III) and europium(III) from 3MHNO 3 [ru

  9. Radiation protection data sheets for the use of Americium 241 in unsealed sources

    International Nuclear Information System (INIS)

    Anon.

    1993-01-01

    This radiation protection data sheet is intended for supervisors and staff in the different medical, hospital, pharmaceutical, university and industrial laboratories and departments where Americium 241 is handled, and also for all those involved in risk prevention in this field. It provides essential data on radiation protection measures during the use of Americium 241 in unsealed sources: physical characteristics, risk assessment, administrative procedures, recommendations, regulations and bibliography

  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. Local Structure in Americium and Californium Hexa-cyanoferrates - Comparison with Their Lanthanide Analogues

    International Nuclear Information System (INIS)

    Dupouy, G.; Bonhoure, I.; Dumas, Th.; Moisy, Ph.; Petit, S.; Den Auwer, Ch.; Conradson, St.D.; Hennig, Ch.; Scheinost, A.C.; Le Naour, C.; Simoni, E.

    2011-01-01

    Metal hexa-cyanoferrates are well known molecular solids for a large variety of cations, although very little has been described for actinide adducts. Two new members of actinide(III) hexa-cyanoferrates were synthesized with the cations americium and californium. They were structurally characterized by infrared and X-ray absorption spectroscopy. Combined EXAFS data at the iron K edge and actinide L 3 edge provide evidence for a three-dimensional model for these two new compounds. Structural data in terms of bond lengths were compared to those reported for the parent lanthanide(III) compounds, neodymium and gadolinium hexa-cyanoferrates, respectively: the americium compound with (KNd(III)Fe(II)-Fe-III(CN) 6 .4H 2 O and the californium compound with (KGd(III)Fe(II)(CN) . 3.5H 2 O and (KGd(III)Fe(II)(CN) 6 .3H 2 O. This comparison between actinide and lanthanide homologues has been carried out on the basis of ionic radii considerations. The americium and neodymium environments appear to be very similar and are arranged in a tri-capped trigonal prism polyhedron of coordination number 9 (CN: 9), in which the americium atom is bonded to six nitrogen atoms and to three water molecules. For the californium adduct, a similar comparison and bond length and angle values derived from EXAFS studies suggest that the californium cation sits in a bi-capped trigonal prism (CN: 8) as in (KGd(III)Fe(II)(CN) 6 . 3H 2 O. This arrangement differs from that in the structure of (KGd(III)Fe(II)(CN) 6 .3.5H 2 O, in which the gadolinium atom is surrounded by 9 atoms. This is one of the rare pieces of information revealed by EXAFS spectroscopy for americium and californium in comparison to lanthanide atoms in molecular solid compounds. A discussion on the decrease in bond length and coordination number from americium to californium is also provided, on the basis of crystallographic results reported in the literature for actinide(III) and lanthanide(III) hydrate series. (authors)

  12. Remobilization of americium in soil columns under experimental rhizo-spheric conditions

    Energy Technology Data Exchange (ETDEWEB)

    Perrier, T.; Martin-Garin, A.; Morello, M. [CEA Cadarache (DEI/SECRE/LRE), Laboratory of Radioecology and Ecotoxicology, Institute for Radioprotection and Nuclear Safety, 13 - Saint-Paul-lez-Durance (France)

    2004-07-01

    The biogeochemical behaviour of americium in subsurface soils plays a dominant role on the potential migration of this actinide, but is currently poorly known. The identification and understanding of these processes is of major concern for this highly (radio)toxic element and can allow the determination of its impact on the natural media. This research investigates the relevant processes controlling americium biogeochemical speciation in the rhizosphere of an agricultural soil. Lixiviation tests were performed on columns packed with a 2 mm-sieved calcareous soil contaminated with {sup 241}Am (500 Bq.g{sup -1}), under steady-state unsaturated or saturated hydric flow conditions. The columns were percolated with soil solution of varied compositions, containing citrate and/or glucose simulating root exudates in non-sterile conditions. The physico-chemical parameters of the outlet solution (pH, conductivity, major ions, organic acids) were monitored, as well as the microbial activity. Inorganic and organic speciation of {sup 241}Am is supported by geochemical modeling with JChess, using a thermodynamic database based on NEA database and the latest PSI recommendations. The percolation of a solution in equilibrium with the soil released small amount of americium (<5 mBq/cm{sup 3}), as predicted by the high {sup 241}Am K{sub d} values. 10{sup -4} M concentrations of citrate, glucose or both combined did not enhance remobilization either. Poor remobilization was also observed at high glucose concentrations (10{sup -2} M), despite an effective glucose microbial degradation, the production of ligands such as acetate, and important changes in the chemistry of the solution. On the contrary, high concentrations of citrate (10{sup -2} M) released 1000 times more americium, which is in accordance with previous studies. Even greater releases (10000 times) were observed when 10{sup -2} M glucose was added to 10{sup -2} M citrate. The remobilization of americium resulting from the

  13. 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

  14. Plutonium-239 and americium-241 uptake by plants from soil. Final report

    International Nuclear Information System (INIS)

    Brown, K.W.

    1979-03-01

    Alfalfa was grown in soil contaminated with plutonium-239 dioxide (239PuO2) at a concentration of 29.7 nanocuries per gram (nCi/g). In addition to alfalfa, radishes, wheat, rye, and tomatoes were grown in soils contaminated with americium-241 nitrate (241Am(NO3)3) at a concentration of 189 nCi/g. The length of exposure varied from 52 days for the radishes to 237 days for the alfalfa. The magnitude of plutonium incorporation by the alfalfa as indicated by the concentration ratio, 0.0000025, was similar to previously reported data using other chemical forms of plutonium. The results did indicate, however, that differences in the biological availability of plutonium isotopes do exist. All of the species exposed to americium-241 assimilated and translocated this radioisotope to the stem, leaf, and fruiting structures. The magnitude of incorporation as signified by the concentration ratios varied from 0.00001 for the wheat grass to 0.0152 for the radishes. An increase in the uptake of americium also occurred as a function of time for four of the five plant species. Evidence indicates that the predominant factor in plutonium and americium uptake by plants may involve the chelation of these elements in soils by the action of compounds such as citric acid and/or other similar chelating agents released from plant roots

  15. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    Science.gov (United States)

    Chen, Kun; Tüysüz, Harun

    2015-11-09

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Kinetics of americium(VI) mass transfer through solid supported liquid membrane with HDEHP

    International Nuclear Information System (INIS)

    Mikheeva, M.N.; Novicoov, P.; Myasoedov, B.F.; Tikhomirov, S.V.

    1994-01-01

    The main regularities of membrane extraction of americium under conditions of different redox potentials in aqueous phases have been studied. The physico-chemical model of the process including steps of americium oxidation in feed solution, extraction by membrane, partial reduction on membrane surface, trans-membrane diffusion and reextraction to strip solution has been developed. The calculation of reduction rate constant on membrane surface has been carried out. (author) 9 refs.; 4 figs.; 3 tabs

  17. 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)

  18. 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.

  19. Making and Breaking of Lead Halide Perovskites

    KAUST Repository

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

    2016-01-01

    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

  20. 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

  1. Environmental impacts of the release of a transuranic actinide, americium-241, from a contaminated facility

    Energy Technology Data Exchange (ETDEWEB)

    Want, J.; Merry-Libby, P.

    1985-10-29

    Americium-241 is widely used as a radiation source, but it also has some potential risk if taken into the body because of its high dose conversion factor. Although the radiotoxicity of americium-241 is small compared to other transuranic actinides, its effects on the reproductive system and on development of the placenta are more damaging than the effects of plutonium-239. In Ohio, a gemologist's laboratory was contaminated with americium-241. Prior to decontamination of the laboratory, potential radiological impacts to the surrounding environment were assessed. A hypothetical fire accident resulting in a unit release (1 curie) was assumed. Potential radiological impacts were simulated using an atmospheric dispersion and dosimetry model with local meteorological data, population census data, and detailed information regarding the neighborhood. The results indicate that there could have been a significant impact on nearby residents from americium-241 via atmospheric dispersion if a major catastrophic release had occurred prior to contamination and decommissioning of the laboratory. 14 refs., 3 figs., 2 tabs.

  2. Airborne plutonium and americium concentrations measured from the top of Rattlesnake Mountain

    International Nuclear Information System (INIS)

    Sehmel, G.A.

    1979-01-01

    Airborne plutonium-239+240 and americium-241 blowing from offsite was measured in an initial experiment at the top of Rattlesnake Mountain. Average airborne concentration measured was similar to fallout concentrations. Airborne plutonium concentrations were independent of wind speed for seven wind speed increments between 0.5 and 31 m/sec. In contrast the airborne americium concentration was a minimum at a wind speed of approximately 7 m/sec. Similarly, the airborne solids concentration in μg/m 3 was a minimum at an intermediate wind speed increment of 7 to 11 m/sec

  3. Americium-241 radioisotope thermoelectric generator development for space applications

    International Nuclear Information System (INIS)

    Ambrosi, Richard; Williams, Hugo; Samara-Ratna, Piyal

    2013-01-01

    Space nuclear power systems are under development in the UK in collaboration with European partners as part of a European Space Agency (ESA) programme. Radioisotope thermoelectric generators (RTG) are an important element of this new capability in Europe. RTG systems being developed in Europe are targeting the 10 W electric to 50 W electric power generation range adopting a modular scalable approach to the design. Radiogenic decay heat from radioisotopes can be converted to electrical power by using appropriate semiconductor based thermoelectric materials. The plan for Europe is to develop radioisotope space nuclear power systems based on both thermoelectric and Stirling power conversion systems. Although primarily focused on delivering up to 50 W of electrical power, the European radioisotope thermoelectric system development programme is targeting americium-241 as a fuel source and is maximizing the use of commercially available thermoelectric manufacturing processes in order to accelerate the development of power conversion systems. The use of americium provides an economic solution at high isotopic purity and is product of a separation process from stored plutonium produced during the reprocessing of civil nuclear fuel. A laboratory prototype that uses electrical heating as a substitute for the radioisotope was developed to validate the designs. This prototype has now been tested. This paper outlines the requirements for a European americium-241 fuelled RTG, describes the most recent updates in system design and provides further insight into recent laboratory prototype test campaigns. (author)

  4. Americium-241 radioisotope thermoelectric generator development for space applications

    Energy Technology Data Exchange (ETDEWEB)

    Ambrosi, Richard; Williams, Hugo; Samara-Ratna, Piyal, E-mail: rma8@le.ac.uk [University of Leicester, (United Kingdom); and others

    2013-07-01

    Space nuclear power systems are under development in the UK in collaboration with European partners as part of a European Space Agency (ESA) programme. Radioisotope thermoelectric generators (RTG) are an important element of this new capability in Europe. RTG systems being developed in Europe are targeting the 10 W electric to 50 W electric power generation range adopting a modular scalable approach to the design. Radiogenic decay heat from radioisotopes can be converted to electrical power by using appropriate semiconductor based thermoelectric materials. The plan for Europe is to develop radioisotope space nuclear power systems based on both thermoelectric and Stirling power conversion systems. Although primarily focused on delivering up to 50 W of electrical power, the European radioisotope thermoelectric system development programme is targeting americium-241 as a fuel source and is maximizing the use of commercially available thermoelectric manufacturing processes in order to accelerate the development of power conversion systems. The use of americium provides an economic solution at high isotopic purity and is product of a separation process from stored plutonium produced during the reprocessing of civil nuclear fuel. A laboratory prototype that uses electrical heating as a substitute for the radioisotope was developed to validate the designs. This prototype has now been tested. This paper outlines the requirements for a European americium-241 fuelled RTG, describes the most recent updates in system design and provides further insight into recent laboratory prototype test campaigns. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Hoppenheit, M.; Murray, C.N.; Woodhead, D.S.

    1980-01-01

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

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

    International Nuclear Information System (INIS)

    Hoppenheit, M.; Murray, C.N.; Woodhead, D.S.

    1980-01-01

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

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

    Science.gov (United States)

    Fried, S.

    1951-03-20

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

  8. An experimental investigation of accumulation and transmutation behavior of americium in the MOX fuel irradiated in a fast reactor

    International Nuclear Information System (INIS)

    Osaka, Masahiko; Koyama, Shin-ichi; Maeda, Shigetaka; Mitsugashira, Toshiaki

    2005-01-01

    Americium isotopes generated in the MOX fuel irradiated in the experimental fast reactor JOYO were analyzed by applying a sophisticated radiochemical technique. Americium was isolated from the irradiated MOX fuel by a combined method of anion-exchange chromatography and oxidation of Am. The isotopic ratios of americium and its content were determined by thermal ionization mass spectroscopy and α-spectrometry, respectively. The americium isotopic ratio was similar for all the specimens, but was significantly different from that of PWR-MOX. On the basis of present analytical results, the accumulation and transmutation behavior of americium nuclides in a fast reactor is discussed from the viewpoints of neutron spectrum dependence and the isomeric ratio of the 241 Am capture reaction. The estimated isomeric ratio is about 87%, which is close to the latest evaluated value. A rapid estimation method of Am content by using the 240 Pu to 239 Pu ratio was adopted and proved to be valid for the spent fuel irradiated in the fast reactor

  9. Experimental studies to validate model calculations and maximum solubility limits for Plutonium and Americium; Experimentelle Arbeiten zur Absicherung von Modellrechnungen und Maximalkonzentrationen fuer Plutonium und Americium

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2017-02-16

    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{sub 2} and CaCl{sub 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{sub 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.).

  10. 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

  11. Molecular localisation of americium, technetium and cesium in edible marine animals. Their metabolic behavior and their consequences; Localisation moleculaire de l'americium, du technetium et du cesium chez des animaux marins comestibles leur comportement metabolique et ses consequences

    Energy Technology Data Exchange (ETDEWEB)

    Pieri, J; Goudard, F; Milcent, M C [Laboratoire de Biochimie et Radiochimie, Faculte des Sciences et des Techniques, Nantes Cedex (France)

    1992-07-01

    We show the molecular behavior of americium, technetium and cesium on the chromatographic pattern of each cytosol in the digestive gland of eel and lobster. The contamination by cadmium seems to compete with americium in the fractions of MW 10,000. Cesium shows an ionic behavior. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-12

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

  13. Muonium centers in the alkali halides

    International Nuclear Information System (INIS)

    Baumeler, H.; Kiefl, R.F.; Keller, H.; Kuendig, W.; Odermatt, W.; Patterson, B.D.; Schneider, J.W.; Savic, I.M.

    1986-01-01

    Muonium centers (Mu) in single crystals and powdered alkali halides have been studied using the high-timing-resolution transverse field μSR technique. Mu has been observed and its hyperfine parameter (HF) determined in every alkali halide. For the rocksalt alkali halides, the HF parameter A μ shows a systematic dependence on the host lattice constant. A comparison of the Mu HF parameter with hydrogen ESR data suggests that the Mu center is the muonic analogue of the interstitial hydrogen H i 0 -center. The rate of Mu diffusion can be deduced from the motional narrowing of the nuclear hyperfine interaction. KBr shows two different Mu states, a low-temperature Mu I -state and a high-temperature Mu II -state. (orig.)

  14. Molecular localisation of americium, technetium and cesium in edible marine animals. Their metabolic behavior and their consequences

    International Nuclear Information System (INIS)

    Pieri, J.; Goudard, F.; Milcent, M.C.

    1992-01-01

    We show the molecular behavior of americium, technetium and cesium on the chromatographic pattern of each cytosol in the digestive gland of eel and lobster. The contamination by cadmium seems to compete with americium in the fractions of MW 10,000. Cesium shows an ionic behavior. (author)

  15. 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.

  16. 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

  17. Americium/curium bushing melter drain tests

    International Nuclear Information System (INIS)

    Smith, M.E.; Hardy, B.J.; Smith, M.E.

    1997-01-01

    Americium and curium were produced in the past at the Savannah River Site (SRS) for research, medical, and radiological applications. They have been stored in a nitric acid solution in an SRS reprocessing facility for a number of years. Vitrification of the americium/curium (Am/Cm) solution will allow the material to be safely stored or transported to the DOE Oak Ridge Reservation. Oak Ridge is responsible for marketing radionuclides for research and medical applications. The bushing melter technology being used in the Am/Cm vitrification research work is also under consideration for the stabilization of other actinides such as neptunium and plutonium. A series of melter drain tests were conducted at the Savannah River Technology Center to determine the relationship between the drain tube assembly operating variables and the resulting pour initiation times, glass flowrates, drain tube temperatures, and stop pour times. Performance criteria such as ability to start and stop pours in a controlled manner were also evaluated. The tests were also intended to provide support of oil modeling of drain tube performance predictions and thermal modeling of the drain tube and drain tube heater assembly. These drain tests were instrumental in the design of subsequent melter drain tube and drain tube heaters for the Am/Cm bushing melter, and therefore in the success of the Am/Cm vitrification and plutonium immobilization programs

  18. Electric resistivity of 241-americium and 244-curium metals. Creation of defects and isochronous annealing of 241-americium metal after self-irradiation

    International Nuclear Information System (INIS)

    Schenkel, R.

    1977-03-01

    The temperature dependence of the electrical resistivity of thin films of bulk 241 Am metal were measured between 300 and 4.5 K. The room temperature resistivity was found to be 68.90μΩcm. At room temperature the electrical resistivity of americium increases with pressure (3% up to 13 kbar). The application of 13 kbar pressure did not change the low temperature power law in the electrical resistivity. The resistivity vs temperature curve can be explained by assuming s-d scattering of conduction electrons. The localized 5f electrons are considered to be about 5eV below the Fermi level. Americium therefore should be the first lanthanide-like element in the actinide series. The defect production due to self-irradiation damage was studied by measuring the increase of the resistivity at 4.2 K over a period of 738 h. A saturation resistivity of 16.036 μΩcm was found corresponding to a defect concentration of about 0.22 a/o. After isochronal annealing two recovery stages were observed at about 65 and 145 K. The two stages shift with increasing initial defect concentration to lower temperatures. Estimates of the activation energies and the reaction order were made and possible defect reactions suggested. The magnetic contribution to the electrical resistivity of curium, which shows an antiferromagnetic transition at 52.5 k, was obtained by subtracting the resistivity of americium (to be considered as phonon part). Comparison with theoretical models were made. At low temperatures the measurements are strongly affected by self-irradiation damage [drho/dt(t=0)=9.8μΩcm/h

  19. Treatment of alcaline metals halides for developing crystals

    International Nuclear Information System (INIS)

    Spurney, R.W.

    1974-01-01

    A process is described whereby crystals of an alkaline metal halide may be dried and placed in a crucible for development by the Bridgeman-Stockbarger method. Purified alkaline halides from a suspension are dried and formed into dense cakes of transverse section slightly smaller than that of the crucible, where they are packed, melted and grown into crystals according to the Bridgeman-Stockbarger technique. This method applies to the preparation of alkaline halide crystals, particularly sodium iodide for optical elements or scintillation counters [fr

  20. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

    Science.gov (United States)

    Sutter-Fella, Carolin M; Ngo, Quynh P; Cefarin, Nicola; Gardner, Kira L; Tamura, Nobumichi; Stan, Camelia V; Drisdell, Walter S; Javey, Ali; Toma, Francesca M; Sharp, Ian D

    2018-06-13

    Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2 ) 2 CsPb-halide (FACsPb-) and CH 3 NH 3 Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

  1. 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)

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

    International Nuclear Information System (INIS)

    Vives i Batlle, J.

    1993-12-01

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

  3. 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

  4. The weak acid resin process: a dustless conversion route for the synthesis of americium bearing-blanket precursors

    International Nuclear Information System (INIS)

    Picart, S.; Gauthe, A.; Parant, P.; Remy, E.; Jobelin, I.; Pomared, J.M.; Grangaud, P.; Dauby, J.; Delahaye, T.; Caisso, M.; Bataille, M.; Bayle, J.P.; Frost, C.; Delage, C.; Martin, C.L.; Ayral, E.

    2016-01-01

    Mixed uranium-americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Conversion and fabrication processes are currently developed to make those materials in the form of dense and homogeneous oxide ceramic pellets or dense granulates incorporating uranium and americium. Their development points out the need of a simplified and optimized process which could lower hazards linked to dust generation of highly contaminating and irradiating compounds and facilitate material transfer in remote handling operations. This reason motivated the development of innovative 'dustless' route such as the Weak Acid Resin route (WAR) which provides the oxide precursors in the form of sub-millimeter-sized microspheres with optimal flowability and limits dust generation during conversion and fabrication steps. This study is thus devoted to the synthesis of mixed uranium-americium oxide microspheres by the WAR process and to the characterization of such precursors. This work also deals with their application to the fabrication of dense or porous pellets and with their potential use as dense spherules to make Sphere-Pac fuel. (authors)

  5. The weak acid resin process: a dustless conversion route for the synthesis of americium bearing-blanket precursors

    Energy Technology Data Exchange (ETDEWEB)

    Picart, S.; Gauthe, A.; Parant, P.; Remy, E.; Jobelin, I.; Pomared, J.M.; Grangaud, P.; Dauby, J.; Delahaye, T. [CEA, Centre de Marcoule, DEN/MAR/DRCP, F-30207 Bagnols-sur-Ceze (France); Caisso, M.; Bataille, M.; Bayle, J.P. [CEA, Centre de Marcoule, DEN/MAR/DTEC, F-30207 Bagnols-sur-Ceze (France); Frost, C. [CEA, Centre de Marcoule, DEN/MAR/DRCP, F-30207 Bagnols-sur-Ceze (France); Institut Europeen des Membranes, CNRS-ENSCM-UM, CC47, University of Montpellier, F-34095 Montpellier (France); Delage, C. [CEA, Centre de Cadarache, DEN/CAD/DEC, Saint-Paul-lez-Durance (France); Martin, C.L. [Univ. Grenoble Alpes, CNRS, SIMAP, F-38000 Grenoble (France); Ayral, E. [Institut Europeen des Membranes, CNRS-ENSCM-UM, CC47, University of Montpellier, F-34095 Montpellier (France)

    2016-07-01

    Mixed uranium-americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Conversion and fabrication processes are currently developed to make those materials in the form of dense and homogeneous oxide ceramic pellets or dense granulates incorporating uranium and americium. Their development points out the need of a simplified and optimized process which could lower hazards linked to dust generation of highly contaminating and irradiating compounds and facilitate material transfer in remote handling operations. This reason motivated the development of innovative 'dustless' route such as the Weak Acid Resin route (WAR) which provides the oxide precursors in the form of sub-millimeter-sized microspheres with optimal flowability and limits dust generation during conversion and fabrication steps. This study is thus devoted to the synthesis of mixed uranium-americium oxide microspheres by the WAR process and to the characterization of such precursors. This work also deals with their application to the fabrication of dense or porous pellets and with their potential use as dense spherules to make Sphere-Pac fuel. (authors)

  6. 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.)

  7. 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.

  8. High temperature reactions between molybdenum and metal halides

    International Nuclear Information System (INIS)

    Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

    2006-01-01

    Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

  9. 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.

  10. 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

  11. 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...

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

    International Nuclear Information System (INIS)

    Rudisill, T.S.

    1999-01-01

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

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

    International Nuclear Information System (INIS)

    Takeda, Seiji

    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 3 2- , F - , PO 4 3- , SO 4 2- , NO 3 - and NH 4 + ). 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)

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

    International Nuclear Information System (INIS)

    Papenia, M.V.; Sokolik, G.A.; Ovsiannikova, S.V.; Voinikava, E.V.; Svirschevsky, S.F.; Brown, J.; Skipperud, L.

    2010-01-01

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

  15. Entropy in halide perovskites

    Science.gov (United States)

    Katan, Claudine; Mohite, Aditya D.; Even, Jacky

    2018-05-01

    Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

  16. 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

  17. Lifetime followup of the 1976 americium accident victim: [Final report

    International Nuclear Information System (INIS)

    Breitenstein, B.D. Jr.; Palmer, H.E.

    1988-05-01

    This report describes the 11 year medical course of Harold R. McCluskey, a Hanford nuclear chemical operator, who, at age 64, was involved in an accident in an americium recovery facility in August 1976. As a result of the accident, he was heavily contaminated with americium (Am-241), 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 immediate and long-term medical care is summarized, including decontamination procedures, chelation therapy, and routine and special clinical laboratories studies. The estimates of the operator's Am-241 deposition, post accident and during the remainder of his life and the special techniques and equipment used to make the estimates, are reported. Post-accident, the total amount of Am-241 excreted in his urine and feces was 41 MBq (1.1 mCi). He died of complications of chronic coronary artery disease on August 17, 1987. 20 refs., 2 figs

  18. Plant uptake of americium, curium, and the chemical analog neodymium

    International Nuclear Information System (INIS)

    Weimer, W.C.; Laul, J.C.; Kutt, J.C.; Bondietti, E.A.

    1977-01-01

    The plant uptake from several bulk soils has been determined for neodymium, a chemical analog to the transuranium elements americium and curium, and several other native rare earth elements as well. These investigations have demonstrated that neodymium, which has very similar chemical properties to amercium and curium and should have a similar environmental behavior, does behave indistinguishably under both laboratory and field conditions. The uptake of the weathered or mobile forms of these elements from soils is expected to be governed primarily by their identical oxidation states and nearly identical ionic radii. This hypothesis is strongly supported by the chondritic (primordial) normalized rare earth element patterns in several plants. In these samples, the entire series of rare earth elements behaves as a smooth function of the REE ionic radii, as is also seen in the contiguous soils. This behavior suggests that the plant uptake of other ions with similar chemical properties (i.e., americium and curium) would also be governed by ionic size and charge

  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. Thermodynamic systematics of oxides of americium, curium, and neighboring elements

    International Nuclear Information System (INIS)

    Morss, L.R.

    1984-01-01

    Recently-obtained calorimetric data on the sesquioxides and dioxides of americium and curium are summarized. These data are combined with other properties of the actinide elements to elucidate the stability relationships among these oxides and to predict the behavior of neighboring actinide oxides. 45 references, 4 figures, 5 tables

  1. 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.)

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

    International Nuclear Information System (INIS)

    Raison, P.E.

    2001-01-01

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

  3. The coacervation of aqueous solutions of tetraalkylammonium halides

    International Nuclear Information System (INIS)

    Mugnier de Trobriand, Anne.

    1979-09-01

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

  4. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

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

    2013-01-01

    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...... 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...... 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...

  5. Catalytic effect of halide additives ball milled with magnesium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

    2010-02-15

    The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

  6. 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.

  7. 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)

  8. 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.

  9. Complexes in polyvalent metal - Alkali halide melts

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1991-03-01

    Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

  10. 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.).

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

    OpenAIRE

    Sourish Chatterjee

    2013-01-01

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

  12. 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

  13. 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.

  14. 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

  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. 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 .

  17. Plutonium and americium extraction studies with bifunctional organophosphorus extractants

    International Nuclear Information System (INIS)

    Navratil, J.D.

    1985-01-01

    Neutral bifunctional organophosphorus extractants, such as octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP), are under study at the Rocky Flats Plant (RFP) to remove plutonium and americium from the 7M nitric acid waste. These compounds extract trivalent actinides from strong nitric acid, a property which distinguishes them from monofunctional organiphosphorus reagents. Furthermore, the reagents extract hydroytic plutonium (IV) polymer which is present in the acid waste stream. The compounds extract trivalent actinides with a 3:1 stoichiometry, whereas tetra- and hexavalent actinides extract with a stoichiometry of 2:1. Preliminary studies indicate that the extracted plutonium polymer complex contains one to two molecules of CMP per plutonium ion and the plutonium(IV) maintains a polymeric structure. Recent studies by Horwitz and co-workers conclude that the CMPO and CMP reagents behave as monodentate ligands. At RFP, three techniques are being tested for using CMP and CMPO to remove plutonium and americium from nitric acid waste streams. The different techniques are liquid-liquid extraction, extraction chromatography, and solid-supported liquid membranes. Recent tests of the last two techniques will be briefly described. In all the experiments, CMP was an 84% pure material from Bray Oil Co. and CMPO was 98% pure from M and T Chemicals

  18. 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

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

    Science.gov (United States)

    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.

  20. 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.

  1. 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

  2. The transmutation of americium: the Ecrix experiments in Phenix; Transmutation de l'americium: les experiences ecrix dans Phenix

    Energy Technology Data Exchange (ETDEWEB)

    Garnier, J C; Schmidt, N [CEA Cadarache, Dept. d' Etudes des Combustibles (DEC/SESC), 13 - Saint-Paul-lez-Durance (France); Croixmarie, Y; Ottaviani, J P [CEA Cadarache, Dept. d' Etudes des Combustibles (DEC/SPUA), 13 - Saint-Paul-lez-Durance (France); Varaine, F; Saint Jean, C de [CEA Cadarache, Dept. d' Etudes des Reacteurs (DER/SPRC), 13 - Saint-Paul-lez-Durance (France)

    1999-07-01

    The first americium transmutation experiment in a specific target in PHENIX will occur with the ECRIX-B and ECRIX-H experiments. Beside material testing, the objective is also to represent a concept of transmutation whose specificity is to enhance the kinetics of transmutation by using a moderated spectrum. The moderator materials will be {sup 11}B{sub 4}C and CaH{sub 2} for ECRIX-B and ECRIXH respectively, the irradiation conditions have been predicted for both the neutronics and thermal. The targets (MgO-AmO{sub X} pellets) are manufactured in the ATALANTE laboratory and the design is performed according to the PHENIX operating conditions. (authors)

  3. 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.

  4. 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

  5. Definition of a high intensity metal halide discharge reference lamp

    NARCIS (Netherlands)

    Stoffels, W.W.; Baede, A.H.F.M.; Mullen, van der J.J.A.M.; Haverlag, M.; Zissis, G.

    2006-01-01

    The design of a ref. metal halide discharge lamp is presented. This lamp is meant as a common study object for researchers working on metal halide discharge lamps, who by using the same design will be able to compare results between research groups, diagnostic techniques and numerical models. The

  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. Unraveling halide hydration: A high dilution approach.

    Science.gov (United States)

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

    2014-07-28

    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 (ΔG [minus sign in circle symbol]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 ΔG [minus sign in circle symbol]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.

  8. A simple approach to determine the diffusivity of americium in granite

    International Nuclear Information System (INIS)

    Song, L.; Feng, X.; Liang, J.; Zhang, Y.; Wang, J.

    2009-01-01

    The diffusivities of the key radionuclides in host rock are important for the performance assessment of repositories. One of the conventional methods for determining the diffusivities of radionuclides is to grind the rock tablet layer by layer and then to measure the radioactivity remaining on the rock tablet before each grinding cycle. Since grinding hard rock samples, especially those with radioactivity, is very difficult, we developed a new approach to determine the diffusivity of americium in granite. The new approach mainly includes two parts: one is to measure the radioactivities from both sides of a rock disk sample by autoradiography with phosphor imaging technique; the other is to study the relationship between the radioactivities and the apparent diffusivity of americium in granite by computer modelling. Because the high contamination risk of grinding radioactive rock samples has been avoided, the new approach is much simpler than the conventional method. It may be a better choice of measuring the diffusivities of radionuclides in rock, especially for those laboratories in which grinding radioactive rock samples is inconvenient. (orig.)

  9. 78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

    Science.gov (United States)

    2013-08-20

    ... merging the metal halide lamp fixture and the high-intensity discharge (HID) lamp rulemakings. This NOPR... Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures; Proposed Rule #0;#0;Federal...: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office of Energy Efficiency and...

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

    KAUST Repository

    Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

    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.

  11. Development of halide copper vapor laser (the characteristics of using Cul)

    International Nuclear Information System (INIS)

    Oouti, Kazumi; Wada, Yukio; Sasao, Nobuyuki

    1990-01-01

    We are developing halide copper vapor laser that is high efficiency and high reputation rate visible laser. Halide copper vapor laser uses halide copper of copper vapor source. It melts low temperature in comporison with metal copper, because laser tube structure is very simple and it can operate easy. This time, we experiment to use Cul for copper vapor source. We resulted maximum output energy 17.8 (W) and maximum efficiency 0.78 (%) when operate condition was reputation rate 30 (kHz), gas pressure 90 (Torr), charging voltage 13 (kV). (author)

  12. 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

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

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1994-01-01

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

  14. 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

  15. Recovery of americium-241 from aged plutonium metal

    International Nuclear Information System (INIS)

    Gray, L.W.; Burney, G.A.; Reilly, T.A.; Wilson, T.W.; McKibben, J.M.

    1980-01-01

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

  16. 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

  17. Two-Dimensional Halide Perovskites for Emerging New- Generation Photodetectors

    DEFF Research Database (Denmark)

    Tang, Yingying; Cao, Xianyi; Chi, Qijin

    2018-01-01

    Compared to their conventional three-dimensional (3D) counterparts, two-dimensional (2D) halide perovskites have attracted more interests recently in a variety of areas related to optoelectronics because of their unique structural characteristics and enhanced performances. In general, there are two...... distinct types of 2D halide perovskites. One represents those perovskites with an intrinsic layered crystal structure (i.e. MX6 layers, M = metal and X = Cl, Br, I), the other defines the perovskites with a 2D nanostructured morphology such as nanoplatelets and nanosheets. Recent studies have shown that 2D...... halide perovskites hold promising potential for the development of new-generation photodetectors, mainly arising from their highly efficient photoluminescence and absorbance, color tunability in the visible-light range and relatively high stability. In this chapter, we present the summary and highlights...

  18. 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

  19. The transmutation of americium: the Ecrix experiments in Phenix; Transmutation de l'americium: les experiences ecrix dans Phenix

    Energy Technology Data Exchange (ETDEWEB)

    Garnier, J.C.; Schmidt, N. [CEA Cadarache, Dept. d' Etudes des Combustibles (DEC/SESC), 13 - Saint-Paul-lez-Durance (France); Croixmarie, Y.; Ottaviani, J.P. [CEA Cadarache, Dept. d' Etudes des Combustibles (DEC/SPUA), 13 - Saint-Paul-lez-Durance (France); Varaine, F.; Saint Jean, C. de [CEA Cadarache, Dept. d' Etudes des Reacteurs (DER/SPRC), 13 - Saint-Paul-lez-Durance (France)

    1999-07-01

    The first americium transmutation experiment in a specific target in PHENIX will occur with the ECRIX-B and ECRIX-H experiments. Beside material testing, the objective is also to represent a concept of transmutation whose specificity is to enhance the kinetics of transmutation by using a moderated spectrum. The moderator materials will be {sup 11}B{sub 4}C and CaH{sub 2} for ECRIX-B and ECRIXH respectively, the irradiation conditions have been predicted for both the neutronics and thermal. The targets (MgO-AmO{sub X} pellets) are manufactured in the ATALANTE laboratory and the design is performed according to the PHENIX operating conditions. (authors)

  20. Co-precipitation of plutonium(IV) and americium(III) from nitric acid-oxalic acid solutions with bismuth oxalate

    International Nuclear Information System (INIS)

    Pius, I.C.; Noronha, D.M.; Chaudhury, Satyajeet

    2017-01-01

    Co-precipitation of plutonium and americium from nitric acid-oxalic acid solutions with bismuth oxalate has been investigated for the removal of these long lived α-active nuclides from waste solutions. Effect of concentration of bismuth and oxalic acid on the co-precipitation of Pu(IV) from 3 M HNO_3 has been investigated. Similar experiments were also carried out from 3.75 M HNO_3 on co-precipitation of Am(III) to optimize the conditions of precipitation. Strong co-precipitation of Pu(IV) and Am(III) with bismuth oxalate indicate feasibility of treatment of plutonium and americium bearing waste solutions. (author)

  1. 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

  2. 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).

  3. 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.

  4. Radiochemical separation and alpha-spectrometric determination of Americium in different matrixes

    International Nuclear Information System (INIS)

    Radenkovic, M.; Joksic, J.; Paligoric, D.

    2009-01-01

    A method of separation and alpha-spectrometric determination of americium, developed in VINCA Institute of Nuclear Sciences is described in the paper. The procedure is convenient to be used for 241 Am determination in environmental matrixes as well as samples of human origin if a very small concentrations are expected, using 243 Am as a tracer for radiochemical yield recovery. (author) [sr

  5. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    Energy Technology Data Exchange (ETDEWEB)

    Curry, J. J.; Henins, A.; Hardis, J. E. [National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Estupinan, E. G. [Osram Sylvania Inc., Beverly, Massachusetts 01915 (United States); Lapatovich, W. P. [Independent Consultant, 51 Pye Brook Lane, Boxford, Massachusetts 01921 (United States); Shastri, S. D. [Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  6. 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)

  7. 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

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

    Science.gov (United States)

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

    2015-09-01

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

  9. 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

  10. 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)

  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. Transfer of environmental plutonium and americium across the human gut

    International Nuclear Information System (INIS)

    Hunt, G.J.; Leonard, D.R.P.; Lovett, M.B.

    1989-01-01

    Following the ingestion of winkles obtained from a coastal area near Sellafield nuclear reprocessing plant, a group of volunteers provided urine for the next 7 days to be analysed for plutonium and americium. From this, estimates of the intake and gut transfer factors for these isotopes were determined. Preliminary estimates of gut transfer factors from a previous study by the same authors were then re-interpreted and combined with the results from the present study. (UK)

  13. 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'.

  14. Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

    Science.gov (United States)

    Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

    2005-05-03

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

  15. Mycoremediation. The study of transfer factor for plutonium and americium uptake from the ground

    International Nuclear Information System (INIS)

    Dusan Galanda; Lubomir Matel; Jana Strisovska; Silvia Dulanska

    2014-01-01

    In our scientific research we have monitored mycoremediation's properties of oyster mushrooms in cultivation on the soil what is contaminated by solutions with radioactive isotopes of 239 Pu and 241 Am with known activity. We monitored specific activities of absorbed radionuclides in fruiting bodies and chemical forms of radionuclides which were compared to calculated specific activities of two background samples of oyster mushrooms intended for consumer purpose. We determined distributive coefficients between the ground and the fruiting body of oyster mushrooms. The average value which was obtained for the transfer factor for plutonium was 0.72 and for americium 3.97. To evaluate a quantity of absorbed radionuclides we used a method of liquid extraction. The emitting alpha radiation of alpha radionuclides was detected by spectrometry. For defining individual fractions of plutonium and americium that are contained in mushroom bodies was used the sequential leaching method. (author)

  16. 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

  17. luminescence in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    have studied the effect of annealing in chlorine gas on the ML of X-rayed KCl crystals. ..... high temperature because of the thermal bleaching of the coloration in alkali halide ..... [31] J Hawkins, Ph.D. Thesis (University of Reading, 1976).

  18. 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)

  19. The extraction of lanthanides and americium by benzyldiakylamines and benzyltrialkylammonium nitrates from the nitrate solutions; structure and aggregation of their salts

    International Nuclear Information System (INIS)

    Jedinakova, V.; Zilkova, J.; Dvorak, Z.; Vojtiskova, M.

    1982-01-01

    Benzyldialkylamine and benzyltrialkylammonium nitrates were used for the extraction of lanthanides and americium from aqueous nitrate solutions. The dependence of the extraction performance for Ln(III) and Am(III) on the concentration of nitric acid, the kind and concentration of salting-out agents in the aqueous phase, and the kind of solvent were investigated. The extraction of Am(III) is compared with the extraction of lanthanides. The difference in distribution coefficients for lanthanides and americium can be utilized for the separation of lanthanides and americium. Using vapor phase osmometry and cryoscopy the association of these compounds was measured at 5.5deg, 25deg and 37deg C, allowing rough estimates of ΔH and ΔS for the formation of the aggregates, monomers in the case of benzyldiethylamine, benzyldibutylamine, benzyldihexylamine and benzyldioctylamine, tetramers for the benzyldibutylamine nitrate and tetramers for benzyldimethyldodecylammonium nitrate. (author)

  20. 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

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

    International Nuclear Information System (INIS)

    Falk, R.B.; Lagerquist, C.R.

    1975-01-01

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

  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. On the influence of the americium isotopic vector on the cooling time of minor actinides bearing blankets in fast reactors

    Directory of Open Access Journals (Sweden)

    Kooyman Timothée

    2018-01-01

    Full Text Available In the heterogeneous minor actinides transmutation approach, the nuclei to be transmuted are loaded in dedicated targets often located at the core periphery, so that long-lived heavy nuclides are turned into shorter-lived fission products by fission. To compensate for low flux level at the core periphery, the minor actinides content in the targets is set relatively high (around 20 at.%, which has a negative impact on the reprocessing of the targets due to their important decay heat level. After a complete analysis of the main contributors to the heat load of the irradiated targets, it is shown here that the choice of the reprocessing order of the various feeds of americium from the fuel cycle depends on the actual limit for fuel reprocessing. If reprocessing of hot targets is possible, it is more interesting to reprocess first the americium feed with a high 243Am content in order to limit the total cooling time of the targets, while if reprocessing of targets is limited by their decay heat, it is more interesting to wait for an increase in the 241Am content before loading the americium in the core. An optimization of the reprocessing order appears to lead to a decrease of the total cooling time by 15 years compared to a situation where all the americium feeds are mixed together when two feeds from SFR are considered with a high reprocessing limit.

  4. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Science.gov (United States)

    2010-01-01

    ... high intensity discharge fixture, the efficiency of a lamp and ballast combination, expressed as a... lamps. Metal halide lamp means a high intensity discharge lamp in which the major portion of the light... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and...

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

    International Nuclear Information System (INIS)

    Baston, G.M.N.; Berry, J.A.; Brownsword, M.; Heath, T.G.; Tweed, C.J.; Williams, S.J.

    1995-01-01

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

  6. Complexes of alkylphenols with aluminium halides

    International Nuclear Information System (INIS)

    Golounin, A.V.

    1997-01-01

    Interaction of aluminium halides with alkylphenols is studied through the NMR method. The peculiarity of complex formation of pentamethylphenol with AlI 3 is revealed. By AlI 3 action on the pentamethylphenol the complexes are formed both of keto- and oxy form [ru

  7. National low-level waste management program radionuclide report series, Volume 14: Americium-241

    International Nuclear Information System (INIS)

    Winberg, M.R.; Garcia, R.S.

    1995-09-01

    This report, Volume 14 of the National Low-Level Waste Management Program Radionuclide Report Series, discusses the radiological and chemical characteristics of americium-241 ( 241 Am). This report also includes discussions about waste types and forms in which 241 Am can be found and 241 Am behavior in the environment and in the human body

  8. 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

  9. 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

  10. Determination by gamma-ray spectrometry of the plutonium and americium content of the Pu/Am separation scraps. Application to molten salts; Determination par spectrometrie gamma de la teneur en plutonium et en americium de produits issus de separation Pu/Am. Application aux bains de sels

    Energy Technology Data Exchange (ETDEWEB)

    Godot, A. [CEA Valduc, Dept. de Traitement des Materiaux Nucleaires, 21 - Is-sur-Tille (France); Perot, B. [CEA Cadarache, Dept. de Technologie Nucleaire, Service de Modelisation des Transferts et Mesures Nucleaires, 13 - Saint-Paul-lez-Durance (France)

    2005-07-01

    Within the framework of plutonium recycling operations in CEA Valduc (France), americium is extracted from molten plutonium metal into a molten salt during an electrolysis process. The scraps (spent salt, cathode, and crucible) contain extracted americium and a part of plutonium. Nuclear material management requires a very accurate determination of the plutonium content. Gamma-ray spectroscopy is performed on Molten Salt Extraction (MSE) scraps located inside the glove box, in order to assess the plutonium and americium contents. The measurement accuracy is influenced by the device geometry, nuclear instrumentation, screens located between the sample and the detector, counting statistics and matrix attenuation, self-absorption within the spent salt being very important. The purpose of this study is to validate the 'infinite energy extrapolation' method employed to correct for self-attenuation, and to detect any potential bias. We present a numerical study performed with the MCNP computer code to identify the most influential parameters and some suggestions to improve the measurement accuracy. A final uncertainty of approximately 40% is achieved on the plutonium mass. (authors)

  11. A new method for the determination of plutonium and americium using high pressure microwave digestion and alpha-spectrometry or ICP-SMS

    International Nuclear Information System (INIS)

    Luisier, F.; Corcho Alvarado, J.A.; Froidevaux, P.; Steinmann, P.; Krachler, M.

    2009-01-01

    Plutonium and americium are radionuclides particularly difficult to measure in environmental samples because they are a-emitters and therefore necessitate a careful separation before any measurement, either using radiometric methods or ICP-SMS. Recent developments in extraction chromatography resins such as Eichrom R TRU and TEVA have resolved many of the analytical problems but drawbacks such as low recovery and spectral interferences still occasionally occur. Here, we report on the use of the new Eichrom R DGA resin in association with TEVA resin and high pressure microwave acid leaching for the sequential determination of plutonium and americium in environmental samples. The method results in average recoveries of 83 ± 15% for plutonium and 73 ± 22% for americium (n = 60), and a less than 10% deviation from reference values of four IAEA reference materials and three samples from intercomparisons exercises. The method is also suitable for measuring 239 Pu in water samples at the μBq/l level, if ICP-SMS is used for the measurement. (author)

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

    OpenAIRE

    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 broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity (narrow full-width at half maximum). In this review, the photophysical propert...

  13. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites

    OpenAIRE

    Sutter-Fella, CM; Ngo, QP; Cefarin, N; Gardener, K; Tamura, N; Stan, CV; Drisdell, WS; Javey, A; Toma, FM; Sharp, ID

    2018-01-01

    © 2018 American Chemical Society. Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photo-induced halide demixing using in-situ photoluminescence spectroscopy and in-situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of comp...

  14. 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.

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

    KAUST Repository

    Bakr, Osman; Peng, Wei; Wang, Lingfei

    2017-01-01

    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

  16. 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)

  17. 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

  18. Americium/Curium Vitrification Pilot Tests - Part II

    International Nuclear Information System (INIS)

    Marra, J.E.; Baich, M.A.; Fellinger, A.P.; Hardy, B.J.; Herman, D.T.; Jones, T.M.; Miller, C.B.; Miller, D.H.; Snyder, T. K.; Stone, M.E.

    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. A previous paper described operation results from the Am-Cm Melter 2A pilot system, a full-scale non-radioactive pilot facility. This paper presents the results from continued testing in the Pilot Facility and also describes efforts taken to look at alternative vitrification process operations and flowsheets designed to address the problems observed during melter 2A pilot testing

  19. Behavior of americium in aqueous carbonate systems

    Energy Technology Data Exchange (ETDEWEB)

    Silva, R.J.

    1983-11-01

    The solubilities of crystalline Am(OH)/sub 3/ and AmOHCO/sub 3/ were measured at 25/sup 0/C in aqueous solutions of 0.1 M NaClO/sub 4/ by determination of the solution concentrations of Am. Prior to use in the measurements, the solid materials were characterized by their x-ray powder diffraction patterns. The solubility product quotients were calculated from the experimental data. The hydrolysis quotients of Am/sup 3 +/ were also estimated from the hydroxide solubility data. Using the thermodynamic data derived from these experiments and the recently reported formation constants for the Am/sup 3 +/ carbonate complexes, the solid phases and concentrations of solution species of americium in several aqueous carbonate systems were calculated using the computer code MINEQL. 20 references, 1 figure, 1 table.

  20. 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

  1. 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

  2. XRD monitoring of α self-irradiation in uranium-americium mixed oxides.

    Science.gov (United States)

    Horlait, Denis; Lebreton, Florent; Roussel, Pascal; Delahaye, Thibaud

    2013-12-16

    The structural evolution under (241)Am self-irradiation of U(1-x)Am(x)O(2±δ) transmutation fuels (with x ≤ 0.5) was studied by X-ray diffraction (XRD). Samples first underwent a preliminary heat treatment performed under a reducing atmosphere (Ar/H2(4%)) aiming to recover the previously accumulated structural defects. Over all measurements (carried out over up to a full year and for integrated doses up to 1.5 × 10(18) α-decay events·g(-1)), only fluorite U(1-x)Am(x)O(2±δ) solid solutions were observed. Within a few days after the end of the heat treatment, each of the five studied samples was slowly oxidized as a consequence of their move to air atmosphere, which is evidenced by XRD by an initial sharp decrease of the unit cell parameter. For the compounds with x ≤ 0.15, this oxidation occurred without any phase transitions, but for U0.6Am0.4O(2±δ) and U0.5Am0.5O(2±δ), this process is accompanied by a transition from a first fluorite solid solution to a second oxidized one, as the latter is thermodynamically stable in ambient conditions. In the meantime and after the oxidation process, (241)Am α self-irradiation caused a structural swelling up to ∼0.8 vol %, independently of the sample composition. The kinetic constants of swelling were also determined by regression of experimental data and are, as expected, dependent on x and thus on the dose rate. The normalization of these kinetic constants by sample α-activity, however, leads to very close swelling rates among the samples. Finally, evolutions of microstrain and crystallite size were also monitored, but for the considered dose rates and cumulated doses, α self-irradiation was found, within the limits of the diffractometer used, to have almost no impact on these characteristics. Microstrain was found to be influenced instead by the americium content in the materials (i.e., by the impurities associated with americium starting material and the increase of cationic charge heterogeneity with

  3. 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

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

    KAUST Repository

    Cai, Bo; Li, Xiaoming; Gu, Yu; Harb, Moussab; Li, Jianhai; Xie, Meiqiu; Cao, Fei; Song, Jizhong; Zhang, Shengli; Cavallo, Luigi; Zeng, Haibo

    2017-01-01

    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.

  5. Quaternary oxide halides of group 15 with zinc and cadmium

    International Nuclear Information System (INIS)

    Rueck, Nadia

    2014-01-01

    The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn"3"+ cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn"3"+ cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

  6. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Salminen, S.

    2009-07-01

    In this work, separation methods have been developed for the analysis of anthropogenic transuranium elements plutonium, americium, curium and neptunium from environmental samples contaminated by global nuclear weapons testing and the Chernobyl accident. The analytical methods utilized in this study are based on extraction chromatography. Highly varying atmospheric plutonium isotope concentrations and activity ratios were found at both Kurchatov (Kazakhstan), near the former Semipalatinsk test site, and Sodankylae (Finland). The origin of plutonium is almost impossible to identify at Kurchatov, since hundreds of nuclear tests were performed at the Semipalatinsk test site. In Sodankylae, plutonium in the surface air originated from nuclear weapons testing, conducted mostly by USSR and USA before the sampling year 1963. The variation in americium, curium and neptunium concentrations was great as well in peat samples collected in southern and central Finland in 1986 immediately after the Chernobyl accident. The main source of transuranium contamination in peats was from global nuclear test fallout, although there are wide regional differences in the fraction of Chernobyl-originated activity (of the total activity) for americium, curium and neptunium. The separation methods developed in this study yielded good chemical recovery for the elements investigated and adequately pure fractions for radiometric activity determination. The extraction chromatographic methods were faster compared to older methods based on ion exchange chromatography. In addition, extraction chromatography is a more environmentally friendly separation method than ion exchange, because less acidic waste solutions are produced during the analytical procedures. (orig.)

  8. 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)

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

    International Nuclear Information System (INIS)

    Umbarger, C.J.; Jett, J.H.

    1976-01-01

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

  10. Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

    Science.gov (United States)

    You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

    2017-02-03

    A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

  11. 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)

  12. Environmental Effects on the Photophysics of Organic-Inorganic Halide Perovskites.

    Science.gov (United States)

    Galisteo-López, Juan F; Anaya, M; Calvo, M E; Míguez, H

    2015-06-18

    The photophysical properties of films of organic-inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials.

  13. 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

  14. Advancement on Lead-Free Organic-Inorganic Halide Perovskite Solar Cells: A Review.

    Science.gov (United States)

    Sani, Faruk; Shafie, Suhaidi; Lim, Hong Ngee; Musa, Abubakar Ohinoyi

    2018-06-14

    Remarkable attention has been committed to the recently discovered cost effective and solution processable lead-free organic-inorganic halide perovskite solar cells. Recent studies have reported that, within five years, the reported efficiency has reached 9.0%, which makes them an extremely promising and fast developing candidate to compete with conventional lead-based perovskite solar cells. The major challenge associated with the conventional perovskite solar cells is the toxic nature of lead (Pb) used in the active layer of perovskite material. If lead continues to be used in fabricating solar cells, negative health impacts will result in the environment due to the toxicity of lead. Alternatively, lead free perovskite solar cells could give a safe way by substituting low-cost, abundant and non toxic material. This review focuses on formability of lead-free organic-inorganic halide perovskite, alternative metal cations candidates to replace lead (Pb), and possible substitutions of organic cations, as well as halide anions in the lead-free organic-inorganic halide perovskite architecture. Furthermore, the review gives highlights on the impact of organic cations, metal cations and inorganic anions on stability and the overall performance of lead free perovskite solar cells.

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

    International Nuclear Information System (INIS)

    Ramsey, W.G.; Miller, D.; Minichan, R.; Coleman, L.; Schumacher, R.; Hardy, B.; Jones, R.

    1994-01-01

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

  16. The transmutation of americium: the Ecrix experiments in Phenix

    International Nuclear Information System (INIS)

    Garnier, J.C.; Schmidt, N.; Croixmarie, Y.; Ottaviani, J.P.; Varaine, F.; Saint Jean, C. de

    1999-01-01

    The first americium transmutation experiment in a specific target in PHENIX will occur with the ECRIX-B and ECRIX-H experiments. Beside material testing, the objective is also to represent a concept of transmutation whose specificity is to enhance the kinetics of transmutation by using a moderated spectrum. The moderator materials will be 11 B 4 C and CaH 2 for ECRIX-B and ECRIXH respectively, the irradiation conditions have been predicted for both the neutronics and thermal. The targets (MgO-AmO X pellets) are manufactured in the ATALANTE laboratory and the design is performed according to the PHENIX operating conditions. (authors)

  17. 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

  18. Metal induced gap states at alkali halide/metal interface

    International Nuclear Information System (INIS)

    Kiguchi, Manabu; Yoshikawa, Genki; Ikeda, Susumu; Saiki, Koichiro

    2004-01-01

    The electronic state of a KCl/Cu(0 0 1) interface was investigated using the Cl K-edge near-edge X-ray absorption fine structure (NEXAFS). A pre-peak observed on the bulk edge onset of thin KCl films has a similar feature to the peak at a LiCl/Cu(0 0 1) interface, which originates from the metal induced gap state (MIGS). The present result indicates that the MIGS is formed universally at alkali halide/metal interfaces. The decay length of MIGS to an insulator differs from each other, mainly due to the difference in the band gap energy of alkali halide

  19. Metal halides vapor lasers with inner reactor and small active volume.

    Science.gov (United States)

    Shiyanov, D. V.; Sukhanov, V. B.; Evtushenko, G. S.

    2018-04-01

    Investigation of the energy characteristics of copper, manganese, lead halide vapor lasers with inner reactor and small active volume 90 cm3 was made. The optimal operating pulse repetition rates, temperatures, and buffer gas pressure for gas discharge tubes with internal and external electrodes are determined. Under identical pump conditions, such systems are not inferior in their characteristics to standard metal halide vapor lasers. It is shown that the use of a zeolite halogen generator provides lifetime laser operation.

  20. Silver halide photographic material providing an image and an unsharp mask

    International Nuclear Information System (INIS)

    Broadhead, P.; Farnell, G.C.

    1981-01-01

    Desirable edge effects are produced by normal imagewise exposure and processing of a sensitive radiographic film comprising a transparent film support bearing a layer of a direct-positive silver halide emulsion and a layer of a negative silver halide emulsion and wherein the film comprises means to reduce crossover between the two emulsion layers, one of said emulsion layers being adapted to record a primary image and the other being adapted to record an unsharp mask image. (author)

  1. In situ characterization of uranium and americium oxide solid solution formation for CRMP process: first combination of in situ XRD and XANES measurements.

    Science.gov (United States)

    Caisso, Marie; Picart, Sébastien; Belin, Renaud C; Lebreton, Florent; Martin, Philippe M; Dardenne, Kathy; Rothe, Jörg; Neuville, Daniel R; Delahaye, Thibaud; Ayral, André

    2015-04-14

    Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

  2. 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

  3. Reactivity of halide and pseudohalide ligands

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

  4. Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

    International Nuclear Information System (INIS)

    Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

    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 (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

  5. Plutonium, americium, and uranium in blow-sand mounds of safety-shot sites at the Nevada Test Site and the Tonopah Test Range

    International Nuclear Information System (INIS)

    Essington, E.H.; Gilbert, R.O.; Wireman, D.L.; Brady, D.N.; Fowler, E.B.

    1977-01-01

    Blow-sand mounds or miniature sand dunes and mounds created by burrowing activities of animals were investigated by the Nevada Applied Ecology Group (NAEG) to determine the influence of mounds on plutonium, americium, and uranium distributions and inventories in areas of the Nevada Test Site and Tonopah Test Range. Those radioactive elements were added to the environment as a result of safety experiments of nuclear devices. Two studies were conducted. The first was to estimate the vertical distribution of americium in the blow-sand mounds and in the desert pavement surrounding the mounds. The second was to estimate the amount or concentration of the radioactive materials accumulated in the mound relative to the desert pavement. Five mound types were identified in which plutonium, americium, and uranium concentrations were measured: grass, shrub, complex, animal, and diffuse. The mount top (that portion above the surrounding land surface datum), the mound bottom (that portion below the mound to a depth of 5 cm below the surrounding land surface datum), and soil from the immediate area surrounding the mound were compared separately to determine if the radioactive elements had concentrated in the mounds. Results of the studies indicate that the mounds exhibit higher concentrations of plutonium, americium, and uranium than the immediate surrounding soil. The type of mound does not appear to have influenced the amount of the radioactive material found in the mound except for the animal mounds where the burrowing activities appear to have obliterated distribution patterns

  6. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    International Nuclear Information System (INIS)

    Magdesieva, Tatiana V.; Graczyk, Magdalena; Vallat, Alain; Nikitin, Oleg M.; Demyanov, Petr I.; Butin, Kim P.; Vorotyntsev, Mikhail A.

    2006-01-01

    We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X-C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X-C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X-C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

  7. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    Energy Technology Data Exchange (ETDEWEB)

    Magdesieva, Tatiana V. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation)]. E-mail: tvm@org.chem.msu.ru; Graczyk, Magdalena [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Vallat, Alain [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Nikitin, Oleg M. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Demyanov, Petr I. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Butin, Kim P. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Vorotyntsev, Mikhail A. [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France)]. E-mail: MV@u-bourgogne.fr

    2006-11-12

    We have studied a reaction between the reduced form of titanocene dichloride (Cp{sub 2}TiCl{sub 2}) and a group of organic halides: benzyl derivatives (4-X-C{sub 6}H{sub 4}CH{sub 2}Cl, X = H, NO{sub 2}, CH{sub 3}; 4-X-C{sub 6}H{sub 4}CH{sub 2}Br, X = H, NO{sub 2}, PhC(O); 4-X-C{sub 6}H{sub 4}CH{sub 2}SCN, X = H, NO{sub 2}) as well as three aryl halides (4-NO{sub 2}C{sub 6}H{sub 4}Hal, Hal = Cl, Br; 4-CH{sub 3}O-C{sub 6}H{sub 4}Cl). It has been shown that the electrochemical reduction of Cp{sub 2}TiCl{sub 2} in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.

  8. Direct ToF-SIMS analysis of organic halides and amines on TLC plates

    Energy Technology Data Exchange (ETDEWEB)

    Parent, Alexander A. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Anderson, Thomas M. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Michaelis, David J. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Jiang, Guilin [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Savage, Paul B. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Linford, Matthew R. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States)]. E-mail: mrlinford@chem.byu.edu

    2006-07-30

    It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups.

  9. Direct ToF-SIMS analysis of organic halides and amines on TLC plates

    International Nuclear Information System (INIS)

    Parent, Alexander A.; Anderson, Thomas M.; Michaelis, David J.; Jiang, Guilin; Savage, Paul B.; Linford, Matthew R.

    2006-01-01

    It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups

  10. Americium-curium vitrification process development

    International Nuclear Information System (INIS)

    Fellinger, A.P.; Baich, M.A.; Hardy, B.J

    1999-01-01

    The successful demonstration of sequentially drying, calcining and vitrifying an oxalate slurry in the Drain Tube Test Stand (DTTS) vessel provided the process basis for testing on a larger scale in a cylindrical induction heated melter. A single processing issue, that of batch volume expansion, was encountered during the initial stage of testing. The increase in batch volume centered on a sintered frit cap and high temperature bubble formation. The formation of a sintered frit cap expansion was eliminated with the use of cullet. Volume expansions due to high temperature bubble formation (oxygen liberation from cerium reduction) were mitigated in the DTTS melter vessel through a vessel temperature profile that effectively separated the softening point of the glass cullet and the evolving oxygen from cerium reduction. An increased processing temperature of 1,470 C and a two hour hold time to find any remaining bubbles successfully reduced bubbles in the poured glass to an acceptable level. The success of the preliminary process demonstrations provided a workable process basis that was directly applicable to the newly installed Cylindrical Induction Melter (CIM) system, making the batch flowsheet the preferred option for vitrification of the americium-curium surrogate feed stream

  11. 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)

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

    International Nuclear Information System (INIS)

    Miramand, P.

    1984-06-01

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

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

    International Nuclear Information System (INIS)

    Zotina, T.A.; Bolsunovsky, A.Y.A.; Bondareva, L.G.

    2004-01-01

    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 241 Am). 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 241 Am by the submerged macrophyte from the Yenisei River: the pond weed (Elodea canadensis) and the aquatic moss (Fontinalis antipyretica), and release of 241 Am from the biomass. The content of 241 Am was measured on a Canberra (USA) gamma-spectrometer. The experiments showed that specific accumulation and concentration factors of 241 Am in the plants were in inverse proportion to their biomass. We obtained new data on release of 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 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 241 Am and retain americium for long periods of time in biomass. (author)

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

    DEFF Research Database (Denmark)

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

    1986-01-01

    Plutonium and americium have been measured in surface waters of the Greenland and Barents Seas and in the northern North Sea from 1980 through 1984. Measurements in water and biota, Fucus, Mytilus and Patella, were carried out in North-English and Scottish waters in 1982 and Fucus samples were co...

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

    Energy Technology Data Exchange (ETDEWEB)

    D' Agata, E., E-mail: elio.dagata@ec.europa.eu [European Commission, Joint Research Centre, Institute for Energy and Transport, P.O. Box 2, 1755 ZG Petten (Netherlands); Knol, S.; Fedorov, A.V. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands); Fernandez, A.; Somers, J. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Klaassen, F. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands)

    2015-10-15

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

  16. 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

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

    International Nuclear Information System (INIS)

    Lawless, W.N.

    1983-01-01

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

  18. Development and melt growth of novel scintillating halide crystals

    Science.gov (United States)

    Yoshikawa, Akira; Yokota, Yuui; Shoji, Yasuhiro; Kral, Robert; Kamada, Kei; Kurosawa, Shunsuke; Ohashi, Yuji; Arakawa, Mototaka; Chani, Valery I.; Kochurikhin, Vladimir V.; Yamaji, Akihiro; Andrey, Medvedev; Nikl, Martin

    2017-12-01

    Melt growth of scintillating halide crystals is reviewed. The vertical Bridgman growth technique is still considered as very popular method that enables production of relatively large and commercially attractive crystals. On the other hand, the micro-pulling-down method is preferable when fabrication of small samples, sufficient for preliminary characterization of their optical and/or scintillation performance, is required. Moreover, bulk crystal growth is also available using the micro-pulling-down furnace. The examples of growths of various halide crystals by industrially friendly melt growth techniques including Czochralski and edge-defined film-fed growth methods are also discussed. Finally, traveling molten zone growth that in some degree corresponds to horizontal zone melting is briefly overviewed.

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

    Science.gov (United States)

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

    2014-01-01

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

  20. 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

  1. 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.

  2. Solvation structures of lithium halides in methanol–water mixtures

    International Nuclear Information System (INIS)

    Sarkar, Atanu; Dixit, Mayank Kumar; Tembe, B.L.

    2015-01-01

    Highlights: • Potentials of mean force for Li + -halides are calculated in methanol–water mixtures. • Stable CIP for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. • The Li + ion is preferentially solvated by methanol molecules. • The halide ions are preferentially solvated by water molecules. - Abstract: The potentials of mean force (PMFs) for the ion pairs, Li + −Cl − , Li + −Br − and Li + −I − have been calculated in five methanol–water compositions. The results obtained are verified by trailing the trajectories and calculating the ion pair distance residence times. Local structures around the ions are studied using the radial distribution functions, density profiles, orientational correlation functions, running coordination numbers and excess coordination numbers. The major change in PMF is observed as the methanol mole fraction (x methanol ) is changed from 1.0 to 0.75. The stable contact ion pair occurring for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. The preferential solvation data show that the halide ions are always preferentially solvated by water molecules. Although the lithium ion is preferentially solvated by methanol molecules, there is significant affinity towards water molecules as well

  3. Explosion of cation exchange column in americium recovery service, Hanford plant, August 30, 1976

    International Nuclear Information System (INIS)

    1976-01-01

    This document is a collection of thirty references related to the explosion of the cation exchange column in the Americium Recovery Service of the Hanford Atomic Products Operation, Richland, Washington, on August 30, 1976. Some of the documents are related to the design and safety studies, while others refer to the accident and resulting decontamination efforts, investigations, and legal consequences

  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. Electron detachment energies in high-symmetry alkali halide solvated-electron anions

    Science.gov (United States)

    Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

    2003-07-01

    We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

  6. Possibility of obtaining enriched americium-242g by the elution of recoil atoms from zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Shafiev, A I; Vityutnev, V M; Ivanov, V M; Yakovlev, G N

    1974-12-31

    On the example of production the possibility of obtaining enriched actinide isotopes by the elution of recotl atoms with the use of a zeolite- americium-241 target was shown. The enrichment factor and the recoil atoms of / sup 242g/Am yield depend on preliminary target treatment and solution composition used for elution. (auth)

  7. 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.

  8. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

    Baumann, Nils; Zirnstein, Isabel; Arnold, Thuro

    2015-07-01

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

  10. Methyl halide fluxes from tropical plants under controlled radiation and temperature regimes

    Science.gov (United States)

    Blei, Emanuel; Yokouchi, Yoko; Saito, Takuya; Nozoe, Susumu

    2015-04-01

    Methyl halides (CH3Cl, CH3Br, CH3I) contribute significantly to the halogen burden of the atmosphere and have the potential to influence the stratospheric ozone layer through their catalytic effect in the Chapman cycle. As such they have been studied over the years, and many plants and biota have been examined for their potential to act as a source of these gases. One of the potentially largest terrestrial sources identified was tropical vegetation such as tropical ferns and Dipterocarp trees. Most of these studies concentrated on the identification and quantification of such fluxes rather than their characteristics and often the chambers used in these studies were either opaque or only partially transparent to the full solar spectrum. Therefore it is not certain to which degree emissions of methyl halides are innate to the plants and how much they might vary due to radiation or temperature conditions inside the enclosures. In a separate development it had been proposed that UV-radiation could cause live plant materials to be become emitters of methane even under non-anoxic conditions. As methane is chemically very similar to methyl halides and had been proposed to be produced from methyl-groups ubiquitously found in plant cell material there is a relatively good chance that such a production mechanism would also apply to methyl halides. To test whether radiation can affect elevated emissions of methyl halides from plant materials and to distinguish this from temperature effects caused by heat build-up in chambers a set of controlled laboratory chamber enclosures under various radiation and temperature regimes was conducted on four different tropical plant species (Magnolia grandiflora, Cinnamonum camphora, Cyathea lepifera, Angiopteris lygodiifolia), the latter two of which had previously been identified as strong methyl halide emitters. Abscised leaf samples of these species were subjected to radiation treatments such UV-B, UV-A and broad spectrum radiation

  11. 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.

  12. 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)

  13. 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...

  14. 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.

  15. Adsorption of molecular additive onto lead halide perovskite surfaces: A computational study on Lewis base thiophene additive passivation

    Science.gov (United States)

    Zhang, Lei; Yu, Fengxi; Chen, Lihong; Li, Jingfa

    2018-06-01

    Organic additives, such as the Lewis base thiophene, have been successfully applied to passivate halide perovskite surfaces, improving the stability and properties of perovskite devices based on CH3NH3PbI3. Yet, the detailed nanostructure of the perovskite surface passivated by additives and the mechanisms of such passivation are not well understood. This study presents a nanoscopic view on the interfacial structure of an additive/perovskite interface, consisting of a Lewis base thiophene molecular additive and a lead halide perovskite surface substrate, providing insights on the mechanisms that molecular additives can passivate the halide perovskite surfaces and enhance the perovskite-based device performance. Molecular dynamics study on the interactions between water molecules and the perovskite surfaces passivated by the investigated additive reveal the effectiveness of employing the molecular additives to improve the stability of the halide perovskite materials. The additive/perovskite surface system is further probed via molecular engineering the perovskite surfaces. This study reveals the nanoscopic structure-property relationships of the halide perovskite surface passivated by molecular additives, which helps the fundamental understanding of the surface/interface engineering strategies for the development of halide perovskite based devices.

  16. 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

  17. An experimental study of americium-241 biokinetics in the Lobster Homarus Gammarus. Analysis of the accumulation/storage and detoxification processes at the subcellular level; Etude experimentale des biocinetiques de l`americium-241 chez le homard homarus gammarus. Analyse des mecanismes d`accumulation et de detoxication au niveau subcellulaire

    Energy Technology Data Exchange (ETDEWEB)

    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 {sup 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.

  18. 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.

  19. 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

  20. Dipole-dipole van der Waals interaction in alkali halides

    International Nuclear Information System (INIS)

    Thakur, B.N.; Thakur, K.P.

    1978-01-01

    Values of van der Waals dipole-dipole constants and interaction energetics of alkali halides are reported using the recent data. The values obtained are somewhat larger than those of earlier workers. (orig.) [de

  1. 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

  2. Separation of americium and plutonium from nuclear wastes by the TRUEX process

    International Nuclear Information System (INIS)

    Leonard, R.A.; Vandegrift, G.F.; Manry, C.W.

    1986-01-01

    Americium and plutonium can be removed from a transuranic (TRU) waste stream to <10 nCi/g by the TRUEX process. The resulting waste is nontransuranic, greatly reducing disposal costs. An overview is given of the TRUEX process and of centrifugal contactors used to implement this process. Then, a plan for the deployment of TRUEX at the Hanford Site is discussed. Finally, details are given on the proposed use of TRUEX to treat the liquid wastes from the Plutonium Finishing Plant at the Hanford Site

  3. 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.

  4. 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.

  5. 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.

  6. The role of halide ions on the electrochemical behaviour of iron in alkali solutions

    Science.gov (United States)

    Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

    2008-02-01

    Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

  7. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    Science.gov (United States)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  8. 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.

  9. Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

    Science.gov (United States)

    Zhang, Dandan; Eaton, Samuel W; Yu, Yi; Dou, Letian; Yang, Peidong

    2015-07-29

    Halide perovskites have attracted much attention over the past 5 years as a promising class of materials for optoelectronic applications. However, compared to hybrid organic-inorganic perovskites, the study of their pure inorganic counterparts, like cesium lead halides (CsPbX3), lags far behind. Here, a catalyst-free, solution-phase synthesis of CsPbX3 nanowires (NWs) is reported. These NWs are single-crystalline, with uniform growth direction, and crystallize in the orthorhombic phase. Both CsPbBr3 and CsPbI3 are photoluminescence active, with composition-dependent temperature and self-trapping behavior. These NWs with a well-defined morphology could serve as an ideal platform for the investigation of fundamental properties and the development of future applications in nanoscale optoelectronic devices based on all-inorganic perovskites.

  10. 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

  11. Spectroscopic investigation of indium halides as substitudes of mercury in low pressure discharges for lighting applications

    Energy Technology Data Exchange (ETDEWEB)

    Briefi, Stefan

    2012-05-22

    Low pressure discharges with indium halides as radiator are discussed as substitutes for hazardous mercury in conventional fluorescent lamps. In this work, the applicability of InBr and InCl in a low pressure discharge light source is investigated. The aim is to identify and understand the physical processes which determine the discharge characteristics and the efficiency of the generated near-UV emission of the indium halide molecule and of the indium atom which is created due to dissociation processes in the plasma. As discharge vessels sealed cylindrical quartz glass tubes which contain a defined amount of indium halide and a rare gas are used. Preliminary investigations showed that for a controlled variation of the indium halide density a well-defined cold spot setup is mandatory. This was realized in the utilized experimental setup. The use of metal halides raises the issue, that power coupling by internal electrodes is not possible as the electrodes would quickly be eroded by the halides. The comparison of inductive and capacitive RF-coupling with external electrodes revealed that inductively coupled discharges provide higher light output and much better long term stability. Therefore, all investigations are carried out using inductive RF-coupling. The diagnostic methods optical emission and white light absorption spectroscopy are applied. As the effects of absorption-signal saturation and reabsorption of emitted radiation within the plasma volume could lead to an underestimation of the determined population densities by orders of magnitude, these effects are considered in the data evaluation. In order to determine the electron temperature and the electron density from spectroscopic measurements, an extended corona model as population model of the indium atom has been set up. A simulation of the molecular emission spectra has been implemented to investigate the rovibrational population processes of the indium halide molecules. The impact of the cold spot

  12. 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

  13. 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)

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

    Indian Academy of Sciences (India)

    The present paper reports the dislocation unpinning model of acoustic emis- sion (AE) from ... Acoustic emission; dislocation; alkali halide crystals; plastic deformation. ..... [5] T Nishimura, A Tahara and T Kolama, Jpn. Metal Inst. 64, 339 (2000).

  15. Alternative route to metal halide free ionic liquids

    International Nuclear Information System (INIS)

    Takao, Koichiro; Ikeda, Yasuhisa

    2008-01-01

    An alternative synthetic route to metal halide free ionic liquids using trialkyloxonium salt is proposed. Utility of this synthetic route has been demonstrated by preparing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid through the reaction between 1-methylimidazole and triethyloxonium tetra-fluoroborate in anhydrous ether. (author)

  16. The thermo-elastic instability model of melting of alkali halides in the Debye approximation

    Science.gov (United States)

    Owens, Frank J.

    2018-05-01

    The Debye model of lattice vibrations of alkali halides is used to show that there is a temperature below the melting temperature where the vibrational pressure exceeds the electrostatic pressure. The onset temperature of this thermo-elastic instability scales as the melting temperature of NaCl, KCl, and KBr, suggesting its role in the melting of the alkali halides in agreement with a previous more rigorous model.

  17. 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

  18. Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

    Science.gov (United States)

    Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

    2018-05-01

    Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN

  19. Resonant halide perovskite nanoparticles

    Science.gov (United States)

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  20. 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

  1. 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

  2. Measurements of α-emitting plutonium and americium in the intertidal sands of west Cumbria, UK

    International Nuclear Information System (INIS)

    Eakins, J.D.; Morgan, A.; Baston, G.M.N.; Pratley, F.W.; Strange, L.P.; Burton, P.J.

    1990-01-01

    Samples of surface sand and sand cores were collected from intertidal regions of west Cumbria between Silloth and Walney Island (including the Duddon Estuary) between 1982 and 1984 and analysed for 238 Pu, 239+240 Pu and 241 Am. Generally, more than 95% of the α-emitting transuranic nuclides were associated with the sand and less than 5% with entrained silt. The greatest concentrations of both plutonium and americium were found at Braystones. Concentrations declined with distance from the Sellafield Works. The largest actinide deposits occurred at Drigg (320 and 720 kBq m -2 of 239+240 Pu and 241 Am respectively). The integrated deposits in intertidal sand between Silloth and Walney Island were about 4.2 and 7.0 TBq respectively, which represent about 1% of the total α-emitting activity discharged to sea from Sellafield Works up to 1982. The corresponding value for the Duddon Estuary is about 0.3%. Only on beaches close to Sellafield did levels of man-made α-emitters exceed those of natural α-emitting nuclides. The radiological consequences of the intertidal inventory of plutonium and americium are shown to be very small and much less than from the seafood pathway. (author)

  3. 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

  4. Elimination of americium-241 after a case of accidental inhalation

    International Nuclear Information System (INIS)

    Edvardsson, K.A.; Lindgren, L.

    1976-01-01

    In handling a 241 Am source one person received an internal contamination of about 140 nCi of americium oxide, which was deposited in the lung region. Elimination of the activity was followed for more than 3 months by external gamma counting and excreta analyses. During the first week after the inhalation about 80% of the total intake was eliminated with an effective half-life of less than 2 days. The remaining activity, deposited in the lung region, was eliminated with an effective half-life of about 17 days. About 15% of the activity eliminated from the lung region from the 10th to the 50th day was eliminated in the faeces. (author)

  5. 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

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

    KAUST Repository

    Peng, Wei

    2017-01-01

    Despite their outstanding charge transport characteristics, organolead halide perovskite single crystals grown by hitherto reported crystallization methods are not suitable for most optoelectronic devices due to their small aspect ratios

  7. Highly Efficient Broadband Yellow Phosphor Based on Zero-Dimensional Tin Mixed-Halide Perovskite.

    Science.gov (United States)

    Zhou, Chenkun; Tian, Yu; Yuan, Zhao; Lin, Haoran; Chen, Banghao; Clark, Ronald; Dilbeck, Tristan; Zhou, Yan; Hurley, Joseph; Neu, Jennifer; Besara, Tiglet; Siegrist, Theo; Djurovich, Peter; Ma, Biwu

    2017-12-27

    Organic-inorganic hybrid metal halide perovskites have emerged as a highly promising class of light emitters, which can be used as phosphors for optically pumped white light-emitting diodes (WLEDs). By controlling the structural dimensionality, metal halide perovskites can exhibit tunable narrow and broadband emissions from the free-exciton and self-trapped excited states, respectively. Here, we report a highly efficient broadband yellow light emitter based on zero-dimensional tin mixed-halide perovskite (C 4 N 2 H 14 Br) 4 SnBr x I 6-x (x = 3). This rare-earth-free ionically bonded crystalline material possesses a perfect host-dopant structure, in which the light-emitting metal halide species (SnBr x I 6-x 4- , x = 3) are completely isolated from each other and embedded in the wide band gap organic matrix composed of C 4 N 2 H 14 Br - . The strongly Stokes-shifted broadband yellow emission that peaked at 582 nm from this phosphor, which is a result of excited state structural reorganization, has an extremely large full width at half-maximum of 126 nm and a high photoluminescence quantum efficiency of ∼85% at room temperature. UV-pumped WLEDs fabricated using this yellow emitter together with a commercial europium-doped barium magnesium aluminate blue phosphor (BaMgAl 10 O 17 :Eu 2+ ) can exhibit high color rendering indexes of up to 85.

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

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1991-09-01

    Melting parameters and transport coefficients in the melt are collated for halides of monovalent, divalent and trivalent metals. A number of systems show a deficit of entropy of melting relative to the linear relationships between entropy change and relative volume change on melting that are found to be approximately obeyed by a majority of halides. These behaviours are discussed on the basis of structural and transport data. The deviating systems are classified into three main classes, namely (i) fast-ion conductors in the high-temperature crystal phase such as AgI, (ii) strongly structured network-like systems such as ZnCl 2 , and (iii) molecular systems melting into associated molecular liquids such as SbCl 3 . (author). 35 refs, 1 fig., 3 tabs

  9. SPHERE: Irradiation of sphere-pac fuel of UPuO2−x containing 3% Americium

    International Nuclear Information System (INIS)

    D’Agata, E.; Hania, P.R.; McGinley, J.; Somers, J.; Sciolla, C.; Baas, P.J.; Kamer, S.; Okel, R.A.F.; Bobeldijk, I.; Delage, F.; Bejaoui, S.

    2014-01-01

    Highlights: • SPHERE is designed to check the behaviour of MADF sphere-pac concept. • MADF sphere-pac are compared with MADF pellet. • Swelling, helium release and restructuring behaviour will be the main output of the experiment. • An experiment to check sphere-pac MABB fuel behaviour is now under design. - Abstract: Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors of long-lived nuclides like 241 Am is therefore an option for the reduction of radiotoxicity of waste packages to be stored in a repository. The SPHERE irradiation experiment is the latest of a series of European experiments on americium transmutation (e.g. EFTTRA-T4, EFTTRA-T4bis, HELIOS, MARIOS) performed in the HFR (High Flux Reactor). The SPHERE experiment is carried out in the framework of the 4-year project FAIRFUELS of the EURATOM 7th Framework Programme (FP7). During the past years of experimental works in the field of transmutation and tests of innovative nuclear fuels, the release or trapping of helium as well as helium induced fuel swelling have been shown to be the key issues for the design of Am-bearing targets. The main objective of the SPHERE experiment is to study the in-pile behaviour of fuel containing 3% of americium and to compare the behaviour of sphere-pac fuel to pellet fuel, in particular the role of microstructure and temperature on fission gas release (mainly He) and on fuel swelling. The SPHERE experiment is being irradiated since September 2013 in the HFR in Petten (The Netherlands) and is expected to be terminated in spring 2015. The experiment has been designed to last up to 18 reactor cycles (corresponding to 18 months) but may reach its target earlier. This paper discusses the rationale and objective of the SPHERE experiment and provides a general description of its design

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

    International Nuclear Information System (INIS)

    Lamouri, A; Naruka, A; Sulcs, J; Varanasi, C V; Brumleve, T R

    2005-01-01

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

  11. Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics.

    Science.gov (United States)

    Hoke, Eric T; Slotcavage, Daniel J; Dohner, Emma R; Bowring, Andrea R; Karunadasa, Hemamala I; McGehee, Michael D

    2015-01-01

    We report on reversible, light-induced transformations in (CH 3 NH 3 )Pb(Br x I 1- x ) 3 . Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

  12. On the Boiling Points of the Alkyl Halides.

    Science.gov (United States)

    Correia, John

    1988-01-01

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

  13. 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)

  14. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

    International Nuclear Information System (INIS)

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun; Gibson, John K.

    2017-01-01

    Although the first organoactinide chloride Cp_3UCl (Cp = η"5-C_5H_5) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT)_2U_2X_n (COT = η"8-C_8H_8; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT)_2U_2X_n, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT)_2U_2X_n species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT)_2U_2X_4 might be accessible through the known (COT)_2U complex. The tetravalent derivatives (COT)_2U_2X_4 are more energetically favorable than the trivalent (COT)_2U_2X_2 analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

  15. 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

  16. Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites.

    Science.gov (United States)

    Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei; Mitzi, David B; Yan, Yanfa

    2017-09-25

    Recently, Cu I - and Ag I -based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only Ag I -based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu I -based analogues. Here we show that, owing to the much higher energy level for the Cu 3d 10 orbitals than for the Ag 4d 10 orbitals, Cu I atoms energetically favor 4-fold coordination, forming [CuX 4 ] tetrahedra (X=halogen), but not 6-fold coordination as required for [CuX 6 ] octahedra. In contrast, Ag I atoms can have both 6- and 4-fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu I halide double perovskites may instead lead to non-perovskites containing [CuX 4 ] tetrahedra, as confirmed by our material synthesis efforts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. 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

  19. 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

  20. 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

  1. 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.

  2. Self-trapped holes in alkali silver halide crystals

    International Nuclear Information System (INIS)

    Awano, T.; Ikezawa, M.; Matsuyama, T.

    1995-01-01

    γ-Ray irradiation at 77 K induces defects in M 2 AgX 3 (M=Rb, K and NH 4 ; X=Br and I) crystals. The irradiation induces self-trapped holes of the form of I 0 in the case of alkali silver iodides, and (halogen) 2 - and (halogen) 0 in the case of ammonium silver halides. The (halogen) 0 is weakly coupled with the nearest alkali metal ion or ammonium ion. It is able to be denoted as RbI + , KI + , NH 4 I + or NH 4 Br + . The directions of hole distribution of (halogen) 2 - and (halogen) 0 were different in each case of the alkali silver iodides, ammonium silver halides and mixed crystal of them. The (halogen) 0 decayed at 160 K in annealing process. The (halogen) 2 - was converted into another form of (halogen) 2 - at 250 K and this decayed at 310 K. A formation of metallic layers was observed on the crystal surface parallel with the c-plane of (NH 4 ) 2 AgI 3 irradiated at room temperature. (author)

  3. 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...

  4. Halide peroxidase in tissues that interact with bacteria in the host squid Euprymna scolopes.

    Science.gov (United States)

    Small, A L; McFall-Ngai, M J

    1999-03-15

    An enzyme with similarities to myeloperoxidase, the antimicrobial halide peroxidase in mammalian neutrophils, occurs abundantly in the light organ tissue of Euprymna scolopes, a squid that maintains a beneficial association with the luminous bacterium Vibrio fischeri. Using three independent assays typically applied to the analysis of halide peroxidase enzymes, we directly compared the activity of the squid enzyme with that of human myeloperoxidase. One of these methods, the diethanolamine assay, confirmed that the squid peroxidase requires halide ions for its activity. The identification of a halide peroxidase in a cooperative bacterial association suggested that this type of enzyme can function not only to control pathogens, but also to modulate the interactions of host animals with their beneficial partners. To determine whether the squid peroxidase functions under both circumstances, we examined its distribution in a variety of host tissues, including those that typically interact with bacteria and those that do not. Tissues interacting with bacteria included those that have specific cooperative associations with bacteria (i.e., the light organ and accessory nidamental gland) and those that have transient nonspecific interactions with bacteria (i.e., the gills, which clear the cephalopod circulatory system of invading microorganisms). These bacteria-associated tissues were compared with the eye, digestive gland, white body, and ink-producing tissues, which do not typically interact directly with bacteria. Peroxidase enzyme assays, immunocytochemical localization, and DNA-RNA hybridizations showed that the halide-dependent peroxidase is consistently expressed in high concentration in tissues that interact bacteria. Elevated levels of the peroxidase were also found in the ink-producing tissues, which are known to have enzymatic pathways associated with antimicrobial activity. Taken together, these data suggest that the host uses a common biochemical response to

  5. Measurements of. alpha. -emitting plutonium and americium in the intertidal sands of west Cumbria, UK

    Energy Technology Data Exchange (ETDEWEB)

    Eakins, J.D.; Morgan, A.; Baston, G.M.N.; Pratley, F.W.; Strange, L.P.; Burton, P.J. (UKAEA Harwell Lab. (UK). Environmental and Medical Science Div.)

    1990-01-01

    Samples of surface sand and sand cores were collected from intertidal regions of west Cumbria between Silloth and Walney Island (including the Duddon Estuary) between 1982 and 1984 and analysed for {sup 238}Pu, {sup 239+240}Pu and {sup 241}Am. Generally, more than 95% of the {alpha}-emitting transuranic nuclides were associated with the sand and less than 5% with entrained silt. The greatest concentrations of both plutonium and americium were found at Braystones. Concentrations declined with distance from the Sellafield Works. The largest actinide deposits occurred at Drigg (320 and 720 kBq m{sup -2} of {sup 239+240}Pu and {sup 241}Am respectively). The integrated deposits in intertidal sand between Silloth and Walney Island were about 4.2 and 7.0 TBq respectively, which represent about 1% of the total {alpha}-emitting activity discharged to sea from Sellafield Works up to 1982. The corresponding value for the Duddon Estuary is about 0.3%. Only on beaches close to Sellafield did levels of man-made {alpha}-emitters exceed those of natural {alpha}-emitting nuclides. The radiological consequences of the intertidal inventory of plutonium and americium are shown to be very small and much less than from the seafood pathway. (author).

  6. 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).

  7. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Gibson, John K. [Lawrence Berkeley National Laboratory, CA (United States). Chemical Sciences Division

    2017-03-01

    Although the first organoactinide chloride Cp{sub 3}UCl (Cp = η{sup 5}-C{sub 5}H{sub 5}) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT){sub 2}U{sub 2}X{sub n} (COT = η{sup 8}-C{sub 8}H{sub 8}; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT){sub 2}U{sub 2}X{sub n}, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT){sub 2}U{sub 2}X{sub n} species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT){sub 2}U{sub 2}X{sub 4} might be accessible through the known (COT){sub 2}U complex. The tetravalent derivatives (COT){sub 2}U{sub 2}X{sub 4} are more energetically favorable than the trivalent (COT){sub 2}U{sub 2}X{sub 2} analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

  8. 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 ...

  9. Spectroscopy on metal-halide lamps under varying gravity conditions

    NARCIS (Netherlands)

    Flikweert, A.J.

    2008-01-01

    Worldwide, 20% of all electricity is used for lighting. For this reason, efficient lamps are economically and ecologically important. High intensity discharge (HID) lamps are efficient lamps. The most common HID lamp these days is the metal-halide (MH) lamp. MH lamps have a good colour rendering

  10. 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 ...

  11. Halide Perovskites: New Science or ``only'' future Energy Converters?

    Science.gov (United States)

    Cahen, David

    Over the years many new ideas and systems for photovoltaic, PV, solar to electrical energy conversion have been explored, but only a few have really impacted PV's role as a more sustainable, environmentally less problematic and safer source of electrical power than fossil or nuclear fuel-based generation. Will Halide Perovskites, HaPs, be able to join the very select group of commercial PV options? To try to address this question, we put Halide Perovskite(HaP) cells in perspective with respect to other PV cells. Doing so also allows to identify fundamental scientific issues that can be important for PV and beyond. What remains to be seen is if those issues lead to new science or scientific insights or additional use of existing models. Being more specific is problematic, given the fact that this will be 4 months after writing this abstract. Israel National Nano-initiative, Weizmann Institute of Science's Alternative sustainable Energy Research Initiative; Israel Ministries of -Science and of -Infrastructure, Energy & Water.

  12. 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.

  13. Aluminum Pitting Corrosion in Halide Media: A Quantum Model and Empirical Evidence

    Science.gov (United States)

    Lashgari, Mohsen; Kianpour, Effat; Mohammadi, Esmaeil

    2013-12-01

    The phenomenon of localized damage of aluminum oxide surface in the presence of halide anions was scrutinized at an atomistic level, through the cluster approach and density functional theory. The phenomenon was also investigated empirically through Tafel polarization plots and scanning electron microscopy. A distinct behavior witnessed in the fluoride medium was justified through the hard-soft acid-base principle. The atomistic investigations revealed the greatest potency for chloride entrance into the metal oxide lattice and rationalized to the severity of damage. The interaction of halide anions with the oxide surface causing some displacements on the position of Al atoms provides a mechanistic insight of the phenomenon.

  14. 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.

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

    KAUST Repository

    Bakr, Osman M.

    2016-02-18

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

  16. Cuprous halides semiconductors as a new means for highly efficient light-emitting diodes

    Science.gov (United States)

    Ahn, Doyeol; Park, Seoung-Hwan

    2016-01-01

    In group-III nitrides in use for white light-emitting diodes (LEDs), optical gain, measure of luminous efficiency, is very low owing to the built-in electrostatic fields, low exciton binding energy, and high-density misfit dislocations due to lattice-mismatched substrates. Cuprous halides I-VII semiconductors, on the other hand, have negligible built-in field, large exciton binding energies and close lattice matched to silicon substrates. Recent experimental studies have shown that the luminescence of I-VII CuCl grown on Si is three orders larger than that of GaN at room temperature. Here we report yet unexplored potential of cuprous halides systems by investigating the optical gain of CuCl/CuI quantum wells. It is found that the optical gain and the luminescence are much larger than that of group III-nitrides due to large exciton binding energy and vanishing electrostatic fields. We expect that these findings will open up the way toward highly efficient cuprous halides based LEDs compatible to Si technology. PMID:26880097

  17. Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites.

    Science.gov (United States)

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2018-02-01

    The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E b ) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E b = 15 meV for MAPbI 3 , in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E b values and highlight the mechanisms underlying E b tuning.

  18. Third-order elastic moduli for alkali-halide crystals possessing the sodium chloride structure

    International Nuclear Information System (INIS)

    Ray, U.

    2010-01-01

    The values of third-order elastic moduli for alkali halides, having NaCl-type crystal structure are calculated according to the Born-Mayer potential model, considering the repulsive interactions up to the second nearest neighbours and calculating the values of the potential parameters for each crystal, independently, from the compressibility data. This work presents the first published account of the calculation of the third-order elastic moduli taking the actual value of the potential parameter unlike the earlier works. Third-order elastic constants have been computed for alkali halides at 0 and 300 K. The results of the third-order elastic constants are compared with the available experimental and theoretical data. Very good agreement between experimental and theoretical third-order elastic constant data (except C 123 ) is found. We have also computed the values of the pressure derivatives of second-order elastic constants and Anderson-Grueneisen parameter for alkali halides, which agree reasonably well with the experimental values, indicating the satisfactory nature of our computed data for third-order elastic constants.

  19. Inhibition of mild steel corrosion in acidic medium using synthetic and naturally occurring polymers and synergistic halide additives

    Energy Technology Data Exchange (ETDEWEB)

    Umoren, S.A. [Department of Chemistry, Faculty of Science, University of Uyo, P.M.B 1017 Uyo (Nigeria)], E-mail: saviourumoren@yahoo.com; Ogbobe, O.; Igwe, I.O. [Department of Polymer and Textile Engineering, School of Engineering and Engineering Technology, Federal University of Technology, P.M.B. 1526 Owerri (Nigeria); Ebenso, E.E. [Department of Chemistry and Chemical Technology, National University of Lesotho, P. O. Roma180, Lesotho (South Africa)

    2008-07-15

    The corrosion inhibition of mild steel in H{sub 2}SO{sub 4} in the presence of gum arabic (GA) (naturally occurring polymer) and polyethylene glycol (PEG) (synthetic polymer) was studied using weight loss, hydrogen evolution and thermometric methods at 30-60 deg. C. PEG was found to be a better inhibitor for mild steel corrosion in acidic medium than GA. The effect of addition of halides (KCl, KBr and KI) was also studied. Results obtained showed that inhibition efficiency (I%) increased with increase in GA and PEG concentration, addition of halides and with increase in temperature. Increase in inhibition efficiency (I%) and degree of surface coverage ({theta}) was found to follow the trend Cl{sup -} < Br{sup -} < I{sup -} which indicates that the radii and electronegativity of the halide ions play a significant role in the adsorption process. GA and PEG alone and in combination with halides were found to obey Temkin adsorption isotherm. Phenomenon of chemical adsorption is proposed from the trend of inhibition efficiency with temperature and values {delta}G{sub ads}{sup 0} obtained. The synergism parameter, S{sub I} evaluated is found to be greater than unity indicating that the enhanced inhibition efficiency caused by the addition of halides is only due to synergism.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-08-01

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

  1. 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.

  2. Demixing in a metal halide lamp, results from modeling

    NARCIS (Netherlands)

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.; Veldhuizen, van E.M.

    2005-01-01

    Metal Halide (MH) lamps are high pressure discharge devices, containing a complex chemical mixture, to emit light on a broad spectrum while maintaining good efficacies. Lamps of this type were first exhibited by General Electric at the 1964 World Fair in New York [1]. They typically consist of an

  3. 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

  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. Synergistic effect of halide ions on the corrosion inhibition of aluminium in H2SO4 using 2-acetylphenothiazine

    International Nuclear Information System (INIS)

    Ebenso, E.E.

    2003-01-01

    The corrosion inhibition of aluminium in H 2 SO 4 in the presence of 2-acetylphenothiazine (2APTZ) at temperature range of 30-60 deg. C was studied using the weight loss and thermometric techniques. The effect of addition of halides (KCl, KBr, KI) is also reported. The inhibition efficiency (I, %) increased with increase in concentration of 2APTZ. The addition of the halides increased the inhibition efficiency to a considerable extent. The temperature increased the corrosion rate and inhibition efficiency in the range 30-60 deg. C in the absence and presence of the inhibitor and halides. Phenomenon of chemical adsorption is proposed. Flory-Huggins adsorption isotherm equation was obeyed at all the concentrations studied. The decrease in inhibition efficiency (and surface coverage values) was found to be in the order I - >Br - >Cl - which clearly indicates that the radii and the electronegativity of halides play a significant role in the adsorption process. All the data acquired reveal that 2APTZ acts as an inhibitor in the acid environment from the two techniques used. The synergistic effect of 2APTZ and halide ions is discussed

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

    KAUST Repository

    Bretschneider, Simon A.; Laquai, Fré dé ric; Bonn, Mischa

    2017-01-01

    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

  7. 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

  8. Halides of BET-TTF: novel hydrated molecular metals

    Energy Technology Data Exchange (ETDEWEB)

    Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

    2000-01-07

    A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

  9. 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.

  10. Building up an electrocatalytic activity scale of cathode materials for organic halide reductions

    International Nuclear Information System (INIS)

    Bellomunno, C.; Bonanomi, D.; Falciola, L.; Longhi, M.; Mussini, P.R.; Doubova, L.M.; Di Silvestro, G.

    2005-01-01

    A wide investigation on the electrochemical activity of four model organic bromides has been carried out in acetonitrile on nine cathodes of widely different affinity for halide anions (Pt, Zn, Hg, Sn, Bi, Pb, Au, Cu, Ag), and the electrocatalytic activities of the latter have been evaluated with respect to three possible inert reference cathode materials, i.e. glassy carbon, boron-doped diamond, and fluorinated boron-doped diamond. A general electrocatalytic activity scale for the process is proposed, with a discussion on its modulation by the configuration of the reacting molecule, and its connection with thermodynamic parameters accounting for halide adsorption

  11. Demixing in a metal halide lamp, results from modelling

    NARCIS (Netherlands)

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.

    2006-01-01

    Convection and diffusion in the discharge region of a metal halide lamp is studied using a computer model built with the plasma modeling package Plasimo. A model lamp contg. mercury and sodium iodide is studied. The effects of the total lamp pressure on the degree of segregation of the light

  12. 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

  13. Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

    NARCIS (Netherlands)

    Zhang, H.; Schubert, U.S.

    2004-01-01

    The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

  14. Effect of halide-mixing on the switching behaviors of organic-inorganic hybrid perovskite memory

    Science.gov (United States)

    Hwang, Bohee; Gu, Chungwan; Lee, Donghwa; Lee, Jang-Sik

    2017-03-01

    Mixed halide perovskite materials are actively researched for solar cells with high efficiency. Their hysteresis which originates from the movement of defects make perovskite a candidate for resistive switching memory devices. We demonstrate the resistive switching device based on mixed-halide organic-inorganic hybrid perovskite CH3NH3PbI3-xBrx (x = 0, 1, 2, 3). Solvent engineering is used to deposit the homogeneous CH3NH3PbI3-xBrx layer on the indium-tin oxide-coated glass substrates. The memory device based on CH3NH3PbI3-xBrx exhibits write endurance and long retention, which indicate reproducible and reliable memory properties. According to the increase in Br contents in CH3NH3PbI3-xBrx the set electric field required to make the device from low resistance state to high resistance state decreases. This result is in accord with the theoretical calculation of migration barriers, that is the barrier to ionic migration in perovskites is found to be lower for Br- (0.23 eV) than for I- (0.29-0.30 eV). The resistive switching may be the result of halide vacancy defects and formation of conductive filaments under electric field in the mixed perovskite layer. It is observed that enhancement in operating voltage can be achieved by controlling the halide contents in the film.

  15. Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Egorov, G.I.

    1994-01-01

    Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

  16. 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

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

    International Nuclear Information System (INIS)

    Selling, J.

    2007-01-01

    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 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 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 2+ /Eu 3+ ratio in the glass ceramics should be determined and optimize favor of the Eu 2+ . We also want to distinguish between Eu 2+ in the glass matrix and Eu 2+ in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a CaF 2 host lattice were carried

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

    International Nuclear Information System (INIS)

    Lopez, M. A.; Broggio, D.; Capello, K.; Cardenas-Mendez, E.; El-Faramawy, N.; Franck, D.; James, A. C.; Kramer, G. H.; Lacerenza, G.; Lynch, T. P.; Navarro, J. F.; Navarro, T.; Perez, B.; Ruehm, W.; Tolmachev, S. Y.; Weitzenegger, E.

    2011-01-01

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

  19. 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

  20. Melting and liquid structure of polyvalent metal halides

    International Nuclear Information System (INIS)

    Tosi, M.P.

    1992-08-01

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

  1. Mechanoluminescence response to the plastic flow of coloured alkali halide crystals

    International Nuclear Information System (INIS)

    Chandra, B.P.; Bagri, A.K.; Chandra, V.K.

    2010-01-01

    The present paper reports the luminescence induced by plastic deformation of coloured alkali halide crystals using pressure steps. When pressure is applied onto a γ-irradiated alkali halide crystal, then initially the mechanoluminescence (ML) intensity increases with time, attains a peak value and later on it decreases with time. The ML of diminished intensity also appears during the release of applied pressure. The intensity I m corresponding to the peak of ML intensity versus time curve and the total ML intensity I T increase with increase in value of the applied pressure. The time t m corresponding to the ML peak slightly decreases with the applied pressure. After t m , initially the ML intensity decreases at a fast rate and later on it decreases at a slow rate. The decay time of the fast decrease in the ML intensity is equal to the pinning time of dislocations and the decay time for the slow decrease of ML intensity is equal to the diffusion time of holes towards the F-centres. The ML intensity increases with the density of F-centres and it is optimum for a particular temperature of the crystals. The ML spectra of coloured alkali halide crystals are similar to the thermoluminescence and afterglow spectra. The peak ML intensity and the total ML intensity increase drastically with the applied pressure following power law, whereby the pressure dependence of the ML intensity is related to the work-hardening exponent of the crystals. The ML also appears during the release of the applied pressure because of the movement of dislocation segments and movements of dislocation lines blocked under pressed condition. On the basis of the model based on the mechanical interaction between dislocation and F-centres, expressions are derived for the ML intensity, which are able to explain different characteristics of the ML. From the measurements of the plastico ML induced by the application of loads on γ-irradiated alkali halide crystals, the pinning time of dislocations

  2. 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....... 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...

  3. 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

  4. Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

    Science.gov (United States)

    Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

    2011-07-01

    Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

  5. Hybrid Lead Halide Perovskites for Ultrasensitive Photoactive Switching in Terahertz Metamaterial Devices.

    Science.gov (United States)

    Manjappa, Manukumara; Srivastava, Yogesh Kumar; Solanki, Ankur; Kumar, Abhishek; Sum, Tze Chien; Singh, Ranjan

    2017-08-01

    The recent meteoric rise in the field of photovoltaics with the discovery of highly efficient solar-cell devices is inspired by solution-processed organic-inorganic lead halide perovskites that exhibit unprecedented light-to-electricity conversion efficiencies. The stunning performance of perovskites is attributed to their strong photoresponsive properties that are thoroughly utilized in designing excellent perovskite solar cells, light-emitting diodes, infrared lasers, and ultrafast photodetectors. However, optoelectronic application of halide perovskites in realizing highly efficient subwavelength photonic devices has remained a challenge. Here, the remarkable photoconductivity of organic-inorganic lead halide perovskites is exploited to demonstrate a hybrid perovskite-metamaterial device that shows extremely low power photoswitching of the metamaterial resonances in the terahertz part of the electromagnetic spectrum. Furthermore, a signature of a coupled phonon-metamaterial resonance is observed at higher pump powers, where the Fano resonance amplitude is extremely weak. In addition, a low threshold, dynamic control of the highly confined electric field intensity is also observed in the system, which could tremendously benefit the new generation of subwavelength photonic devices as active sensors, low threshold optically controlled lasers, and active nonlinear devices with enhanced functionalities in the infrared, optical, and the terahertz parts of the electromagnetic spectrum. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Standardization of a method to study the distribution of Americium in purex process

    International Nuclear Information System (INIS)

    Dapolikar, T.T.; Pant, D.K.; Kapur, H.N.; Kumar, Rajendra; Dubey, K.

    2017-01-01

    In the present work the distribution of Americium in PUREX process is investigated in various process streams. For this purpose a method has been standardized for the determination of Am in process samples. The method involves extraction of Am with associated actinides using 30% TRPO-NPH at 0.3M HNO 3 followed by selective stripping of Am from the organic phase into aqueous phase at 6M HNO 3 . The assay of aqueous phase for Am content is carried out by alpha radiometry. The investigation has revealed that 100% Am follows the HLLW route. (author)

  7. Application of extraction chromatography to the recovery of neptunium, plutonium and americium from an industrial waste

    International Nuclear Information System (INIS)

    Madic, C.; Kertesz, C.; Sontag, R.; Koehly, G.

    1980-01-01

    A pilot scale investigation was made to evaluate the possible application of the extraction chromatographic method (LLC) to the partitioning of alpha emitters from liquid wastes containing traces of transuranium elements. A secondary purpose was to obtain pure Am0 2 , which is used to produce alpha, gamma, and neutron sources. The process developed for alpha partitioning consists essentially of the extraction of macro amounts of uranium with 30% TBP in dodecane in mixer-settlers, then coextraction of Np-237, Pu-239, and Am-241 by LLC on a macro column filled with di-n-hexyl-octoxy-methyl-phosphine oxide (POX.11) adsorbed on an inert support. In each run about 200 liters of initial waste are decontaminated of alpha emitters. The loading step is followed by selective elution of americium, neptunium, and plutonium. The americium eluate is then subjected to the following operations: (1) separation of Am from Fe and Cd by LLC on a TBP column and (2) separation of Am from lanthanide traces by LLC on an HD(DiBM)P column after oxidation of Am(III) to Am(VI). The Am in the eluate is subsequently reduced to Am(III) and precipitated as oxalate with oxalic acid. The oxalate is then filtered and calcined to yield pure AmO 2

  8. 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).

  9. 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)

  10. 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

  11. 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

    International Nuclear Information System (INIS)

    Runde, W.; Kim, J.I.

    1994-09-01

    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 2 -free atmosphere and 10 -2 atm CO 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.) [de

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

    OpenAIRE

    Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

    2016-01-01

    Organic−inorganic halide perovskites have proven highly successful for photovoltaics but suffer from low stability, which deteriorates their performance over time. Recent experiments have demonstrated that low dimensional phases of the hybrid perovskites may exhibit improved stability. Here we 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 ...

  13. 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.

  14. 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%.

  15. 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.

  16. Finding New Perovskite Halides via Machine learning

    Science.gov (United States)

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

    2016-04-01

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

  17. 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

  18. 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

  19. Chemistry of gaseous lower-valent actinide halides. Technical progress report

    International Nuclear Information System (INIS)

    Hildenbrand, D.L.

    1984-01-01

    Objective is to provide thermochemical data for key actinide halide and oxyhalide systems. Progress is reported on bond dissociation energies of gaseous ThCl 4 , ThCl 3 , ThCl 2 , and ThCl; bond dissociation energies of ruthenium fluorides; and mass spectroscopy of UF 6

  20. 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…

  1. 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.)

  2. 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

  3. Americium-241 in surface soil associated with the Hanford site and vicinity

    International Nuclear Information System (INIS)

    Price, K.R.; Gilbert, R.O.; Gano, K.A.

    1981-05-01

    Various kinds of surface soil samples were collected and analyzed for Americium-241 ( 241 Am) to examine the feasibility of improving soil sample data for the Hanford Surface Environmental Surveillance Program. Results do not indicate that a major improvement would occur if procedures were changed from the current practices. Conclusions from this study are somewhat tempered by the very low levels of 241 Am ( 241 Am in soil crust (0 to 1.0 cm deep) was greater than the corresponding subsurface layer (1.0 to 2.5 cm deep), and the average concentration of 241 Am in some onsite samples collected near the PUREX facility was greater than comparable samples collected 60 km upwind at an offsite location

  4. 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

  5. Plasmonic characterization of photo-induced silver nanoparticles extracted from silver halide based TEM film

    Energy Technology Data Exchange (ETDEWEB)

    Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Rai, V. N.; Srivastava, A. K. [Indus Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India); Varshney, G. K. [Laser Bio-medical Applications & Instrumentation Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India)

    2016-05-23

    The plasmonic responses of silver nanoparticles extracted from silver halide based electron microscope film are investigated. Photo-reduction process is carried out to convert the silver halide grains into the metallic silver. The centrifuge technique is used for separating the silver nanoparticles from the residual solution. Morphological study performed by field emission scanning electron microscope (FESEM) shows that all the nanoparticles have an average diameter of ~120 nm with a high degree of mono dispersion in size. The localized surface plasmon resonance (LSPR) absorption peak at ~537 nm confirms the presence of large size silver nanoparticles.

  6. 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

  7. 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

  8. Biosorption of americium-241 by Candida sp

    International Nuclear Information System (INIS)

    Luo Shunzhong; Zhang Taiming; Liu Ning; Yang Yuanyou; Jin Jiannan; Liao Jiali

    2003-01-01

    As an important radioisotope in nuclear industry and other fields, americium-241 is one of the most serious contamination concerns duo to its high toxicity and long half-life. In this experiment, the biosorption of 241 Am from solution by Candida sp., and the effects of various experimental conditions on the adsorption were investigated. The preliminary results showed that the adsorption of 241 Am by Candida sp. was efficient. 241 Am could be removed by Candida sp. of 0.82 g/L (dry weight) from 241 Am solutions of 5.6-111 MBq/L (44.3-877.2 μg/L)(C 0 ), with maximum adsorption rate (R) of 98% and maximum adsorption capacities (W) of 63.5 MBq/g biomass (dry weight) (501.8 μg/g). The biosorption equilibrium was achieved within 4 hour and the optimum pH was pH = 2. No significant differences on 241 Am adsorption were observed at 10 C-45 C, or in solutions containing Au 3+ or Ag + , even 1500 times or 4500 times above the 241 Am concentration, respectively. The relationship between concentrations and adsorption capacities of 241 Am indicated the biosorption process should be described by a Langmuir adsorption isotherm. (orig.)

  9. Synergistic effect of halide ions on the corrosion inhibition of aluminium in H{sub 2}SO{sub 4} using 2-acetylphenothiazine

    Energy Technology Data Exchange (ETDEWEB)

    Ebenso, E.E

    2003-03-05

    The corrosion inhibition of aluminium in H{sub 2}SO{sub 4} in the presence of 2-acetylphenothiazine (2APTZ) at temperature range of 30-60 deg. C was studied using the weight loss and thermometric techniques. The effect of addition of halides (KCl, KBr, KI) is also reported. The inhibition efficiency (I, %) increased with increase in concentration of 2APTZ. The addition of the halides increased the inhibition efficiency to a considerable extent. The temperature increased the corrosion rate and inhibition efficiency in the range 30-60 deg. C in the absence and presence of the inhibitor and halides. Phenomenon of chemical adsorption is proposed. Flory-Huggins adsorption isotherm equation was obeyed at all the concentrations studied. The decrease in inhibition efficiency (and surface coverage values) was found to be in the order I{sup -}>Br{sup -}>Cl{sup -} which clearly indicates that the radii and the electronegativity of halides play a significant role in the adsorption process. All the data acquired reveal that 2APTZ acts as an inhibitor in the acid environment from the two techniques used. The synergistic effect of 2APTZ and halide ions is discussed.

  10. The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

    KAUST Repository

    Zhumekenov, Ayan A.; Burlakov, Victor M.; Saidaminov, Makhsud I.; Alofi, Abdulilah; Haque, Mohammed; Turedi, Bekir; Davaasuren, Bambar; Dursun, Ibrahim; Cho, Nam Chul; El-Zohry, Ahmed M.; de Bastiani, Michele; Giugni, Andrea; Torre, Bruno; Di Fabrizio, Enzo M.; Mohammed, Omar F.; Rothenberger, Alexander; Wu, Tao; Goriely, Alain; Bakr, Osman

    2017-01-01

    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

  11. 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)

  12. Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

    Science.gov (United States)

    Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

    2017-08-01

    Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. Monocrystallomimicry in the aerosols of ammonium and cesium halides

    International Nuclear Information System (INIS)

    Melikhov, I.V.; Kitova, E.N.; Kozlovskaya, EhD.; Kamenskaya, A.N.; Mikheev, N.B.; Kulyukhin, S.A.

    1997-01-01

    It is experimentally shown that initial CsI and NH 4 Hal nanocrystals combining into mixed aggregates of polyhedral form (pseudo monocrystals) are formed in the process of cocrystallization of ammonium halide and cesium iodide. The origination and growth of the pseudo monocrystals on the account of successive addition of initial crystals is described by the Fokker-Plank equation [ru

  15. The biokinetics and radiotoxicology of curium: A comparison with americium

    Energy Technology Data Exchange (ETDEWEB)

    Menetrier, F. [CEA, Fontenay-aux-Roses (France); Taylor, D.M. [School of Chemistry, Cardiff University, Cardiff CF10 3AT (United Kingdom)], E-mail: davtay@btinternet.com; Comte, A. [CEA, Fontenay-aux-Roses (France)

    2008-05-15

    The human and animal data on the biokinetics of {sup 242}Cm and {sup 244}Cm are reviewed and shown to be very similar to those for {sup 241}Am. Liver and skeleton are the main organs of deposition and the retention of curium in the skeleton is very prolonged in all the species examined. Retention of both curium and americium in the liver appears to be species-dependent, being relatively rapidly removed from the liver of rats, and probably humans, but being tenaciously retained in dogs and some other species. The radiotoxicity of curium is also reviewed and it is shown that, as with {sup 241}Am, lung and bone tumour induction are the major hazards from inhaled and systemically deposited {sup 244}Cm. The use of chelating agents for the treatment of accidental contamination of the human body with {sup 242,244}Cm is also discussed.

  16. Line emissions from sonoluminescence in aqueous solutions of halide salts without noble gases

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Jinfu, E-mail: liang.shi2007@163.com [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China); School of Physics and Electronic Science, Guizhou Normal University, Guiyang 550001 (China); Chen, Weizhong, E-mail: wzchen@nju.edu.cn [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China); Zhou, Chao; Cui, Weicheng; Chen, Zhan [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China)

    2015-02-20

    Line emissions of trivalent terbium (Tb{sup 3+}) ion were observed from single-bubble sonoluminescence (SL) in an aqueous solution of terbium chloride (TbCl{sub 3}) that contained no noble gas. In addition, sodium (Na) lines were observed in multi-bubble SL in aqueous solutions of various halide salts that contained no noble gas. These observations show that the halide ions, such as Cl{sup −}, Br{sup −}, and I{sup −}, help for line emissions as the noble gases. The intensity of a line emission depends on both the chemical species produced by cavitation bubbles and the temperature of SL bubble that responds to the driving ultrasound pressure. With the increase of driving pressure, some line emissions attached to the continuous spectrum may become increasingly clear, while other line emissions gradually become indistinct. - Highlights: • Line emissions of Tb(III) ions were observed without the presence of noble gases. • The halide ions help to generate a line emission during sonoluminescence. • The intensity of a line emission mainly depends on the bubble's temperature. • The definition of a line emission is related to the temperature of caviation bubble and the kind of host liquid.

  17. Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

    Science.gov (United States)

    Lignos, Ioannis; Protesescu, Loredana; Emiroglu, Dilara Börte; Maceiczyk, Richard; Schneider, Simon; Kovalenko, Maksym V; deMello, Andrew J

    2018-02-14

    Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX 3 , X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl 1-x Br x ) 3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl 1-x Br x ) 3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl 1-x Br x ) 3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

  18. 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)

  19. Transfer across the human gut of environmental plutonium, americium, cobalt, caesium and technetium: studies with cockles (Cerastoderma edule) from the Irish Sea

    International Nuclear Information System (INIS)

    Hunt, G.J.

    1998-01-01

    Our previous studies have indicated lower values of the gut transfer factor ('f L values') for plutonium and americium in winkles (Littorina littorea) than adopted by ICRP. The present study was undertaken primarily to investigate whether this observation extends to other species. Samples of cockles (Cerastoderma edule) from Ravenglass, Cumbria were eaten by volunteers who provided 24 samples of urine and faeces. Urine samples indicated f L values for cockles which were higher than for winkles; for plutonium these ranged overall up to 7x10 -4 with an arithmetic mean in the range (2-3)x10 -4 , and for americium up to 2.6x10 -4 with an arithmetic mean of 1.2x10 -4 . Limited data based on volunteers eating cockles from the Solway suggest that f L values for americium may be greater at distance from Sellafield. The measured values compare with 5x10 -4 used by the ICRP for environmental forms of both elements, which would appear to provide adequate protection when calculating doses from Cumbrian cockles. Data for other nuclides were obtained by analysing faecal samples from the volunteers who ate the Ravenglass cockles. Cobalt-60 showed an f L value in the region of 0.2, twice the value currently used by ICRP. For 137 Cs, variabilities were indicated in the range 0.08 to 0.43, within the ICRP value of f L =1.0. Technetium-99 gave f L values up to about 0.6, in reasonable conformity with the ICRP value of 0.5. (author)

  20. Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

    Energy Technology Data Exchange (ETDEWEB)

    Schurz, Christian M.; Shlyk, Larysa; Schleid, Thomas; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2011-07-01

    Two different polymorphs of the metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) are known to crystallize in layered structures. The two crystal structures differ in the way {sub {infinity}}{sup 2}{l_brace}X[M{sub 2}N{sub 2}]X{r_brace} slabs are stacked along the c-axes. Metal atoms and/or organic molecules can be intercalated into the van-der-Waals gap between these layers. After such an electron-doping via intercalation the prototypic band insulators change into superconductors with moderate high critical temperatures T{sub c} up to 25.5 K. This review gathers information on synthesis routes, structural characteristics and properties of the prototypic nitride halides and the derivatives after electron-doping with a focus on superconductivity. (orig.)

  1. Manipulating Ion Migration for Highly Stable Light-Emitting Diodes with Single-Crystalline Organometal Halide Perovskite Microplatelets.

    Science.gov (United States)

    Chen, Mingming; Shan, Xin; Geske, Thomas; Li, Junqiang; Yu, Zhibin

    2017-06-27

    Ion migration has been commonly observed as a detrimental phenomenon in organometal halide perovskite semiconductors, causing the measurement hysteresis in solar cells and ultrashort operation lifetimes in light-emitting diodes. In this work, ion migration is utilized for the formation of a p-i-n junction at ambient temperature in single-crystalline organometal halide perovskites. The junction is subsequently stabilized by quenching the ionic movement at a low temperature. Such a strategy of manipulating the ion migration has led to efficient single-crystalline light-emitting diodes that emit 2.3 eV photons starting at 1.8 V and sustain a continuous operation for 54 h at ∼5000 cd m -2 without degradation of brightness. In addition, a whispering-gallery-mode cavity and exciton-exciton interaction in the perovskite microplatelets have both been observed that can be potentially useful for achieving electrically driven laser diodes based on single-crystalline organometal halide perovskite semiconductors.

  2. Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part I. Transmission Holographic Optical Elements

    Science.gov (United States)

    Kim, Jong Man; Choi, Byung So; Kim, Sun Il; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

    2001-02-01

    Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOE s). The drawback of DCG is its low sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-high-resolution silver halide emulsions. An optimized processing technique for transmission HOE s recorded in these materials is introduced. Diffraction efficiencies over 90% can be obtained for transmissive diffraction gratings. Understanding the importance of the selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOE s.

  3. Transport phenomena in metal-halide lamps : a poly-diagnostic study

    NARCIS (Netherlands)

    Nimalasuriya, T.

    2007-01-01

    Worldwide about 20% of all electricity is used for lighting. It is therefore of great interest to develop a lamp that has high e±cacy, good colour rendering and long lifetime. The metal-halide lamp is a gas discharge lamp that meets all these demands. Unfortunately there are still issues with this

  4. Inorganic Lead Halide Perovskite Single Crystals: Phase-Selective Low-Temperature Growth, Carrier Transport Properties, and Self-Powered Photodetection

    KAUST Repository

    Saidaminov, Makhsud I.

    2016-12-06

    A rapid, low-temperature, and solution-based route is developed for growing large-sized cesium lead halide perovskite single crystals under ambient conditions. An ultralow minority carrier concentration was measured in CsPbBr3 (≈108 holes per cm3, much lower than in any other lead halide perovskite and crystalline silicon), which enables to realize self-powered photodetectors with a high ON/OFF ratio (105).

  5. 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.

  6. 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.

  7. 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)

  8. Metal-halide lamp design: atomic and molecular data needed

    International Nuclear Information System (INIS)

    Lapatovich, Walter P

    2009-01-01

    Metal-halide lamps are a subset of high intensity discharge (HID) lamps so named because of their high radiance. These lamps are low temperature (∼0.5 eV), weakly ionized plasmas sustained in refractory but light transmissive envelopes by the passage of electric current through atomic and molecular vapors. For commercial applications, the conversion of electric power to light must occur with good efficiency and with sufficient spectral content throughout the visible (380-780 nm) to permit the light so generated to render colors comparable to natural sunlight. This is achieved by adding multiple metals to a basic mercury discharge. Because the vapor pressure of most metals is very much lower than mercury itself, metal-halide salts of the desired metals, having higher vapor pressures, are used to introduce the material into the basic discharge. The metal compounds are usually polyatomic iodides, which vaporize and subsequently dissociate as they diffuse into the bulk plasma. Metals with multiple visible transitions are necessary to achieve high photometric efficiency (efficacy) and good color. Compounds of Sc, Dy, Ho, Tm, Ce, Pr, Yb and Nd are commonly used. The electrons, atoms and radicals are in local thermodynamic equilibrium (LTE), but not with the radiation field. Strong thermal (10 6 K m -1 ) and density gradients are sustained in the discharge. Atomic radiation produced in the high-temperature core transits through colder gas regions where it interacts with cold atoms and un-dissociated molecules before exiting the lamp. Power balance and spectral output of the lamp are directly affected by the strength of atomic transitions. Attempts to simulate the radiative output of functional metal-halide lamps have been successful only in very simple cases. More data (e.g. the atomic transition probabilities of Ce i) are necessary to improve lamp performance, to select appropriate radiators and in scaling the lamp geometry to various wattages for specific applications.

  9. Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

    International Nuclear Information System (INIS)

    Rodriguez M, R.; Perez S, R.; Vazquez P, G.; Riveros, H.; Gonzalez M, P.

    2014-08-01

    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 x KBr 1-x and KBr x RbBr 1-x . (Author)

  10. 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

  11. Contribution to the study of pseudohalides complexes of tervalent, lanthanides and actinides in solution

    International Nuclear Information System (INIS)

    Cuillerdier, Christine.

    1981-10-01

    Some complexes formed with halides or pseudohalides (iodide, cyanide, azide and thiocyanate) and tervalent lanthanides and actinides have been studied in solution. Methods like solvent extraction, polarography have been used to measure inner plus outer sphere complexation and spectroscopic methods have been chosen to study inner sphere complexes only. It has been found that inner sphere complexe of americium and neodymium with cyanide exist in aqueous solutions. Tervalent actinides form stronger inner sphere complexes with azide than lanthanide in solution. Thiocyanate complexes appear to be inner sphere and N-bonded [fr

  12. 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…

  13. 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...

  14. 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.

  15. Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

    KAUST Repository

    Chawla, Mohit; Credendino, Raffaele; Poater, Albert; Oliva, Romina M.; Cavallo, Luigi

    2015-01-01

    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.

  16. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Science.gov (United States)

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  17. Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

    NARCIS (Netherlands)

    Bae, D.; Palmstrom, A.; Roelofs, K.; Mei, Bastian Timo; Chorkendorf, I.; Bent, S.F.; Vesborg, P.C.

    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,

  18. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao

    2012-08-01

    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  19. Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites.

    Science.gov (United States)

    Meng, Weiwei; Wang, Xiaoming; Xiao, Zewen; Wang, Jianbo; Mitzi, David B; Yan, Yanfa

    2017-07-06

    Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB 2+ X 3 ) and double perovskites (A 2 B + B 3+ X 6 ) (A = Cs or monovalent organic ion, B 2+ = non-Pb divalent metal, B + = monovalent metal, B 3+ = trivalent metal, X = halogen). We show that if B 2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B + = In, Tl and B 3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoelectronic applications.

  20. Inverse kinetic solvent isotope effect in TiO2 photocatalytic dehalogenation of non-adsorbable aromatic halides: a proton-induced pathway.

    Science.gov (United States)

    Chang, Wei; Sun, Chunyan; Pang, Xibin; Sheng, Hua; Li, Yue; Ji, Hongwei; Song, Wenjing; Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai

    2015-02-09

    An efficient redox reaction between organic substrates in solution and photoinduced h(+) vb /e(-) cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE ≥ 1). Reported herein is a universal inverse KSIE (0.6-0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0 ]methanol/[D4 ]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H(+) /D(+) from solvent oxidation, accompanies a change in hybridization from sp(2) to sp(3) at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  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. Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation.

    Science.gov (United States)

    Zhao, Xin-Gang; Yang, Ji-Hui; Fu, Yuhao; Yang, Dongwen; Xu, Qiaoling; Yu, Liping; Wei, Su-Huai; Zhang, Lijun

    2017-02-22

    Hybrid organic-inorganic halide perovskites with the prototype material of CH 3 NH 3 PbI 3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues-the poor device stabilities associated with their intrinsic material instability and the toxicity due to water-soluble Pb 2+ -need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb 2+ ions into one monovalent M + and one trivalent M 3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify 11 optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them.

  3. 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

  4. Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

    Science.gov (United States)

    Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

    2018-03-01

    The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

  5. Ground state depletion – A step towards mid-IR lasing of doped silver halides

    Energy Technology Data Exchange (ETDEWEB)

    Tsur, Yuval, E-mail: yuvaltsu@post.tau.ac.il [Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 6997801 (Israel); Goldring, Sharone [Applied Physics Division, Soreq NRC, Yavne 81800 (Israel); Galun, Ehud [DDR& D, Ministry of Defense (Israel); Katzir, Abraham [Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 6997801 (Israel)

    2016-07-15

    We show for the first time ground state absorption saturation in a doped silver halide crystal (AgCl{sub x}Br{sub 1−x}), specifically with cobalt. Spectroscopic studies showed absorption bands in the 1.4–2.5 μm region and emission bands in the 3.8–5.0 μm region, with a 1.5 ms lifetime at low temperatures. Absorption saturation indicates a good low and room temperature lasing feasibility at 4.1 μm. In addition, a comparison of cobalt, nickel and iron as dopants is presented. These doped silver halide crystals can be extruded to form optical fibers, possibly introducing a new family of fiber lasers for the middle infrared.

  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. 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.

  8. Investigation of sodalites for conditioning halide salts (NaCl and NaI): Comparison of two synthesis routes

    Energy Technology Data Exchange (ETDEWEB)

    Bardez, Isabelle; Campayo, Lionel; Rigaud, Danielle; Chartier, Myriam; Calvet, Aurelie [CEA, Laboratoire d' Etudes des Materiaux Ceramiques pour le Conditionnement, Site de Marcoule, Batiment 208, B.P. 17171, 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    Sodalites with the general formula Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}X{sub 2} (where X = Cl or I) were investigated for ceramic conditioning of halide salts (NaCl and NaI). Because of the tendency of halides to volatilize at high temperature, two synthesis routes were tested to optimize the halide content in the sodalite phase. The first is based on heating at high temperature of a [nepheline NaAlSiO{sub 4} + salt] mixture prepared by a dry process. The second, performed at low temperature, consists of the reaction in aqueous media between kaolinite (Al{sub 2}Si{sub 2}O{sub 5}(OH){sub 4}), sodium hydroxide (NaOH) and the salt. The present study compares these two syntheses and examines differences between chloro-sodalite and iodo-sodalite based on X-ray diffraction and infrared spectroscopy. The next step will consist in sintering the resulting powder samples to obtain dense ceramics. (authors)

  9. Corrosion inhibition of iron in 0.5 mol L-1 H2SO4 by halide ions

    Directory of Open Access Journals (Sweden)

    Jeyaprabha C.

    2006-01-01

    Full Text Available The inhibition effect of halide ions such as iodide, bromide and chloride ions on the corrosion of iron in 0.5 mol L-1 H2SO4 and the adsorption behaviour of these ions on the electrode surface have been studied by polarization and impedance methods. It has been found that the inhibition of nearly 90% has been observed for iodide ions at 2.5 10-3 mol L-1, for bromide ions at 10 10-3 mol L-1 and 80% for chloride ions at 2.5 10-3 mol L-1. The inhibition effect is increased with increase of halide ions concentration in the case of I- and Br- ions, whereas it has decreased in the case of Cl- ion at concentrations higher than 5 10-3 mol L-1. The double layer capacitance values have decreased considerably in the presence of halide ions which indicate that these anions are adsorbed on iron at the corrosion potential.

  10. 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).

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

    KAUST Repository

    Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

    2014-01-01

    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

  12. (e,2e) momentum spectroscopic study of the C=C π orbitals of the vinyl halides

    International Nuclear Information System (INIS)

    Gorunganthu, R.R.; Coplan, M.A.; Leung, K.T.; Tossell, J.A.; Moore, J.H.; Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada; Department of Chemistry, University of Maryland, College Park, Maryland 20742)

    1989-01-01

    The distribution of electron momentum density has been measured for the outermost occupied orbitals of the vinyl halides and ethylene using the (e,2e) technique. In contrast to the ionization potentials for these π orbitals which decrease monotonically from vinyl fluoride to vinyl iodide, the values of the momenta where the distributions are a maximum, p max , increase from the fluoride through the bromide and then shift back to a lower value for the iodide. This observation can be analyzed in terms of B(r), the Fourier transform of the observed momentum distribution, and ΔB(r), the difference between B(r) functions. The shape of ΔB(r) for the fluoride, chloride, and bromide in comparison to ethylene reflects the effect of the carbon--halogen antibonding interaction in these vinyl halides. On the other hand, in vinyl iodide the antibonding interaction is compensated for by the diffuse iodine 5p character of the molecular orbital. The relation of these observations to chemical properties of the vinyl halides is discussed along with differences between experiment and calculations at low momentum

  13. 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)

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

    International Nuclear Information System (INIS)

    Reichley-Yinger, L.; Vandegrift, G.F.

    1987-01-01

    Plutonium and americium can be recovered from aqueous waste solutions containing a mixture of HCl and chloride salt wastes by the coupling of two solvent extraction systems: tributyl phosphate (TBP) in tetrachloroethylene (TCE) and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in TCE. In the flowsheet developed, the salt wastes are dissolved in HCl, the Pu(III) is oxidized to the IV state with NaClO 2 and recovered in the TBP-TCE cycle, and the Am is then removed from the resultant raffinate by the CMPO-TCE cycle. The consequences of the feed solution composition and extraction behavior of these species on the process flowsheet design, the Pu-product purity, and the decontamination of the aqueous raffinate from transuranic elements are discussed. 16 refs., 6 figs

  15. 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.

  16. 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

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

    International Nuclear Information System (INIS)

    Tanaka, Kosuke; Hirosawa, Takashi; Obayashi, Hiroshi; Koyama, Shin Ichi; Yoshimochi, Hiroshi; Tanaka, Kenya

    2008-01-01

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

  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......Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat...

  19. Modulation of electronic and optical properties in mixed halide perovskites CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x)

    Science.gov (United States)

    Zhou, Ziqi; Cui, Yu; Deng, Hui-Xiong; Huang, Le; Wei, Zhongming; Li, Jingbo

    2017-03-01

    The recent discovery of lead halide perovskites with band gaps in the visible presents important potential in the design of high efficient solar cells. CsPbCl3, CsPbBr3 and CsPbI3 are stable compounds within this new family of semiconductors. By performing the first-principles calculation, we explore the structural, electronic and optical properties of CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with various compositions of halide atoms. Structural stability is demonstrated with halide atoms distributing randomly at the halide atomic sites. CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) exhibit the modulation of their band gaps by varying the halide composition. Our results also indicate that CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with different halide compositions are suitable to application to solar cells for the general features are well preserved. Good absorption to lights of different wavelengths has been obtained in these mixed halide perovskites.

  20. 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

  1. 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.

  2. The importance of moisture in hybrid lead halide perovskite thin film fabrication

    NARCIS (Netherlands)

    Eperon, G.E.; Habisreutinger, S.N.; Leijtens, T.; Bruijnaers, B.J.; van Franeker, J.J.; deQuilettes, D.W.; Pathak, S.; Sutton, R.J.; Grancini, G.; Ginger, D.S.; Janssen, R.A.J.; Petrozza, A.; Snaith, H.J.

    2015-01-01

    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

  3. 40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

    Science.gov (United States)

    2010-07-01

    ... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this subpart that... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

  4. [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.

  5. 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.

  6. Protonation of octadecylamine Langmuir monolayer by adsorption of halide counterions

    Science.gov (United States)

    Sung, Woongmo; Avazbaeva, Zaure; Lee, Jonggwan; Kim, Doseok

    Langmuir monolayer consisting of octadecylamine (C18H37NH2, ODA) was investigated by heterodyne vibrational sum-frequency generation (HD-VSFG) spectroscopy in conjunction with surface pressure-area (π- A) isotherm, and the result was compared with that from cationic-lipid (DPTAP) Langmuir monolayer. In case of ODA monolayer on pure water, both SF intensity of water OH band and the surface pressure were significantly smaller than those of the DPTAP monolayer implying that only small portion of the amine groups (-NH3+ is protonated in the monolayer. In the presence of sodium halides (NaCl and NaI) in the subphase water, it was found that the sign of Imχ (2) of water OH band remained the same as that of the ODA monolayer on pure water, but there was a substantial increase in the SF amplitude. From this, we propose that surface excess of the halide counterions (Cl- and I-) makes the solution condition near the ODA monolayer/water interface more acidic so that ODA molecules in the monolayer are more positively charged, which works to align the water dipoles at the interface.

  7. Liquid-liquid extraction of plutonium and americium by cekanoic acid from alkaline medium

    International Nuclear Information System (INIS)

    Venugopal Chetty, K.; Sagar, V.; Swarup, R.

    2001-01-01

    Liquid-liquid extraction studies of plutonium and americium from aqueous carbonate medium using a high molecular weight carboxylic acid namely cekanoic acid in different diluents has been carried out. The distribution ratio (D) values for Pu(IV) and Am(III) under various parameters such as concentration of extractant, Na 2 CO 3 and initial pH were obtained. Results indicated that Pu(IV) and Am(III) could be satisfactorily extracted together or individually from aqueous carbonate medium using cekanoic acid in different diluents like carbon tetrachloride, cyclohexane, toluene, n-dodecane or solvesso-100. The D values for Pu(IV) and Am(III) also indicated the possibility of their mutual separation. The back extraction of Pu and Am with different reagents was also studied. (orig.)

  8. 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...

  9. Analogy between temperature dependent radiation effects in alkali halide crystals and crystalline ammonia

    International Nuclear Information System (INIS)

    Blum, A.

    1977-01-01

    Pikaev, Ershov, and Makarov recently reported the characteristic shape of Arrhenius-type dependence for F-centers slow part (millisecond) decay in alkali halide crystals irradiated at different temperatures. The decay rate is constant when the temperature is below the limiting value (T/sub lim/) and exhibits constant activation energy (E/sub A/) at temperatures above T/sub lim/ up to the melting point. A similar dependence has been observed for crystalline ammonia radiolysis yields (H 2 and N 2 ) in the temperature range from 77 to 195 0 K (ammonia melting point) with a limiting value of 105 0 K for N 2 and 119 0 K for H 2 . The coincidence between the alkali halide and ammonia data does not seem to be formal and there are indications showing a closer analogy between these two cases

  10. 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.

  11. Sodium-Metal-Halide Battery Energy Storage for DoD Installations

    Science.gov (United States)

    2017-10-24

    electrical equipment for AC interface PDE Pacific Data Electric V&F Voltage and Frequency, power quality measurements VA Volt-Amp, units for apparent...Metal-Halide technology could operate at extreme ambient temperatures, but the early prototypes did struggle with managing sand ingress.  The...peak power Not tested 3. PV smoothing Measure improvement in power quality Power meter measurements Power quality improvements 15-min

  12. 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.

  13. Efficient Photon Recycling and Radiation Trapping in Cesium Lead Halide Perovskite Waveguides

    KAUST Repository

    Dursun, Ibrahim

    2018-05-26

    Cesium lead halide perovskite materials have attracted considerable attention for potential applications in lasers, light emitting diodes and photodetectors. Here, we provide the experimental and theoretical evidence for photon recycling in CsPbBr3 perovskite microwires. Using two-photon excitation, we recorded photoluminescence (PL) lifetimes and emission spectra as a function of the lateral distance between PL excitation and collection positions along the microwire, with separations exceeding 100 µm. At longer separations, the PL spectrum develops a red-shifted emission peak accompanied by an appearance of well-resolved rise times in the PL kinetics. We developed quantitative modeling that accounts for bimolecular recombination and photon recycling within the microwire waveguide and is sufficient to account for the observed decay modifications. It relies on a high radiative efficiency in CsPbBr3 perovskite microwires and provides crucial information about the potential impact of photon recycling and waveguide trapping on optoelectronic properties of cesium lead halide perovskite materials.

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

    International Nuclear Information System (INIS)

    Paik, Seung Uk; Jung, Myoung Geun

    2012-01-01

    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

  15. Radiation processes in organic halides (Cl, Br, I) studied by ESR spectroscopy

    International Nuclear Information System (INIS)

    Symons, M.C.R.

    1980-01-01

    Electron-loss from alkyl halides (Cl, Br, I) gives Rhal. + which may dimerise to give (Rhal-halR) + σ* radicals with characteristic ESR spectra, or may lose H + to give α-halo radicals (R 2 Chal) also with well characterised ESR spectra. Electron-capture gives dissociation, but there may be weak residual charge-transfer interaction between R. and hal - which gives rise to well defined hyperfine coupling from the halide nuclei. Loss of β-hydrogen gives β-halo radicals, R 2 C-CH 2 hal (Cl,Br) whose conformation, established by ESR spectroscopy, is such that the halogen atom lies out of the radical plane so that overlap between the half-filled 2p(π) orbital and the C-hal (σ) orbital is maximised. Electron addition to α-halocarboxylates and related compounds probably gives β-halo radical anions, (R 2 C[hal]CO 2 H) - with a similar preferred conformation. Alternative structures are considered for these species. (author)

  16. 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)

  17. Annual report for FY 1976 on project AN0115A: the migration of plutonium and americium in the lithosphere

    International Nuclear Information System (INIS)

    Fried, S.; Friedman, A.M.; Hines, J.J.; Atcher, R.W.; Quarterman, L.A.; Volesky, A.

    1976-12-01

    Studies have been carried out on the migration of plutonium and americium in solutions flowing through porous and crushed rock and through fissures. The migration process can be described in terms of the surface absorption of these elements. In addition, chemical effects on the absorption have been observed. One of these effects is possibly due to the presence of a plutonium polymer that migrates at a more rapid rate than normal plutonium

  18. Relationship between thermoluminescence and X-ray induced luminescence in alkali halides

    International Nuclear Information System (INIS)

    Aguilar, M.; Lopez, F.J.; Jaque, F.

    1978-01-01

    The wavelength spectra of thermoluminescence and X-ray induced luminescence in pure and divalent cation doped alkali halides, in the temperature range LNT-RT have been studied. The more important conclusion is that the wavelength spectra in both cases are very similar. This allows a new point of view to be presented on thermoluminescence mechanisms. (author)

  19. 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.)

  20. 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.

  1. Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

    International Nuclear Information System (INIS)

    Babushkin, A.N.; Babushkina, G.V.

    1999-01-01

    The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

  2. Calcium looping process for high purity hydrogen production integrated with capture of carbon dioxide, sulfur and halides

    Science.gov (United States)

    Ramkumar, Shwetha; Fan, Liang-Shih

    2013-07-30

    A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.

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

    Science.gov (United States)

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

    2014-09-28

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer 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 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

  4. 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.

  5. 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

  6. Effects of Annealing Conditions on Mixed Lead Halide Perovskite Solar Cells and Their Thermal Stability Investigation.

    Science.gov (United States)

    Yang, Haifeng; Zhang, Jincheng; Zhang, Chunfu; Chang, Jingjing; Lin, Zhenhua; Chen, Dazheng; Xi, He; Hao, Yue

    2017-07-21

    In this work, efficient mixed organic cation and mixed halide (MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃) perovskite solar cells are demonstrated by optimizing annealing conditions. AFM, XRD and PL measurements show that there is a better perovskite film quality for the annealing condition at 100 °C for 30 min. The corresponding device exhibits an optimized PCE of 16.76% with V OC of 1.02 V, J SC of 21.55 mA/cm² and FF of 76.27%. More importantly, the mixed lead halide perovskite MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃ can significantly increase the thermal stability of perovskite film. After being heated at 80 °C for 24 h, the PCE of the MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃ device still remains at 70.00% of its initial value, which is much better than the control MAPbI₃ device, where only 46.50% of its initial value could be preserved. We also successfully fabricated high-performance flexible mixed lead halide perovskite solar cells based on PEN substrates.

  7. Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part 2. Reflection Holographic Optical Elements

    Science.gov (United States)

    Kim, Jong Man; Choi, Byung So; Choi, Yoon Sun; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

    2002-03-01

    Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOEs). The drawback of DCG is its low energetic sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-fine-grain silver halide (AgHal) emulsions. In particular, high spatial-frequency fringes associated with HOEs of the reflection type are difficult to construct when SHSG processing methods are employed. Therefore an optimized processing technique for reflection HOEs recorded in the new AgHal materials is introduced. Diffraction efficiencies over 90% can be obtained repeatably for reflection diffraction gratings. Understanding the importance of a selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOEs, also including high-quality display holograms of the reflection type in both monochrome and full color.

  8. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Science.gov (United States)

    2010-07-01

    ... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

  9. Quantitative positron annihilation studies in citrates, halides and oxyhalides chemisorbed on γ-alumina catalyst

    International Nuclear Information System (INIS)

    Luo, X.H.; Jean, Y.C.; Cheng, K.L.

    1987-01-01

    A quantitative study of the γ-alumina catalyst chemisorbed by nitrates, halides, and oxyhalides has been conducted with the positron annihilation spectroscopy (PAS). Catalysts containing Fe, Co, or Ni have been extensively used in chemical industry and petroleum refining. The positron or Ps annihilation can provide a profile information about the bulk, near surface, and void. It is an in-situ surface technique. The PAS technique has shown its capability to determine the nitrate or chloride in γ-alumina as low as 0.02% in solids. It is interesting to note that the PAS may offer the oxidation state information in solids. This is not surprising because the positron annihilation is sensitive to the electron density variation in environments. Positron annihilation models for halides and oxyhalides are proposed

  10. 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

  11. 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

  12. 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.

  13. F-center and self-trapped exciton formation in strongly excited alkali halide crystals

    International Nuclear Information System (INIS)

    Kravchenko, V.A.; Yakovlev, V.Yu.

    1988-01-01

    Method of luminescent and absorption spectroscopy with time resolution was used to study the effect of density of electron pulse excitation (t p =10 -8 s, P=(10 5 -10 8 ) WXcm -2 ) on efficiency of η ε two-halide autolocalized exciton (TALE) and F-centers (η F ) formation in CsI, CsBr, KBr, KI alkali halide crystals. It was established that for all studied systems the elevation of P power of electron beam (EB) from 10 5 up to 5X10 7 WXcm -2 resulted to sufficient decrease of production efficiency and yield of TALE luminescence. In the case when F-centers of colour are induced predominantly by pulsed irradiation in crystals, F-center yield is independent of P. If F-centers and TALE are produced in comparable amounts (CsBr crystals, T=80 K), η ε decrease with P growth is accompanied by η F growth

  14. A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Neus Mesquida

    2012-04-01

    Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

  15. Surface passivation of mixed-halide perovskite CsPb(BrxI1-x)3 nanocrystals by selective etching for improved stability.

    Science.gov (United States)

    Jing, Qiang; Zhang, Mian; Huang, Xiang; Ren, Xiaoming; Wang, Peng; Lu, Zhenda

    2017-06-08

    In recent years, there has been an unprecedented rise in the research of halide perovskites because of their important optoelectronic applications, including photovoltaic cells, light-emitting diodes, photodetectors and lasers. The most pressing question concerns the stability of these materials. Here faster degradation and PL quenching are observed at higher iodine content for mixed-halide perovskite CsPb(Br x I 1-x ) 3 nanocrystals, and a simple yet effective method is reported to significantly enhance their stability. After selective etching with acetone, surface iodine is partially etched away to form a bromine-rich surface passivation layer on mixed-halide perovskite nanocrystals. This passivation layer remarkably stabilizes the nanocrystals, making their PL intensity improved by almost three orders of magnitude. It is expected that a similar passivation layer can also be applied to various other kinds of perovskite materials with poor stability issues.

  16. Nature of the superionic transition in Ag+ and Cu+ halides

    International Nuclear Information System (INIS)

    Keen, D.A.; Hull, S.; Barnes, A.C.; Berastegui, P.; Crichton, W.A.; Madden, P.A.; Tucker, M.G.; Wilson, M.

    2003-01-01

    Silver and copper halides generally display an abrupt (first-order) transition to the superionic state. However, powder diffraction studies and molecular dynamics (MD) simulations of AgI under hydrostatic pressure both indicate that a continuous superionic transition occurs on heating. The gradual onset of the highly conducting state is accompanied by an increasing fraction of dynamic Frenkel defects, a peak in the specific heat and anomalous behavior of the lattice expansion. Similar methods have been employed to investigate the proposed continuous superionic transition between the two ambient pressure face centered cubic phases of CuI. This is difficult to examine experimentally, because the hexagonal β phase exists over a narrow temperature range between the γ (cation ordered) and α (cation disordered) phases. MD simulations performed with the simulation box constrained to remain cubic at all temperatures show that, although limited Cu + Frenkel disorder occurs within γ-CuI, CuI undergoes an abrupt superionic transition at 670 K to the superionic α phase. This is supported by powder neutron diffraction studies of CuI lightly doped with Cs + to prevent stabilization of the β phase. The implications of these results on the phase transitions of other copper and silver halide superionic conductors are discussed

  17. Dehalogenation of aromatic halides by polyaniline/zero-valent iron composite nanofiber: Kinetics and mechanisms

    CSIR Research Space (South Africa)

    Giri, S

    2016-03-01

    Full Text Available Dehalogenation of aryl halides was demonstrated using polyaniline/zero valent iron composite nanofiber (termed as PANI/Fe0) as a cheap, efficient and environmentally friendly heterogeneous catalyst. The catalyst was prepared via rapid mixing...

  18. Kinetics of halide release of haloalkane dehalogenase : Evidence for a slow conformational change

    NARCIS (Netherlands)

    Schanstra, JP; Janssen, DB; Schanstra, Joost P.

    1996-01-01

    Haloalkane dehalogenase converts haloalkanes to their corresponding alcohols and halides, The reaction mechanism involves the formation of a covalent alkyl-enzyme complex which is hydrolyzed by water. The active site is a hydrophobic cavity buried between the main domain and the cap domain of the

  19. 2-D images of the metal-halide lamp obtained by experiment and model

    NARCIS (Netherlands)

    Flikweert, A.J.; Beks, M.L.; Nimalasuriya, T.; Kroesen, G.M.W.; Mullen, van der J.J.A.M.; Stoffels, W.W.

    2008-01-01

    The metal-halide lamp shows color segregation caused by diffusion and convection. Two-dimensional imaging of the arc discharge under varying gravity conditions aids in the understanding of the flow phenomena. In this paper, we show results obtained by experiments and by numerical simulations in

  20. Behaviour of alkali halides as materials for optical components of high power lasers

    International Nuclear Information System (INIS)

    Apostol, D.I.; Mihailescu, N.I.; Ghiordanescu, V.; Nistor, C.L.; Nistor, V.S.; Teodorescu, V.; Voda, M.

    1978-01-01

    The physical phenomena taking place in alkali halides when a CO 2 laser radiation is passing through have been reviewed. A special emphasis has been put on the specific qualities which such materials should have for being used as components for high power lasers. (author)

  1. The MARINE experiment: Irradiation of sphere-pac fuel and pellets of UO{sub 2−x} for americium breeding blanket concept

    Energy Technology Data Exchange (ETDEWEB)

    D' Agata, E., E-mail: elio.dagata@ec.europa.eu [European Commission, Joint Research Centre, Institute for Energy and Transport, P.O. Box 2, NL-1755 ZG Petten (Netherlands); Hania, P.R. [Nuclear Research and Consultancy Group, P.O. Box 25, NL-1755 ZG Petten (Netherlands); Freis, D.; Somers, J. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Bejaoui, S. [Commissariat à l’Energie Atomique et aux Energies Alternatives, DEN/DEC, F-13108 St. Paul lez Durance Cedex (France); Charpin, F.F.; Baas, P.J.; Okel, R.A.F.; Til, S. van [Nuclear Research and Consultancy Group, P.O. Box 25, NL-1755 ZG Petten (Netherlands); Lapetite, J.-M. [European Commission, Joint Research Centre, Institute for Energy and Transport, P.O. Box 2, NL-1755 ZG Petten (Netherlands); Delage, F. [Commissariat à l’Energie Atomique et aux Energies Alternatives, DEN/DEC, F-13108 St. Paul lez Durance Cedex (France)

    2017-01-15

    Highlights: • MARINE is designed to check the behaviour of MABB sphere-pac concept. • MABB sphere-pac are compared with MABB pellet. • Swelling and helium release behaviour will be the main output of the experiment. • An experiment to check sphere-pac MADF fuel behaviour has been already performed. - Abstract: Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors of long-lived nuclides like {sup 241}Am is therefore an option for the reduction of radiotoxicity and heat production of waste packages to be stored in a repository. The MARINE irradiation experiment is the latest of a series of European experiments on americium transmutation (e.g. EFTTRA-T4, EFTTRA-T4bis, HELIOS, MARIOS, SPHERE) performed in the High Flux Reactor (HFR). The MARINE experiment is developed and carried out in the framework of the collaborative research project PELGRIMM of the EURATOM 7th Framework Programme (FP7). During the past years of experimental works in the field of transmutation and tests of innovative nuclear fuels, the release or trapping of helium as well as swelling have been shown to be the key issues for the design of such kind of fuel both as drivers and even more for Am-bearing blanket targets (due to the higher Am contents). The main objective of the MARINE experiment is to study the in-pile behaviour of uranium oxide fuel containing 13% of americium and to compare the behaviour of sphere-pac versus pellet fuel, in particular the role of microstructure and temperature on fission gas release and He on fuel swelling. The MARINE experiment will be irradiated in 2016 in the HFR in Petten (The Netherlands) and is expected to be completed in spring 2017. This paper discusses the rationale and objective of the MARINE experiment and provides a general description of its design for which some innovative features have been adopted.

  2. INTERRELATION OF ACIDITY-BASICITY, SOLUBILITY AND ABILITY TO INTERACTION OF HALIDES OF MX AND M'X2 (M - Li ÷ Cs, M' - Be ÷ Ba, X - Cl ÷ I TYPES

    Directory of Open Access Journals (Sweden)

    V. F. Zinchenko

    2015-11-01

    Full Text Available The size-charge factor of basicity for definition of the acid-base properties of alkaline both alkaline-earth metals and Be halides is offered. The certain interrelation of the specified factor, and also the magnitudes connected with energy of a crystal lattice (temperature of boiling and enthalpy of evaporation of salt with its solubility in water, and also with enthalpy of hydration is established. It is shown that the minimum solubility possess alkaline metals halides (KCl for chlorides, RbBr for Rubidium halides and CsI for alkaline metals halides as a whole at which value of the factor of basicity is equal to 0.83, i.e. it is slightly less than 1. Among alkaline-earth metals halides the lowest solubility has BaCl2 with the highest value of the factor of basicity (0.4. An absolute value of enthalpy of hydration for salts crystal-hydrates possesses tens kJ/mol H2O and increases with reduction of the factor of basicity at transition from metals chlorides to iodides, and also at cationic substitution by easier analogue. Qualitative correlation between a difference of basicity of binary halides and their ability to interaction with formation of complex compounds of various degree of durability is established. At an average difference of basicities 0.4 in halide systems are formed incongruently melting, and at 0.6-0.8 and more – congruently melting compounds. Forecasting of solubility of complex halide of CsSrCl3 composition on the basis of its value of equalized basicity is carried out.

  3. Quaternary oxide halides of group 15 with zinc and cadmium; Quaternaere Oxidhalogenide der Gruppe 15 mit Zink und Cadmium

    Energy Technology Data Exchange (ETDEWEB)

    Rueck, Nadia

    2014-07-30

    The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn{sup 3+} cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn{sup 3+} cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

  4. Hot working alkali halides for laser window applications

    International Nuclear Information System (INIS)

    Koepke, B.G.; Anderson, R.H.; Stokes, R.J.

    1975-01-01

    The techniques used to hot work alkali halide crystals into laser window blanks are reviewed. From the point of view of high power laser window applications one of the materials with a high figure of merit is KCl. Thus the materials examined are KCl and alloys of KCl-KBr containing 5 mole percent KBr. The fabrication techniques include conventional and constrained press forging, isostatic press forging and hot rolling. Optical properties are paramount to the ultimate usefulness of these materials. Results on the optical properties of the hot worked material are included together with mechanical properties and microstructural data

  5. 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...

  6. 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

    2018-03-14

    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.

  7. 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)

  8. Thermochromic halide perovskite solar cells.

    Science.gov (United States)

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  9. Thermochromic halide perovskite solar cells

    Science.gov (United States)

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  10. Surface and zeta-potentials of silver halide single crystals: pH-dependence in comparison to particle systems

    International Nuclear Information System (INIS)

    Selmani, Atiða; Kallay, Nikola; Preočanin, Tajana; Lützenkirchen, Johannes

    2014-01-01

    We have carried out surface and zeta-potential measurements on AgCl and AgBr single crystals. As for particle systems we find that, surprisingly and previously unnoted, the zeta-potential exhibits pH-dependence, while the surface potential does not. A possible interpretation of these observations is the involvement of water ions in the interfacial equilibria and in particular, stronger affinity of the hydroxide ion compared to the proton. The pH-dependence of the zeta-potential can be suppressed at sufficiently high silver concentrations, which agrees with previous measurements in particle systems where no pH-dependence was found at high halide ion concentrations. The results suggest a subtle interplay between the surface potential determining the halide and silver ion concentrations, and the water ions. Whenever the charge due to the halide and silver ions is sufficiently high, the influence of the proton/hydroxide ion on the zeta-potential vanishes. This might be related to the water structuring at the relevant interfaces which should be strongly affected by the surface potential. Another interesting observation is accentuation of the assumed water ion effect on the zeta-potential at the flat single crystal surfaces compared to the corresponding silver halide colloids. Previous generic MD simulations have indeed predicted that hydroxide ion adsorption is accentuated on flat/rigid surfaces. A thermodynamic model for AgI single crystals was developed to describe the combined effects of iodide, silver and water ions, based on two independently previously published models for AgI (that only consider constituent and background electrolyte ions) and inert surfaces (that only consider water and background electrolyte ions). The combined model correctly predicts all the experimentally observed trends. (paper)

  11. A comparative study of semi-empirical interionic potentials for alkali halides - II

    International Nuclear Information System (INIS)

    Khwaja, F.A.; Naqvi, S.H.

    1985-08-01

    A comprehensive study of some semi-empirical interionic potentials is carried out through the calculation of the cohesive energy, relative stability and pressure induced solid-solid phase transformations in alkali halides. The theoretical values of these properties of the alkali halides are obtained using a new set of van der Waals coefficients and zero-point energy in the expression for interionic potential. From the comparison of the present calculations with some previous sophisticated ab-initio quantum-mechanical calculations and other semi-empirical approaches, it is concluded that the present calculations in the simplest central pairwise interaction description with the new values of the van der Waals coefficients and zero-point energy are in better agreement with the experimental data than the previous calculations. It is also concluded that in some cases the better choice of the interionic potential alone in the simplest semi-empirical picture of interaction gives an agreement of the theoretical predictions with the experimental data much superior to the ab-initio quantum mechanical approaches. (author)

  12. Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells.

    Science.gov (United States)

    Park, Byung-wook; Jain, Sagar M; Zhang, Xiaoliang; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2015-02-24

    Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

  13. 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.

  14. REPLACEMENT OF TRYPTOPHAN RESIDUES IN HALOALKANE DEHALOGENASE REDUCES HALIDE BINDING AND CATALYTIC ACTIVITY

    NARCIS (Netherlands)

    KENNES, C; PRIES, F; KROOSHOF, GH; BOKMA, E; Kingma, Jacob; JANSSEN, DB

    1995-01-01

    Haloalkane dehalogenase catalyzes the hydrolytic cleavage of carbon-halogen bonds in short-chain haloalkanes. Two tryptophan residues of the enzyme (Trp125 and Trp175) form a halide-binding site in the active-site cavity, and were proposed to play a role in catalysis. The function of these residues

  15. Theoretical investigation of pressure-induced structural transitions in americium using GGA+U and hybrid density functional theory methods

    DEFF Research Database (Denmark)

    Verma, Ashok K.; Modak, P.; Sharma, Surinder M.

    2013-01-01

    First-principles calculations have been performed for americium (Am) metal using the generalized gradient approximation + orbital-dependent onsite Coulomb repulsion via Hubbard interaction (GGA+U) and hybrid density functional theory (HYB-DFT) methods to investigate various ground state properties......-I to Am-II transition. Good agreement was found between calculated and experimental equations of states for all phases, but the first three phases need larger U (α) parameters (where α represents the fraction of Hartree-Fock exchange energy replacing the DFT exchange energy) than the fourth phase in order...

  16. 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

  17. Radiation chemistry of the alkali halides

    International Nuclear Information System (INIS)

    Robinson, V.J.; Chandratillake, M.R.

    1987-01-01

    By far the most thoroughly investigated group of compounds in solid-state radiation chemistry are the alkali halides. Some of the reasons are undoubtedly practical: large single crystals of high purity are readily prepared. The crystals are transparent over a wide range of wavelengths. They are more sensitive to radiation damage than most other ionic solids. The crystals have simple well-defined structures, and the products of radiolysis have also in many cases been clearly identified by a variety of experimental techniques, the most important being optical methods and electron paramagnetic resonance (EPR). In recent years the application of pulse techniques-radiolysis and laser photolysis-has yielded a wealth of information concerning the mechanisms of the primary processes of radiation damage, on the one hand, and of thermal and photolytic reactions that the radiolysis products undergo, on the other

  18. Preparation of curium-americium oxide microspheres by resin-bead loading

    International Nuclear Information System (INIS)

    Chattin, F.R.; Benker, D.E.; Lloyd, M.H.; Orr, P.B.; Ross, R.G.; Wiggins, J.T.

    1980-01-01

    Resin-bead loading and calcination techniques have been used to produce all curium and americium oxide feed material (about 2.2 kg) for HFIR targets since 1971. The process based on Dowex 50W resin has progressed from a series of test runs, through special production runs, into routine production in permanent equipment beginning in 1975. Key attributes of this process are its reliability, high yields, and ease of operation. The process is suited for remote operation in hot cells. Yields approaching 95% are routinely obtained and only one unacceptable product has been generated during routine production operations. There have been no problems in fabricating targets from this oxide or in the subsequent irradiation of these targets. The present scale of production of 150 to 250 g/y supplies the present need and is comparable with the level of other chemical process operations at TRU. Since the annual production is accomplished in two 8 to 12 day periods, there has been no reason to consider further scale-up. However, the rate of production could easily be doubled by simply adding a second set of calcination equipment

  19. 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.

  20. Halide based MBE of crystalline metals and oxides

    Energy Technology Data Exchange (ETDEWEB)

    Greenlee, Jordan D.; Calley, W. Laws; Henderson, Walter; Doolittle, W. Alan [Georgia Institute of Technology, School of Electrical and Computer Engineering, Atlanta, Georgia (United States)

    2012-02-15

    A halide based growth chemistry has been demonstrated which can deliver a range of transition metals using low to moderate effusion cell temperatures (30-700 C) even for high melting point metals. Previously, growth with transition metal species required difficult to control electron beam or impurity inducing metal organic sources. Both crystalline oxide and metal films exhibiting excellent crystal quality are grown using this halide-based growth chemistry. Films are grown using a plasma assisted Molecular Beam Epitaxy (MBE) system with metal-chloride precursors. Crystalline niobium, cobalt, iron, and nickel were grown using this chemistry but the technology can be generalized to almost any metal for which a chloride precursor is available. Additionally, the oxides LiNbO{sub 3} and LiNbO{sub 2} were grown with films exhibiting X-ray diffraction (XRD) rocking curve full-widths at half maximum of 150 and 190 arcseconds respectively. LiNbO{sub 2} films demonstrate a memristive response due to the rapid movement of lithium in the layered crystal structure. The rapid movement of lithium ions in LiNbO{sub 2} memristors is characterized using impedance spectroscopy measurements. The impedance spectroscopy measurements suggest an ionic current of.1 mA for a small drive voltage of 5 mV AC or equivalently an ionic current density of {proportional_to}87 A/cm{sup 2}. This high ionic current density coupled with low charge transfer resistance of {proportional_to}16.5 {omega} and a high relaxation frequency (6.6 MHz) makes this single crystal material appealing for battery applications in addition to memristors. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)