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Sample records for hydride generation-atomic absorption

  1. Determination of arsenic in a nickel alloy by flow injection hydride generation atomic absorption spectrometry

    Science.gov (United States)

    Hanna, C. P.; Tyson, J. F.; Offley, S. G.

    1992-08-01

    The development of a method for the direct determination of trace arsenic quantities in nickel alloy digests, by flow injection hydride generation atomic absorption spectrometry, is described. An optimization study of the manifold and chemical parameters produced system performance, in terms of tolerance of the nickel matrix and sensitivity, such that matrix removal and pre-reduction of As(V) to As (III) prior to arsine generation were eliminated. Full recovery of the As(V) signal from a solution containing 5 ng ml -1 in the presence of 60 μg ml -1 nickel was obtained. Validation of the method was achieved by analyzing a British Chemical Standard (BCS) Certified Reference Material (CRM) #346 IN nickel alloy containing arsenic at a concentration of 50 μg g -1. Following dissolution in nitric and hydrofluoric acids by a microwave assisted procedure, the only subsequent preparation required was dilution by the appropriate factor. Up to 60 injections h -1 may be made, with a detection limit of 0.5 ng ml -1 arsenic (250 pg absolute) as As(V) in a 500 μl sample. The peak height characteristic concentration is 0.46 ng ml -1, with a relative standard deviation of 3.5% for a 10 ng ml -1 As(V) standard ( n = 6).

  2. Determination of Inorganic Arsenic Species by Electrochemical Hydride Generation Atomic Absorption Spectrometry with Selective Electrochemical Reduction

    Institute of Scientific and Technical Information of China (English)

    LI Xun; WANG Zheng-Hao

    2007-01-01

    A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry (EcHG-AAS) with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As(Ⅲ) shows significantly higher absorbance at low electrolytic currents than As(Ⅴ) in 0.3 mol·L-1 H2SO4.The electrolytic current used for the determination of As(Ⅲ) without considerable interferences of As(V) was 0.4 A, whereas the current for the determination of As(Ⅲ)and As(V) was 1.2 A. For equal concentrations of As(Ⅲ) and As(V) in a sample, the interferences of As(V) during the As(Ⅲ) determination were smaller than 5%. The absorbance for As(V) could be calculated by subtracting that for As(Ⅲ) measured at 0.4 A from the total absorbance for As(Ⅲ) and As(V) measured at 1.2 A, and then the concentration of As(V) can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·ml-1 for As(Ⅲ) and As(V) respectively.The relative standrad deviations were of 3.5% for 20 ng·ml-1 As(Ⅲ) and 302% for 20 ng·ml-1 As(V).The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine.

  3. Arsenic in marine tissues — The challenging problems to electrothermal and hydride generation atomic absorption spectrometry

    Science.gov (United States)

    Karadjova, Irina B.; Petrov, Panayot K.; Serafimovski, Ivan; Stafilov, Trajče; Tsalev, Dimiter L.

    2007-03-01

    Analytical problems in determination of arsenic in marine tissues are addressed. Procedures for the determination of total As in solubilized or extracted tissues with tetramethylammonium hydroxide and methanol have been elaborated. Several typical lyophilized tissues were used: NIST SRM 1566a 'Oyster Tissue', BCR-60 CRM 'Trace Elements in an Aquatic Plant ( Lagarosiphon major)', BCR-627 'Forms of As in Tuna Fish Tissue', IAEA-140/TM 'Sea Plant Homogenate', NRCC DOLT-1 'Dogfish Liver' and two representatives of the Black Sea biota, Mediterranean mussel ( Mytilus galloprovincialis) and Brown algae ( Cystoseira barbata). Tissues (nominal 0.3 g) were extracted in tetramethylammonium hydroxide (TMAH) 1 ml of 25% m/v TMAH and 2 ml of water) or 5 ml of aqueous 80% v/v methanol (MeOH) in closed vessels in a microwave oven at 50 °C for 30 min. Arsenic in solubilized or extracted tissues was determined by electrothermal atomic absorption spectrometry (ETAAS) after appropriate dilution (nominally to 25 ml, with further dilution as required) under optimal instrumental parameters (pyrolysis temperature 900 °C and atomization temperature 2100 °C) with 1.5 μg Pd as modifier on Zr-Ir treated platform. Platforms have been pre-treated with 2.7 μmol of zirconium and then with 0.10 μmol of iridium which served as a permanent chemical modifier in direct ETAAS measurements and as an efficient hydride sequestration medium in flow injection hydride generation (FI-HG)-ETAAS. TMAH and methanol extract 96-108% and 51-100% of As from CRMs. Various calibration approaches have been considered and critically evaluated. The effect of species-dependent slope of calibration graph or standard additions plot for total As determination in a sample comprising of several individual As species with different ETAAS behavior has been considered as a kind of 'intrinsic element speciation interference' that cannot be completely overcome by standard additions technique. Calibration by means of CRMs has

  4. Arsenic in marine tissues - The challenging problems to electrothermal and hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Karadjova, Irina B.; Petrov, Panayot K. [Faculty of Chemistry, University of Sofia, 1 James Bourchier Blvd., Sofia 1164 (Bulgaria); Serafimovski, Ivan [Food Institute, Faculty of Veterinary Medicine, Sts. Cyril and Methodius University, P.O. Box 95, MK-1000, Skopje (Macedonia, The Former Yugoslav Republic of); Stafilov, Trajce [Institute of Chemistry, Faculty of Science, Sts. Cyril and Methodius University, P.O. Box 162, MK-1000, Skopje (Macedonia, The Former Yugoslav Republic of); Tsalev, Dimiter L. [Faculty of Chemistry, University of Sofia, 1 James Bourchier Blvd., Sofia 1164 (Bulgaria)], E-mail: tsalev@chem.uni-sofia.bg

    2007-03-15

    Analytical problems in determination of arsenic in marine tissues are addressed. Procedures for the determination of total As in solubilized or extracted tissues with tetramethylammonium hydroxide and methanol have been elaborated. Several typical lyophilized tissues were used: NIST SRM 1566a 'Oyster Tissue', BCR-60 CRM 'Trace Elements in an Aquatic Plant (Lagarosiphon major)', BCR-627 'Forms of As in Tuna Fish Tissue', IAEA-140/TM 'Sea Plant Homogenate', NRCC DOLT-1 'Dogfish Liver' and two representatives of the Black Sea biota, Mediterranean mussel (Mytilus galloprovincialis) and Brown algae (Cystoseira barbata). Tissues (nominal 0.3 g) were extracted in tetramethylammonium hydroxide (TMAH) 1 ml of 25% m/v TMAH and 2 ml of water) or 5 ml of aqueous 80% v/v methanol (MeOH) in closed vessels in a microwave oven at 50 deg. C for 30 min. Arsenic in solubilized or extracted tissues was determined by electrothermal atomic absorption spectrometry (ETAAS) after appropriate dilution (nominally to 25 ml, with further dilution as required) under optimal instrumental parameters (pyrolysis temperature 900 deg. C and atomization temperature 2100 deg. C) with 1.5 {mu}g Pd as modifier on Zr-Ir treated platform. Platforms have been pre-treated with 2.7 {mu}mol of zirconium and then with 0.10 {mu}mol of iridium which served as a permanent chemical modifier in direct ETAAS measurements and as an efficient hydride sequestration medium in flow injection hydride generation (FI-HG)-ETAAS. TMAH and methanol extract 96-108% and 51-100% of As from CRMs. Various calibration approaches have been considered and critically evaluated. The effect of species-dependent slope of calibration graph or standard additions plot for total As determination in a sample comprising of several individual As species with different ETAAS behavior has been considered as a kind of 'intrinsic element speciation interference' that cannot be completely

  5. Dielectric barrier discharge plasma atomizer for hydride generation atomic absorption spectrometry—Performance evaluation for selenium

    Energy Technology Data Exchange (ETDEWEB)

    Duben, Ondřej [Institute of Analytical Chemistry of the CAS, v.v.i., Veveří 97, CZ-602 00 Brno (Czech Republic); Faculty of Science, Department of Analytical Chemistry, Charles University in Prague, Hlavova 8, Prague, CZ 128 43 Czech Republic (Czech Republic); Boušek, Jaroslav [Faculty of Electrical Engineering and Communications, Brno University of Technology, Technická 1058/10, 61600 Brno (Czech Republic); Dědina, Jiří [Institute of Analytical Chemistry of the CAS, v.v.i., Veveří 97, CZ-602 00 Brno (Czech Republic); Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz [Institute of Analytical Chemistry of the CAS, v.v.i., Veveří 97, CZ-602 00 Brno (Czech Republic)

    2015-09-01

    Atomization of selenium hydride in a quartz dielectric barrier discharge (DBD) atomizer was optimized and its performance was compared to that of the externally heated quartz multiatomizer. Argon was found as the best DBD discharge gas employing a flow rate of 75 ml min{sup −1} Ar while the DBD power was optimized at 14 W. The detection limits reached 0.24 ng ml{sup −1} Se in the DBD and 0.15 ng ml{sup −1} Se in the multiatomizer. The tolerance of DBD to interferences is even better than with the multiatomizer. - Highlights: • SeH{sub 2} atomization in a dielectric barrier discharge (DBD) was optimized for AAS. • Atomizer performance was compared for DBD and externally heated quartz atomizer. • Detection limits were quantified and interferences were studied in both atomizers. • Atomization efficiency in the DBD was estimated.

  6. Determination of total arsenic in coal and wood using oxygen flask combustion method followed by hydride generation atomic absorption spectrometry.

    Science.gov (United States)

    Geng, Wenhua; Furuzono, Takuya; Nakajima, Tsunenori; Takanashi, Hirokazu; Ohki, Akira

    2010-04-15

    A simple and sensitive procedure for the determination of total arsenic in coal and wood was conducted by use of oxygen flask combustion (OFC) followed by hydride generation atomic absorption spectrometry (HGAAS). The effect of various items (composition of absorbent, standing time between the combustion and filtration, particle size and mass of sample) was investigated. Under the optimized conditions of the OFC method, nine certified reference materials were analyzed, and the values of arsenic concentration obtained by this method were in good accordance with the certified values. The limit of detection (LOD) and relative standard deviation (RSD) of the method were 0.29 microg g(-1) and less than 8%, respectively. In addition, eight kinds of coals and four chromated copper arsenate (CCA)-treated wood wastes were analyzed by the present method, and the data were compared to those from the microwave-acid digestion (MW-AD) method. The determination of arsenic in solid samples was discussed in terms of applicable scope and concentration range of arsenic.

  7. Determination of Mecruy at Trace Level in Natural Water Samples by Hydride Generation Atomic Absorption Spectrophotometry after Cloud Point Extraction Preconcentration

    Institute of Scientific and Technical Information of China (English)

    Ji Ying SONG; Ming HOU; Li Xiang ZHANG

    2006-01-01

    A method for the determination of trace mercury in water samples by hydride generation atomic absorption spectrophotometry after cloud point extraction was proposed in the present work.The effects of pH, concentration of surfactant, and equilibration time on cloud point extraction were discussed. The enhancement factor of 20 and the detection limit of 0.039 μg/L were obtained for mercury with relative standard deviation of 4.8% (n = 11).

  8. Determination of ultra trace arsenic species in water samples by hydride generation atomic absorption spectrometry after cloud point extraction

    Energy Technology Data Exchange (ETDEWEB)

    Ulusoy, Halil Ibrahim, E-mail: hiulusoy@yahoo.com [University of Cumhuriyet, Faculty of Science, Department of Chemistry, TR-58140, Sivas (Turkey); Akcay, Mehmet; Ulusoy, Songuel; Guerkan, Ramazan [University of Cumhuriyet, Faculty of Science, Department of Chemistry, TR-58140, Sivas (Turkey)

    2011-10-10

    Graphical abstract: The possible complex formation mechanism for ultra-trace As determination. Highlights: {yields} CPE/HGAAS system for arsenic determination and speciation in real samples has been applied first time until now. {yields} The proposed method has the lowest detection limit when compared with those of similar CPE studies present in literature. {yields} The linear range of the method is highly wide and suitable for its application to real samples. - Abstract: Cloud point extraction (CPE) methodology has successfully been employed for the preconcentration of ultra-trace arsenic species in aqueous samples prior to hydride generation atomic absorption spectrometry (HGAAS). As(III) has formed an ion-pairing complex with Pyronine B in presence of sodium dodecyl sulfate (SDS) at pH 10.0 and extracted into the non-ionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114). After phase separation, the surfactant-rich phase was diluted with 2 mL of 1 M HCl and 0.5 mL of 3.0% (w/v) Antifoam A. Under the optimized conditions, a preconcentration factor of 60 and a detection limit of 0.008 {mu}g L{sup -1} with a correlation coefficient of 0.9918 was obtained with a calibration curve in the range of 0.03-4.00 {mu}g L{sup -1}. The proposed preconcentration procedure was successfully applied to the determination of As(III) ions in certified standard water samples (TMDA-53.3 and NIST 1643e, a low level fortified standard for trace elements) and some real samples including natural drinking water and tap water samples.

  9. Simple decomposition procedure for determination of selenium in whole blood, serum and urine by hydride generation atomic absorption spectroscopy.

    Science.gov (United States)

    Tiran, B; Tiran, A; Rossipal, E; Lorenz, O

    1993-12-01

    A digestion procedure for selenium determination by hydride generation atomic absorption spectroscopy (AAS) in whole blood, serum and urine is described, it employs sulfuric acid, hydrogen peroxide and vanadium (V) sulfuric acid reagent solution. The method is rapid, uses no explosive reagents and can be performed at a constant temperature of 100 degrees C. Therefore, it is easily applicable in a routine clinical laboratory for a large amount of samples. The coefficient of intra-assay variation was 4.3-5.6%, the coefficient for inter-assay variation was 5-5.9% in the medium and high concentration range, and 5.8-8.6% in the low range. In analyzing several commercial reference materials our results showed good agreement with the target values. Analytical recovery by addition of sodium selenite and seleno-DL-methionine to samples ranged between 97 and 104%. The correlation between the described digestion procedure and the nitric, sulfuric and perchloric acid digestion procedure recommended by the International Union of Pure and Applied Chemistry showed good agreement for whole blood, serum and for urine. We determined selenium in serum (n = 58) and whole blood (n = 50) in a collective of healthy children from 1 to 5 years living in Styria, Austria. The low values in serum (35 +/- 11 micrograms/L) and whole blood (42 +/- 6 micrograms/L) at one year of life increased significantly to 48 +/- 13 mu/L (p = 0.033) and 55 +/- 6 micrograms/L (p = 0.004) at three years of life in serum and whole blood, respectively. The selenium concentration showed no further increase up to five years of age.(ABSTRACT TRUNCATED AT 250 WORDS)

  10. Determination of total arsenic in fish by hydride-generation atomic absorption spectrometry: method validation, traceability and uncertainty evaluation

    Science.gov (United States)

    Nugraha, W. C.; Elishian, C.; Ketrin, R.

    2017-03-01

    Fish containing arsenic compound is one of the important indicators of arsenic contamination in water monitoring. The high level of arsenic in fish is due to absorption through food chain and accumulated in their habitat. Hydride generation (HG) coupled with atomic absorption spectrometric (AAS) detection is one of the most popular techniques employed for arsenic determination in a variety of matrices including fish. This study aimed to develop a method for the determination of total arsenic in fish by HG-AAS. The method for sample preparation from American of Analytical Chemistry (AOAC) Method 999.10-2005 was adopted for acid digestion using microwave digestion system and AOAC Method 986.15 - 2005 for dry ashing. The method was developed and validated using Certified Reference Material DORM 3 Fish Protein for trace metals for ensuring the accuracy and the traceability of the results. The sources of uncertainty of the method were also evaluated. By using the method, it was found that the total arsenic concentration in the fish was 45.6 ± 1.22 mg.Kg-1 with a coverage factor of equal to 2 at 95% of confidence level. Evaluation of uncertainty was highly influenced by the calibration curve. This result was also traceable to International Standard System through analysis of Certified Reference Material DORM 3 with 97.5% of recovery. In summary, it showed that method of preparation and HG-AAS technique for total arsenic determination in fish were valid and reliable.

  11. Determination of lead in wine and rum samples by flow injection-hydride generation-atomic absorption spectrometry.

    Science.gov (United States)

    Elçi, Latif; Arslan, Zikri; Tyson, Julian F

    2009-03-15

    A method for direct determination of lead in wine and rum samples was developed, using a flow injection hydride generation system coupled to an atomic absorption spectrometer with flame-quartz atomizer (FI-HG-AAS). Lead hyride (PbH(4)) was generated using potassium ferricyanide (K(3)Fe(CN)(6)), as oxidant and sodium tetrahydroborate (NaBH(4)) as reductant. Samples were acidified to 0.40% (v/v) HCl for wine and to 0.30% (v/v) HCl for rum, which were then mixed on-line with 3% (m/v) K(3)Fe(CN)(6) solution in 0.03% (v/v) HCl prior to reaction with 0.2% (m/v) alkaline NaBH(4) solution. Lead contents of a rum and two different red wine samples were determined by FI-HG-AAS agreed with those obtained by ICP-MS. The analytical figures of merit of method developed were determined. The calibration curve was linear up to 8.0 microg L(-1) Pb with a regression coefficient of 0.998. The relative error was lower than 4.58%. The relative standard deviation (n=7) was better than 12%. A detection limit of 0.16 microg L(-1) was achieved for a sample volume of 170 microL.

  12. Quantitation of toxic arsenic species and arsenobetaine in Pacific oysters using an off-line process with hydride generation-atomic absorption spectroscopy.

    Science.gov (United States)

    Hsiung, Tung-Ming; Huang, Chia-Wei

    2006-04-05

    An off-line process-based speciation technique was devised here to quantitatively determine toxic inorganic arsenic (iAs), methylarsonic acid (MA), dimethylarsinic acid (DMA), and the dominant, albeit virtually nontoxic, arsenobetaine (AB) in Pacific oysters (Crassostrea gigas). Oysters were extracted with fresh methanol-water (8+2), and this was replicated three times. They were then evaporated to near dryness and subsequently redissolved in pure water; defatting was then performed with a C18 cartridge. The trace hydride active arsenic species, that is, iAs, MA, and DMA, in the defatted solutions were determined with a sensitive hydride generation-packed coldfinger trap-atomic absorption spectrometric (HG-PCFT-AAS) coupled system. The arsenicals that were desorbed from the cation-exchange resin (Dowex 50W-X8) in the washings of 4 M NH3 were categorized on the basis of AB + DMA. The total quantity of arsenic in the recovered AB + DMA was determined with a commercial hydride generation-atomic absorption spectrometric (HG-AAS) system, and finally, AB was calculated from (AB + DMA) - DMA. The average concentrations of iAs, MA, DMA, AB, and total arsenic (TAs) in the oysters collected from six aquacultural sites along the west coast of Taiwan were, respectively, 0.15, 0.06, 0.64, 6.93, and 13.74 mg kg(-1) of dry weight. AB was the major species, whereas iAs (arsenite + arsenate) were the most toxic species, although the iAs made up only approximately 1% of the TAs in the oysters. The lifetime target cancer risk, as determined by the concentration of iAs on a fresh weight basis in the oysters, was well below the ordinary health protection criteria (10(-6)).

  13. On-line electrochemically controlled in-tube solid phase microextraction of inorganic selenium followed by hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Asiabi, Hamid [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Yamini, Yadollah, E-mail: yyamini@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Seidi, Shahram [Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran (Iran, Islamic Republic of); Shamsayei, Maryam; Safari, Meysam; Rezaei, Fatemeh [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2016-05-30

    In this work, for the first time, a rapid, simple and sensitive microextraction procedure is demonstrated for the matrix separation, preconcentration and determination of inorganic selenium species in water samples using an electrochemically controlled in-tube solid phase microextraction (EC-in-tube SPME) followed by hydride generation atomic absorption spectrometry (HG-AAS). In this approach, in which EC-in-tube SPME and HG-AAS system were combined, the total analysis time, was decreased and the accuracy, repeatability and sensitivity were increased. In addition, to increases extraction efficiency, a novel nanostructured composite coating consisting of polypyrrole (PPy) doped with ethyleneglycol dimethacrylate (EGDMA) was prepared on the inner surface of a stainless-steel tube by a facile electrodeposition method. To evaluate the offered setup and the new PPy-EGDMA coating, it was used to extract inorganic selenium species in water samples. Extraction of inorganic selenium species was carried out by applying a positive potential through the inner surface of coated in-tube under flow conditions. Under the optimized conditions, selenium was detected in amounts as small as 4.0 parts per trillion. The method showed good linearity in the range of 0.012–200 ng mL{sup −1}, with coefficients of determination better than 0.9996. The intra- and inter-assay precisions (RSD%, n = 5) were in the range of 2.0–2.5% and 2.7–3.2%, respectively. The validated method was successfully applied for the analysis of inorganic selenium species in some water samples and satisfactory results were obtained. - Graphical abstract: An electrochemically controlled in-tube solid phase microextraction followed by hydride generation atomic absorption spectrometry was developed for extraction and determination ultra-trace amounts of Se in aqueous solutions. - Highlights: • A nanostructured composite coating consisting of PPy doped with EGDMA was prepared. • The coating was

  14. Determination of As(III) and total inorganic As in water samples using an on-line solid phase extraction and flow injection hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Sigrist, Mirna, E-mail: msigrist@fiq.unl.edu.ar [Laboratorio Central, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2654-Piso 6, (3000) Santa Fe (Argentina); Albertengo, Antonela; Beldomenico, Horacio [Laboratorio Central, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2654-Piso 6, (3000) Santa Fe (Argentina); Tudino, Mabel [Laboratorio de Analisis de Trazas, Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE, Facultad de Ciencias Exactas y Naturales, Pabellon II, Ciudad Universitaria (1428), Buenos Aires (Argentina)

    2011-04-15

    A simple and robust on-line sequential injection system based on solid phase extraction (SPE) coupled to a flow injection hydride generation atomic absorption spectrometer (FI-HGAAS) with a heated quartz tube atomizer (QTA) was developed and optimized for the determination of As(III) in groundwater without any kind of sample pretreatment. The method was based on the selective retention of inorganic As(V) that was carried out by passing the filtered original sample through a cartridge containing a chloride-form strong anion exchanger. Thus the most toxic form, inorganic As(III), was determined fast and directly by AsH{sub 3} generation using 3.5 mol L{sup -1} HCl as carrier solution and 0.35% (m/v) NaBH{sub 4} in 0.025% NaOH as the reductant. Since the uptake of As(V) should be interfered by several anions of natural occurrence in waters, the effect of Cl{sup -}, SO{sub 4}{sup 2-}, NO{sub 3}{sup -}, HPO{sub 4}{sup 2-}, HCO{sub 3}{sup -} on retention was evaluated and discussed. The total soluble inorganic arsenic concentration was determined on aliquots of filtered samples acidified with concentrated HCl and pre-reduced with 5% KI-5% C{sub 6}H{sub 8}O{sub 6} solution. The concentration of As(V) was calculated by difference between the total soluble inorganic arsenic and As(III) concentrations. Detection limits (LODs) of 0.5 {mu}g L{sup -1} and 0.6 {mu}g L{sup -1} for As(III) and inorganic total As, respectively, were obtained for a 500 {mu}L sample volume. The obtained limits of detection allowed testing the water quality according to the national and international regulations. The analytical recovery for water samples spiked with As(III) ranged between 98% and 106%. The sampling throughput for As(III) determination was 60 samples h{sup -1}. The device for groundwater sampling was especially designed for the authors. Metallic components were avoided and the contact between the sample and the atmospheric oxygen was carried to a minimum. On-field arsenic species

  15. Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

    Science.gov (United States)

    McCleskey, R. Blaine; Nordstrom, D. Kirk; Ball, James W.

    2003-01-01

    Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using

  16. [Study on Content Determination of Lead and Arsenic in Four Traditional Tibetan Medicine Prescription Preparations by Wet Digestion Flow Injection-Hydride Generation-Atomic Absorption Spectrometry].

    Science.gov (United States)

    Zheng, Zhi-yuan; Du, Yu-zhi; Zhang, Ming; Yu, Ming-jie; Li, Cen; Yang, Hong-xia; Zhao, Jing; Xia, Zheng-hua; Wei, Li-xin

    2015-04-01

    Four common traditional tibetan medicine prescription preparations "Anzhijinghuasan, Dangzuo, Renqingchangjue and Rannasangpei" in tibetan areas were selected as study objects in the present study. The purpose was to try to establish a kind of wet digestion and flow injection-hydride generation-atomic absorption spectrometry (FI-HAAS) associated analysis method for the content determinations of lead and arsenic in traditional tibetan medicine under optimized digestion and measurement conditions and determine their contents accurately. Under these optimum operating conditions, experimental results were as follows. The detection limits for lead and arsenic were 0.067 and 0.012 µg · mL(-1) respectively. The quantification limits for lead and arsenic were 0.22 and 0.041 µg · mL(-1) respectively. The linear ranges for lead and arsenic were 25-1,600 ng · mL(-1) (r = 0.9995) and 12.5-800 ng · mL(-1) (r = 0.9994) respectively. The degrees of precision(RSD) for lead and arsenic were 2.0% and 3.2% respectively. The recovery rates for lead and arsenic were 98.00%-99.98% and 96.67%-99.87% respectively. The content determination results of lead and arsenic in four traditional tibetan medicine prescription preparations were as fol- lows. The contents of lead and arsenic in Anzhijinghuasan are 0.63-0.67 µg · g(-1) and 0.32-0.33 µg · g(-1) in Anzhijinghua- san, 42.92-43.36 µg · g(-1) and 24.67-25.87 µg · g(-1) in Dangzuo, 1,611. 39-1,631.36 µg · g(-1) and 926.76-956.52 µg- g(-1) in Renqing Changjue, and 1,102.28-1,119.127 µg-g(-1) and 509.96-516.87 µg · g(-1) in Rannasangpei, respectively. This study established a method for content determination of lead and arsenic in traditional tibetan medicine, and determined the content levels of lead and arsenic in four tibetan medicine-prescription preparations accurately. In addition, these results also provide the basis for the safe and effective use of those medicines in clinic.

  17. Graphite furnace and hydride generation atomic absorption spectrometric determination of cadmium, lead, and tin traces in natural surface waters: study of preconcentration technique performance.

    Science.gov (United States)

    Tsogas, George Z; Giokas, Dimosthenis L; Vlessidis, Athanasios G

    2009-04-30

    In this study three major types of preconcentration methods based upon different principles (cation exchange, physical absorption and hydrophobic extraction) were evaluated and optimized for the extraction and determination of three highly toxic heavy metals namely Cd, Pb and Sn by graphite furnace and hybrid generation atomic absorption spectrometry in real samples. The optimum analytical conditions were examined and the analytical features of each method were revealed and compared. Detection limits as low as 0.003-0.025 microg L(-1) for Cd(2+), 0.05-0.10 microg L(-1) for Pb(2+) and 0.1-0.25 microg L(-1) for Sn(4+) depending on the extraction method were obtained with RSD values between 3.08% and 6.11%. A preliminary assessment of the pollution status of three important natural ecosystems in Epirus region (NW Greece) was performed and some early conclusions were drawn and discussed.

  18. An improved method for the determination of trace levels of arsenic and antimony in geological materials by automated hydride generation-atomic absorption spectroscopy

    Science.gov (United States)

    Crock, J.G.; Lichte, F.E.

    1982-01-01

    An improved, automated method for the determination of arsenic and antimony in geological materials is described. After digestion of the material in sulfuric, nitric, hydrofluoric and perchloric acids, a hydrochloric acid solution of the sample is automatically mixed with reducing agents, acidified with additional hydrochloric acid, and treated with a sodium tetrahydroborate solution to form arsine and stibine. The hydrides are decomposed in a heated quartz tube in the optical path of an atomic absorption spectrometer. The absorbance peak height for arsenic or antimony is measured. Interferences that exist are minimized to the point where most geological materials including coals, soils, coal ashes, rocks and sediments can be analyzed directly without use of standard additions. The relative standard deviation of the digestion and the instrumental procedure is less than 2% at the 50 ??g l-1 As or Sb level. The reagent-blank detection limit is 0.2 ??g l-1 As or Sb. ?? 1982.

  19. [Investigation of enhancing effect for hydride generation-atomic fluorescence of transition metal elements].

    Science.gov (United States)

    Sun, Han-Wen; Suo, Ran

    2008-11-01

    A mechanism of hydride generation based on disassembly reaction of hydrogen-transferred interim state [M(BH4)m]* was developed by investigating the effect of reaction medium acidity on hydride generation. The effects of Co2+ and Ni2+, phenanthroline and 8-hydroxyquinoline on hydride generation-atomic fluorescence signals of Zn, Cd, Cu and Ni were studied, respectively, and their enhancing mechnism was discussed. The enhancing effect Co2+ and Ni2+ on the fluorescence signals of Zn and Cd was due to the increase in transmission efficiency of hydride of Zn and Cd. There was a synergic enhancing effect between phenanthroline or 8-hydroxyquinoline and Co2+ on the fluorescence signals of Zn and Cd, however no synergic enhancing effect between phenanthroline and 8-hydroxyquinoline on the fluorescence signals of Zn and Cd. The simulative action of cationic surfactant, anion surfactant and non-ionic surfactant surfactant to hydride generation was investigated. It is shown that both cationic surfactant and non-ionic surfactant have obvious enhancing effect on the fluorescence signals of analytes because of the decrease in surface tension of reaction solution. The release characteristics of hydride from the absorption solution containing surfactant was ulteriorly examined by using graphite furnace atomic absorption spectrometry, and the mechanism of enhancing effect of surfactant on hydride generation and transmission was proposed.

  20. Improved microwave-assisted wet digestion procedures for accurate Se determination in fish and shellfish by flow injection-hydride generation-atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lavilla, I. [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas - Marcosende s/n, 36310 Vigo (Spain); Gonzalez-Costas, J.M. [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas - Marcosende s/n, 36310 Vigo (Spain); Bendicho, C. [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas - Marcosende s/n, 36310 Vigo (Spain)]. E-mail: bendicho@uvigo.es

    2007-05-22

    Accurate determination of Se in biological samples, especially fish and shellfish, by hydride generation techniques has generally proven troublesome owing to the presence of organoselenium that cannot readily converted into inorganic selenium under usual oxidising conditions. Further improvements in the oxidation procedures are needed so as to obtain accurate concentration values when this type of samples is analyzed. Microwave-assisted wet digestion (MAWD) procedures of seafood based on HNO{sub 3} or the mixture HNO{sub 3}/H{sub 2}O{sub 2} and further thermal reduction of the Se(VI) formed to Se(IV) were evaluated. These procedures were as follows: (I) without H{sub 2}O{sub 2} and without heating to dryness; (II) without H{sub 2}O{sub 2} and with heating to dryness; (III) with H{sub 2}O{sub 2} and without heating to dryness; (IV) with H{sub 2}O{sub 2} and with heating to dryness. In general, low recoveries of selenium are obtained for several marine species (e.g., crustaceans and cephalopods), which may be ascribed to the presence of Se forms mainly associated with nonpolar proteins and lipids. Post-digestion UV irradiation proved very efficient since not only complete organoselenium decomposition was achieved but also the final step required for prereduction of Se(VI) into Se(IV) (i.e. heating at 90 deg. C for 30 min in 6 M HCl) could be avoided. With the MAWD/UV procedure, the use of strong oxidising agents (persuphate, etc.) or acids (e.g. perchloric acid) which are typically applied prior to Se determination by hydride generation techniques is overcome, and as a result, sample pre-treatment is significantly simplified. The method was successfully validated against CRM DOLT-2 (dogfish liver), CRM DORM-2 (dogfish muscle) and CRM TORT-2 (lobster hepatopancreas). Automated ultrasonic slurry sampling with electrothermal atomic absorption spectrometry was also applied for comparison. Total Se contents in ten seafood samples were established. Se levels ranged from 0

  1. Differential determination of arsenic(III) and arsenic(V), and antimony(III) and antimony-(V) by hydride generation-atomic absorption spectrophotometry, and its application to the determination of these species in sea water

    Science.gov (United States)

    Yamamoto, Manabu; Urata, Keiji; Murashige, Kiyoto; Yamamoto, Yuroku

    A method is described for the differential determination of As(III) and As(V). and Sb(III) and Sb(V) by hydride generation-atomic absorption spectrophotometry with hydrogen-nitrogen flame using sodium borohydride solution as a reductant. For the determination of As(III) and Sb(III), most of the elements, other than Ag +, Cu 2+, Sn 2+, Se 4+ and Te 4+, do not interfere in an at least 30,000 fold excess with respect to As(III) or Sb(III). This method was applied to the determination of these species in sea water and it was found that a sample size of only 100 ml is enough to determine them with a precision of 1.5-2.5%. Analytical results for surface sea water of Hiroshima Bay were 0.72 μgl -1, 0.27 μgl -1 and 0.22 μgl -1 for As(total), As(III) and Sb(total), respectively, but Sb(III) was not detected in the present sample. The effect of acidification on storage was also examined.

  2. Determination of As(III) and As(V) by Flow Injection-Hydride Generation-Atomic Absorption Spectrometry via On-line Reduction of As(V) by KI

    DEFF Research Database (Denmark)

    Nielsen, Steffen; Hansen, Elo Harald

    1997-01-01

    A volume-based flow injection (FI) procedure is described for the determination and speciation of trace inorganic arsenic, As(III) and As(V), via hydride generation-atomic absorption spectrometry (HG-AAS) of As(III). The determination of total arsenic is obtained by on-line reduction of As(V) to As...... volume is 100 mu l while the total sample consumption per assay is 1.33 ml, and the sampling frequency is 180 samples per hour. The detection limit (3 sigma) for the on-line reduction procedure was 37 ng l(-1) and at the 5.0 mu g l(-1), the relative standard deviation (RSD) was 1.1% (n=10) by calibrating...... with As(III) standards; by calibrating with As(V) standards the detection limit was 33 ng l(-1) and the RSD was 1.3% (n=10). For the selective determination of As(III) the detection limit was 111 ng l(-1) and the RSD was 0.7% (n=10) at 5.0 mu g l(-1). Both procedures are most tolerant to potential...

  3. Determination of Tetraethyl Lead in Water by Hydride Generation-Atomic Absorption Spectrophotometry%水中痕量铜的SBA-15修饰碳糊电极溶出伏安测定法

    Institute of Scientific and Technical Information of China (English)

    杨振兴

    2011-01-01

    Objective To establish a method for the determination of tetraethyl lead in water by hydride generation-atomic absorption spectrophotometry. Methods By solvent extraction of trichloromethane and low-temperature degradation,the best optimum experimental condition of optimal design of orthogonal test: wavelength was 217 nm, lamp current was 3.0 mA, band pass was 0.2 nm, supporting gas was argon GAS (99.99%), argon gas flux was 0.8 L/min, peak height measurement, oxidizing flame, 20 g/L NaBH4 solution,5 mi HNO3 (1.42 g/mi) solution, 1.5 ml HCl(1.19 g/ml) solution, 100 g/L K3Fe(CN)6 solution. Results The limit of detection was 0.049 μg/L,the average recovery rates were 89.7%-101.4% and RSDs were 3.3%-5.3%. Conclusion This method is simple, sensitive, accurate and applicable to the determination of the tetraethyl lead in water.%目的 建立介孔材料修饰碳糊电极测定水中痕量铜的方法.方法 制备SBA-15修饰碳糊电极,并在pH值为4.2的乙酸-乙酸钠缓冲溶液中,采用溶出伏安法对水中痕量铜进行测定.结果 优化实验条件下,相关系数达到0.997 3,测得Cu2+的线性范围和最低检出限分别为2.0×10-10~4.0×10-8mol/L和1.0×10-10mol/L,样品加标回收率为97.0%~101.8%.结论该方法简单、快速、灵敏,可用于实际水样中痕量铜的测定.

  4. Determination of Tetraethyl Lead in Water by Hydride Generation-Atomic Absorption Spectrophotometry%水中四乙基铅的氢化原子吸收测定法

    Institute of Scientific and Technical Information of China (English)

    公丕峰

    2011-01-01

    Objective To establish a method for the determination of tetraethyl lead in water by hydride generation-atomic absorption spectrophotometry. Methods By solvent extraction of trichloromethane and low-temperature degradation,the best optimum experimental condition of optimal design of orthogonal test: wavelength was 217 nm, lamp current was 3.0 mA, band pass was 0.2 nm, supporting gas was argon GAS (99.99%), argon gas flux was 0.8 L/min, peak height measurement, oxidizing flame, 20 g/L NaBH4 solution,5 ml HNO3 (1.42 g/ml) solution, 1.5 ml HCl(1.19 g/ml) solution, 100 g/L K3Fe(CN)6 solution. Results The limit of detection was 0.049 μg/L,the average recovery rates were 89.7%-101.4% and RSDs were 3.3%-5.3%. Conclusion This method is simple, sensitive, accurate and applicable to the determination of the tetraethyl lead in water.%目的 建立水中四乙基铅的氢化原子吸收测定方法.方法 样品经三氯甲烷萃取,低温消解后,采用氢化原子吸收法进行分析.经正交设计优化后的试验条件:波长为217.0 nm,灯电流为3.0 mA,光谱通带为0.2 nm;载气为99.99%氩气,载气流量为0.8 L/min,测量方式为峰高,氧化性蓝色焰,NaBH4溶液浓度为20g/L,1.42g/ml硝酸用量为5 ml,1.19g/ml盐酸用量为1.5 ml,K3Fe(CN)6溶液浓度为100g/L.结果 在0.049~100μg/L线性范围内,所得四乙基铅的标准曲线回归方程为γ=1.07×10-34+3.49×10-3x,相关系数为0.999 6.该方法的检出限为0.049 μg/L,平均回收率为89.7%~101.4%,RSD为3.3%~53%.结论该方法操作方便,所用试验装置价格低廉,灵敏度和准确度均较高,适合各级单位用于水中四乙基铅的测定.

  5. On the Arsenic Amount Determination in Tungsten Concentrate by Optimal Design of Uniform-hydride Generation Atomic Absorption Spectrometry%均匀优化设计-氢化物发生原子吸收光谱法测定钨精矿中砷量

    Institute of Scientific and Technical Information of China (English)

    陈涛; 潘建忠

    2011-01-01

    A technology based on uniform design is proposed in the optimization of arsenic amount determination in tungsten concentrate by hydride generation atomic Absorption Spectrometry. The optimized analysis condition is obtained by means of experiments: the sample is decomposed by sulfuric acid-ammonium sulfate, coordinated with tungsten, iron, manganese in ammonia medium using citric acid, then reduced pentavalent arsenic to trivalent arsenic by ascorbic acid. Arsenic amount at the degree of 15 % acid solution is measured by the united equipments:flow injection-hydride generator-atomic absorption spectrophotometer. This technology has many advantages, such as high sensitivity, good accuracy, fast and simple, little elements interfering. The detection limit of arsenic amount can be 0.001%.%该方法应用均匀设计这一优化试验设计理论,采用氢化物发生原子吸收光谱法测定钨精矿中砷量.经实验确定了测定砷量的最佳分析条件:经硫酸-硫酸铵分解,用柠檬酸在氨性介质中络合钨、铁、锰等干扰元素,用抗坏血酸预还原五价的砷到三价.样品溶液在15%的酸度中,经流动注射-氢化物发生与原子吸收光谱仪联用测定砷量.该方法具有灵敏度高,准确性好,快速简便,干扰元素少等优点.

  6. [Research on optimization of mathematical model of flow injection-hydride generation-atomic fluorescence spectrometry].

    Science.gov (United States)

    Cui, Jian; Zhao, Xue-Hong; Wang, Yan; Xiao, Ya-Bing; Jiang, Xue-Hui; Dai, Li

    2014-01-01

    Flow injection-hydride generation-atomic fluorescence spectrometry was a widely used method in the industries of health, environmental, geological and metallurgical fields for the merit of high sensitivity, wide measurement range and fast analytical speed. However, optimization of this method was too difficult as there exist so many parameters affecting the sensitivity and broadening. Generally, the optimal conditions were sought through several experiments. The present paper proposed a mathematical model between the parameters and sensitivity/broadening coefficients using the law of conservation of mass according to the characteristics of hydride chemical reaction and the composition of the system, which was proved to be accurate as comparing the theoretical simulation and experimental results through the test of arsanilic acid standard solution. Finally, this paper has put a relation map between the parameters and sensitivity/broadening coefficients, and summarized that GLS volume, carrier solution flow rate and sample loop volume were the most factors affecting sensitivity and broadening coefficients. Optimizing these three factors with this relation map, the relative sensitivity was advanced by 2.9 times and relative broadening was reduced by 0.76 times. This model can provide a theoretical guidance for the optimization of the experimental conditions.

  7. 流动注射氢化物发生-原子吸收光谱法 测定镍基合金中的硒和锡%Determination of Selenium and Tin in Nickel Alloys by Flow Injection Hydride Generation Atomic Absorption Spectrometry

    Institute of Scientific and Technical Information of China (English)

    陈天裕; 汪正

    2001-01-01

    建立了流动注射氢化物发生-原子吸收光谱法测定高温镍基合金中痕量硒和锡的方法。样品用HNO3和HF经微波消解后,制成以EDTA作掩蔽剂的碱性溶液(pH12~13),用标准加入法测定。方法测定硒和锡的检出限分别为1.0μg.g-1和1.8μg.g-1,RSD分别为3%~8%和3%~7%。%Determination of trace Se and Sn in high-temperature nickelalloys by flow injection hydride generation atomic absorption spectrometry was studied. The sample was dissolved by microwave digestion in HNO3 and HF. After addition of EDTA as the masking agent and adjustment of pH to 12~13, Se and Sn were determined by standard addition method. Some reference materials were analysed and satisfactory results were obtained. The detection limits of the method for Se and Sn are 1.0 μg.g-1 and 1.8 μg.g-1, respectively, the RSD of determination are 3%~8% for Se and 3%~7% for Sn.

  8. Determination of inorganic species of Sb and Te in cereals by hydride generation atomic fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Reyes, Mariela N.M.; Cervera, Maria L.; Guardia, Miguel de la, E-mail: m.luisa.cervera@uv.e [University of Valencia, Valencia (Spain). Dept. of Analytical Chemistry

    2011-07-01

    A non-chromatographic fast, sensitive and easy method has been developed for the determination of Sb(III), Sb(V), Te(IV) and Te(VI) in cereal samples. The procedure is based on ultrasound assisted extraction and determination by hydride generation atomic fluorescence spectrometry (HG AFS). Preliminary studies were made in order to get the best extraction efficiency using 1 mol L{sup -1} phosphoric acid, 1 mol L{sup -1} nitric acid, aqua regia, 1 mol L{sup -1} sulfuric acid and 6 mol L{sup -1} hydrochloric acid. The extraction with aqua regia showed a clear interconversion of the species during the process, being H{sub 2}SO{sub 4} the best extractant with efficiencies greater than 90% from the total content of Sb and Te quantified previously and without species interconversion. This point was checked by recovery experiments at different spiked levels. The method provided limits of detection values from 0.1 to 0.5 ng g{sup -1} with relative standard deviation values from 5.4 to 9.2% of 10 independent analysis of samples containing few ng g-1 of Sb and Te species. (author)

  9. Determination of lead in wine by hydride generation atomic fluorescence spectrometry in the presence of hexacyanoferrate(III).

    Science.gov (United States)

    Karadjova, Irina B; Lampugnani, Leonardo; D'Ulivo, Alessandro; Onor, Massimo; Tsalev, Dimiter L

    2007-06-01

    A rapid, accurate, and precise method is described for the determination of Pb in wine using continuous-flow hydride generation atomic fluorescence spectrometry (CF-HGAFS). Sample pretreatment consists of ten-fold dilution of wine followed by direct plumbane generation in the presence of 0.1 mol L(-1) HCl and 1% m/v K(3)[Fe(CN)(6)] with 1% m/v NaBH(4) as reducing agent. An aqueous standard calibration curve is recommended for Pb quantification in wine sample. The method provides a limit of detection and a limit of quantification of 0.3 microg L(-1) and 1 microg L(-1), respectively. The relative standard deviation varies between 2-6% (within-run) and 4-11% (between-run) at 3-30 microg L(-1) Pb levels in wine. Good agreement has been demonstrated between results obtained by CF-HGAFS and direct electrothermal atomic absorption spectrometry in analyses of red and white wines within the concentration range of 9.2-25.8 microg L(-1) Pb.

  10. Antimony speciation analysis in sediment reference materials using high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Potin-Gautier, M. [Laboratoire de Chimie Analytique, BioInorganique et Environnement LCABIE (UMR CNRS 3054), Universite de Pau et des pays de l' Adour, 64000 Pau (France); Pannier, F. [Laboratoire de Chimie Analytique, BioInorganique et Environnement LCABIE (UMR CNRS 3054), Universite de Pau et des pays de l' Adour, 64000 Pau (France)]. E-mail: Florence.pannier@univ-pau.fr; Quiroz, W. [Laboratoire de Chimie Analytique, BioInorganique et Environnement LCABIE (UMR CNRS 3054), Universite de Pau et des pays de l' Adour, 64000 Pau (France); Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Pontificia Universidad catolica de Valparaiso (Chile); Pinochet, H. [Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Pontificia Universidad catolica de Valparaiso (Chile); Gregori, I. de [Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Pontificia Universidad catolica de Valparaiso (Chile)

    2005-11-30

    This work presents the development of suitable methodologies for determination of the speciation of antimony in sediment reference samples. Liquid chromatography with a post-column photo-oxidation step and hydride generation atomic fluorescence spectrometry as detection system is applied to the separation and determination of Sb(III), Sb(V) and trimethylantimony species. Post-column decomposition and hydride generation steps were studied for sensitive detection with the AFS detector. This method was applied to investigate the conditions under which speciation analysis of antimony in sediment samples can be carried out. Stability studies of Sb species during the extraction processes of solid matrices, using different reagents solutions, were performed. Results demonstrate that for the extraction yield and the stability of Sb species in different marine sediment extracts, citric acid in ascorbic acid medium was the best extracting solution for antimony speciation analysis in this matrix (between 55% and 65% of total Sb was recovered from CRMs, Sb(III) being the predominant species). The developed method allows the separation of the three compounds within 6 min with detection limits of 30 ng g{sup -1} for Sb(III) and TMSbCl2 and 40 ng g{sup -1} for Sb(V) in sediment samples.

  11. Development of an analytical method for antimony speciation in vegetables by HPLC-hydride generation-atomic fluorescence spectrometry.

    Science.gov (United States)

    Olivares, David; Bravo, Manuel; Feldmann, Jorg; Raab, Andrea; Neaman, Alexander; Quiroz, Waldo

    2012-01-01

    A new method for antimony speciation in terrestrial edible vegetables (spinach, onions, and carrots) was developed using HPLC with hydride generation-atomic fluorescence spectrometry. Mechanical agitation and ultrasound were tested as extraction techniques. Different extraction reagents were evaluated and optimal conditions were determined using experimental design methodology, where EDTA (10 mmol/L, pH 2.5) was selected because this chelate solution produced the highest extraction yield and exhibited the best compatibility with the mobile phase. The results demonstrated that EDTA prevents oxidation of Sb(III) to Sb(V) and maintains the stability of antimony species during the entire analytical process. The LOD and precision (RSD values obtained) for Sb(V), Sb(III), and trimethyl Sb(V) were 0.08, 0.07, and 0.9 microg/L and 5.0, 5.2, and 4.7%, respectively, for a 100 microL sample volume. The application of this method to real samples allowed extraction of 50% of total antimony content from spinach, while antimony extracted from carrots and onion samples ranged between 50 and 60 and 54 and 70%, respectively. Only Sb(V) was detected in three roots (onion and spinach) that represented 60-70% of the total antimony in the extracts.

  12. Cloud point extraction for trace inorganic arsenic speciation analysis in water samples by hydride generation atomic fluorescence spectrometry

    Science.gov (United States)

    Li, Shan; Wang, Mei; Zhong, Yizhou; Zhang, Zehua; Yang, Bingyi

    2015-09-01

    A new cloud point extraction technique was established and used for the determination of trace inorganic arsenic species in water samples combined with hydride generation atomic fluorescence spectrometry (HGAFS). As(III) and As(V) were complexed with ammonium pyrrolidinedithiocarbamate and molybdate, respectively. The complexes were quantitatively extracted with the non-ionic surfactant (Triton X-114) by centrifugation. After addition of antifoam, the surfactant-rich phase containing As(III) was diluted with 5% HCl for HGAFS determination. For As(V) determination, 50% HCl was added to the surfactant-rich phase, and the mixture was placed in an ultrasonic bath at 70 °C for 30 min. As(V) was reduced to As(III) with thiourea-ascorbic acid solution, followed by HGAFS. Under the optimum conditions, limits of detection of 0.009 and 0.012 μg/L were obtained for As(III) and As(V), respectively. Concentration factors of 9.3 and 7.9, respectively, were obtained for a 50 mL sample. The precisions were 2.1% for As(III) and 2.3% for As(V). The proposed method was successfully used for the determination of trace As(III) and As(V) in water samples, with satisfactory recoveries.

  13. Determination of arsenic speciation in sulfidic waters by Ion Chromatography Hydride-Generation Atomic Fluorescence Spectrometry (IC-HG-AFS).

    Science.gov (United States)

    Keller, Nicole S; Stefánsson, Andri; Sigfússon, Bergur

    2014-10-01

    A method for the analysis of arsenic species in aqueous sulfide samples is presented. The method uses an ion chromatography system connected with a Hydride-Generation Atomic Fluorescence Spectrometer (IC-HG-AFS). With this method inorganic As(III) and As(V) species in water samples can be analyzed, including arsenite (HnAs(III)O3(n-3)), thioarsenite (HnAs(III)S3(n-3)), arsenate (HnAs(V)O4(n-3)), monothioarsenate (HnAs(V)SO3(n-3)), dithioarsenate (HnAs(V)S2O2(n-3)), trithioarsenate (HnAs(V)S3O(n-3)) and tetrathioarsenate (HnAs(V)S4(n-3)). The peak identification and retention times were determined based on standard analysis of the various arsenic compounds. The analytical detection limit was ~1-3 µg L(-1) (LOD), depending on the quality of the baseline. This low detection limit makes this method also applicable to discriminate between waters meeting the drinking water standard of max. 10 µg L(-1) As, and waters that do not meet this standard. The new method was successfully applied for on-site determination of arsenic species in natural sulfidic waters, in which seven species were unambiguously identified.

  14. Determination of trace selenium in high purity tellurium by hydride generation atomic fluorescence spectrometry after solid phase extraction of a diaminobenzidine-selenium chelate

    Science.gov (United States)

    Tong, Wang; Ying, Zeng; Jinyong, Xu

    2016-09-01

    Macroporous adsorption resin was used as the sorbent for solid phase extraction and determination of the trace Se content in high purity tellurium prior to hydride generation atomic fluorescence spectrometry analysis. Selenium was converted into an organic Se chelate using 3,3‧-diaminobenzidine and was separated from the tellurium matrix by solid phase extraction. The resin was packed as a column for solid phase extraction. Under optimum conditions, trace Se can be quantitatively extracted and the tellurium matrix can be removed. The Se in the eluate was determined by hydride generation atomic fluorescence spectrometry. The limit of detection (3σ) of this method was 0.22 ng g- 1 and the relative standard deviation (RSD, n = 5) ranged from 2.0 to 2.5% for the three investigated tellurium samples. The proposed method was successfully applied for the determination of the trace Se content in high purity tellurium samples.

  15. Cloud point extraction for trace inorganic arsenic speciation analysis in water samples by hydride generation atomic fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shan, E-mail: ls_tuzi@163.com; Wang, Mei, E-mail: wmei02@163.com; Zhong, Yizhou, E-mail: yizhz@21cn.com; Zhang, Zehua, E-mail: kazuki.0101@aliyun.com; Yang, Bingyi, E-mail: e_yby@163.com

    2015-09-01

    A new cloud point extraction technique was established and used for the determination of trace inorganic arsenic species in water samples combined with hydride generation atomic fluorescence spectrometry (HGAFS). As(III) and As(V) were complexed with ammonium pyrrolidinedithiocarbamate and molybdate, respectively. The complexes were quantitatively extracted with the non-ionic surfactant (Triton X-114) by centrifugation. After addition of antifoam, the surfactant-rich phase containing As(III) was diluted with 5% HCl for HGAFS determination. For As(V) determination, 50% HCl was added to the surfactant-rich phase, and the mixture was placed in an ultrasonic bath at 70 °C for 30 min. As(V) was reduced to As(III) with thiourea–ascorbic acid solution, followed by HGAFS. Under the optimum conditions, limits of detection of 0.009 and 0.012 μg/L were obtained for As(III) and As(V), respectively. Concentration factors of 9.3 and 7.9, respectively, were obtained for a 50 mL sample. The precisions were 2.1% for As(III) and 2.3% for As(V). The proposed method was successfully used for the determination of trace As(III) and As(V) in water samples, with satisfactory recoveries. - Highlights: • Cloud point extraction was firstly established to determine trace inorganic arsenic(As) species combining with HGAFS. • Separate As(III) and As(V) determinations improve the accuracy. • Ultrasonic release of complexed As(V) enables complete As(V) reduction to As(III). • Direct HGAFS analysis can be performed.

  16. Flow injection on-line solid phase extraction for ultra-trace lead screening with hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Wan, Zhuo; Xu, Zhangrun; Wang, Jianhua

    2006-01-01

    A flow injection (FI) on-line solid phase extraction (SPE) procedure for ultra-trace lead separation and preconcentration was developed, followed by hydride generation and atomic fluorescence spectrometric (AFS) detection. Lead is retained on an iminodiacetate chelating resin packed microcolumn, and is afterward eluted with 2.5% (v/v) hydrochloric acid to facilitate the hydride generation by reaction with alkaline tetrahydroborate solution with 1% (m/v) potassium ferricyanide as an oxidizing (or sensitizing) reagent. The hydride was separated from the reaction medium in the gas-liquid separator and swept into the atomizer for quantification. The chemical variables and the FI flow parameters were carefully optimized. With a sample loading volume of 4.8 ml, quantitative retention of lead was obtained, along with an enrichment factor of 11.3 and a sampling frequency of 50 h(-1). A detection limit of 4 ng l(-1), defined as 3 times the blank standard deviation (3 sigma), was achieved along with a RSD value of 1.6% at the 0.4 microg l(-1) level. The procedure was validated by determining lead contents in two certified reference materials, and its practical applicability was further demonstrated by analysing a variety of biological and environmental samples.

  17. Determination of total Sb,Se Te, and Bi and evaluation of their inorganic species in garlic by hydride-generation-atomic-fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Matos Reyes, M.N.; Cervera, M.L.; Guardia, M. de la [University of Valencia, Department of Analytical Chemistry, Burjassot, Valencia (Spain)

    2009-07-15

    A sensitive and simple analytical method has been developed for determination of Sb(III), Sb(V), Se(IV), Se(VI), Te(IV), Te(VI), and Bi(III) in garlic samples by using hydride-generation-atomic-fluorescence spectrometry (HG-AFS). The method is based on a single extraction of the inorganic species by sonication at room temperature with 1 mol L{sup -1} H{sub 2}SO{sub 4} and washing of the solid phase with 0.1% (w/v) EDTA, followed by measurement of the corresponding hydrides generated under two different experimental conditions directly and after a pre-reduction step. The limit of detection of the method was 0.7 ng g{sup -1} for Sb(III), 1.0 ng g{sup -1} for Sb(V), 1.3 ng g{sup -1} for Se(IV), 1.0 ng g{sup -1} for Se(VI), 1.1 ng g{sup -1} for Te(IV), 0.5 ng g{sup -1} for Te(VI), and 0.9 ng g{sup -1} for Bi(III), in all cases expressed in terms of sample dry weight. (orig.)

  18. Determination of Trace Germanium in Marine Sediments by Hydride Generation-Atomic Fluorescence Spectrometry (HG-AFS)

    Institute of Scientific and Technical Information of China (English)

    LI Jing; ZHAO Shilan; ZHANG Zhaohui; ZENG Xianjie

    2004-01-01

    A method for the analysis of trace germanium in marine sediments by HG-AFS has been investigated. The experimental conditions such as the acidity of reduction reaction, the amount of sodium boro-hydride, the carrier gas flow rate, etc., were tested and optimized by using a kind of orthogonal design. The detection limit of the presented method is 0.95 μg L-1 for germanium. The calibration curve shows a satisfactory line in the concentration range 0-320 μg L-1 Ge with a variation coefficient of ±2.1%.

  19. Electrochemical hydride generation atomic fluorescence spectrometry for detection of tin in canned foods using polyaniline-modified lead cathode.

    Science.gov (United States)

    Jiang, Xianjuan; Gan, Wuer; Wan, Lingzhong; Deng, Yun; Yang, Qinghua; He, Youzhao

    2010-12-15

    An electrochemical hydride generation system with polyaniline-modified lead cathode was developed for tin determination by coupling with atomic fluorescence spectrometry. The tin fluorescence signal intensity was improved evidently as the polyaniline membrane could facilitate the transformation process from atomic tin to the SnH(4) and prevent the aggradation of Sn atom on Pb electrode surface. The effects of experimental parameters and interferences have been studied. The limit of detection (LOD) was 1.5 ng mL(-1) (3σ) and the relative standard deviation (RSD) was 3.3% for 11 consecutive measurements of 50 ng mL(-1) Sn(IV) standard solution.

  20. Electrochemical hydride generation atomic fluorescence spectrometry for detection of tin in canned foods using polyaniline-modified lead cathode

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Xianjuan [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gan Wuer, E-mail: wgan@ustc.edu.cn [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Wan Lingzhong; Deng Yun; Yang Qinghua; He Youzhao [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2010-12-15

    An electrochemical hydride generation system with polyaniline-modified lead cathode was developed for tin determination by coupling with atomic fluorescence spectrometry. The tin fluorescence signal intensity was improved evidently as the polyaniline membrane could facilitate the transformation process from atomic tin to the SnH{sub 4} and prevent the aggradation of Sn atom on Pb electrode surface. The effects of experimental parameters and interferences have been studied. The limit of detection (LOD) was 1.5 ng mL{sup -1} (3{sigma}) and the relative standard deviation (RSD) was 3.3% for 11 consecutive measurements of 50 ng mL{sup -1} Sn(IV) standard solution.

  1. A comparative evaluation of different ionic liquids for arsenic species separation and determination in wine varietals by liquid chromatography - hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Castro Grijalba, Alexander; Fiorentini, Emiliano F; Martinez, Luis D; Wuilloud, Rodolfo G

    2016-09-02

    The application of different ionic liquids (ILs) as modifiers for chromatographic separation and determination of arsenite [As(III)], arsenate [As(V)], dimethylarsonic acid (DMA) and monomethylarsonic acid (MMA) species in wine samples, by reversed-phase high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry detection (RP-HPLC-HG-AFS) was studied in this work. Several factors influencing the chromatographic separation of the As species, such as pH of the mobile phase, buffer solution concentration, buffer type, IL concentration and length of alkyl groups in ILs were evaluated. The complete separation of As species was achieved using a C18 column in isocratic mode with a mobile phase composed of 0.5% (v/v) 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) and 5% (v/v) methanol at pH 8.5. A multivariate methodology was used to optimize the variables involved in AFS detection of As species after they were separated by HPLC. The ILs showed remarkable performance for the separation of As species, which was obtained within 18min with a resolution higher than 0.83. The limits of detection for As(III), As(V), MMA and DMA were 0.81, 0.89, 0.62 and 1.00μg As L(-1). The proposed method was applied for As speciation analysis in white and red wine samples originated from different grape varieties.

  2. [Determination of arsenic, mercury and selenium in Gynostemma pentaphyllum and rhizospheric soil samples collected from different regions by hydride generation atomic fluorescence spectrometry].

    Science.gov (United States)

    Wang, Jing; Xiao, Ya-ping; Liang, Xiao-qing; Shao, Xian-hui; Zhang, Ke

    2012-03-01

    The contents of arsenic (As), mercury (Hg) and selenium (Se) in Gynostemma pentaphyllum and rhizospheric soil samples collected from seven provinces were determined, through the optimization of the hydride generation atomic fluorescence spectrometry working conditions. The results show that: the contents of As, Hg and Se in Gynostemma pentaphyllum from seven provinces revealed large differences, but compared with the limits of the two kinds of heavy metal element: As and Hg set by the Green Trade Standards of Importing & Exporting Medicinal Plants & Preparations (As Gynostemma pentaphyllum samples are both lower than them. The Se content in Gynostemma pentaphyllum samples and in rhizospheric soil samples revealed significant correlation, and as a result, the Gynostemma pentaphyllum from the Fu Xi area Enshi in Hu Bei province had obviously higher Se content than others in the 6 provinces. From this study, a preliminary conclusion can be drawn that Se in Gynostemma pentaphyllum is mainly from the soil, moreover, the As and Hg show the difference from Se, possibly they are still affected by the dry and wet deposition of atmospheric aerosols.

  3. Speciation analysis of inorganic arsenic in coal samples by microwave-assisted extraction and high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Sun, Mei; Liu, Guijian; Wu, Qianghua; Liu, Wenqi

    2013-03-15

    A new method was developed for the speciation analysis of inorganic arsenic in coal samples by high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry after microwave-assisted extraction. Effective extract of As(III) and As(V) in coal sample was achieved by 1.0 mol L(-1)H₃PO₄ and 0.1 mol L(-1)ascorbic acid. Under the optimized conditions, the limits of detection (LOD) were 0.01 μg L(-1) and 0.02 μg L(-1), the relative standard deviations (RSD) were 2.4% and 3.3% (c=10.0 μg L(-1), n=7), recoveries were 102.5% and 96.5% for As(III) and As(V). The proposed method was successfully applied for the determination of speciation of inorganic arsenic in coal samples and GBW11117 coal standard reference material with complex matrix. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Studies in hydride generation atomic fluorescence determination of selenium and tellurium. Part 1 — self interference effect in hydrogen telluride generation and the effect of KI

    Science.gov (United States)

    D'Ulivo, A.; Marcucci, K.; Bramanti, E.; Lampugnani, L.; Zamboni, R.

    2000-08-01

    The effects of tetrahydroborate (0.02-1%) and iodide (0-3 M) were investigated in determination of tellurium and selenium by hydride generation atomic fluorescence spectrometry. The effect of tetrahydroborate and iodide concentration were tested on the shape of calibration curves in concentration range of 1-1000 ng ml -1 analyte. Reductant deficiency resulted in a moderate sensitivity depression for tellurium but dramatically reduced the useful dynamic range down to 50 ng ml -1. On the contrary, selenium calibration curves retained a linear character even under conditions generating strong sensitivity depression. Curvature and rollover of tellurium calibration curves has been addressed to a self-interference effect caused by the formation of finely dispersed elemental tellurium. Iodide ions were found to have beneficial or no negative effects in the hydrogen telluride generation. Addition of iodide on-line to the sample has been proved effective in the control of the self-interference effect and allows to work in mild reaction conditions. Moreover, it allows a good control of Cu(II) interference and eliminates Ni(II) and Co(II) interferences. The method has been successfully applied to determination of tellurium in copper and lead ores certified reference materials.

  5. Arsenic fractionation in agricultural soil using an automated three-step sequential extraction method coupled to hydride generation-atomic fluorescence spectrometry.

    Science.gov (United States)

    Rosas-Castor, J M; Portugal, L; Ferrer, L; Guzmán-Mar, J L; Hernández-Ramírez, A; Cerdà, V; Hinojosa-Reyes, L

    2015-05-18

    A fully automated modified three-step BCR flow-through sequential extraction method was developed for the fractionation of the arsenic (As) content from agricultural soil based on a multi-syringe flow injection analysis (MSFIA) system coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS). Critical parameters that affect the performance of the automated system were optimized by exploiting a multivariate approach using a Doehlert design. The validation of the flow-based modified-BCR method was carried out by comparison with the conventional BCR method. Thus, the total As content was determined in the following three fractions: fraction 1 (F1), the acid-soluble or interchangeable fraction; fraction 2 (F2), the reducible fraction; and fraction 3 (F3), the oxidizable fraction. The limits of detection (LOD) were 4.0, 3.4, and 23.6 μg L(-1) for F1, F2, and F3, respectively. A wide working concentration range was obtained for the analysis of each fraction, i.e., 0.013-0.800, 0.011-0.900 and 0.079-1.400 mg L(-1) for F1, F2, and F3, respectively. The precision of the automated MSFIA-HG-AFS system, expressed as the relative standard deviation (RSD), was evaluated for a 200 μg L(-1) As standard solution, and RSD values between 5 and 8% were achieved for the three BCR fractions. The new modified three-step BCR flow-based sequential extraction method was satisfactorily applied for arsenic fractionation in real agricultural soil samples from an arsenic-contaminated mining zone to evaluate its extractability. The frequency of analysis of the proposed method was eight times higher than that of the conventional BCR method (6 vs 48 h), and the kinetics of lixiviation were established for each fraction.

  6. Arsenic fractionation in agricultural soil using an automated three-step sequential extraction method coupled to hydride generation-atomic fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Rosas-Castor, J.M. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León, C.P. 66451 Nuevo León (Mexico); Group of Analytical Chemistry, Automation and Environment, University of Balearic Islands, Cra. Valldemossa km 7.5, 07122 Palma de Mallorca (Spain); Portugal, L.; Ferrer, L. [Group of Analytical Chemistry, Automation and Environment, University of Balearic Islands, Cra. Valldemossa km 7.5, 07122 Palma de Mallorca (Spain); Guzmán-Mar, J.L.; Hernández-Ramírez, A. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León, C.P. 66451 Nuevo León (Mexico); Cerdà, V. [Group of Analytical Chemistry, Automation and Environment, University of Balearic Islands, Cra. Valldemossa km 7.5, 07122 Palma de Mallorca (Spain); Hinojosa-Reyes, L., E-mail: laura.hinojosary@uanl.edu.mx [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León, C.P. 66451 Nuevo León (Mexico)

    2015-05-18

    Highlights: • A fully automated flow-based modified-BCR extraction method was developed to evaluate the extractable As of soil. • The MSFIA–HG-AFS system included an UV photo-oxidation step for organic species degradation. • The accuracy and precision of the proposed method were found satisfactory. • The time analysis can be reduced up to eight times by using the proposed flow-based BCR method. • The labile As (F1 + F2) was <50% of total As in soil samples from As-contaminated-mining zones. - Abstract: A fully automated modified three-step BCR flow-through sequential extraction method was developed for the fractionation of the arsenic (As) content from agricultural soil based on a multi-syringe flow injection analysis (MSFIA) system coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS). Critical parameters that affect the performance of the automated system were optimized by exploiting a multivariate approach using a Doehlert design. The validation of the flow-based modified-BCR method was carried out by comparison with the conventional BCR method. Thus, the total As content was determined in the following three fractions: fraction 1 (F1), the acid-soluble or interchangeable fraction; fraction 2 (F2), the reducible fraction; and fraction 3 (F3), the oxidizable fraction. The limits of detection (LOD) were 4.0, 3.4, and 23.6 μg L{sup −1} for F1, F2, and F3, respectively. A wide working concentration range was obtained for the analysis of each fraction, i.e., 0.013–0.800, 0.011–0.900 and 0.079–1.400 mg L{sup −1} for F1, F2, and F3, respectively. The precision of the automated MSFIA–HG-AFS system, expressed as the relative standard deviation (RSD), was evaluated for a 200 μg L{sup −1} As standard solution, and RSD values between 5 and 8% were achieved for the three BCR fractions. The new modified three-step BCR flow-based sequential extraction method was satisfactorily applied for arsenic fractionation in real agricultural

  7. [Cloud Point extraction for determination of mercury in Chinese herbal medicine by hydride generation atomic fluorescence spectrometry with optimization using Box-Behnken design].

    Science.gov (United States)

    Wang, Mei; Li, Shan; Zhou, Jian-dong; Xu, Ying; Long, Jun-biao; Yang, Bing-yi

    2014-08-01

    Cloud point extraction (CPE) is proposed as a pre-concentration procedure for the determination of Hg in Chinese herbal medicine samples by hydride generation-atomic fluorescence spectrometry (HG-AFS). Hg2+ was reacted with dithizone to form hydrophobic chelate under the condition of pH. Using Triton X-114, as surfactant, chelate was quantitatively extracted into small volume of the surfactant-rich phase by heating the solution in a water bath for 15 min and centrifuging. Four variables including pH, dithizone concentration, Triton X-114 concentration and equilibrium temperature (T) showed the significant effect on extraction efficiency of total Hg evaluated by single-factor experiment, and Box-Behnken design and response surface method- ology were adopted to further investigate the mutual interactions between these variables and to identify their optimal values that would generate maximum extraction efficiency. The results showed that the binomial was used to fit the response to experimental levels of each variable. ALL linear, quadratic terms of four variables, and interactions between pH and Trion X-114, pH and di- thizone affected the response value(extraction efficiency) significantly at 5% level. The optimum extraction conditions were as follows: pH 5.1, Triton X-114 concentration of 1.16 g x L(-1), dithizone concentration of 4.87 mol x L(-1), and T 58.2 degrees C, the predicted value of fluorescence was 4528.74 under the optimum conditions, and the experimental value had only 2.1% difference with it. Under the conditions, fluorescence was linear to mercury concentration in the range of 1-5 microg x L(-1). The limit of detection obtained was 0.01247 microg x L(-1) with the relative standard deviations (R.S.D.) for six replicate determinations of 1.30%. The proposed method was successfully applied to determination of Hg in morindae Radix, Andrographitis and dried tangerine samples with the recoveries of 95.0%-100.0%. Apparently Box-Behnken design combined with

  8. Ultratrace determination of tin by hydride generation in-atomizer trapping atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Průša, Libor [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Hlavova 8, Prague 2, CZ 128 43 Czech Republic (Czech Republic); Dědina, Jiří [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic)

    2013-12-04

    Graphical abstract: -- Highlights: •In-atomizer trapping HG-AAS was optimized for Sn. •A compact quartz trap-and-atomizer device was employed. •Generation, preconcentration and atomization steps were investigated in detail. •Hundred percent preconcentration efficiency for tin was reached. •Routine analytical method was developed for Sn determination (LOD of 0.03 ng mL{sup −1} Sn). -- Abstract: A quartz multiatomizer with its inlet arm modified to serve as a trap (trap-and-atomizer device) was employed to trap tin hydride and subsequently to volatilize collected analyte species with atomic absorption spectrometric detection. Generation, atomization and preconcentration conditions were optimized and analytical figures of merit of both on-line atomization as well as preconcentration modes were quantified. Preconcentration efficiency of 95 ± 5% was found. The detection limits reached were 0.029 and 0.14 ng mL{sup −1} Sn, respectively, for 120 s preconcentration period and on-line atomization mode without any preconcentration. The interference extent of other hydride forming elements (As, Se, Sb and Bi) on tin determination was found negligible in both modes of operation. The applicability of the developed preconcentration method was verified by Sn determination in a certified reference material as well as by analysis of real samples.

  9. Determination of tellurium by hydride generation with in situ trapping flame atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Matusiewicz, H.; Krawczyk, M. [Politechn Poznanska, Poznan (Poland)

    2007-03-15

    The analytical performance of coupled hydride generation - integrated atom trap (HG-IAT) atomizer flame atomic absorption spectrometry (FAAS) system was evaluated for determination of Te in reference material (GBW 07302 Stream Sediment), coal fly ash and garlic. Tellurium, using formation of H{sub 2}Te vapors, is atomized in air-acetylene flame-heated IAT. A new design HG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangernents (a water-cooled single silica tube, double-slotted quartz tube or an 'integrated trap') was investigated. An improvement in detection limit was achieved compared with using either of the above atom trapping techniques separately. The concentration detection limit, defined as 3 times the blank standard deviation (3{sigma}), was 0.9 ng mL{sup -1} for Te. For a 2 min in situ preconcentration time (sample volume of 2 mL), sensitivity enhancement compared to flame AAS, was 222 fold, using the hydride generation atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision, expressed as RSD, was 7.0% (n = 6) for Te. The accuracy of the method was verified using a certified reference material (GBW 07302 Stream Sediment) by aqueous standard calibration curves. The measured Te contents of the reference material was in agreement with the information value. The method was successfully applied to the determination of tellurium in coal fly ash and garlic.

  10. Determination of copper in airborne particulate matter using slurry sampling and chemical vapor generation atomic absorption spectrometry.

    Science.gov (United States)

    Silva, Laiana O B; Leao, Danilo J; dos Santos, Debora C; Matos, Geraldo D; de Andrade, Jailson B; Ferreira, Sergio L C

    2014-09-01

    The present paper describes the development of a method for the determination of copper in airborne particulate matter using slurry sampling and chemical vapor generation atomic absorption spectrometry (CVG AAS). Chemometric tools were employed to characterize the influence of several factors on the generation of volatile copper species. First, a two-level full factorial design was performed that included the following chemical variables: hydrochloric acid concentration, tetrahydroborate concentration, sulfanilamide concentration and tetrahydroborate volume, using absorbance as the response. Under the established experimental conditions, the hydrochloric acid concentration had the greatest influence on the generation of volatile copper species. Subsequently, a Box-Behnken design was performed to determine the optimum conditions for these parameters. A second chemometric study employing a two-level full factorial design was performed to evaluate the following physical factors: tetrahydroborate flow rate, flame composition, alcohol volume and sample volume. The results of this study demonstrated that the tetrahydroborate flow rate was critical for the process. The chemometric experiments determined the following experimental conditions for the method: hydrochloric acid concentration, 0.208 M; tetrahydroborate concentration, 4.59%; sulfanilamide concentration, 0.79%; tetrahydroborate volume, 2.50 mL; tetrahydroborate flow rate, 6.50 mL min(-1); alcohol volume, 200 µL; and sample volume, 7.0 mL. Thus, this method, using a slurry volume of 500 µL and a final dilution of 7 mL, allowed for the determination of copper with limits of detection and quantification of 0.30 and 0.99 µg L(-1), respectively. Precisions, expressed as RSD%, of 4.6 and 2.8% were obtained using copper solutions at concentrations of 5.0 and 50.0 µg L(-1), respectively. The accuracy was evaluated by the analysis of a certified reference material of urban particulate matter. The copper concentration

  11. Masking Agents Evaluation for Lead Determination by Flow Injection-Hydride Generation-Atomic Fluorescence Spectrometry Technique: Effect of KI, L-Cysteine, and 1,10-Phenanthroline.

    Science.gov (United States)

    Beltrán, Blanca G; Leal, Luz O; Ferrer, Laura; Cerdà, Víctor

    2016-01-01

    Hydride generation (HG) of lead technique presents interferences from foreign ions of complex matrix samples. In order to minimize these interferences, the effect of masking agents such as KI, L-cysteine, and 1,10-phenanthroline was studied in the absence and in the presence of selected interfering species (As, Cr, Cu, and Fe). Different modes of addition of masking agents were accomplished, that is, to either sample or KBH4 reducing solution. The lead determinations were performed using a flow injection analysis (FIA) system coupled to HG and atomic fluorescence spectrometry (AFS). The linearity of calibration curves (1-10 μg Pb L(-1)) was not affected by the addition of the masking agents. The use of KI in the reducing solution diminished interferences from concentrations of As and Cu, while 1,10-phenanthroline showed a positive effect on the interference by As. Moreover, Cr and Cu appeared to be the most serious interfering ions for plumbane (PbH4), because they drastically reduced the analytical signal of lead. Fe did not present any interference under the employed experimental conditions, even at high levels. The accuracy was established through the analysis of certified reference material (i.e., BCR-610, groundwater) using KI as masking agent. The detection limit reached by FIA-HG-AFS proposed methodology was 0.03 μg Pb L(-1).

  12. 离子色谱-氢化物发生原子荧光法测定尿中形态砷%Determination of arsenic species in urine by ion chromatography-hydride generation-atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    魏静; 梁琼; 刘俊娓

    2013-01-01

    Objective:To develop a method for the determination of arsenic species in urine by Ion chromatography - hydride Generation - atomic fluorescence spectrometry. Methods; The urine sample was filtered by 0.45 μm membrane. Using ( NH4 ) 2 HPO4 as mobile phase to explore the best ion chromatographic separation condition and the atomic fluorescence determination condition. The content of various forms of arsenic was determined by Ion chromatography - hydride Generation - atomic fluorescence spectrometry. Results; This method had good relativity and good precision(2.60% ~4. 30% ). The detection limits of As( Ⅲ), DMA, MMA and As( V ) were 2. 0 (μg/L, 4.0 μg/L,4.0 μg/L,8.0 μg/L, the average recoveries of samples were 90.48% ~ 102.90%. Conclusion; The method had the advantages of convenience, speediness, high sensitivity, less interference and high practical value without chemical pretreatment.%目的:建立离子色谱-氢化物发生原子荧光法测定尿中形态砷的方法.方法:尿样经0.45 μm滤膜过滤,以(NH4)2HPO4为流动相,采用离子色谱-氢化物发生原子荧光联机测定不同形态砷的含量.结果:实验结果相关性好,线性范围宽,精密度RSD为2.60%~4.30%,方法检出限为As(Ⅲ)2.0 μg/L,DMA4.0 μg/L,MMA4.0 μg/L,As(V)8.0 μg/L,该方法所得回收率为90.48% ~ 102.90%.结论:方法简便、快速、无需化学预处理、干扰少、灵敏度高,有较高的实用价值.

  13. Determination of trace germanium in health protection food by hydride generation atomic fluorescence spectrometry%氢化物-原子荧光光谱法测定保健食品中痕量锗

    Institute of Scientific and Technical Information of China (English)

    宋伟明; 倪刚; 胡奇林; 全晓塞

    2001-01-01

    A new method was introduced for the determination of trace germanium by hydride generation atomic fluorescence spectrometry(HGAFS).The effect of the medium amounts of acid, action of hydride and screening agent of the determination of germanium was investigated. The operating condition of the instrument was optimized. The interference from foreign ions was eliminated by adding phosphoric acid and tartaric acid. This method was applied to the determination of germanium in some health protection and nourishing food. The detection limit (3δ) is 6.2 ng/g with a RSD of 5% .The recovery of standard addition is in 95%~105%.%提出了以氢化物-原子荧光光谱法测定保健食品中锗的新方法,研究了酸介质、氢化物发生、增敏掩蔽剂等因素对测定的影响,并选择出仪器的最佳工作条件;采用磷酸-酒石酸介质进行测定,不但可有效消除共存离子的干扰,而且起到增敏作用,方法的检出限为6.2,ng/g,相对标准偏差(RSD)在5%以内,加标回收率为95%~105%,结果令人满意.

  14. 氢化物发生-原子荧光光谱法测定红土镍矿中砷%DETERMINATION OF ARSENIC IN LATERITE NICKEL ORES BY HYDRIDE GENERATION-ATOMIC FLUORESCENCE SPECTROMETRY

    Institute of Scientific and Technical Information of China (English)

    陈殿耿; 袁玉霞; 何飞顶

    2012-01-01

    提出了以硫脲-抗坏血酸作为还原掩蔽剂,氢化物发生-原子荧光光谱法( HG-AFS)直接测定红土镍矿中砷的方法.考察了测定的最佳条件、共存元素对测定的影响及方法的精密度和回收率.方法适用于红土镍矿中0.005%~0.1%砷的测定.%A method for the determination of arsenic in laterite nickel ores by hydride generation-atomic fluorescence spectrometry (HG-AFS) directly with thiourea-ascorbic acid hydrochloride as masking is proposed. The optimum experimental parameters, the effect of coexistent elements on the determination of arsenic, the precision and recovery of the method are investigated. The method can be applied to the determination of 0. 005% ~ 0. 1% arsenic in laterite nickel ores.

  15. A simple and sensitive flow-injection on-line preconcentration coupled with hydride generation atomic fluorescence spectrometry for the determination of ultra-trace lead in water, wine, and rice.

    Science.gov (United States)

    Wu, Hong; Jin, Yan; Luo, Mingbiao; Bi, Shuping

    2007-09-01

    A simple and sensitive flow-injection on-line separation and preconcentration system coupled to hydride generation atomic fluorescence spectrometry (HG-AFS) was developed for ultra-trace lead determination in water, wine, and rice samples, with the salient advantages of its minimization of transition-metal interferences and tolerance to an ethanol matrix. A lead hydroxide precipitate was achieved by the on-line merging of a sample and an ammonium buffer solution and collected onto the inner walls of a knotted reactor (KR). Removal of the residual solution from KR was achieved by air flow, and dissolution of the precipitate was carried out by using 0.2 mol l(-1) HCl. With a sample consumption of 11.7 ml, an enhancement factor of 16 was obtained at a sample throughput of 30 h(-1). The limit of detection (3s) was 16 ng l(-1) and the precision (RSD) for 1.0 microg l(-1) Pb was 3.4%.

  16. Simultaneous Determination of Arsenic and Antimony in Water by Hydride Generation-Atomic Fluorescence Spectrometry%氢化物发生-原子荧光光谱法同时测定水中砷和锑

    Institute of Scientific and Technical Information of China (English)

    黄选忠; 万忠卫; 杜宏山; 郑丽

    2013-01-01

    建立在硝酸介质中用氢化物发生-原子荧光光谱法同时测定水中砷和锑的方法。优化了仪器工作条件、酸度、硼氢化钾及还原剂浓度。砷、锑的线性范围为0~10.0µg/L;检出限分别为0.02,0.01µg/L;测定结果的相对标准偏差分别为1.77%~3.72%,2.95%~4.87%(n=6);加标回收率分别为98%~106%,96%~105%。该法操作简便,灵敏度高,快速,便于推广,适用于水中砷和锑的同时测定。%The method for simultaneous determination of arsenic and antimony in water was established by hydride-generation atomic fluorescence spectrometry in nitric acid medium. Instrument condition,acidity,concentration of potassium borohydride and thiourea-ascorbic acid were selected. The linear relationship of arsenic and antimony was 0-10.0 µg/L. The detection limit of arsenic and antimony was 0.02 µg/L and 0.01 µg/L, the relative standard deviation of arsenic and antimony determination results was 1.77%-3.72%and 2.95%-4.87%(n=6) , the recovery of standard addition of arsenic and antimony was 98%-106%and 96%-105%respectively. This method has the advantages of simple operation and high sensitivity,it is rapid and easy to spread,which is suitable for simultaneous determination of arsenic and antimony in water.

  17. Speciation of the immediately mobilisable As(III), As(V), MMA and DMA in river sediments by high performance liquid chromatography-hydride generation-atomic fluorescence spectrometry following ultrasonic extraction

    Energy Technology Data Exchange (ETDEWEB)

    Huerga, A. [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Facultad de Ciencias (Quimica), Universidad de Vigo, As Lagoas-Marcosende s/n, 36200 Vigo (Spain); Lavilla, I. [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Facultad de Ciencias (Quimica), Universidad de Vigo, As Lagoas-Marcosende s/n, 36200 Vigo (Spain); Bendicho, C. [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Facultad de Ciencias (Quimica), Universidad de Vigo, As Lagoas-Marcosende s/n, 36200 Vigo (Spain)]. E-mail: bendicho@uvigo.es

    2005-04-04

    In this work, a fast method is developed for the speciation of As(III), As(V), MMA and DMA in the immediately mobilisable fraction of river sediments (i.e. water-soluble and phosphate-exchangeable) by high performance liquid chromatography-hydride generation-atomic fluorescence detection (HPLC-HG-AFD) after extraction using focused ultrasound. The influence of relevant parameters influencing an ion-pairing chromatographic separation following isocratic elution (i.e. amount of MeOH in the mobile phase, ion pair reagent concentration, pH, flow rate) was studied. Focused ultrasound transmitted from an ultrasonic probe provided the same extractable contents as conventional extraction with no changes in the species distribution. The effect of the drying step over extraction of As species was investigated. The following drying procedures were compared: freeze-, oven-, microwave- and air-drying. No influence of the drying operation on the water-extractable fraction was observed. However, freeze- and air-drying yielded significantly higher phosphate-extractable amounts of As(III) and As(V) as compared to oven and microwaves. Detection limits for the As species were in the range 1.3-4.1 ng/g for the water-soluble fraction and 1.6-4.8 ng/g for the phosphate buffer exchangeable fraction. The method was applied to the speciation of immediately mobilisable As(III), As(V), DMA and MMA in 11 sediment samples collected along the beds of the Louro River (southern Galicia, Spain)

  18. Determination of Se in Saffron by Using Hydride Generation Atomic Fluorescence Spectrometry%氢化物发生原子荧光光谱法测定西红花柱头中的硒

    Institute of Scientific and Technical Information of China (English)

    张宏; 张新申; 颜钫; 陈放

    2001-01-01

    A method for determination of Se in saffron using AFS-230 hydride generation atomic fluorescence spectrometry was introduced.Detections were completed made in every possible best condition.The optimal analytical conditions in HClO4-HNO3 were examined.The detection limit is 0.5μg/L.The linear range is 1.5~15.0 μg/L.The correlation coefficient is 0.9999,and the recovery rate is about 90%~97%.Se of saffrons from 4 regions was determined by standard curve method.The experiment results show that this method has low detection limit,high accurate,simple operation,fast and low cost.It's easy to be spread.%应用AFS-230型双道原子荧光光谱计进行了氢化物发生原子荧光光谱法测定西红花柱头中硒的研究,方法中采用硝酸做介质,并对各种最佳分析条件进行了测定。线性范围为1.5~15μg/L,相关系数R=0.9999,回收率为90%~97%。采用标准曲线法对4种不同产地的西红花干燥柱头中硒进行了测定。该方法操作简单、快速,精密度好,准确性高,检出限较低,经济,便于推广应用。

  19. Optimize parameters of hydride generation-atomic fluorescence spectrometry for inorganic arsenic determination in grain%氢化物发生-原子荧光法测定粮食中无机砷条件的研究

    Institute of Scientific and Technical Information of China (English)

    杨庆惠

    2012-01-01

    应用氢化物发生—原子荧光分析技术进行粮食中无机砷测定的研究,通过优化酸度、硼氢化钾、载气流量、灯电流以及原子化器高度等分析条件,结果表明,砷浓度在0~30 ng/ml内呈线性关系,相关系数为0.999 9,相对标准偏差为1.6%,检出限为0.054 μg/L,用此方法测定粮食中无机砷,回收率为96.5%~103.5%.该方法简便、快速、灵敏,在实际样品测定中获得到了满意的结果,便于推广应用.%Hydride generation- atomic fluorescence spectrometry was adopted for determine the inorganic arsenic in grain. The experimental parameters such as Ph, KHB4 concentration, flow rate, lamp current and the height of atomizer were optimized. There is linear relation when the arsenic concentration was between 0~30 ng/ml with a correlation coefficient of 0. 999 9. The relative standard deviation was 1. 6%, and the detection limit was 0. 054μg/L. The recovery rate reached to 96. 5%~103. 5%. This method is simple,rapid and sensitive, and got satisfactory results in practicle,it is worth for generalize.

  20. Optimización y validación metodológica de la cuantificación de arsénico por inyección en flujo-generación de hidruros- espectrometría de absorción atómicas (IF-GH-EAA previa derivatizacíon con L-Cisteína Optimización and validation method for arsenic quantification by flow injection-hydride generation - atomic absorption spectrometry (fi-hg-aas after L-Cysteine derivatization

    Directory of Open Access Journals (Sweden)

    Julio A Navoni

    2009-12-01

    Full Text Available El arsénico (As es un contaminante natural que afecta una amplia zona de Argentina. El nivel de As en agua de consumo es utilizado para evaluar la fuente de exposición y en orina para evaluar exposición a este tóxico. El presente trabajo tuvo como objetivo la optimización y validación metodológica de una técnica para la cuantificación de As [As suma = As inorgánico (AsI + especies metiladas: ácido monometilarsónico (MMA y ácido dimetilarsínico (DMA], producto del metabolismo del AsI, por inyección en flujo- generación de hidruros- espectrometría de absorción atómica (IF-GH-EAA, previa derivatización con L-cisteína. La recuperación de las especies estudiadas: AsI (AsIII y AsV, MMA y DMA fue cercana al 100% en todos los casos. Los límites de detección y cuantificación encontrados fueron para agua y orina: 2 y 3 μg/L; 5 y 8 μg/L respectivamente y el rango dinámico de trabajo establecido fue desde 5 a 75 μg/L, permitiendo cuantificar As en muestras de agua cercanos a los estándares internacionales vigentes para valores máximos de As en agua de consumo y en orina en niveles comparables con los establecidos en población laboralmente no expuesta. Esta propuesta metodológica es una alternativa para evaluar la exposición al As en muestras de agua y orina, sin necesidad de utilizar prolongados pre-tratamientos de muestra, de forma más rápida y económica.Arsenic (As is a natural contaminant that affects a large area of Argentina. Quantification of As in drinking water has been used to evaluate the source of exposure and As in urine to assess exposure to this toxic. This study aimed to optimize and validate a methodological technique for the quantification of As [As sum = inorganic As (AsI + methylated species: monometilarsonic acid (MMA and dimetilarsinic acid (DMA], product of AsI metabolism by flow injectionhydride generation-atomic absorption spectrometry (FI-GH-AAS, after derivatization with L-cysteine. The recovery

  1. 氢化物发生-原子荧光光谱法测定Inconel 718合金中痕量硒%Determination of trace selenium in 718 alloy by hydride generation-atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    向祥蓉; 刘虹; 王佼

    2012-01-01

    本文采用氢化物发生-原子荧光光谱法测定Inconel718合金中痕量硒.对影响其测定的负高压、灯电流、载气流量、屏蔽气流量、载流酸类酸度、硼氢化钾等因素进行了较为详细的研究,优化了测定条件,考察了Inconel718合金主要组成元素和基体元素对硒测定的影响.结果表明,用氟化氨溶液络合,柠檬酸溶液作干扰抑制剂能基本消除基体元素和主要组成元素的干扰.硒浓度在0~100μg/L与荧光强度有良好的线性关系,方法的检出限为0.0083μg/L.对铁镍基高温合金标准样品和Inconel 718合金样品进行9次测定,相对标准偏差为1.6%~3.5%.%In this paper a simple and fast analytical procedure for the determination of selenium in Inconel 718 alloy by hydride generation atomic fluorescence spectrometry(HG-AFS) was developed. The in fluence of instrument parameters such as voltage of PMT, current of lamp, atomizer height, carrier gas rate,shield gas rate and concentration of HCI and KBH4 on the determination of selenium were studied, and the optimized conditions were obtained. Interference of coexistent elements and methods to eliminate the interference were investigated in detail. The results showed that ammonium fluoride and citric acid mo nohydrate were the best masking. Under the optimized conditions, the linear range of selenium is 0 ~ 100μg/L, and the detection limit is 0. 0083 μg/L. The relative standard deviation is 1. 6%~3. 5%(n=9) for the standard sample and the sample of Inconel 718 alloy.

  2. Determination of Inorganic Arsenic in Atmospheric Particles by Hydride Generation-atomic Fluorescence Spectrometry%氢化物发生-原子荧光光谱法测定大气颗粒物中的砷形态

    Institute of Scientific and Technical Information of China (English)

    梁淑轩; 吴虹; 齐学先; 郑璇; 何晓娇

    2011-01-01

    Concentration of atmospheric particles is one of the atmospheric pollution indicators. Heavy metals in the atmospheric particles can risk for human health in both direct and indirect way. Arsenic is one of the higher metal content in them. The inorganic compounds are far more toxic than their organic metabolites. In this paper, the hydride generation atomic fluorescence spectrometric method was employed to the determination of As ( Ⅲ ) and As (V) in the Atmospheric particles. The amount of reducing agent,acid medium and its acidity, carrier gas and shield gas flow rate and observation height of the fluorescence intensity were investigated, and the interference experiment was carried out for concomitant elements. In the best conditions, the detection limit was 0. 34 μg/L, the recovery ranged from 98.18% ~ 102.54%,and the relative standard deviation was about 0.8%. The method was featured by easy operation, fast speed and it has been applied to the analysis of arsenic in the particles with satisfactory results.%采用氢化物发生原子荧光法直接测定不同粒径大气颗粒物中As(Ⅲ)和As(Ⅴ)的含量.研究了还原剂用量、酸介质及其酸度、载气及屏蔽气流量和观测高度等对荧光强度的影响,探讨了共存离子对砷测定的干扰.在选定的最佳条件下,得到检出限为0.34μg/L,方法检出限为0.21μg/g,加标回收率为98.18%~102.54%,相对标准偏差为0.8%左右.用该方法测定大气颗粒物中不同形态的砷,操作简便,快速,灵敏度高.

  3. Hydride phase formation in LaMg{sub 2}Ni during H{sub 2} absorption

    Energy Technology Data Exchange (ETDEWEB)

    Di Chio, M.; Baricco, M. [Dipartimento di Chimica IFM and NIS/CNISM/INSTM, Universita di Torino, Via P.Giuria, 9 10125 Torino (Italy); Schiffini, L.; Enzo, S.; Cocco, G. [Dipartimento di Chimica and INSTM, Universita di Sassari, Via Vienna, 2 07100 Sassari (Italy)

    2008-02-15

    Hydrogen absorption and desorption properties in nanocrystalline LaMg{sub 2}Ni are presented. Nanostructured phases have been obtained by milling grain coarse ingot and by mechanically alloying the parent elements. The structural and hydriding properties were examined by X-ray diffraction, thermal analysis and thermal desorption measurements. Ball milling and mechanical alloying give a significant refinement of the microstructure. Reactive milling has been used for hydrogen absorption experiments. Hydrogenation by means of reactive milling at 300 K under a pressure of 0.4 MPa leads to the formation of a stable La-hydride phase together with an amorphous phase. Thermal desorption up to 983 K of hydrogenated samples leads again to parent LaMg{sub 2}Ni phase. (author)

  4. Hydride generation – in-atomizer collection of Pb in a quartz trap-and-atomizer device for atomic absorption spectrometry – an interference study

    Energy Technology Data Exchange (ETDEWEB)

    Novotný, Pavel [Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno (Czech Republic); High School in Hořice, Husova 1414, 508 01 Hořice (Czech Republic); Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz [Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno (Czech Republic)

    2013-01-01

    Interferences of selected hydride forming elements (As, Sb, Bi, Se and Sn) on lead determination by hydride generation atomic absorption spectrometry were extensively studied in both on-line atomization and preconcentration (collection) modes. The commonly used on-line atomization mode was found free of significant interferences, whereas strong interference from Bi was observed when employing the preconcentration mode with plumbane collection in a quartz trap-and-atomizer device. Interference of Bi seems to take place in the preconcentration step. Interference of Bi in the collection mode cannot be reduced by increased hydrogen radical amount in the trap and/or the atomizer. - Highlights: ► Interference study on Pb determination by in-atomizer trapping was performed for the first time. ► Bi was found as a severe interferent in the preconcentration mode (Pb:Bi ratio 1:100). ► No interference was found in the on-line atomization (no preconcentration). ► Bi interference occurs during preconcentration.

  5. 氢化物原子荧光光谱法同时测定生活饮用水中砷和硒%Simulatneous Determination of Arsenic and selenium in Drinking Water Samples by Hydride Generation Atomic Fluorescence Spectrometry

    Institute of Scientific and Technical Information of China (English)

    张祥楼

    2014-01-01

    建立了氢化物发生原子荧光光谱法同时测定生活饮用水中砷和硒的方法.测试结果表明砷和硒在质量浓度分别为0.00μg/L~10.00μg/L和0.00μg/L~40.00μg/L范围内呈线性关系,相关系数分别为(砷r=0.9998,硒r=0.9997)。仪器检出限为砷:0.03μg/L硒:0.05μg/L。本方法检出限砷为0.075μg/L;硒为0.125μg/L。水质样品中砷的回收率为92.6%~96.5%,精密度为0.8%~1.4%;硒的回收率为91.2%~97.4%,精密度为1.0%~1.6%。应用本方法测定生活饮用水中的砷和硒方法简便、快速,结果准确可靠,较好地提高了工作效率。%A method for simulatneous determination of Arsenic and selenium in drinking water samples by hydride generation atomic fluorescence spectrometry.As a matter of fact ,the linear range of Arsenic was 0.00μg/L~10.00μg/L and the related coefficient was 0.9998;While the linear range of Selenium was 0.00μg/L~40.00μg/L and the related coefficient was0.9997. Instrument detection limit was 0.03μg/L(arsenic)and 0.05μg/L(selenium).Detection limits of the method was 0.075μg/L (arsenic)and 0.125μg/L(selenium). The rate of arsenic recovery was 92.6%~96.5%and the precision in the drinking water was in the range of 0.8%~1.4%.while the rate of selenium recovery was 92.6%~96.5%and the precision in the drinking water was in the range of 1.0%~1.6%.The experimental results shows that the method is applicable .

  6. 氢化物发生原子荧光光谱法测量化妆品中Sb的价态%Valent speciation analysis of antimony in cosmetics by hydride generation atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    肖融; 张新智; 王昌钊; 冯礼; 秦德元; 刘霁欣

    2012-01-01

    考察了NaF、8-羟基喹啉、柠檬酸对Sb(Ⅲ)和Sb(V)原子荧光信号的掩蔽作用和还原解柠檬酸除掩蔽作用的方法.结果表明,0.10mol/L柠檬酸对Sb(V)掩蔽作用最强,且对Sb(Ⅲ)有增敏作用,最适于作为Sb价态测量的掩蔽剂,而10g/L碘化钾(KI)+ 10g/L硫脲(Tu)可在5h内完全解除柠檬酸对Sb(V)的掩蔽作用.据此建立了化妆品中Sb价态的非色谱氢化物发生原子荧光测量方法.样品经0.10mol/L柠檬酸提取两次后,离心去上清液,合并定容,得到提取液;提取液酸化后直接测得Sb(Ⅲ)含量;提取液酸化并加入KI+Tu,放置5h以上后可测得Sb(V)与Sb(Ⅲ)的含量和,此值减去Sb(Ⅲ)含量可得Sb(V)含量.计算表明,该方法对Sb(Ⅲ)和Sb(V)的检出限(3σ)均为0.32μg/L,定量限(3σ)均为1.0μg/L.对实际化妆品作了测量,Sb(Ⅲ)和Sb(V)的加标回收率在70%~130%之间.实验中存在少量Sb(Ⅲ)到Sb(V)的转化.%The masking effects of NaF, 8-hydroxygquinoline and citric acid on the atomic fluorescence signals of Sb(Ⅲ ) and Sb( V ) And the method for eliminating the masking effect of citric acid were investigated. The results show that 0. 10 mol/L citric acid has the strongest masking effect on Sb(V) and can increase the sensitivity of Sb(Ⅲ) , and l0g/L KI+l0g/L thiourea can completely eliminate the masking effect of citric acid in >5h. Based on this, a method for analyzing the valent speciation of Sb in cosmetics by hydride generation atomic fluorescence spectrometry (HGAFS) was developed. The samples were extracted twice with 0. L0ml/L citric acid. The supernatant was removed by centrifugation and the residues were merged asextract solution. After the acidification of the extract solution, the Sb(Ⅲ) content was determined directly. Then the extract solution was added with KI (10g/L)+ thiourea (l0g/L) and set aside for >5h before the total content of Sb(V) and Sb(Ⅲ) was determined. The Sb( V) content was obtained by subtracting Sb

  7. Study on Kinetics of Hydrogen Absorption by Metal Hydride Slurries Ⅰ. Absorption of Hydrogen by Hydrogen Storage Alloy MlNi5 Suspended in Benzene

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

    The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three-phase mass transfer model. It is also concluded that the suitable absorption temperature is 313 K.

  8. THE ABSORPTION OF HYDROGEN ON LOW PRESSURE HYDRIDE MATERIALS

    Energy Technology Data Exchange (ETDEWEB)

    Morgan, G.; Korinko, P.

    2012-04-03

    For this study, hydrogen getter materials (Zircaloy-4 and pure zirconium) that have a high affinity for hydrogen (and low overpressure) have been investigated to determine the hydrogen equilibrium pressure on Zircaloy-4 and pure zirconium. These materials, as with most getter materials, offered significant challenges to overcome given the low hydrogen equilibrium pressure for the temperature range of interest. Hydrogen-zirconium data exists for pure zirconium at 500 C and the corresponding hydrogen overpressure is roughly 0.01 torr. This manuscript presents the results of the equilibrium pressures for the absorption and desorption of hydrogen on zirconium materials at temperatures ranging from 400 C to 600 C. The equilibrium pressures in this temperature region range from 150 mtorr at 600 C to less than 0.1 mtorr at 400 C. It has been shown that the Zircaloy-4 and zirconium samples are extremely prone to surface oxidation prior to and during heating. This oxidation precludes the hydrogen uptake, and therefore samples must be heated under a minimum vacuum of 5 x 10{sup -6} torr. In addition, the Zircaloy-4 samples should be heated at a sufficiently low rate to maintain the system pressure below 0.5 mtorr since an increase in pressure above 0.5 mtorr could possibly hinder the H{sub 2} absorption kinetics due to surface contamination. The results of this study and the details of the testing protocol will be discussed.

  9. In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes.

    Science.gov (United States)

    Hugenbruch, Stefan; Shafaat, Hannah S; Krämer, Tobias; Delgado-Jaime, Mario Ulises; Weber, Katharina; Neese, Frank; Lubitz, Wolfgang; DeBeer, Serena

    2016-04-28

    Metal hydrides are invoked as important intermediates in both chemical and biological H2 production. In the [NiFe] hydrogenase enzymes, pulsed EPR and high-resolution crystallography have argued that the hydride interacts primarily at the Ni site. In contrast, in [NiFe] hydrogenase model complexes, it is observed that the bridging hydride interacts primarily with the Fe. Herein, we utilize a combination of Ni and Fe X-ray absorption (XAS) and emission (XES) spectroscopies to examine the contribution of the bridging hydride to the observed spectral features in [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)3](+). The corresponding data on (dppe)Ni(μ-pdt)Fe(CO)3 are used as a reference for the changes that occur in the absence of a hydride bridge. For further interpretation of the observed spectral features, all experimental spectra were calculated using a density functional theory (DFT) approach, with excellent agreement between theory and experiment. It is found that the iron valence-to-core (VtC) XES spectra reveal clear signatures for the presence of a Fe-H interaction in the hydride bridged model complex. In contrast, the Ni VtC XES spectrum largely reflects changes in the local Ni geometry and shows little contribution from a Ni-H interaction. A stepwise theoretical analysis of the hydride contribution and the Ni site symmetry provides insights into the factors, which govern the different metal-hydride interactions in both the model complexes and the enzyme. Furthermore, these results establish the utility of two-color XES to reveal important insights into the electronic structure of various metal-hydride species.

  10. Evaluation of health risk and arsenic levels in vegetables sold in markets of Dhaka (Bangladesh) and Salamanca (Spain) by hydride generation atomic absorption spectroscopy.

    Science.gov (United States)

    Anawar, Hossain Md; Garcia-Sanchez, A; Hossain, Md Nur; Akter, Shamima

    2012-09-01

    The main objective of this study was to determine arsenic (As) levels in vegetables collected from the markets of Dhaka, Bangladesh and for comparison from Salamanca, Spain by HGAAS under optimal conditions, and the potential health risk from consumption of these vegetables. The mean and range of the total As concentration in the vegetables from the markets of Dhaka, Bangladesh were 114 and 1.0-293 μg/kg, respectively. Total As concentration in 77% of Bangladesh vegetables measured was higher than that recommended by the standard. The mean and range of As concentrations for vegetables grown in Spain were 65 and bdl-130 μg/kg, respectively, for Salamanca, 102 and bdl-423 μg/kg, respectively, for Almeria. The As content of the Bangladesh vegetables was approximately twofold to threefold higher than those observed for the vegetables from Almeria and Salamanca (Spain), but in some cases, were similar or less. Daily consumption of As-rich vegetables may result in an additional source of As in the diet, based on the provisional tolerable intake of As for adults recommended by WHO.

  11. Preliminary results on the determination of ultratrace amounts of cadmium in tea samples using a flow injection on-line solid phase extraction separation and preconcentration technique to couple with a sequential injection hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Duan, Taicheng; Song, Xuejie; Jin, Dan; Li, Hongfei; Xu, Jingwei; Chen, Hangting

    2005-10-31

    In this work, a method was developed for determination of ultra-trace levels of Cd in tea samples by atomic fluorescence spectrometry (AFS). A flow injection solid phase extraction (FI-SPE) separation and preconcentration technique, to on-line couple with a sequential injection hydride generation (SI-HG) technique is employed in this study. Cd was preconcentrated on the SPE column, which was made from a neutral extractant named Cyanex 923, while other matrix ions or interfering ions were completely or mostly separated off. Conditions for the SPE separation and preconcentration, as well as conditions for the HG technique, were studied. Due to the separation of interfering elements, Cd hydride generation efficiency could be greatly enhanced with the sole presence of Co(2+) with a concentration of 200mugL(-1), which is much lower than those in other works previously reported. Interferences on both the Cd separation and preconcentration, and Cd hydride generation (HG) were investigated; it showed that both the separation and preconcentration system, and the HG system had a strong anti-interference ability. The SPE column could be repeatedly used at least 400 times, a R.S.D. of 0.97% was obtained for 6 measurements of Cd with 0.2mugL(-1) and a correlation coefficiency of 1.0000 was obtained for the measurement of a series of solutions with Cd concentrations from 0.1 to 2mugL(-1). The method has a low detection limit of 10.8ngL(-1) for a 25mL solution and was successfully validated by using two tea standard reference materials (GBW08513 and GBW07605).

  12. A high-efficiency power cycle in which hydrogen is compressed by absorption in metal hydrides.

    Science.gov (United States)

    Powell, J R; Salzano, F J; Yu, W S; Milau, J S

    1976-07-23

    A high-efficiency power cycle is proposed in which molecular hydrogen gas is used as a working fluid in a regenerative closed Brayton cycle. The hydrogen gas is compressed by an absorption-desorption cycle on metal hydride (FeTiH(x)) beds. Low-temperature solar or geothermal heat (temperature about 100 degrees C) is used for the compression process, and high-temperature fossil fuel or nuclear heat (temperature about 700 degrees C) supplies the expansion work in the turbine. Typically, about 90 percent of the high-temperature heat input is converted to electricity, while about 3 kilowatts of low-temperature heat is required per kilowatt of electrical output.

  13. Herschel-HIFI detections of hydrides towards AFGL 2591 (Envelope emission versus tenuous cloud absorption)

    CERN Document Server

    Bruderer, S; van Dishoeck, E F; Melchior, M; Doty, S D; van der Tak, F; Stäuber, P; Wampfler, S F; Dedes, C; Yıldız, U A; Pagani, L; Giannini, T; de Graauw, Th; Whyborn, N; Teyssier, D; Jellema, W; Shipman, R; Schieder, R; Honingh, N; Caux, E; Bächtold, W; Csillaghy, A; Monstein, C; Bachiller, R; Baudry, A; Benedettini, M; Bergin, E; Bjerkeli, P; Blake, G A; Bontemps, S; Braine, J; Caselli, P; Cernicharo, J; Codella, C; Daniel, F; di Giorgio, A M; Dominik, C; Encrenaz, P; Fich, M; Fuente, A; Goicoechea, J R; Helmich, F; Herczeg, G J; Herpin, F; Hogerheijde, M R; Jacq, T; Johnstone, D; Jørgensen, J K; Kristensen, L E; Larsson, B; Lis, D; Liseau, R; Marseille, M; McCoey, C; Melnick, G; Neufeld, D; Nisini, B; Olberg, M; Parise, B; Pearson, J C; Plume, R; Risacher, C; Santiago-Garcia, J; Saraceno, P; Shipman, R; Tafalla, M; van Kempen, T A; Visser, R; Wyrowski, F

    2010-01-01

    The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel Space Observatory allows the first observations of light diatomic molecules at high spectral resolution and in multiple transitions. Here, we report deep integrations using HIFI in different lines of hydrides towards the high-mass star forming region AFGL 2591. Detected are CH, CH+, NH, OH+, H2O+, while NH+ and SH+ have not been detected. All molecules except for CH and CH+ are seen in absorption with low excitation temperatures and at velocities different from the systemic velocity of the protostellar envelope. Surprisingly, the CH(JF,P = 3/2_2,- - 1/2_1,+) and CH+(J = 1 - 0, J = 2 - 1) lines are detected in emission at the systemic velocity. We can assign the absorption features to a foreground cloud and an outflow lobe, while the CH and CH+ emission stems from the envelope. The observed abundance and excitation of CH and CH+ can be explained in the scenario of FUV irradiated outflow walls, where a cavity etched out by the outflow al...

  14. Colloidal mercury (Hg) distribution in soil samples by sedimentation field-flow fractionation coupled to mercury cold vapour generation atomic absorption spectroscopy.

    Science.gov (United States)

    Santoro, A; Terzano, R; Medici, L; Beciani, M; Pagnoni, A; Blo, G

    2012-01-01

    Diverse analytical techniques are available to determine the particle size distribution of potentially toxic elements in matrices of environmental interest such as soil, sediments, freshwater and groundwater. However, a single technique is often not exhaustive enough to determine both particle size distribution and element concentration. In the present work, the investigation of mercury in soil samples collected from a polluted industrial site was performed by using a new analytical approach which makes use of sedimentation field-flow fractionation (SdFFF) coupled to cold vapour generation electrothermal atomic absorption spectroscopy (CV-ETAAS). The Hg concentration in the SdFFF fractions revealed a broad distribution from about 0.1 to 1 μm, roughly following the particle size distributions, presenting a maximum at about 400-700 nm in diameter. A correlation between the concentration of Hg in the colloidal fraction and organic matter (O.M.) content in the soil samples was also found. However, this correlation is less likely to be related to Hg sorption to soil O.M. but rather to the presence of colloidal mercuric sulfide particles whose size is probably controlled by the occurrence of dissolved O.M. The presence of O.M. could have prevented the aggregation of smaller particles, leading to an accumulation of mercuric sulfides in the colloidal fraction. In this respect, particle size distribution of soil samples can help to understand the role played by colloidal particles in mobilising mercury (also as insoluble compounds) and provide a significant contribution in determining the environmental impact of this toxic element.

  15. Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

    Science.gov (United States)

    This paper describes an automated system for the oxidation state specific speciation of inorganic and methylated arsenicals by selective hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer. The corresponding arsines are ge...

  16. Actuation of Pneumatic Artificial Muscle via Hydrogen Absorption/Desorption of Metal Hydride-LaNi5

    OpenAIRE

    Thanana Nuchkrua; Thananchai Leephakpreeda

    2015-01-01

    This paper presents experimental studies on mechanical actuations of a pneumatic artificial muscle (PAM), which is driven by hydrogen gas based metal hydride (MH). The dynamic performances of hydrogen absorption/desorption, taking place within a MH reactor, are controlled via implementing cooling/heating effects of a thermoelectric module (TEM). Hydrogen pressure is applied as a driving force to commanding work outputs of the PAM as desired mechanical actuations. Due to strong inherent nonlin...

  17. Body centered cubic magnesium niobium hydride with facile room temperature absorption and four weight percent reversible capacity.

    Science.gov (United States)

    Tan, XueHai; Wang, Liya; Holt, Chris M B; Zahiri, Beniamin; Eikerling, Michael H; Mitlin, David

    2012-08-21

    We have synthesized a new metastable metal hydride with promising hydrogen storage properties. Body centered cubic (bcc) magnesium niobium hydride (Mg(0.75)Nb(0.25))H(2) possesses 4.5 wt% hydrogen gravimetric density, with 4 wt% being reversible. Volumetric hydrogen absorption measurements yield an enthalpy of hydride formation of -53 kJ mol(-1) H(2), which indicates a significant thermodynamic destabilization relative to the baseline -77 kJ mol(-1) H(2) for rutile MgH(2). The hydrogenation cycling kinetics are remarkable. At room temperature and 1 bar hydrogen it takes 30 minutes to absorb a 1.5 μm thick film at sorption cycle 1, and 1 minute at cycle 5. Reversible desorption is achieved in about 60 minutes at 175 °C. Using ab initio calculations we have examined the thermodynamic stability of metallic alloys with hexagonal close packed (hcp) versus bcc crystal structure. Moreover we have analyzed the formation energies of the alloy hydrides that are bcc, rutile or fluorite.

  18. Study on determination of lead in aluminium polychlorid by continuous flow-hydride generation atomic fluorescence spectrometry%连续流动-氢化物发生原子荧光光谱法测定聚合氯化铝中铅

    Institute of Scientific and Technical Information of China (English)

    龚胜芳; 高树林; 李志华; 王红柳

    2014-01-01

    采用连续流动-氢化物发生原子荧光光谱法(CF-HGAFS)测定聚合氯化铝中的铅,优化了实验条件,在最佳实验条件下,铅的荧光强度在0~25μg /L范围内与浓度呈良好的线性关系,方法检出限为0.043μg/L ,方法回收率在95.3%~105.6%之间,本法操作简便、快捷,而且具有很好的准确性和精密度,应用前景良好。%A method for the determination of lead in aluminium polychlorid by continuous flow-hydride generation atomic fluorescence spectrometry was established .The effect of experimental conditions on the atomic fluorescence intensity were investigated and optimized .In this condition ,the calibration curve was linear up to 25μg/L ,the detection limit was 0 .043μg/L ,and the recovery was in range of 95 .3%-105.6% . The method is not only simple and rapid but also precise and accurate ,and shows good application pros-pects .

  19. A novel analytical system involving hydride generation and gold-coated W-coil trapping atomic absorption spectrometry for selenium determination at ng l{sup -1} level

    Energy Technology Data Exchange (ETDEWEB)

    Kula, I. [Department of Chemistry, Mugla University, 48000 Mugla (Turkey); Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Arslan, Y. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Department of Chemistry, Atatuerk University, 25240 Erzurum (Turkey); Bakirdere, S. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Department of Chemistry, Zonguldak Karaelmas University, 67100 Zonguldak (Turkey); Ataman, O.Y. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)], E-mail: ataman@metu.edu.tr

    2008-08-15

    A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. Gold coating on W-coil was prepared by using an organic solution of Au. The atom trap is held at 165 {sup o}C during the collection stage and is heated up to 675 deg. C for revolatilization; analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. The carrier gas consisted of 112.5 ml min{sup -1} Ar with 75 ml min{sup -1} H{sub 2} during the collection step and 112.5 ml min{sup -1} Ar with 450 ml min{sup -1} H{sub 2} in the revolatilization step. The half width of the transient signal obtained is less than 0.5 s. The RSD for the measurements was found to be 3.9% (n = 11) for 0.10 {mu}g l{sup -1} Se using peak height measurements. The calibration plot for 27.0 ml of sample collected in 4.0 min using a flow rate of 6.75 ml min{sup -1} was linear between 0.13 and 2.0 {mu}g l{sup -1} of Se. The limit of detection (3 s) is 39 ng l{sup -1}. The enhancement factor for the characteristic concentration (C{sub o}) was found to be 20.1 when compared to conventional hydride generation atomic absorption spectrometry system without trap. In order to check the accuracy of the method, standard reference material, natural water NIST 1640 was employed; the result was found to be in good agreement with the certified value at the 95% confidence level.

  20. A novel analytical system involving hydride generation and gold-coated W-coil trapping atomic absorption spectrometry for selenium determination at ng l - 1 level

    Science.gov (United States)

    Kula, İ.; Arslan, Y.; Bakırdere, S.; Ataman, O. Y.

    2008-08-01

    A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. Gold coating on W-coil was prepared by using an organic solution of Au. The atom trap is held at 165 °C during the collection stage and is heated up to 675 °C for revolatilization; analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. The carrier gas consisted of 112.5 ml min - 1 Ar with 75 ml min - 1 H 2 during the collection step and 112.5 ml min - 1 Ar with 450 ml min - 1 H 2 in the revolatilization step. The half width of the transient signal obtained is less than 0.5 s. The RSD for the measurements was found to be 3.9% ( n = 11) for 0.10 µg l - 1 Se using peak height measurements. The calibration plot for 27.0 ml of sample collected in 4.0 min using a flow rate of 6.75 ml min - 1 was linear between 0.13 and 2.0 µg l - 1 of Se. The limit of detection (3 s) is 39 ng l - 1 . The enhancement factor for the characteristic concentration ( Co) was found to be 20.1 when compared to conventional hydride generation atomic absorption spectrometry system without trap. In order to check the accuracy of the method, standard reference material, natural water NIST 1640 was employed; the result was found to be in good agreement with the certified value at the 95% confidence level.

  1. 高效液相色谱氢化物发生原子荧光光谱联用检测海藻中砷形态%Determination of arsenic speciation in seaweeds using high performance liquid chromatography-ultraviolet photo-oxidation-hydride generation-atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    高鹭; 董伟峰; 彭心婷; 史立娟; 李妍; 庞艳华; 徐静; 曹际娟

    2015-01-01

    目的:测定14种海藻样品中总砷和无机砷的含量,同时分析样品中6种砷形态。方法将海藻样品经过微波消解的前处理方法,通过电感耦合等离子体质谱(inductively coupled plasma mass spectrometry, ICP-MS)测定总砷含量;根据国标方法中无机砷检测的前处理方法,通过原子荧光光谱(atomic fluorescence spectrometry, AFS)测定无机砷含量;最后通过酸提的前处理方法,利用高效液相色谱-氢化物发生-原子荧光光谱法(high performance liquid chromatography-ultraviolet photo-oxidation-hydride generation-atomic fluorescence spectrometry, HPLC-(UV)-HG-AFS)测定海藻样品中6种形态砷含量并与国标无机砷方法比较。结果14种海藻样品中总砷含量为0.038~46.2 mg/kg;无机砷含量为0.006~19.3 mg/kg;对HPLC-(UV)-HG-AFS仪器的优化和方法的摸索后,从海藻样品中主要测得的砷形态为As(III)、As(V)和DMA, MMA含量较少,没有测出AsB和 AsC。结论在砷形态较为复杂的海藻样品检测中,通过 HPLC-(UV)-HG-AFS 检测方法可以有效避免无机砷前处理中可能出现的有机砷向无机砷转变的现象,降低干扰,增加测试的准确性,更为具体地表现海藻样品中主要的砷形态含量。%Objective The content of total arsenic and inorganic arsenic were determined in 14 seaweeds and 6 kinds of arsenic species were determined at the same time. Methods The content of total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS) after microwave digestion. According to the pretreatment method of national standard method, the content of inorganic arsenic was determined by atomic fluorescence spectrometry (AFS). The results of 6 arsenic species were studied by high performance liquid chromatography-ultraviolet photo-oxidation-hydride generation-atomic fluorescence spectrometry (HPLC-(UV)-HG-AFS) after acid extraction, which were compared with the national standard method. Results In 14

  2. 人血和尿中锡的高压微波络合消解氢化物发生-原子荧光测定法%Determination of tin in human blood and urine with high-pressure microwave digestion and complexing ligand and hydride generation-atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    陈峰; 谢超

    2013-01-01

    Objective To establish the hydride generation-atomic fluorescence spectrometric method for the determination of tin in human blood and urine with high-pressure microwave digestion and complexing ligand.Methods Human blood and urine samples were digested by using high-pressure microwave.Then complexing ligand 1% EDTA,5 ml 150 g/L thiourea and ascorbic acid were added to mask the interfering ions such as nickel,iron,arsenic,selenium and etc.Tin concentration was determined with hydride-generation atomic fluorescence spectrometric method with sodium borohydride as the reductant in 2% sulphuric acid media.Results The linear range of tin was 10-100 μg/ml,the regression equations and correlation coefficients in blood and urine were y=9.391 1 x-16.312,r=0.999 7,y=8.244 7x-27.849 6,r=0.998 2,respectively.The limits of detection of tin in blood and urine were 0.090,0.020 μg/L respectively.The relative standard derivation of this method was 1.4%-6.1%.The rates of recovery were between 98.1% and 101.8%.Conclusion This method presents many advantages,such as completed sample digestion,rapid,less matrix disturbance,accurate,sensitive and is applicable to the determination of tin in blood and urine in grass-roots units.%目的 建立人血、尿中锡的高压微波络合消解氢化物发生-原子荧光测定法.方法 利用高压微波络合消解已加入1% EDTA溶液的人血和尿液,在样品测定液中加入150 g/L硫脲-抗坏血酸5ml来掩蔽镍、铁、砷、硒等干扰离子;以2%硫酸作为介质,以2%的硼氢化钠溶液作为还原剂,采用氢化物发生-原子荧光法测定锡浓度.结果 在10~100 μg/ml的线性范围内,血中锡所得回归方程为y=9.391 1x-16.312,r=0.999 7;尿中锡所得回归方程为y=8.244 7x-27.849 6,r=0.998 2.血、尿中锡的检出限分别为0.090、0.020 μg/L.该方法的RSD为1.4%~6.1%,回收率在98.1%~101.8%之间.结论 该方法样品消解完全,测定时间短,待测元素

  3. 微波消解-氢化物原子荧光光谱法测定粤东地区海产品中砷的研究%Determination of Arsenic in Seafood by Hydride Generation-atomic Fluorescence Spectrometry Combined with Microwave Oven Digestion

    Institute of Scientific and Technical Information of China (English)

    蔡龙飞; 徐春秀; 张应钦; 邱新红

    2011-01-01

    [目的]建立一种测定海产品中微量砷的有效方法.[方法]采用微波消解-氢化物原子荧光光谱法测定了粤东地区海产品中砷的含量.[结果]砷在1.0~50.0μg/L范围内线性关系良好,相关系数为0.995,方法的检出限为0.02107μg/L,相对标准偏差为0.932%.部分海产品的含砷量超过国家标准,其超标原因可能与沿海地区的工业污染有关.[结论]该方法试剂用量少、污染小、简便、快速、准确,适于各类海产品中砷含量的检测.%[Objective] The aim was to establish an effective determination method of arsenic in seafood. [Method] Contents of arsenic in seafood samples from eastern Guangdong area were determined by hydride generation-atomic fluorescence spectrometry combined with microwave oven digestion. [Result] The linear range for detection of arsenic was 1.0- 50.0 μg/L, which showed a good linear relationship,and its correlation coefficient was 0.995. The detection limit and relative standard deviation were 0.021 07 μg/L and 0.932% .respectively. Contents of arsenic in some seafood samples were more than the national standard,which could be caused by industrial pollution in coastal areas. [Conclusion] The method is simple,rapid and accurate,so it is applied to the determination of arsenic in seafood samples.

  4. Determination of As,Hg and Cd in FAPAS Canned Fish in UK by Hydride Generation-Atomic Fluorescence Spectrometry%氢化物-原子荧光光谱法测定英国FAPAS鱼罐头中砷汞镉

    Institute of Scientific and Technical Information of China (English)

    叶海辉; 谢德芳; 谢轶; 吴学进

    2012-01-01

    [Objective] To prove that the determination of As, Hg and Cd by the hydride generation-atomic fluorescence spectrometry (HG-AFS) has reached the international level of advanced detection instrument. [ Method] The parameters and testing methods of the HG-AFS were optimized. Through the testing of samples and the recovery test, a set of methods were established for determining the three elements in FAPAS canned fish. [Result] By comparing the detection report provided by FAPAS with the results of multiple laboratories, the Z value was -0.2 for As, 0. 5 for Hg, and 0.4 for Cd, the evaluation of results was satisfactory. [ Conclusion] It is feasible'to apply the HG-AFS method for the determination of As, Hg and Cd in seafood products.%[目的]证实原子荧光仪对这砷汞镉3种元素的检测已达到国际先进检测仪器的水平.[方法]利用氢化物-原子荧光光谱法,优化仪器条件参数和试验方法,通过测试质控样品与加标回收试验,建立一套测试英国FAPAS鱼罐头中砷汞镉的方法.[结果]根据FAPAS提供回来的检测报告,与全球众多实验室比对的结果为:砷的Z值为-0.2,汞的Z值为0.5,镉的Z值为0.4,对结果的评价为很满意.[结论]应用氢化物-原子荧光光谱法对海产品中砷汞镉进行检测是可行的.

  5. Activity and Stability of Rare Earth-Based Hydride Alloys as Catalysts of Hydrogen Absorption-Oxidation Reactions

    Institute of Scientific and Technical Information of China (English)

    Ying Taokai(应桃开); Gao Xueping(高学平); Hu Weikang(胡伟康); Noréus Dag

    2004-01-01

    Rare earth-based AB5-type hydrogen storage alloys as catalysts of hydrogen-diffusion electrodes for hydrogen absorption and oxidation reactions in alkaline fuel cells were investigated. It is demonstrated that the meta-hydride hydrogen-diffusion electrodes could be charged by hydrogen gas and electrochemically discharged at the same time to retain a stable oxidation potential for a long period. The catalytic activities and stability are almost comparable with a Pt catalyst on the active carbon. Further improvement of performances is expected via reduction of catalyst size into nanometers.

  6. Arsenic speciation by hydride generation-quartz furnace atomic absorption spectrometry. Optimization of analytical parameters and application to environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Molenat, N.; Astruc, A.; Holeman, M.; Pinel, R. [Laboratoire de Chimie Analytique Bioinorganique et Environnement, Dept. de Chimie, Faculte des Sciences et Techniques, 64 - Pau (France); Maury, G. [Montpellier-2 Univ., 34 (France). Dept. de Chimie Organique Fine

    1999-11-01

    Analytical parameters of hydride generation, trapping, gas chromatography and atomic absorption spectrometry detection in a quartz cell furnace (HG/GC/QFAAS) device have been optimized in order to develop an efficient and sensitive method for arsenic compounds speciation. Good performances were obtained with absolute detection limits in the range of 0.1 - 0.5 ng for arsenite, arsenate, mono-methyl-arsonic acid (MMAA), dimethyl-arsinic acid (DMAA) and trimethyl-arsine oxide (TMAO). A pH selective reduction for inorganic arsenic speciation was successfully reported. Application to the accurate determination of arsenic compounds in different environmental samples was performed. (authors)

  7. Herschel/HIFI detections of hydrides towards AFGL 2591. Envelope emission versus tenuous cloud absorption

    DEFF Research Database (Denmark)

    Bruderer, S.; Benz, A. O.; van Dishoeck, E. F.

    2010-01-01

    The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel Space Observatory allows the first observations of light diatomic molecules at high spectral resolution and in multiple transitions. Here, we report deep integrations using HIFI in different lines of hydrides towards the h...

  8. Determination of inorganic arsenic in coal by hydride generation atomic fluorescence spectrometry combined with ultrasonic extraction%超声提取-顺序注射氢化物发生-原子荧光光谱法测定煤中无机砷

    Institute of Scientific and Technical Information of China (English)

    王长芹; 刘贵勤

    2011-01-01

    A determination method of inorganic arsemc in coal was established by sequence injection hydride generation-atomic fluorescence spectrometry ( HG-AFS) , after the ultrasonic extraction with 6 mol/L HCl as extraction reagent. The ultrasonic extraction conditions were optimized, including extraction reagent, time and temperature. Under the optimized experimental condition, arsemc in concentration range of 0. 20-100 μg/L showed linearity to the fluorescence intensity with correlation coefficient of 0. 999 7. The detection limit of arsenic was 0. 025 μg/L. The relative standard deviation (RSD) for 10 μg/L As was 0. 9 % (n=11). The proposed method has been applied to the analysis of coal fly ash component analysis certified reference material (GBW08401) and coal samples with recoveries of 95%-102 %, and the result of GBW08401 was consist with the certified value.%利用6 mol/L盐酸作为提取试剂,样品经超声提取后,用顺序注射氢化物发生-原子荧光光谱法测定煤中无机砷的含量.对超声提取条件(提取试剂浓度、时间、温度)进行了优化.在优化的实验条件下,砷的浓度在0.20~100μg/L范围内与荧光强度呈线性关系,相关系数为0.999 7,砷的检出限为0.025μg/L,对10 μg/L砷标准溶液进行重复11次测量,得出相对标准偏差(RSD)为0.9%.用该法对煤飞灰成分分析标准物质GBW08401和煤样进行分析,测得回收率在95%~102%之间,标准样品的测定值和认定值相符.

  9. 氢化物发生-原子荧光光谱法直接测定土壤水溶态Sb(Ⅲ)和Sb(Ⅴ)%Direct Determination of Water-Soluble Antimony(Ⅲ) and Antimony(Ⅴ) in Soil by Hydride Generation Atomic Fluorescence Spectrometry

    Institute of Scientific and Technical Information of China (English)

    于兆水; 张勤

    2009-01-01

    在HCl介质中,Sb(Ⅲ)和Sb(Ⅴ)在氢化物发生过程中的化学反应效率不同,通过测定经还原剂还原后和还原前Sb的荧光强度,求解联立方程计算出Sb(Ⅲ)和Sb(Ⅴ)的含量,据此建立了氧化物发生-原子荧光光谱法直接测定土壤水溶态Sb(Ⅲ)和Sb(Ⅴ)方法,操作简便,实用性强.考察了 HCl浓度和KBH_4浓度对Sb(Ⅲ)和Sb(Ⅴ)测定灵敏度的影响以及共存元素的干扰情况,并比较了丽种还原剂对Sb(Ⅴ)的还原效果.方法检出限为Sb(Ⅲ)1.11 ng·g~(-1),Sb(Ⅴ)1.57 ng·g~(-1).加标回收试验表明方法准确、可靠.%A simple, rapid and useful method for the determination of water-soluble antimony( Ⅲ ) and antimony(Ⅴ) in soil was established using hydride generation atomic fluorescence spectrometry. The method was based on the different chemical reaction efficiency between Sb( Ⅲ ) and Sb( Ⅴ ) with KBH_4 in the media of HCL The amounts of Sb( Ⅲ) and Sb( Ⅴ ) can be obtained through measuring antimony fluorescence intensities before and after reduction with reductant. The effects of HCI and KBH_4 on the sensitivities of Sb(Ⅲ) and Sb(Ⅴ) were investigated, and the interferences from coexistent elements were studied. The re-duction efficiencies of both reductants were compared. The detection limits of the method were 1.11 ng·g~(-1) for Sb( Ⅲ ) and 1.57 ng·g~(-1) for Sb( Ⅴ ). The accuracy of the method was verified by recovery experiments on spiked real soil samples.

  10. Determination of Lead in Tea Garden Soil by Hydride Generation Atomic Fluorescence Spectrometry with Microwave Digestion%微波消解-氢化物发生原子荧光光谱法测定茶园土壤中的铅

    Institute of Scientific and Technical Information of China (English)

    凤海元; 时晓露; 黄勤

    2013-01-01

    样品用王水微波消解浸提,氢化物发生-原子荧光光谱法测定茶园土壤中痕量铅的含量.对样品浸取方法、实验条件、增感剂和共存元素进行了条件实验.结果表明,王水微波消解浸取,铅浸出量最大,减少了试剂用量和环境污染;铁氰化钾-盐酸羟胺体系有显著的增感作用,铁氰化钾在配制溶液时用米糠除去试剂中可能存在的铅,降低了空白;钴、锌、砷、镉等共存离子不干扰铅的测定,通过加入邻菲啰啉-硫氰酸钠消除铁和铜的干扰,提高了铅的回收率.方法检出限为0.65 μg/L,精密度(RSD,n=10)为1.89%,回收率在86.8% ~ 110.4%之间.用土壤标准物质验证,测定值与标准值相符,方法快速准确,适合于大批量样品的分析检测.%The microwave digestion system with aqua regia was developed for the determination of trace lead in tea garden soil using Hydride Generation-Atomic Fluorescence Spectrometry ( HG-AFS). The leaching methods, experimental conditions, booster and coexisting element were optimized. The largest amount of lead was leached out by microwave digestion with aqua regia, which has the advantages of less usage of reagent and less environmental pollution. An appropriate amount of potassium ferricyanide and hydroxylamine hydrochloride improved the hydride generation efficiency of Pb. The lead blank was reduced significantly when Potassium ferricyanide solution was treated with rice husk to remove Pb in the reagent. It was found that Co, Zn, As, and Cd did not interfere with the determination of lead. The addition of 1,10-phenanthroline monohydrate and sodium hydrosulfide could effectively eliminate the interferences from Fe and Cu, which improved the recovery rate of lead. The limit of detection was 0. 65 μg/L and the precision was 1. 89% (n = 10) with recoveries of 86. 8% - 110. 4% for Pb. The reliability of the method has been tested by determination of Pb in the Soils Standard Reference

  11. Design and evaluation of a continuous flow, integrated nebulizer-hydride generator for flame atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    Miguel Murillo

    2008-01-01

    Full Text Available An evaluation of the performance of a continuous flow hydride generator-nebulizer for flame atomic absorption spectrometry was carried out. Optimization of nebulizer gas flow rate, sample acid concentration, sample and tetrahydroborate uptake rates and reductant concentration, on the As and Se absorbance signals was carried out. A hydrogen-argon flame was used. An improvement of the analytical sensitivity relative to the conventional bead nebulizer used in flame AA was obtained (2 (As and 4.8 (Se µg L-1. Detection limits (3σb of 1 (As and 1.3 (Se µg L-1 were obtained. Accuracy of the method was checked by analyzing an oyster tissue reference material.

  12. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  13. Determination of Water Soluble As ( Ⅲ ) and As ( Ⅴ ) in Soil by Hydride Generation-Atomic Fluorescence Spectrometry%氢化物发生-原子荧光光谱法测定土壤中水溶态砷(Ⅲ)和砷(Ⅴ)

    Institute of Scientific and Technical Information of China (English)

    于兆水; 张勤; 刘玲

    2012-01-01

    以氢气发生器为氩-氢火焰提供纯净、稳定的氢气,原子荧光光谱法测定土壤中水溶态和可交换态Sb(Ⅲ)和Sb(Ⅴ)已有应用,本研究进一步将此方法用于测定土壤样品中的As(Ⅲ)和As(Ⅴ).在0.3mol/L NaH2PO4 - Na2HPO4缓冲液中,采用氢化物发生-原子荧光光谱法测定土壤中水溶态As(Ⅲ)和总砷的含量,通过差减法计算As(Ⅴ)的含量.实验考察了0.02~0.4 mol/L NaH2PO4 - Na2 HPO4对As(Ⅲ)和As(Ⅴ)测定的影响,结果表明0.3 mol/L NaH2PO4 - Na2HPO4可以有效掩蔽As(Ⅴ).As(Ⅲ)的检出限为2.92 ng/g,总砷的检出限为2.35 ng/g;As(Ⅲ)和As(Ⅴ)的加标回收率分别为96% ~ 104%和101% ~103%.本方法不再依靠化学反应产生氢气来点燃并维持氩氢火焰,可在发生氢化反应的任何介质中测定砷,且不需要考虑酸度问题.方法操作简便,准确度高,能满足大批量样品分析要求.%Based on the determination method of Sb ( HI) and Sb ( V ) in soil, a method for the determination of water soluble As ( M ) and total arsenic in soil has been established by using Hydride Generation-Atomic Fluorescence Spectrometry (HG-AFS) in the media of 0. 3 mol/L NaH2PO4-Na2HPO4. An amount of As( V ) was obtained by subtracting As( HI ) from total arsenic. The hydrogen was provided from a hydrogen generator instead of chemical reaction to ignite a H2-Ar flame. Therefore, arsenic in any media was measurable since the arsenic was reduced into AsH3. Effects on the determination of As ( M ) and As ( V ) were investigated for concentrations of NaH2PO4-Na2HPO4 from 0. 02 mol/L to 0. 4 mol/L. The results show As( V ) can be screened by 0. 3 mol/L NaH2PO4-Na2HPO4. The detection limits were 2. 92 ng/g for As( HJ ) and 2. 35 ng/g for total As. The recoveries of As( HI) and As( V ) are 96% - 104% and 101% - 103% , respectively. The method was simple and highly accurate, meeting the requirements for multiple sample analysis.

  14. THE DETERMINATION OF ANTIMONY (Ⅲ) AND ANTOMONY (Ⅴ) IN GEOLOGICAL SAMPLES BY HYDRIDE GENERATION-ATOMIC FLUORESCENCE SPECTROMETRY%氢化物发生—原子荧光光谱法测定地质样品中的锑(Ⅲ)和锑(Ⅴ)

    Institute of Scientific and Technical Information of China (English)

    郝志红; 杨帆; 刑夏; 汤志勇; 张勤

    2012-01-01

    A method for the determination of antimony ( Ⅲ ) and antimony ( V ) in geological samples (stream sediments) by hydride generation-atomic fluorescence spectrometry was developed in the paper. 4. 8 mol/L HC1 could be used as the extraclant with ultrasonic-assisted extraction. In the medium of 0. 24 mol/L hydrochloric acid, antimony ( Ⅲ) could be alternatively determined with 6 g/mL sodium citrate as the masking agent for Sb (V). Then antimony ( V ) could be figured out by the subtraction method. The detection limit of the method was 0. 075 × 10 -6 for Sb ( 1) and 0. 097 × 10 -6 for Sb ( V ) , and the relative standard deviation was 1. 1 % and 0. 64% ( n = 11) for 40 ng/mL Sb ( Ⅲ ) and 40 ng/mL Sb( V ) standard solution. The proposed method was applied to the determination of antimony ( Ⅲ) and antimony ( V ) in geological samples, and a comparison between the extraction results and the aqua regia dissolution results shows that the extraction rate of antimony was higher than 80% , the recoveries were in the ranges of 83% - 107% and 98% -114% for Sb ( Ⅲ) and Sb (V) respectively.%提出了一种氢化物发生—原子荧光光谱法测定地质样品(水系沉积物)中Sb(Ⅲ)和Sb(Ⅴ)的方法.选取4.8 mol/L HC1为提取剂,采用超声波辅助提取,以6 g/mL柠檬酸钠作为Sb(Ⅴ)的掩蔽剂,在0.24 mol/L的HC1介质中选择性测定Sb(Ⅲ),用差减法求得Sb(Ⅴ).Sb(Ⅲ)的方法检出限为0.075×10-6,Sb(Ⅴ)的方法检出限为0.097×10-6.对40 ng/mL的Sb(Ⅲ)和Sb(Ⅴ)分别连续测定11次,得到相对标准偏差分别为1.1%和0.64%.应用该方法对地质样品中的Sb(Ⅲ)和Sb(Ⅴ)进行分析测定,并与王水溶解值相比较,该方法测定的总Sb提取率在80%以上,Sb(Ⅲ)和Sb(Ⅴ)的加标回收率分别为83% ~ 107%和98% ~ 114%.

  15. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  16. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of antimony by automated-hydride atomic absorption spectrophotometry

    Science.gov (United States)

    Brown, G.E.; McLain, B.J.

    1994-01-01

    The analysis of natural-water samples for antimony by automated-hydride atomic absorption spectrophotometry is described. Samples are prepared for analysis by addition of potassium and hydrochloric acid followed by an autoclave digestion. After the digestion, potassium iodide and sodium borohydride are added automatically. Antimony hydride (stibine) gas is generated, then swept into a heated quartz cell for determination of antimony by atomic absorption spectrophotometry. Precision and accuracy data are presented. Results obtained on standard reference water samples agree with means established by interlaboratory studies. Spike recoveries for actual samples range from 90 to 114 percent. Replicate analyses of water samples of varying matrices give relative standard deviations from 3 to 10 percent.

  17. Actuation of Pneumatic Artificial Muscle via Hydrogen Absorption/Desorption of Metal Hydride-LaNi5

    Directory of Open Access Journals (Sweden)

    Thanana Nuchkrua

    2015-01-01

    Full Text Available This paper presents experimental studies on mechanical actuations of a pneumatic artificial muscle (PAM, which is driven by hydrogen gas based metal hydride (MH. The dynamic performances of hydrogen absorption/desorption, taking place within a MH reactor, are controlled via implementing cooling/heating effects of a thermoelectric module (TEM. Hydrogen pressure is applied as a driving force to commanding work outputs of the PAM as desired mechanical actuations. Due to strong inherent nonlinearity, a conventional proportional integral derivative (PID control law is not capable of regulating thermodynamic variables of the HM reaction according to desired performances of the PAM. In this study, the fuzzy adaptive PID control is proposed in manipulating the MH reaction via the TEM. This viability of the proposed methodology is confirmed by the fact that the gains of PID control law are adapted by fuzzy rule-based tuning scheme at various operating conditions of the MH reactor. The experimental results show that the proposed control technique is much more effective than a PID control in both transient and steady state performances of the MH reactor for servo mechanical actuation of the PAM.

  18. Quantifying uncertainty in the measurement of arsenic in suspended particulate matter by Atomic Absorption Spectrometry with hydride generator

    Directory of Open Access Journals (Sweden)

    Ahuja Tarushee

    2011-04-01

    Full Text Available Abstract Arsenic is the toxic element, which creates several problems in human being specially when inhaled through air. So the accurate and precise measurement of arsenic in suspended particulate matter (SPM is of prime importance as it gives information about the level of toxicity in the environment, and preventive measures could be taken in the effective areas. Quality assurance is equally important in the measurement of arsenic in SPM samples before making any decision. The quality and reliability of the data of such volatile elements depends upon the measurement of uncertainty of each step involved from sampling to analysis. The analytical results quantifying uncertainty gives a measure of the confidence level of the concerned laboratory. So the main objective of this study was to determine arsenic content in SPM samples with uncertainty budget and to find out various potential sources of uncertainty, which affects the results. Keeping these facts, we have selected seven diverse sites of Delhi (National Capital of India for quantification of arsenic content in SPM samples with uncertainty budget following sampling by HVS to analysis by Atomic Absorption Spectrometer-Hydride Generator (AAS-HG. In the measurement of arsenic in SPM samples so many steps are involved from sampling to final result and we have considered various potential sources of uncertainties. The calculation of uncertainty is based on ISO/IEC17025: 2005 document and EURACHEM guideline. It has been found that the final results mostly depend on the uncertainty in measurement mainly due to repeatability, final volume prepared for analysis, weighing balance and sampling by HVS. After the analysis of data of seven diverse sites of Delhi, it has been concluded that during the period from 31st Jan. 2008 to 7th Feb. 2008 the arsenic concentration varies from 1.44 ± 0.25 to 5.58 ± 0.55 ng/m3 with 95% confidence level (k = 2.

  19. Determination of Ultra-trace Amounts of Arsenic(III) by Flow Injection Hydride Generation Atomic Absorption Spectrometry with On-line Preconcentration by Coprecipitation with Lanthanum Hydroxide or Hafnium Hydroxide

    DEFF Research Database (Denmark)

    Nielsen, Steffen; Sloth, Jens Jørgen; Hansen, Elo Harald

    1996-01-01

    (III) is more effectively collected by lanthanum hydroxide than by hafnium hydroxide, the sensitivity achieved by the former being ca. 25% better. With optimal experimental conditions and with a sample consumption of 6.7 ml per assay, an enrichment factor of 32 was obtained at a sample frequency of 33 samples...

  20. 氢化物发生-原子吸收光谱法测定食品中的汞%Determination of Mereury in Food by Hydride Generation-Atomic Absorption Spectrometry

    Institute of Scientific and Technical Information of China (English)

    艾明

    2013-01-01

    研究了采用氢化物发生-原子吸收光谱法测定食品中痕量汞的方法,通过采用氢化物发生器,选择合适浓度的载流和硼氢化钾,获得了较为满意的分析结果.在测定汞含量5~20 μg/kg的食品标准样品时,测试结果相对标准偏差RSD为2.2%~3.7%,回收率为84.9%~97.5%,检出限为0.2 μg/L,完全满足食品行业汞元素痕量检测要求,操作简便、快速.

  1. Electrochemical hydride generation atomic fluorescence spectrometry with a polyanline modified electrode for detection of tin%聚苯胺修饰电极-电化学氢化物发生原子荧光光谱法测定食品中锡含量

    Institute of Scientific and Technical Information of China (English)

    姜宪娟; 淦五二

    2012-01-01

    An electrochemical hydride generation (EC-HG) system with a polyaniline modified electrode (Pan-ME) as cathode material was developed for Sn ( Ⅳ) determination by couped with atomic fluorescence spectrometry. The electrochemical hydride generation efficiency for Sn (Ⅳ) was improved evidently as the Pan membrane could obstruct the aggradation of Sn atom on cathode surface and facilitate the hydride generation. The effects of experimental parameters and interferences have been studied. The limit of detection ( LOD) was 1. 2 ng/mL (3σ) and the relative standard deviation (RSD) was 2. 3% for eleven consecutive measurements of 50 ng/mL Sn(IV) standard solution.%运用以聚苯胺修饰的石墨电极为阴极的电化学氢化物发生装置实现了锡元素的电化学氢化物发生.在电极表面聚合一层聚苯胺,能够有效地提高锡元素的电化学氢化物发生效率,通过与原子荧光光谱仪联用,成功地测定了食品中的锡含量.本工作对各种实验参数和干扰情况进行了详细研究.方法对锡的检出限为1.2 ng/mL(3σ);样品分析精密度(RSD)为2.3% (50 ng/mL,n=11).

  2. Development of an analytical method for the determination of arsenic in gasoline samples by hydride generation-graphite furnace atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Becker, Emilene M. [Universidade Federal do Pampa, Bage, RS (Brazil); Universidade Federal de Pelotas, Pelotas, RS (Brazil); Dessuy, Morgana B.; Boschetti, Wiliam [Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Av. Bento Goncalves, 9500, 91501-970 Porto Alegre, RS (Brazil); Vale, Maria Goreti R., E-mail: mgrvale@ufrgs.br [Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Av. Bento Goncalves, 9500, 91501-970 Porto Alegre, RS (Brazil); Instituto Nacional de Ciencia e Tecnologia do CNPq, INCT de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA (Brazil); Ferreira, Sergio L.C. [Instituto Nacional de Ciencia e Tecnologia do CNPq, INCT de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA (Brazil); Instituto de Quimica, Universidade Federal da Bahia, Salvador, BA (Brazil); Welz, Bernhard [Instituto Nacional de Ciencia e Tecnologia do CNPq, INCT de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA (Brazil); Departamento de Quimica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil)

    2012-05-15

    The purpose of the present work was to optimize the conditions for the determination of arsenic in gasoline with hydride generation-graphite furnace atomic absorption spectrometry after acid digestion using a full two-level factorial design with center point. The arsine was generated in a batch system and collected in a graphite tube coated with 150 {mu}g Ir as a permanent modifier. The sample volume, the pre-reduction conditions, the temperature program and modifier mass were kept fixed for all experiments. The estimated main effects were: reducing agent concentration (negative effect), acid concentration (negative effect) and trapping temperature (positive effect). It was observed that there were interactions between the variables. Moreover, the curvature was significant, indicating that the best conditions were at the center point. The optimized parameters for arsine generation were 2.7 mol L{sup -1} hydrochloric acid and 1.6% (w/v) sodium tetrahydroborate. The optimized conditions to collect arsine in the graphite furnace were a trapping temperature of 250 Degree-Sign C and a collection time of 30 s. The limit of detection was 6.4 ng L{sup -1} and the characteristic mass was 24 pg. Two different systems for acid digestion were used: a digester block with cold finger and a microwave oven. The concentration of arsenic found with the proposed method was compared with that obtained using a detergentless microemulsion and direct graphite furnace determination. The results showed that the factorial design is a simple tool that allowed establishing the appropriate conditions for sample preparation and also helped in evaluating the interaction between the factors investigated. - Highlights: Black-Right-Pointing-Pointer We determined As in gasoline using hydride generation-graphite furnace AAS. Black-Right-Pointing-Pointer We compared three sample preparation procedures. Black-Right-Pointing-Pointer A multivariate approach was used to optimize the conditions. Black

  3. Determination of Mercuryalkylide in Water Using High Performance Liquid Chromatography with Hydride Generation Atomic Fluorescence Detection%高效液相色谱-氢化物发生-原子荧光光谱联用技术测定水中烷基汞

    Institute of Scientific and Technical Information of China (English)

    陈邵鹏; 顾海东; 秦宏兵

    2012-01-01

    A method for the determination of Mercury species in both surface water and waste water was established by high performance liquid chromatography ( HPLC ) -hydride generation ( HG) -atomic fluorescence spectrophotometry ( AFS). Sample was extracted by dichloromethane, subsequently back-extracted by mixed extractant containing cysteine and ammonium acetate before HPLC-HG-AFS detection. Under the optimized conditions, both methyl mercury and ethyl mercury responded linearly in the concentration of 1-50μg/L. The recoveries for both standard samples and actual samples were 80%-110%. The relative standard deviations for the determination of methyl and ethylmercury with the concentration of 1μg/L were 5. 2% and 3. 9% , respectively. The detection limits for them were 0.4 ng/L and 0.7 ng/L, respectively with the American EPA methord. The proposed method is of good accuracy, high repeatability, precision, less interferences from impurities and low cost, which is benefit for expanding and applying in the common laboratory.%建立了高效液相色谱(HPLC)-氢化物发生(HG)-原子荧光光谱(AFS)联用技术分析地表水及废水中甲基汞和乙基汞的方法.样品经二氯甲烷萃取,再以半胱氨酸+乙酸铵溶液反萃取富集,并进入高效液相色谱分离,经形态分析预处理装置后,借助原子荧光光谱法检测.在优化分离条件下,甲基汞和乙基汞在1 ~ 50 μg/L范围内呈现良好的线性关系,对于标准水样、地表水和废水实际水样,加标平均回收率均为80% ~ 110%.平行进样7次1μg/L的汞混合标准溶液,甲基汞和乙基汞的色谱峰面积的相对标准偏差分别为5.2%和3.9%,检出限则分别为0.4 ng/L和0.7 ng/L.该检测方法前处理简单、回收率稳定、灵敏度和准确度高、检出限低、杂质干扰少、监测费用低,便于在普通实验室推广和应用.

  4. Determination of arsenic in antimony ingot and antimony trioxide by hydride generation-atomic fluorescence spectrometry%氢化物发生-原子荧光光谱法测定锑锭及三氧化二锑中的砷

    Institute of Scientific and Technical Information of China (English)

    钱光敏; 赵国杏

    2012-01-01

    The antimony slab and antimonous oxide samples were dissolved by sulfuric acid and hydrochloric acid, respectively. The Sb3+ in solution was precipitated with sodium hydroxide to separate trace arsenic from matrix antimony. The thiourea-ascorbic acid was added to reduce As5+ to As3+. Then, the arsenic in antimony slab and antimonous oxide was determined by atomic fluorescence spec-trometry. The hydride generation conditions were investigated: the concentration of reducing agent potassium borohydride was 25 g/L, the determination medium was 20% (V/V) hydrochloric acid, and the dosage of thiourea - ascorbic acid solution was 5 mL. The interference test of coexisting elements showed that, the interference of residual antimony in solution after precipitation could be fully eliminated by adding 1 mL of tartaric acid solution. Other impurity elements in sample did not interfere with the determination of arsenic after adding thiourea-ascorbic acid solution. The detection limit of method was 0. 156 ng/mL. The antimony slab and antimonous oxide samples were analyzed by the proposed method, and the relative standard deviation (RSD) was 0. 95%-1.2%. The determination results were consistent with those obtained by national standard methods.%采用硫酸溶解锑锭样品,盐酸溶解三氧化二锑样品,用氢氧化钠溶液使Sb3+沉淀从而使基体锑与微量砷分离,通过加入硫脲-抗坏血酸将As5+还原成As3+,然后在原子荧光仪上测定锑锭及三氧化二锑中的砷.对氢化物发生条件进行考察,确定还原剂硼氢化钾的浓度为25 g/L、测定介质为20%(V/V)盐酸、硫脲-抗坏血酸溶液用量为5 mL.共存元素干扰试验表明,沉淀后溶液中残留少量锑的干扰在加入1 mL酒石酸溶液后可以完全消除,而样品中其他杂质元素在加入硫脲-抗坏血酸溶液后不干扰砷的测定.方法的检出限为0.156 ng/mL.对锑锭及三氧化二锑样品进行分析,相对标准偏差为0.95%~1.2%,测定

  5. SPE speciation of inorganic arsenic in rice followed by hydride-generation atomic fluorescence spectrometric quantification

    Science.gov (United States)

    Due to high toxicity, inorganic arsenics (iAs) are the focus of monitoring effort worldwide. In this work, extraction was performed by microwave-assisted digestion in HCl-H2O2, during which AsIII was oxidized to AsV. AsV was separated from organoarsenic species using silica-based SAX cartridge and r...

  6. Arsenic species analysis in porewaters and sediments using hydride generation atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    LIAO Meng-xia; DENG Tian-long

    2006-01-01

    It was observed that the atomic fluorescence emission due to As(Ⅴ) could has a 10% to 40% of fluorescence emission signal during the determination of As(Ⅲ) in the mixture of As(Ⅲ) and As(Ⅴ). Besides, interferes from heavy metals such as Pb(Ⅱ),Cu(Ⅱ) can cause severe increase of the signals as compared to the insignificant effects caused by Cd(Ⅱ), Zn(Ⅱ), Mn(Ⅱ) and Fe(Ⅲ). On the basis of further studies, the masking agent of 8-hydroxyquinoline was used as an efficient agent to eliminate interference of As(Ⅴ)emission and the heavy metal of Cu2+ and Pb2+ in the measurements of arsenic species. After a series standard additions and CRM researches, a sensitive and interference-free analytical procedure was developed for the speciation of arsenic in samples ofporewaters and sediments in Poyang Lake, China.

  7. Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry.

    Science.gov (United States)

    Shaltout, Abdallah A; Castilho, Ivan N B; Welz, Bernhard; Carasek, Eduardo; Martens, Irland B Gonzaga; Martens, Andreas; Cozzolino, Silvia M F

    2011-09-15

    The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L(-1) Se and 101 ng L(-1) Se, respectively, corresponding to about 3 ng g(-1) and 10 ng g(-1), respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5±0.4 ng g(-1) and 1726±55 ng g(-1), and that in soil samples varied between 113±6.5 ng g(-1) and 1692±21 ng g(-1).

  8. On the optical absorption coefficient of Gd hydride thin films: coexistence of the Gd (GdH{sub 2}) and GdH{sub x} (GdH{sub 2+y}) phases

    Energy Technology Data Exchange (ETDEWEB)

    Vargas, W E; Azofeifa, D E; Clark, N [Centro de Investigacion en Ciencias e IngenierIa de Materiales and Escuela de Fisica, Universidad de Costa Rica, 2060 San Jose (Costa Rica)], E-mail: william.vargascastro@ucr.ac.cr

    2009-01-07

    Electron beam evaporated Pd-capped Gd thin films were deposited on quartz substrates and subsequently hydrided. Transmittance spectra of these bilayer systems, under unpolarized normal illumination, were obtained and used in an inversion approach from which the spectral dependence of the effective optical constants is obtained. The optical absorption coefficient of the {beta}-phase GdH{sub x} (with 1 < x {<=} 2) is reported. The semiconductor GdH{sub 2+y} state (with 0 < y {<=} 1) is characterized in terms of the optical absorption coefficient and the optical gap. By assuming a granular morphology of the films, with some of the grains in the metal GdH{sub 2} phase and other grains covered with a transition layer containing the semiconducting GdH{sub 2+y} phase, the hydrogen concentration dependence of the optical gap is shown and the optical absorption edge of the stoichiometric {gamma}-phase GdH{sub 3} is reported.

  9. Boron Hydrides

    Science.gov (United States)

    1946-07-01

    of direct interest could be b.P.4d. ’Thus the discovory of a now proj.ect, since silano is probably too readily infla-zmablo for practical usc’ this...devoted, ho specc4fie compounds vhitih a’-ould be tocdte at prescnt arc: nron tiy * silano , %;2.SiFi3 , diothyl sila~no, (C2 115 )2 Si112, mono r.-rop; ! (n...Bcrohydrido or Li h.... I .A-4A- The prepuation of Silano med of Stannane by the interaction or lithium aluzirun hydride v-ithl silicon tetrtchiorido and

  10. Flow injection-chemical vapor generation atomic fluorescence spectrometry hyphenated system for organic mercury determination: A step forward

    Energy Technology Data Exchange (ETDEWEB)

    Angeli, Valeria [National Research Council of Italy, C.N.R., Istituto di Chimica dei Composti Organo Metallici - ICCOM-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy); Biagi, Simona [National Research Council of Italy, C.N.R., Istituto per i Processi Chimico-Fisici - IPCF-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy); Ghimenti, Silvia [University of Pisa, Department of Chemistry and Industrial Chemistry, Via Risorgimento 35, 56126 Pisa (Italy); Onor, Massimo; D' Ulivo, Alessandro [National Research Council of Italy, C.N.R., Istituto di Chimica dei Composti Organo Metallici - ICCOM-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy); Bramanti, Emilia, E-mail: bramanti@pi.iccom.cnr.it [National Research Council of Italy, C.N.R., Istituto di Chimica dei Composti Organo Metallici - ICCOM-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy)

    2011-11-15

    Monomethylmercury and ethylmercury were determined on line using flow injection-chemical vapor generation atomic fluorescence spectrometry without neither requiring a pre-treatment with chemical oxidants, nor UV/MW additional post column interface, nor organic solvents, nor complexing agents, such as cysteine. Inorganic mercury, monomethylmercury and ethylmercury were detected by atomic fluorescence spectrometry in an Ar/H{sub 2} miniaturized flame after sodium borohydride reduction to Hg{sup 0}, monomethylmercury hydride and ethylmercury hydride, respectively. The effect of mercury complexing agent such as cysteine, ethylendiaminotetracetic acid and HCl with respect to water and Ar/H{sub 2} microflame was investigated. The behavior of inorganic mercury, monomethylmercury and ethylmercury and their cysteine-complexes was also studied by continuous flow-chemical vapor generation atomic fluorescence spectrometry in order to characterize the reduction reaction with tetrahydroborate. When complexed with cysteine, inorganic mercury, monomethylmercury and ethylmercury cannot be separately quantified varying tetrahydroborate concentration due to a lack of selectivity, and their speciation requires a pre-separation stage (e.g. a chromatographic separation). If not complexed with cysteine, monomethylmercury and ethylmercury cannot be separated, as well, but their sum can be quantified separately with respect to inorganic mercury choosing a suitable concentration of tetrahydroborate (e.g. 10{sup -5} mol L{sup -1}), thus allowing the organic/inorganic mercury speciation. The detection limits of the flow injection-chemical vapor generation atomic fluorescence spectrometry method were about 45 nmol L{sup -1} (as mercury) for all the species considered, a relative standard deviation ranging between 1.8 and 2.9% and a linear dynamic range between 0.1 and 5 {mu}mol L{sup -1} were obtained. Recoveries of monomethylmercury and ethylmercury with respect to inorganic mercury were

  11. Flow injection-chemical vapor generation atomic fluorescence spectrometry hyphenated system for organic mercury determination: A step forward

    Science.gov (United States)

    Angeli, Valeria; Biagi, Simona; Ghimenti, Silvia; Onor, Massimo; D'Ulivo, Alessandro; Bramanti, Emilia

    2011-11-01

    Monomethylmercury and ethylmercury were determined on line using flow injection-chemical vapor generation atomic fluorescence spectrometry without neither requiring a pre-treatment with chemical oxidants, nor UV/MW additional post column interface, nor organic solvents, nor complexing agents, such as cysteine. Inorganic mercury, monomethylmercury and ethylmercury were detected by atomic fluorescence spectrometry in an Ar/H 2 miniaturized flame after sodium borohydride reduction to Hg 0, monomethylmercury hydride and ethylmercury hydride, respectively. The effect of mercury complexing agent such as cysteine, ethylendiaminotetracetic acid and HCl with respect to water and Ar/H 2 microflame was investigated. The behavior of inorganic mercury, monomethylmercury and ethylmercury and their cysteine-complexes was also studied by continuous flow-chemical vapor generation atomic fluorescence spectrometry in order to characterize the reduction reaction with tetrahydroborate. When complexed with cysteine, inorganic mercury, monomethylmercury and ethylmercury cannot be separately quantified varying tetrahydroborate concentration due to a lack of selectivity, and their speciation requires a pre-separation stage (e.g. a chromatographic separation). If not complexed with cysteine, monomethylmercury and ethylmercury cannot be separated, as well, but their sum can be quantified separately with respect to inorganic mercury choosing a suitable concentration of tetrahydroborate (e.g. 10 - 5 mol L - 1 ), thus allowing the organic/inorganic mercury speciation. The detection limits of the flow injection-chemical vapor generation atomic fluorescence spectrometry method were about 45 nmol L - 1 (as mercury) for all the species considered, a relative standard deviation ranging between 1.8 and 2.9% and a linear dynamic range between 0.1 and 5 μmol L - 1 were obtained. Recoveries of monomethylmercury and ethylmercury with respect to inorganic mercury were never less than 91%. Flow injection

  12. Numerical simulation and performance test of metal hydride hydrogen storage system

    Directory of Open Access Journals (Sweden)

    Tzu-Hsiang Yen, Bin-Hao Chen, Bao-Dong Chen

    2011-05-01

    Full Text Available Metal hydride reactors are widely used in many industrial applications, such as hydrogen storage, thermal compression, heat pump, etc. According to the research requirement of metal hydride hydrogen storage, the thermal analyses have been implemented in the paper. The metal hydride reaction beds are considered as coupled cylindrical tube modules which combine the chemical absorption and desorption in metal hydride. The model is then used metal hydride LaNi5 as an example to predict the performance of metal hydride hydrogen storage devices, such as the position of hydration front and the thermal flux. Under the different boundary condition the characteristics of heat transfer and mass transfer in metal hydride have influence on the hydrogen absorption and desorption. The researches revealed that the scroll design can improve the temperature distribution in the reactor and the porous tube for directing hydrogen can increase the penetration depth of hydride reaction to decrease the hydrogen absorption time.

  13. Properties of nanoscale metal hydrides.

    Science.gov (United States)

    Fichtner, Maximilian

    2009-05-20

    Nanoscale hydride particles may exhibit chemical stabilities which differ from those of a macroscopic system. The stabilities are mainly influenced by a surface energy term which contains size-dependent values of the surface tension, the molar volume and an additional term which takes into account a potential reduction of the excess surface energy. Thus, the equilibrium of a nanoparticular hydride system may be shifted to the hydrogenated or to the dehydrogenated side, depending on the size and on the prefix of the surface energy term of the hydrogenated and dehydrogenated material. Additional complexity appears when solid-state reactions of complex hydrides are considered and phase segregation has to be taken into account. In such a case the reversibility of complex hydrides may be reduced if the nanoparticles are free standing on a surface. However, it may be enhanced if the system is enclosed by a nanoscale void which prevents the reaction partners on the dehydrogenated side from diffusing away from each other. Moreover, the generally enhanced diffusivity in nanocrystalline systems may lower the kinetic barriers for the material's transformation and, thus, facilitate hydrogen absorption and desorption.

  14. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-01-01

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, cold,'' process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility's metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  15. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-12-31

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, ``cold,`` process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility`s metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  16. Synthesis of ruthenium hydride

    Science.gov (United States)

    Kuzovnikov, M. A.; Tkacz, M.

    2016-02-01

    Ruthenium hydride was synthesized at a hydrogen pressure of about 14 GPa in a diamond-anvil cell. Energy-dispersive x-ray diffraction was used to monitor the ruthenium crystal structure as a function of hydrogen pressure up to 30 GPa. The hydride formation was accompanied by phase transition from the original hcp structure of the pristine metal to the fcc structure. Our results confirmed the theoretical prediction of ruthenium hydride formation under hydrogen pressure. The standard Gibbs free energy of the ruthenium hydride formation reaction was calculated assuming the pressure of decomposition as the equilibrium pressure.

  17. Hysteresis in Metal Hydrides.

    Science.gov (United States)

    Flanagan, Ted B., And Others

    1987-01-01

    This paper describes a reproducible process where the irreversibility can be readily evaluated and provides a thermodynamic description of the important phenomenon of hysteresis. A metal hydride is used because hysteresis is observed during the formation and decomposition of the hydride phase. (RH)

  18. Quantitative Determination of Arsenic in Bottled Drinking Water Using Atomic Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Maria Guţu Claudia

    2013-10-01

    Full Text Available Background: Many studies have been performed in the past few years, to determine arsenic speciation in drinking water, food chain and environment, arsenic being a well-recognized carcinogenic and toxic agent mainly in its inorganic species. The instrumental techniques used for arsenic determination, such as hydride generation atomic absorption spectrometry (HGAAS, graphite furnace atomic absorption spectrometry (GFAAS and inductively coupled plasma mass spectrometry (ICP-MS, can provide a great sensitivity only on the total amount. Objective: The aim of this study was to develop a simple and rapid method and to analyze the concentration of total inorganic arsenic in bottled drinking water. Methods: Total arsenic was determined in samples from six different types of commercially available bottled drinking water using atomic absorption spectrometry with electrothermal or hydride generation vaporisation. All drinking water samples were acidified with 0.1M nitric acid to match the acidity of the standards. Results: The method was linear within the studied range (1-5 μg/L, R = 0.9943. The quantification limits for arsenic determination were 0.48 μg/L (HGAAS and 0.03 μg/L (GFAAS. The evaluated arsenic content in drinking water was within the accepted limits provided by law. Conclusions: A simple and sensitive method for the quantification of arsenic in drinking water using atomic absorbtion spectroscopy was described, which can be further used in toxicological studies. As an additional advantage, the system is very fast, efficient and environmental friendly

  19. Technical and economic aspects of hydrogen storage in metal hydrides

    Science.gov (United States)

    Schmitt, R.

    1981-01-01

    The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

  20. Suppression of the critical temperature in binary vanadium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Dolan, M.D., E-mail: michael.dolan@csiro.au [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); McLennan, K.G. [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); Chandra, D. [Department of Chemical and Materials Engineering, University of Nevada, Reno, Reno, NV 89557 (United States); Kochanek, M.A. [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); Song, G. [CSIRO Process Science and Engineering, Gate 4, Normanby Rd, Clayton, VIC 3168 (Australia)

    2014-02-15

    Highlights: • Addition of 10 mol% Cr to V increases the β-hydride T{sub C} to >200 °C. • Addition of 10 mol% Ni to V increases the β-hydride T{sub C} to >400 °C. • Addition of 10 mol% Al to V decreases the β-hydride T{sub C} to <30 °C. • V{sub 90}Al{sub 10} membrane can be cycled to <30 °C under H{sub 2} without β-hydride formation. -- Abstract: The tendency of vanadium-based alloy membranes to embrittle is the biggest commercialisation barrier for this hydrogen separation technology. Excessive hydrogen absorption and the α → β hydride transition both contribute to brittle failure of these membranes. Alloying is known to reduce absorption, but the influence of alloying on hydride phase formation under conditions relevant to membrane operation has not been studied in great detail previously. Here, the effect of Cr, Ni, and Al alloying additions on V–H phase equilibrium has been studied using hydrogen absorption measurements and in situ X-ray diffraction studies. The addition of 10 mol% Ni increases the critical temperature for α + β hydride formation to greater than 400 °C, compared to 170 °C for V. Cr also increases the critical temperature, to between 200 and 300 °C. The addition of 10 mol% Al, however, suppresses the critical temperature to less than 30 °C, thereby enabling this material to be cycled thermally and hydrostatically while precluding formation of the β-hydride phase. This is despite Al also decreasing hydrogen absorption. The implication of this finding is that one of the mechanisms of brittle failure in vanadium-based hydrogen-selective membranes has been eliminated, thereby increasing the robustness of this material relative to V.

  1. In situ La, Ce, and Nd L-edge X-ray absorption fine structure study of an intermetallic metal hydride electrode in an operating alkaline battery

    Energy Technology Data Exchange (ETDEWEB)

    Tryk, D.A.; Bae, I.T.; Scherson, D. [Case Western Reserve Univ., Cleveland, OH (United States). Dept. of Chemistry; Antonio, M.R. [Argonne National Lab., IL (United States). Chemistry Division; Jordan, G.W.; Huston, E.L. [Energizer Power Systems, Gainesville, FL (United States)

    1995-05-01

    The X-ray absorption fine structure of a technologically important MmL{sub 5} intermetallic compound (Mm = La{sub 0.52}Ce{sub 0.34}Nd{sub 0.10}Pr{sub 0.04}, L{sub 5} Ni{sub 3.5}Ca{sub 0.8}Mn{sub 0.3}Al{sub 0.4}) in the form of a hydrogen storage cathode was recorded in situ in the region 5440-6290 eV using an electrochemical cell which is essentially a fully functioning alkaline battery. Significant differences were observed in the X-ray absorption near edge structure (XANES) of all of the absorption edges (La, Ce, and Nd) between the uncharged and fully charged states. In particular, a clear increase in the intensity of the La and Nd L{sub III}-edge resonances (due to 2P{sub 3/2} {r_arrow} 5d electronic transitions) was found upon charging the cell. This phenomenon was attributed to an increase in the density of empty d-like states near the Fermi level following hydrogen injection into the lattice. Furthermore, the behavior of the Ca L{sub II,III}-edges of this battery material upon charging was nearly the same as that observed for the gas phase hydrogenation of the Ce{sub 2}Fe{sub 17} and Ce{sub 2}Fe{sub 14}B intermetallics reported in the literature.

  2. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    the electrochemical hydride absorption/desorption reaction were observed. The results indicated r

  3. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    the electrochemical hydride absorption/desorption reaction were observed. The results indicated r

  4. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  5. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  6. Submillimeter Spectroscopy of Hydride Molecules

    Science.gov (United States)

    Phillips, T. G.

    1998-05-01

    Simple hydride molecules are of great importance in astrophysics and astrochemistry. Physically they dominate the cooling of dense, warm phases of the ISM, such as the cores and disks of YSOs. Chemically they are often stable end points of chemical reactions, or may represent important intermediate stages of the reaction chains, which can be used to test the validity of the process. Through the efforts of astronomers, physicists, chemists, and laboratory spectroscopists we have an approximate knowledge of the abundance of some of the important species, but a great deal of new effort will be required to achieve the comprehensive and accurate data set needed to determine the energy balance and firmly establish the chemical pathways. Due to the low moment of inertia, the hydrides rotate rapidly and so have their fundamental spectral lines in the submillimeter. Depending on the cloud geometry and temperature profile they may be observed in emission or absorption. Species such as HCl, HF, OH, CH, CH(+) , NH_2, NH_3, H_2O, H_2S, H_3O(+) and even H_3(+) have been detected, but this is just a fraction of the available set. Also, most deduced abundances are not nearly sufficiently well known to draw definitive conclusions about the chemical processes. For example, the most important coolant for many regions, H_2O, has a possible range of deduced abundance of a factor of 1000. The very low submillimeter opacity at the South Pole site will be a significant factor in providing a new capabilty for interstellar hydride spectroscopy. The new species and lines made available in this way will be discussed.

  7. Results of NDE Technique Evaluation of Clad Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kunerth, Dennis C. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-09-01

    This report fulfills the M4 milestone, M4FT-14IN0805023, Results of NDE Technique Evaluation of Clad Hydrides, under Work Package Number FT-14IN080502. During service, zirconium alloy fuel cladding will degrade via corrosion/oxidation. Hydrogen, a byproduct of the oxidation process, will be absorbed into the cladding and eventually form hydrides due to low hydrogen solubility limits. The hydride phase is detrimental to the mechanical properties of the cladding and therefore it is important to be able to detect and characterize the presence of this constituent within the cladding. Presently, hydrides are evaluated using destructive examination. If nondestructive evaluation techniques can be used to detect and characterize the hydrides, the potential exists to significantly increase test sample coverage while reducing evaluation time and cost. To demonstrate the viability this approach, an initial evaluation of eddy current and ultrasonic techniques were performed to demonstrate the basic ability to these techniques to detect hydrides or their effects on the microstructure. Conventional continuous wave eddy current techniques were applied to zirconium based cladding test samples thermally processed with hydrogen gas to promote the absorption of hydrogen and subsequent formation of hydrides. The results of the evaluation demonstrate that eddy current inspection approaches have the potential to detect both the physical damage induced by hydrides, e.g. blisters and cracking, as well as the combined effects of absorbed hydrogen and hydride precipitates on the electrical properties of the zirconium alloy. Similarly, measurements of ultrasonic wave velocities indicate changes in the elastic properties resulting from the combined effects of absorbed hydrogen and hydride precipitates as well as changes in geometry in regions of severe degradation. However, for both approaches, the signal responses intended to make the desired measurement incorporate a number of contributing

  8. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

    Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

    2002-01-01

    The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

  9. Caesium hydride: MS-CASPT2 potential energy curves and A1Σ+ →X1Σ+ absorption/emission spectroscopy

    Science.gov (United States)

    Škoviera, Ján; Neogrády, Pavel; Louis, Florent; PitoÅák, Michal; Černušák, Ivan

    2017-03-01

    Correlated ab initio methods (CASPT2 and CCSD(T)) in conjunction with the ANO-RCC basis sets were used to calculate potential energy curves (PECs) of the ground, valence, and Rydberg electronic states of CsH with the inclusion of the scalar relativistic effects. The spectroscopic constants of bound states were calculated from the PECs and compared with previous theoretical and/or available experimental data. Absorption and emission spectra arising from the transition between X1Σ+ and A1Σ+ states were modelled using vibrational and rotational energy levels and corresponding nuclear wave functions obtained via the direct numerical integration of one-dimensional rovibrational Schrödinger equation in the CASPT2/ANO-RCC electronic potentials. The anharmonic shape of the A1Σ+ potential and the shape of the pertinent vibrational wave functions have an interesting impact on the final shape of the spectrum and result in the complicated fine structure of individual emission bands.

  10. Lightweight hydride storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W. [Sandia National Labs., Livermore, CA (United States)

    1995-09-01

    The need for lightweight hydrides in vehicular applications has prompted considerable research into the use of magnesium and its alloys. Although this earlier work has provided some improved performance in operating temperature and pressure, substantial improvements are needed before these materials will significantly enhance the performance of an engineered system on a vehicle. We are extending the work of previous investigators on Mg alloys to reduce the operating temperature and hydride heat of formation in light weight materials. Two important results will be discussed in this paper: (1) a promising new alloy hydride was found which has better pressure-temperature characteristics than any previous Mg alloy and, (2) a new fabrication process for existing Mg alloys was developed and demonstrated. The new alloy hydride is composed of magnesium, aluminum and nickel. It has an equilibrium hydrogen overpressure of 1.3 atm. at 200{degrees}C and a storage capacity between 3 and 4 wt.% hydrogen. A hydrogen release rate of approximately 5 x 10{sup -4} moles-H{sub 2}/gm-min was measured at 200{degrees}C. The hydride heat of formation was found to be 13.5 - 14 kcal/mole-H{sub 2}, somewhat lower than Mg{sub 2}Ni. The new fabrication method takes advantage of the high vapor transport of magnesium. It was found that Mg{sub 2}Ni produced by our low temperature process was better than conventional materials because it was single phase (no Mg phase) and could be fabricated with very small particle sizes. Hydride measurements on this material showed faster kinetic response than conventional material. The technique could potentially be applied to in-situ hydride bed fabrication with improved packing density, release kinetics, thermal properties and mechanical stability.

  11. Hydrogen, lithium, and lithium hydride production

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

    2017-06-20

    A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

  12. Strategies for the improvement of the hydrogen storage properties of metal hydride materials.

    Science.gov (United States)

    Wu, Hui

    2008-10-24

    Metal hydrides are an important family of materials that can potentially be used for safe, efficient and reversible on-board hydrogen storage. Light-weight metal hydrides in particular have attracted intense interest due to their high hydrogen density. However, most of these hydrides have rather slow absorption kinetics, relatively high thermal stability, and/or problems with the reversibility of hydrogen absorption/desorption cycling. This paper discusses a number of different approaches for the improvement of the hydrogen storage properties of these materials, with emphasis on recent research on tuning the ionic mobility in mixed hydrides. This concept opens a promising pathway to accelerate hydrogenation kinetics, reduce the activation energy for hydrogen release, and minimize deleterious possible by-products often associated with complex hydride systems.

  13. Air and metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Lampinen, M.; Noponen, T. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Applied Thermodynamics

    1998-12-31

    The main goal of the air and metal hydride battery project was to enhance the performance and manufacturing technology of both electrodes to such a degree that an air-metal hydride battery could become a commercially and technically competitive power source for electric vehicles. By the end of the project it was possible to demonstrate the very first prototype of the air-metal hydride battery at EV scale, achieving all the required design parameters. (orig.)

  14. Experimental comparison on heat transfer-enhancing component of metal hydride bed

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Hyun-goo, E-mail: hgkang@nfri.re.kr; Chung, Dong-you; Oh, Yun Hee; Chang, Min Ho; Yun, Sei-Hun

    2016-11-01

    Highlights: • Two small ZrCo metal hydride beds were developed. • Copper foam or fin as heat transfer-enhancing component are experimentally compared. • Copper foam bed is more efficient for uniform and rapid heating of metal hydride. • Copper foam bed is more efficient in removal of reaction heat during absorption. - Abstract: Metal hydride bed will be one of the key components for safe handling of tritium in fusion fuel cycle. In case of normal or emergency shutdown of fuel cycle, metal hydride bed installed in storage and delivery system (SDS) of tritium plant will absorb tritium gas in the system as soon as possible. Supply of hydrogen isotope gas to fueling system of fusion reactor will start from the metal hydride beds. Rapid delivery, rapid recovery including rapid heating and cooling are key issues. For better performance of metal hydride bed, various forms of heat transfer enhancing component or design can be applied. This study aims to help the selection of heat transfer enhancing component. Two small ZrCo beds with copper foam and copper fin were developed and experimented with hydrogen gas. Recovery and delivery performance, heating and cooling performance are compared. Experimental results show metal hydride bed with copper foam has improved performance. Uniform heating of metal hydride during desorption and removal of reaction heat during absorption are more efficient with copper foam bed than copper fin bed.

  15. Hydrogen Outgassing from Lithium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L N; Schildbach, M A; Smith, R A; Balazs1, B; McLean II, W

    2006-04-20

    Lithium hydride is a nuclear material with a great affinity for moisture. As a result of exposure to water vapor during machining, transportation, storage and assembly, a corrosion layer (oxide and/or hydroxide) always forms on the surface of lithium hydride resulting in the release of hydrogen gas. Thermodynamically, lithium hydride, lithium oxide and lithium hydroxide are all stable. However, lithium hydroxides formed near the lithium hydride substrate (interface hydroxide) and near the sample/vacuum interface (surface hydroxide) are much less thermally stable than their bulk counterpart. In a dry environment, the interface/surface hydroxides slowly degenerate over many years/decades at room temperature into lithium oxide, releasing water vapor and ultimately hydrogen gas through reaction of the water vapor with the lithium hydride substrate. This outgassing can potentially cause metal hydriding and/or compatibility issues elsewhere in the device. In this chapter, the morphology and the chemistry of the corrosion layer grown on lithium hydride (and in some cases, its isotopic cousin, lithium deuteride) as a result of exposure to moisture are investigated. The hydrogen outgassing processes associated with the formation and subsequent degeneration of this corrosion layer are described. Experimental techniques to measure the hydrogen outgassing kinetics from lithium hydride and methods employing the measured kinetics to predict hydrogen outgassing as a function of time and temperature are presented. Finally, practical procedures to mitigate the problem of hydrogen outgassing from lithium hydride are discussed.

  16. Nanostructured Magnesium Hydride for Reversible Hydrogen Storage

    Science.gov (United States)

    de Rango, P.; Chaise, A.; Fruchart, D.; Miraglia, S.; Marty, Ph.

    2013-05-01

    The aim of this work was to develop suitable materials to store hydrogen in a solid state. A systematic investigation of the co-milling process of magnesium hydride with a transition metal was undertaken in order to produce nanostructured and highly reactive powders. The initiating role of the transition metal was evidenced by in situ neutron diffraction experiments. High performances in terms of thermal and mechanical behavior were achieved introducing expanded graphite and compacting the mixture to form composite materials. Absorption and desorption kinetics have been measured versus temperature and H2 pressure.

  17. Review of magnesium hydride-based materials: development and optimisation

    Science.gov (United States)

    Crivello, J.-C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.; Latroche, M.; Milanese, C.; Milčius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    2016-02-01

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the slow rates for some processes such as hydrogen diffusion through the bulk create challenges for large-scale implementation. The present paper reviews fundamentals of the Mg-H system and looks at the recent advances in the optimisation of magnesium hydride as a hydrogen storage material through the use of catalytic additives, incorporation of defects and an understanding of the rate-limiting processes during absorption and desorption.

  18. Ab-initio study of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Ramesh [Dept. of Physics, Feroze Gandhi Insititute of Engineering and Technology, Raebareli-229001 (India); Shukla, Seema, E-mail: sharma.yamini62@gmail.com; Dwivedi, Shalini, E-mail: sharma.yamini62@gmail.com; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Theoretical Condensed Matter Physics Laboratory, Dept. of Physics Feroze Gandhi College, Raebareli-229001 (India)

    2014-04-24

    We have performed ab initio self consistent calculations based on Full potential linearized augmented plane wave (FP-LAPW) method to investigate the optical and thermal properties of yttrium hydrides. From the band structure and density of states, the optical absorption spectra and specific heats have been calculated. The band structure of Yttrium metal changes dramatically due to hybridization of Y sp orbitals with H s orbitals and there is a net charge transfer from metal to hydrogen site. The electrical resistivity and specific heats of yttrium hydrides are lowered but the thermal conductivity is slightly enhanced due to increase in scattering from hydrogen sites.

  19. Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger

    Science.gov (United States)

    Oi, Tsutomu; Maki, Kohei; Sakaki, Yoshinori

    Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger were investigated. Metal hydride beds were filled with AB 2 type hydrogen-storage alloy's particles, Ti 0.42Zr 0.58Cr 0.78Fe 0.57Ni 0.2Mn 0.39Cu 0.03, with a storage capacity of 0.92 wt.%. Heat transfer model in the metal hydride bed based on the heat transfer mechanism for packed bed proposed by Kunii and co-workers is presented. The time-dependent hydrogen absorption/desorption rate and pressure in the metal hydride vessel calculated by the model were compared with the experimental results. During the hydriding, calculated hydrogen absorption rates agreed with measured ones. Calculated thermal equilibrium hydrogen pressures were slightly lower than the measured hydrogen pressures at the inlet of metal hydride vessel. Taking account of the pressure gradient between the inlet of metal hydride vessel and the metal hydride bed, it is considered that this discrepancy is reasonable. During the dehydriding, there were big differences between the calculated hydrogen desorption rates and measured ones. As calculated hydrogen desorption rates were lower than measured ones, there were big differences between the calculated thermal equilibrium hydrogen pressures and the measured hydrogen pressures at the inlet of metal hydride vessel. It is considered that those differences are due to the differences of the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity between the assumed and actual ones. It is important to obtain the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity both during the hydriding and dehydriding to design a metal hydride vessel.

  20. Hydrogenation reaction characteristics and properties of its hydrides for magnetic regenerative material HoCu2

    Institute of Scientific and Technical Information of China (English)

    金滔; 吴梦茜; 黄迦乐; 汤珂; 陈立新

    2016-01-01

    The hydrogenation reaction characteristics and the properties of its hydrides for the magnetic regenerative material HoCu2 (CeCu2-type) of a cryocooler were investigated. The XRD testing reveals that the hydrides of HoCu2 were a mixture of Cu, unknown hydride I, and unknown hydride II. Based on the PCT (pressure−concentration−temperature) curves under different reaction temperatures, the relationships among reaction temperature, equilibrium pressure, and maximum hydrogen absorption capacity were analyzed and discussed. The enthalpy changeΔH and entropy changeΔS as a result of the whole hydrogenation process were also calculated from the PCT curves. The magnetization and volumetric specific heat capacity of the hydride were also measured by SQUID magnetometer and PPMS, respectively.

  1. Thin-film metal hydrides.

    Science.gov (United States)

    Remhof, Arndt; Borgschulte, Andreas

    2008-12-01

    The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

  2. In situ probing of surface hydrides on hydrogenated amorphous silicon using attenuated total reflection infrared spectroscopy

    CERN Document Server

    Kessels, W M M; Sanden, M C M; Aydil, E S

    2002-01-01

    An in situ method based on attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is presented for detecting surface silicon hydrides on plasma deposited hydrogenated amorphous silicon (a-Si:H) films and for determining their surface concentrations. Surface silicon hydrides are desorbed by exposing the a-Si:H films to low energy ions from a low density Ar plasma and by comparing the infrared spectrum before and after this low energy ion bombardment, the absorptions by surface hydrides can sensitively be separated from absorptions by bulk hydrides incorporated into the film. An experimental comparison with other methods that utilize isotope exchange of the surface hydrogen with deuterium showed good agreement and the advantages and disadvantages of the different methods are discussed. Furthermore, the determination of the composition of the surface hydrogen bondings on the basis of the literature data on hydrogenated crystalline silicon surfaces is presented, and quantification of the h...

  3. Metal Hydride Compression

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Bowman, Robert [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Smith, Barton [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Anovitz, Lawrence [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jensen, Craig [Hawaii Hydrogen Carriers LLC, Honolulu, HI (United States)

    2017-07-01

    Conventional hydrogen compressors often contribute over half of the cost of hydrogen stations, have poor reliability, and have insufficient flow rates for a mature FCEV market. Fatigue associated with their moving parts including cracking of diaphragms and failure of seal leads to failure in conventional compressors, which is exacerbated by the repeated starts and stops expected at fueling stations. Furthermore, the conventional lubrication of these compressors with oil is generally unacceptable at fueling stations due to potential fuel contamination. Metal hydride (MH) technology offers a very good alternative to both conventional (mechanical) and newly developed (electrochemical, ionic liquid pistons) methods of hydrogen compression. Advantages of MH compression include simplicity in design and operation, absence of moving parts, compactness, safety and reliability, and the possibility to utilize waste industrial heat to power the compressor. Beyond conventional H2 supplies of pipelines or tanker trucks, another attractive scenario is the on-site generating, pressuring and delivering pure H2 at pressure (≥ 875 bar) for refueling vehicles at electrolysis, wind, or solar generating production facilities in distributed locations that are too remote or widely distributed for cost effective bulk transport. MH hydrogen compression utilizes a reversible heat-driven interaction of a hydride-forming metal alloy with hydrogen gas to form the MH phase and is a promising process for hydrogen energy applications [1,2]. To deliver hydrogen continuously, each stage of the compressor must consist of multiple MH beds with synchronized hydrogenation & dehydrogenation cycles. Multistage pressurization allows achievement of greater compression ratios using reduced temperature swings compared to single stage compressors. The objectives of this project are to investigate and demonstrate on a laboratory scale a two-stage MH hydrogen (H2) gas compressor with a

  4. First-principles calculations of niobium hydride formation in superconducting radio-frequency cavities

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Denise C.; Cooley, Lance D.; Seidman, David N.

    2013-09-01

    Niobium hydride is suspected to be a major contributor to degradation of the quality factor of niobium superconducting radio-frequency (SRF) cavities. In this study, we connect the fundamental properties of hydrogen in niobium to SRF cavity performance and processing. We modeled several of the niobium hydride phases relevant to SRF cavities and present their thermodynamic, electronic, and geometric properties determined from calculations based on density-functional theory. We find that the absorption of hydrogen from the gas phase into niobium is exothermic and hydrogen becomes somewhat anionic. The absorption of hydrogen by niobium lattice vacancies is strongly preferred over absorption into interstitial sites. A single vacancy can accommodate six hydrogen atoms in the symmetrically equivalent lowest-energy sites and additional hydrogen in the nearby interstitial sites affected by the strain field: this indicates that a vacancy can serve as a nucleation center for hydride phase formation. Small hydride precipitates may then occur near lattice vacancies upon cooling. Vacancy clusters and extended defects should also be enriched in hydrogen, potentially resulting in extended hydride phase regions upon cooling. We also assess the phase changes in the niobium-hydrogen system based on charge transfer between niobium and hydrogen, the strain field associated with interstitial hydrogen, and the geometry of the hydride phases. The results of this study stress the importance of not only the hydrogen content in niobium, but also the recovery state of niobium for the performance of SRF cavities.

  5. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  6. Hydride development for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.; Yang, N.Y.C. [Sandia National Lab., Livermore, CA (United States); Sandrock, G. [SunaTech, Inc., Ringwood, NJ (United States)

    1996-10-01

    The purpose of this project is to develop and demonstrate improved hydride materials for hydrogen storage. The work currently is organized into four tasks: hydride development, bed fabrication, materials support for engineering systems, and IEA Annex 12 activities. At the present time, hydride development is focused on Mg alloys. These materials generally have higher weight densities for storing hydrogen than rare earth or transition metal alloys, but suffer from high operating temperatures, slow kinetic behavior and material stability. The authors approach is to study bulk alloy additions which increase equilibrium overpressure, in combination with stable surface alloy modification and particle size control to improve kinetic properties. This work attempts to build on the considerable previous research in this area, but examines specific alloy systems in greater detail, with attention to known phase properties and structures. The authors have found that specific phases can be produced which have significantly improved hydride properties compared to previous studies.

  7. Metal hydride air conditioner

    Institute of Scientific and Technical Information of China (English)

    YANG; Ke; DU; Ping; LU; Man-qi

    2005-01-01

    The relationship among the hydrogen storage properties, cycling characteristics and thermal parameters of the metal hydride air conditioning systems was investigated. Based on a new alloy selection model, three pairs of hydrogen storage alloys, LaNi4.4 Mn0.26 Al0.34 / La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1, LaNi4.61Mn0. 26 Al0.13/La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1 and LaNi4.61 Mn0.26 Al0.13/La0.6 Y0.4 Ni4.8 Mn0. 2, were selected as the working materials for the metal hydride air conditioning system. Studies on the factors affecting the COP of the system showed that higher COP and available hydrogen content need the proper operating temperature and cycling time,large hydrogen storage capacity, flat plateau and small hysterisis of hydrogen alloys, proper original input hydrogen content and mass ratio of the pair of alloys. It also needs small conditioning system was established by using LaNi4.61 Mn0.26 Al0. 13/La0.6 Y0.4 Ni4.8 Mn0.2 alloys as the working materials, which showed that under the operating temperature of 180℃/40℃, a low temperature of 13℃ was reached, with COP =0.38 and Wnet =0.09 kW/kg.

  8. Geoneutrino and Hydridic Earth model

    CERN Document Server

    Bezrukov, Leonid

    2013-01-01

    Uranium, Thorium and Potassium-40 abundances in the Earth were calculated in the frame of Hydridic Earth model. Terrestrial heat producton from U, Th and K40 decays was calculated also. We must admit the existance of Earth expansion process to understand the obtained large value of terrestrial heat producton. The geoneutrino detector with volume more than 5 kT (LENA type) must be constructed to definitely separate between Bulk Silicat Earth model and Hydridic Earth model.

  9. Optical studies of neutron-irradiated lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Oparin, D.V.; Pilipenko, G.I.; Tyutyunnik, O.I.; Gavrilov, F.F.; Sulimov, E.M. (Ural' skij Politekhnicheskij Inst., Sverdlovsk (USSR))

    1984-09-01

    Lithium hydride single crystals irradiated with neutrons were studied by the optical method. Wide bands belonging to the large F-aggregate and quasimetallic F-centres and to the metallic lithium colloids were discovered in the absorption spectra at room temperature. The small Fsub(n)-centres and molecular lithium centres were detected at 77 K. From the electron-vibrational structure of the absorption spectra of these centres the energies of acoustic phonons in X, W, L points of the Brillouin zone of lithium hydride have been found out: TA(L)-235 cm/sup -1/, TA(X)-27g cm/sup -1/, TA(W)-327 cm/sup -1/, LA(W)-384 cm/sup -1/, LA(X)-426 cm/sup -1/.

  10. Metal Hydrides as hot carrier cell absorber materials

    Science.gov (United States)

    Wang, Pei; Wen, Xiaoming; Shrestha, Santosh; Conibeer, Gavin; Aguey-Zinsou, Kondo-Francois

    2016-09-01

    The hot Carrier Solar Cell (HCSC) allows the photon-induced hot carriers (the carriers with energy larger than the band gap) to be collected before they completely thermalise. The absorber of the HCSC should have a large phononic band gap to supress Klemens Decay, which results in a slow carrier cooling speed. In fact, a large phononic band gap likely exists in a binary compound whose constituent elements have a large mass ratio between each other. Binary hydrides with their overwhelming mass ratio of the constituent elements are important absorber candidates. Study on different types of binary hydrides as potential absorber candidates is presented in this paper. Many binary transition metal hydrides have reported theoretical or experimental phonon dispersion charts which show large phononic band gaps. Among these hydrides, the titanium hydride (TiHX) is outstanding because of its low cost, easy fabrication process and is relatively inert to air and water. A TiHX thin film is fabricated by directly hydrogenating an evaporated titanium thin film. Characterisation shows good crystal quality and the hydrogenation process is believed to be successful. Ultrafast transient absorption (TA) spectroscopy is used to study the electron cooling time of TiHX. The result is very noisy due to the low absorption and transmission of the sample. The evolution of the TA curves has been explained by band to band transition using the calculated band structure of TiH2. Though not reliable due to the high noise, decay time fitting at 700nm and 600nm shows a considerably slow carrier cooling speed of the sample.

  11. From permanent magnets to rechargeable hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Willems, J.J.G.; Buschow, K.H.J.

    1987-02-15

    A brief historical survey is given of how the study of coercitivity mechanisms in SmCo/sub 5/ permanent-magnet materials eventually led to the discovery of the favourable hydrogen sorption properties of the compound LaNi/sub 5/. It is shown how continued research by many investigators dealing with a variety of different physical and chemical properties has resulted in an advanced understanding of some of the principles that govern hydrogen absorption and which are responsible for the changes in physical properties that accompany it. The problems associated with various applications of LaNi/sub 5/-based hydrogen-storage materials are also briefly discussed. A large part of this paper is devoted to the applicability of LaNi/sub 5/-type materials in batteries. Research in this area has resulted in the development of a new type of rechargeable battery: the nickel-hydride cell. This battery can be charged and discharged at high rates and is relatively insensitive to overcharging and overdischarging. Special attention is given to the nature of the electrode degradation process and the effect of composition variations in LaNi/sub 5/-related materials on the lifetime of the corresponding hydride electrodes when subjected to severe electrochemical charge-discharge cycles.

  12. Physics of hydride fueled PWR

    Science.gov (United States)

    Ganda, Francesco

    The first part of the work presents the neutronic results of a detailed and comprehensive study of the feasibility of using hydride fuel in pressurized water reactors (PWR). The primary hydride fuel examined is U-ZrH1.6 having 45w/o uranium: two acceptable design approaches were identified: (1) use of erbium as a burnable poison; (2) replacement of a fraction of the ZrH1.6 by thorium hydride along with addition of some IFBA. The replacement of 25 v/o of ZrH 1.6 by ThH2 along with use of IFBA was identified as the preferred design approach as it gives a slight cycle length gain whereas use of erbium burnable poison results in a cycle length penalty. The feasibility of a single recycling plutonium in PWR in the form of U-PuH2-ZrH1.6 has also been assessed. This fuel was found superior to MOX in terms of the TRU fractional transmutation---53% for U-PuH2-ZrH1.6 versus 29% for MOX---and proliferation resistance. A thorough investigation of physics characteristics of hydride fuels has been performed to understand the reasons of the trends in the reactivity coefficients. The second part of this work assessed the feasibility of multi-recycling plutonium in PWR using hydride fuel. It was found that the fertile-free hydride fuel PuH2-ZrH1.6, enables multi-recycling of Pu in PWR an unlimited number of times. This unique feature of hydride fuels is due to the incorporation of a significant fraction of the hydrogen moderator in the fuel, thereby mitigating the effect of spectrum hardening due to coolant voiding accidents. An equivalent oxide fuel PuO2-ZrO2 was investigated as well and found to enable up to 10 recycles. The feasibility of recycling Pu and all the TRU using hydride fuels were investigated as well. It was found that hydride fuels allow recycling of Pu+Np at least 6 times. If it was desired to recycle all the TRU in PWR using hydrides, the number of possible recycles is limited to 3; the limit is imposed by positive large void reactivity feedback.

  13. Activation and discharge kinetics of metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, Stein Egil

    2003-07-01

    Potential step chronoamperometry and Electrochemical Impedance Spectroscopy (eis) measurements were performed on single metal hydride particles. For the {alpha}-phase, the bulk diffusion coefficient and the absorption/adsorption rate parameters were determined. Materials produced by atomisation, melt spinning and conventional casting were investigated. The melt spun and conventional cast materials were identical and the atomised material similar in composition. The particles from the cast and the melt spun material were shaped like parallelepipeds. A corresponding equation, for this geometry, for diffusion coupled to an absorption/adsorption reaction was developed. It was found that materials produced by melt spinning exhibited lower bulk diffusion (1.7E-14 m2/s) and absorption/adsorption reaction rate (1.0E-8 m/s), compared to materials produced by conventionally casting (1.1E-13 m2/s and 5.5E-8 m/s respectively). In addition, the influence of particle active surface and relative diffusion length were discussed. It was concluded that there are uncertainties connected to these properties, which may explain the large distribution in the kinetic parameters measured on metal hydride particles. Activation of metal hydride forming materials has been studied and an activation procedure, for porous electrodes, was investigated. Cathodic polarisation of the electrode during a hot alkaline surface treatment gave the maximum discharge capacity on the first discharge of the electrode. The studied materials were produced by gas atomisation and the spherical shape was retained during the activation. Both an AB{sub 5} and an AB{sub 2} alloy was successfully activated and discharge rate properties determined. The AB{sub 2} material showed a higher maximum discharge capacity, but poor rate properties, compared to the AB{sub 5} material. Reduction of surface oxides, and at the same time protection against corrosion of active metallic nickel, can explain the satisfying results of

  14. Optimization of Internal Cooling Fins for Metal Hydride Reactors

    Directory of Open Access Journals (Sweden)

    Vamsi Krishna Kukkapalli

    2016-06-01

    Full Text Available Metal hydride alloys are considered as a promising alternative to conventional hydrogen storage cylinders and mechanical hydrogen compressors. Compared to storing in a classic gas tank, metal hydride alloys can store hydrogen at nearly room pressure and use less volume to store the same amount of hydrogen. However, this hydrogen storage method necessitates an effective way to reject the heat released from the exothermic hydriding reaction. In this paper, a finned conductive insert is adopted to improve the heat transfer in the cylindrical reactor. The fins collect the heat that is volumetrically generated in LaNi5 metal hydride alloys and deliver it to the channel located in the center, through which a refrigerant flows. A multiple-physics modeling is performed to analyze the transient heat and mass transfer during the hydrogen absorption process. Fin design is made to identify the optimum shape of the finned insert for the best heat rejection. For the shape optimization, use of a predefined transient heat generation function is proposed. Simulations show that there exists an optimal length for the fin geometry.

  15. A New Reducing Regent: Dichloroindium Hydride

    Institute of Scientific and Technical Information of China (English)

    A. BABA; I. SHIBATA; N. HAYASHI

    2005-01-01

    @@ 1Introduction Among the hydride derivatives of group 13 elements, various types of aluminum hydrides and boron hydrides have been employed as powerful reduction tools. Indium hydrides have not received much attention,whereas the synthesis of indium trihydride (InH3) was reported several decades ago[1]. There have been no precedents for monometallic indium hydrides having practical reactivity, while activated hydrides such as an ate complex LiPhn InH4-n (n = 0- 2) and phosphine-coordinated indium hydrides readily reduce carbonyl compounds. In view of this background, we focused on the development of dichloroindium hydrides (Cl2InH) as novel reducing agents that bear characteristic features in both ionic and radical reactions.

  16. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

    This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

  17. Complex and liquid hydrides for energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Callini, Elsa; Atakli, Zuleyha Özlem Kocabas; Hauback, Bjørn C.; Orimo, Shin-ichi; Jensen, Craig; Dornheim, Martin; Grant, David; Cho, Young Whan; Chen, Ping; Hjörvarsson, Bjørgvin; de Jongh, Petra; Weidenthaler, Claudia; Baricco, Marcello; Paskevicius, Mark; Jensen, Torben R.; Bowden, Mark E.; Autrey, Thomas S.; Züttel, Andreas

    2016-03-10

    The research on complex hydrides for hydrogen storage was imitated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized and the knowledge on the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant part of the research groups active in the field of complex hydrides are collaborators in the IEA task 32. This paper reports about the important issues in the field of the complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides and their thermodynamic properties, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and excellent summary of the recent achievements.

  18. Luminescent properties of aluminum hydride

    Energy Technology Data Exchange (ETDEWEB)

    Baraban, A.P.; Gabis, I.E.; Dmitriev, V.A. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Dobrotvorskii, M.A., E-mail: mstislavd@gmail.com [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Kuznetsov, V.G. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Matveeva, O.P. [National Mineral Resources University, Saint Petersburg 199106 (Russian Federation); Titov, S.A. [Petersburg State University of Railway Transport, Saint-Petersburg 190031 (Russian Federation); Voyt, A.P.; Elets, D.I. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation)

    2015-10-15

    We studied cathodoluminescence and photoluminescence of α-AlH{sub 3}– a likely candidate for use as possible hydrogen carrier in hydrogen-fueled vehicles. Luminescence properties of original α-AlH{sub 3} and α-AlH{sub 3} irradiated with ultraviolet were compared. The latter procedure leads to activation of thermal decomposition of α-AlH{sub 3} and thus has a practical implementation. We showed that the original and UV-modified aluminum hydride contain luminescence centers ‐ structural defects of the same type, presumably hydrogen vacancies, characterized by a single set of characteristic bands of radiation. The observed luminescence is the result of radiative intracenter relaxation of the luminescence center (hydrogen vacancy) excited by electrons or photons, and its intensity is defined by the concentration of vacancies, and the area of their possible excitation. UV-activation of the dehydrogenation process of aluminum hydride leads to changes in the spatial distribution of the luminescence centers. For short times of exposure their concentration increases mainly in the surface regions of the crystals. At high exposures, this process extends to the bulk of the aluminum hydride and ends with a decrease in concentration of luminescence centers in the surface region. - Highlights: • Aluminum hydride contains hydrogen vacancies which serve as luminescence centers. • The luminescence is the result of radiative relaxation of excited centers. • Hydride UV-irradiation alters distribution and concentration of luminescence centers.

  19. Photochemistry of Transition Metal Hydrides.

    Science.gov (United States)

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

    Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

  20. 原子吸收光谱法测定食品中重金属元素的研究进展%Research Progress of Heavy Metals in Foods by Atomic Absorption Spectrometry

    Institute of Scientific and Technical Information of China (English)

    帅瑾; 巩卫东; 刘胜男; 卫星; 张国庆

    2014-01-01

    近年来,原子吸收光谱法广泛用于食品中重金属含量的检测,该法具有检出限低、准确度高、选择性好及分析速度快等特点。本文综述了使用石墨炉原子吸收、火焰原子吸收和氢化物发生原子吸收3种原子吸收法测定粮食、蔬菜、水果和海产品中的铅、镉、铬、砷和汞等重金属元素的研究进展。此外,对原子吸收法在食品检测中的应用进行展望。%Atomic absorption spectrometry is widely used in detection of heavy metals in foods in recent years, which has low detection limit, high accuracy, good selectivity, fast analysis speed and so on. In this article, research advance in determination of heavy metals such as lead, cadmium, chromium, mercury and arsenic in cereals, vegeta-bles, fruits and seafoods were summarized by graphite furnace atomic absorption spectrometry, flame atomic absorption spectrometry and hydride generation atomic absorption spectrometry. In addition, application of atomic absorption method in food detection were prospected.

  1. Method of producing a chemical hydride

    Science.gov (United States)

    Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

    2007-11-13

    A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

  2. Hydrogen, lithium, and lithium hydride production

    Science.gov (United States)

    Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

    2014-03-25

    A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

  3. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today......’s hydride batteries, but a much poorer stability towards repeated charge/discharge cycling. The aim was to see if the cycleability of CaNi5 could be enhanced enough by modifications to make the compound a suitable electrode material. An alloying method based on mechanical alloying in a planetary ball mill...... by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated...

  4. Hydrogen Storage in Metal Hydrides

    Science.gov (United States)

    1990-08-01

    Hydrogen Storage Capacity Hydride by weight (%) [1) by volume (g/ml) [2] MgH2 7.00 0.101 Mg2NiH4 3.84 0,081 Mg2CuH4 2.04 - - 27 ...Include Security Classification) Hydrogen Storage in Metal Hydrides (U) 12. PERSONAL AUTHOR(S) DelaRosa, Mark J. 13a. TYPE OF REPORT 13b. TIME...objective of this program was to develop an economical process for pr-ducing a lightweight hydrogen storage medium by the chemical vapor infiltration

  5. Crystallography of shear transformations in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Cassidy, Michael Philip [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1978-01-01

    The crystallography and substructure of the transformations which have been hypothesized as involving a martensitic shear, and which occur between zirconium hydrides were investigated. Specifically, the formation of gamma zirconium hydride from delta hydride and the delta hydride to epsilon hydride transformation were studied. The habit planes, orientation relationships, lattice invariant shears, and interface structures were determined by transmission electron microscopy and diffraction. Surface tilts were observed and measured with an interference microscope. The direction and magnitude of the shape strain produced by the formation of gamma were determined by the measurement of fiducial scratch displacements. These results were compared with the phenomenological crystallographic theory of martensitic transformations.

  6. Characteristics and Applications of Metal Hydrides

    Science.gov (United States)

    Egan, G. J.; Lynch, F. E.

    1987-01-01

    Report discusses engineering principles of uses of metal hydrides in spacecraft. Metal hydrides absorb, store, pump, compress, and expand hydrogen gas. Additionally, they release or absorb sizeable amounts of heat as they form and decompose - property adapted for thermal-energy management or for propulsion. Describes efforts to: Identify heat sources and sinks suitable for driving metal hydride thermal cycles in spacecraft; develop concepts for hydride subsystems employing available heating and cooling methods; and produce data base on estimated sizes, masses, and performances of hydride devices for spacecraft.

  7. Ultratrace determination of lead by hydride generation in-atomizer trapping atomic absorption spectrometry: Optimization of plumbane generation and analyte preconcentration in a quartz trap-and-atomizer device

    Energy Technology Data Exchange (ETDEWEB)

    Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz

    2012-05-15

    A compact trap-and-atomizer device and a preconcentration procedure based on hydride trapping in excess of oxygen over hydrogen in the collection step, both constructed and developed previously in our laboratory, were employed to optimize plumbane trapping in this device and to develop a routine method for ultratrace lead determination subsequently. The inherent advantage of this preconcentration approach is that 100% preconcentration efficiency for lead is reached in this device which has never been reported before using quartz or metal traps. Plumbane is completely retained in the trap-and-atomizer device at 290 Degree-Sign C in oxygen-rich atmosphere and trapped species are subsequently volatilized at 830 Degree-Sign C in hydrogen-rich atmosphere. Effect of relevant experimental parameters on plumbane trapping and lead volatilization are discussed, and possible trapping mechanisms are hypothesized. Plumbane trapping in the trap-and-atomizer device can be routinely used for lead determination at ultratrace levels reaching a detection limit of 0.21 ng ml{sup -1} Pb (30 s preconcentration, sample volume 2 ml). Further improvement of the detection limit is feasible by reducing the blank signal and increasing the trapping time. - Highlights: Black-Right-Pointing-Pointer In-atomizer trapping HG-AAS was optimized for Pb. Black-Right-Pointing-Pointer A compact quartz trap-and-atomizer device was employed. Black-Right-Pointing-Pointer Generation, preconcentration and atomization steps were investigated in detail. Black-Right-Pointing-Pointer 100% preconcentration efficiency for lead was reached. Black-Right-Pointing-Pointer Routine analytical method was developed for Pb determination (LOD of 0.2 ng ml{sup -1} Pb).

  8. Antimony speciation in soils: improving the detection limits using post-column pre-reduction hydride generation atomic fluorescence spectroscopy (HPLC/pre-reduction/HG-AFS).

    Science.gov (United States)

    Quiroz, Waldo; Olivares, David; Bravo, Manuel; Feldmann, Jorg; Raab, Andrea

    2011-04-15

    HG-AFS is highly sensitive and low cost detection system and its use for antimony chemical speciation coupled to HPLC is gaining popularity. However speciation analysis in soils is strongly hampered because the most efficient extractant reported in the literature (oxalic acid) strongly inhibits the generation of SbH(3) by Sb(V), the major species in this kind of matrix, severely affecting its detection limits. The purpose of this research is to reduce the detection limit of Sb(V), by using a post column on-line reduction system with l-cysteine reagent (HPLC/pre-reduction/HG-AFS). The system was optimized by experimental design, optimum conditions found were 2% (w/v) and 10°C temperature coil. Detection limits of Sb(V) and Sb(III) in oxalic acid (0.25 mol L(-1)) were improved from 0.3 and 0.1 μg L(-1) to 0.07 and 0.07 μg L(-1), respectively. The methodology developed was applied to Chilean soils, where Sb(V) was the predominant species. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Determination of Lead in Urine with Hydride Generation Atomic Fluorescence Spectrophotometry%尿铅的氢化物原子荧光测定法

    Institute of Scientific and Technical Information of China (English)

    罗晓芳; 孙世义; 王翠

    2006-01-01

    为了建立氢化物原子荧光法测定尿铅的方法,采用尿液经消化后,加入铁氰化钾、草酸、盐酸的混合溶液,用AFS-920双道原子荧光光度计测定.结果显示,盐酸为0.096 mol/L,铁氰化钾为8 g/L,草酸为0.4 g/L,硼氢化钾为15 g/L时,为最佳测定条件.本法的检出限为0.2μg/L,相对标准偏差为2.7%.提示,应用氢化物原子荧光法可测定尿液中的微量铅.

  10. Speciation of AsIII and AsV in fruit juices by dispersive liquid–liquid microextraction and hydride generation-atomic fluorescence spectrometry

    Science.gov (United States)

    A new procedure was developed to speciate and quantify As(III) and As(V) in fruit juices. At pH 3.0, As(III) and ammonium pyrrolidine dithiocarbamate (APDC) formed a complex, which was extracted into carbon tetrachloride by dispersive liquid–liquid microextraction (DLLME) and subsequently quantified...

  11. 原子荧光光谱法测定饲料中镉%Determination of cadmiun in feedstuffs by the hydride generation atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    丁红梅; 胡承迅

    2005-01-01

    介绍氢化物发生-原子荧光光谱法对饲料中镉的定量分析方法,样品干法灰化后用硫酸溶解,以二硫脲-四氯化碳去除离子干扰,最佳工作条件下,该法测定线性范围0~70ng/mL,加标回收率为90%~103%,RSD为2.24%~3.41%,最低检测限为0.15ng/mL,标准曲线相关系数为0.9996,该法具有精密度高、准确性好、检出限低等优点.

  12. Characterization of hydrides and delayed hydride cracking in zirconium alloys

    Science.gov (United States)

    Fang, Qiang

    This thesis tries to fill some of the missing gaps in the study of zirconium hydrides with state-of-art experiments, cutting edge tomographical technique, and a novel numerical algorithm. A new hydriding procedure is proposed. The new anode material and solution combination overcomes many drawbacks of the AECLRTM hydriding method and leads to superior hydriding result compared to the AECL RTM hydriding procedure. The DHC crack growth velocity of as-received Excel alloy and Zr-2.5Nb alloy together with several different heat treated Excel alloy samples are measured. While it already known that the DHC crack growth velocity increases with the increase of base metal strength, the finding that the transverse plane is the weaker plane for fatigue crack growth despite having higher resistance to DHC crack growth was unexpected. The morphologies of hydrides in a coarse grained Zircally-2 sample have been studied using synchrotron x-rays at ESRF with a new technique called Diffraction Contrast Tomography that uses simultaneous collection of tomographic data and diffraction data to determine the crystallographic orientation of crystallites (grains) in 3D. It has been previously limited to light metals such as Al or Mg (due to the use of low energy x-rays). Here we show the first DCT measurements using high energy x-rays (60 keV), allowing measurements in zirconium. A new algorithm of a computationally effcient way to characterize distributions of hydrides - in particular their orientation and/or connectivity - has been proposed. It is a modification of the standard Hough transform, which is an extension of the Hough transform widely used in the line detection of EBSD patterns. Finally, a basic model of hydrogen migration is built using ABAQUS RTM, which is a mature finite element package with tested modeling modules of a variety of physical laws. The coupling of hydrogen diffusion, lattice expansion, matrix deformation and phase transformation is investigated under

  13. Hydriding and Dehydriding Properties of Zinc Borohydride, Nickel, and Titanium-Added Magnesium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Young Jun; Kwon, Sung Nam; Song, Myoung Youp [Chonbuk National University, Jeonju (Korea, Republic of)

    2015-11-15

    A Zn(BH{sub 4}){sub 2} sample was prepared by milling ZnCl{sub 2} and NaBH{sub 4} in a planetary ball mill under Ar gas. This sample contained NaCl. Then, 90 wt% MgH{sub 2}-5 wt% Zn(BH{sub 4}){sub 2}-2.5 wt% Ni-2.5 wt% Ti samples [named 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti] were prepared by milling in a planetary ball mill under H{sub 2} gas. The hydrogen absorption and release properties of the prepared samples were investigated. In particular, the variations of the initial hydriding and dehydriding rates with temperature were examined. SEM micrographs and XRD patterns of 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti after reactive mechanical grinding and after hydriding-dehydriding were also studied. Particle size distributions and BET specific surface areas of 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti after reactive mechanical grinding and after 11 hydriding-dehydriding cycles were analyzed. The 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti had an effective hydrogen storage capacity (the quantity of hydrogen absorbed for 60 min) of near 5 wt% (4.91 wt% at 593 K).

  14. Real-time measurement of desorption temperature and kinetics of magnesium hydride powder sample based on optical reflection

    Energy Technology Data Exchange (ETDEWEB)

    Poh, Chung-Kiak [Institute for Superconducting and Electronic Materials, University of Wollongong, Innovation Campus, Squires Way, Fairy Meadow, NSW 2519 (Australia); Guo, Zaiping; Liu, Hua-Kun [Institute for Superconducting and Electronic Materials, University of Wollongong, Innovation Campus, Squires Way, Fairy Meadow, NSW 2519 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia)

    2009-11-15

    We demonstrate the proof-of-principle that interaction between visible light and a magnesium hydride sample in reflective mode can be used to determine the desorption temperature and kinetics of magnesium hydride in powder form. The demonstrated optical technique requires only milligrams of sample and can potentially be used to measure the de/absorption temperature and kinetics of magnesium nanostructures, which are often fabricated via the physical vapor deposition method inside an optically transparent quartz tube. This would help to eliminate the common problem of oxidation associated with removal and transport of the freshly fabricated nanostructures into an inert protective environment. This optical technique could be applied to any hydrogen-storage material in the form of powder which shows a significant difference in its optical absorption between the hydride and the non-hydride phase. (author)

  15. Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

    Institute of Scientific and Technical Information of China (English)

    WU Zhe; CHEN Lixin; XIAO Xuezhang; FAN Xiulin; LI Shouquan; WANG Qidong

    2013-01-01

    NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al+xmol.% RE-H composites (RE=La,Ce; x=2,4,6) using NaHl and A1 powder as raw materials.The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated.It was found that the composite doped with 2 mol.% La.H3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% and desorption capacity of 4.66wt.%,respectively.Moreover,the composite doped with 6 mol% CeH2.51 showed the best hydriding/dehydriding reaction kinetics.The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles,which were scattering on the surface of NaH and A1 particles,acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.

  16. Protein Nano-Object Integrator (ProNOI for generating atomic style objects for molecular modeling

    Directory of Open Access Journals (Sweden)

    Smith Nicholas

    2012-12-01

    Full Text Available Abstract Background With the progress of nanotechnology, one frequently has to model biological macromolecules simultaneously with nano-objects. However, the atomic structures of the nano objects are typically not available or they are solid state entities. Because of that, the researchers have to investigate such nano systems by generating models of the nano objects in a manner that the existing software be able to carry the simulations. In addition, it should allow generating composite objects with complex shape by combining basic geometrical figures and embedding biological macromolecules within the system. Results Here we report the Protein Nano-Object Integrator (ProNOI which allows for generating atomic-style geometrical objects with user desired shape and dimensions. Unlimited number of objects can be created and combined with biological macromolecules in Protein Data Bank (PDB format file. Once the objects are generated, the users can use sliders to manipulate their shape, dimension and absolute position. In addition, the software offers the option to charge the objects with either specified surface or volumetric charge density and to model them with user-desired dielectric constants. According to the user preference, the biological macromolecule atoms can be assigned charges and radii according to four different force fields: Amber, Charmm, OPLS and PARSE. The biological macromolecules and the atomic-style objects are exported as a position, charge and radius (PQR file, or if a default dielectric constant distribution is not selected, it is exported as a position, charge, radius and epsilon (PQRE file. As illustration of the capabilities of the ProNOI, we created a composite object in a shape of a robot, aptly named the Clemson Robot, whose parts are charged with various volumetric charge densities and holds the barnase-barstar protein complex in its hand. Conclusions The Protein Nano-Object Integrator (ProNOI is a convenient tool for

  17. Protein Nano-Object Integrator (ProNOI) for generating atomic style objects for molecular modeling.

    Science.gov (United States)

    Smith, Nicholas; Campbell, Brandon; Li, Lin; Li, Chuan; Alexov, Emil

    2012-12-05

    With the progress of nanotechnology, one frequently has to model biological macromolecules simultaneously with nano-objects. However, the atomic structures of the nano objects are typically not available or they are solid state entities. Because of that, the researchers have to investigate such nano systems by generating models of the nano objects in a manner that the existing software be able to carry the simulations. In addition, it should allow generating composite objects with complex shape by combining basic geometrical figures and embedding biological macromolecules within the system. Here we report the Protein Nano-Object Integrator (ProNOI) which allows for generating atomic-style geometrical objects with user desired shape and dimensions. Unlimited number of objects can be created and combined with biological macromolecules in Protein Data Bank (PDB) format file. Once the objects are generated, the users can use sliders to manipulate their shape, dimension and absolute position. In addition, the software offers the option to charge the objects with either specified surface or volumetric charge density and to model them with user-desired dielectric constants. According to the user preference, the biological macromolecule atoms can be assigned charges and radii according to four different force fields: Amber, Charmm, OPLS and PARSE. The biological macromolecules and the atomic-style objects are exported as a position, charge and radius (PQR) file, or if a default dielectric constant distribution is not selected, it is exported as a position, charge, radius and epsilon (PQRE) file. As illustration of the capabilities of the ProNOI, we created a composite object in a shape of a robot, aptly named the Clemson Robot, whose parts are charged with various volumetric charge densities and holds the barnase-barstar protein complex in its hand. The Protein Nano-Object Integrator (ProNOI) is a convenient tool for generating atomic-style nano shapes in conjunction with

  18. Application of thermal electrochemical equation to metal-hydride half-cell system

    Institute of Scientific and Technical Information of China (English)

    LIU Kai-yu; HUANG Bai-yun; ZHANG Ping-min; HE Yue-hui; ZHOU Ke-chao; SU Geng

    2006-01-01

    Application of thermal electrochemical equation to metal-hydride half-cell system was investigated, and the influence of state of charge on the thermal electrochemical performance of hydrogen storage materials was studied. The results show that both the absolute value of the molar enthalpy change and the internal resistance of evolution hydrogen reaction are less than that of absorption hydrogen reaction at the same state of charge. The molar reaction enthalpy change of absorption and evolution of hydride electrode change contrarily with the enhancement of filling degree of hydrogen in hydride electrode. The relation curve of molar reaction enthalpy change to state of charge, both absorption and evolution hydrogen reaction, is close to a constant when the state of charge is 10%-60%, and during state of charge below 10% or state of charge above 60%, the molar reaction enthalpy change varies sharply. Meanwhile, the internal resistance of electrode reaction has an ascending trend with the enhancement on filling degree of hydrogen in hydride electrode in both absorption and evolution hydrogen reaction.

  19. The renaissance of hydrides as energy materials

    Science.gov (United States)

    Mohtadi, Rana; Orimo, Shin-Ichi

    2017-02-01

    Materials based on hydrides have been the linchpin in the development of several practical energy storage technologies, of which the most prominent example is nickel-metal hydride batteries. Motivated by the need to meet the future's energy demand, the past decade has witnessed substantial advancements in the research and development of hydrides as media for hydrogen energy storage. More recently, new and rapidly evolving discoveries have positioned hydrides as highly promising materials for future electrochemical energy storage, such as electrolytes for mono- and divalent batteries, and anodes for lithium-ion batteries. In addition, the potential of hydrides in efficient power transmission has been recently revealed. In this Review, we highlight key advances and illustrate how the versatility of hydrides has not only yielded a meaningful past, but also ensures a very bright future.

  20. Rechargeable metal hydrides for spacecraft application

    Science.gov (United States)

    Perry, J. L.

    1988-01-01

    Storing hydrogen on board the Space Station presents both safety and logistics problems. Conventional storage using pressurized bottles requires large masses, pressures, and volumes to handle the hydrogen to be used in experiments in the U.S. Laboratory Module and residual hydrogen generated by the ECLSS. Rechargeable metal hydrides may be competitive with conventional storage techniques. The basic theory of hydride behavior is presented and the engineering properties of LaNi5 are discussed to gain a clear understanding of the potential of metal hydrides for handling spacecraft hydrogen resources. Applications to Space Station and the safety of metal hydrides are presented and compared to conventional hydride storage. This comparison indicates that metal hydrides may be safer and require lower pressures, less volume, and less mass to store an equivalent mass of hydrogen.

  1. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

    Full Text Available Complex hydride systems for hydrogen (H2 generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4 with the following additives: nanoiron (n-Fe, lithium amide (LiNH2 (a hydride/hydride system and manganese chloride MnCl2 (a hydride/halide system. Another hydride/hydride system consists of lithium amide (LiNH2 and magnesium hydride (MgH2, and finally, there is a LiBH4-FeCl2 (hydride/halide system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C. In this group lithium alanate (LiAlH4 ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH42 obtained by mechano-chemical activation synthesis (MCAS. In a ball milled (2LiBH4 + MnCl2 nanocomposite, Mn(BH42 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.

  2. Use of reversible hydrides for hydrogen storage

    Science.gov (United States)

    Darriet, B.; Pezat, M.; Hagenmuller, P.

    1980-01-01

    The addition of metals or alloys whose hydrides have a high dissociation pressure allows a considerable increase in the hydrogenation rate of magnesium. The influence of temperature and hydrogen pressure on the reaction rate were studied. Results concerning the hydriding of magnesium rich alloys such as Mg2Ca, La2Mg17 and CeMg12 are presented. The hydriding mechanism of La2Mg17 and CeMg12 alloys is given.

  3. Inhibited solid propellant composition containing beryllium hydride

    Science.gov (United States)

    Thompson, W. W. (Inventor)

    1978-01-01

    An object of this invention is to provide a composition of beryllium hydride and carboxy-terminated polybutadiene which is stable. Another object of this invention is to provide a method for inhibiting the reactivity of beryllium hydride toward carboxy-terminated polybutadiene. It was found that a small amount of lecithin inhibits the reaction of beryllium hydride with the acid groups in carboxy terminated polybutadiene.

  4. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated......This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today...... was developed. The parameters milling time, milling intensity, number of balls and form of the alloying metals were investigated. Based on this a final alloying technique for the subsequent preparation of electrode materials was established. The technique comprises milling for 4 hours twice possibly followed...

  5. Modellization of Metal Hydride Canister for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Rocio Maceiras

    2015-06-01

    Full Text Available Hydrogen shows very interesting features for its use on-board applications as fuel cell vehicles. This paper presents the modelling of a tank with a metal hydride alloy for on-board applications, which provides good performance under ambient conditions. The metal hydride contained in the tank is Ti0.98Zr0.02V0.43Fe0.09Cr0.05Mn1.5. A two-dimensional model has been performed for the refuelling process (absorption and the discharge process (desorption. For that, individual models of mass balance, energy balance, reaction kinetics and behaviour of hydrogen gas has been modelled. The model has been developed under Matlab / Simulink© environment. Finally, individual models have been integrated into a global model, and simulated under ambient conditions. With the aim to analyse the temperature influence on the state of charge and filling and emptying time, other simulations were performed at different temperatures. The obtained results allow to conclude that this alloy offers a good behaviour with the discharge process under normal ambient conditions. Keywords: Hydrogen storage; metal hydrides; fuel cell; simulation; board applications

  6. Predicting formation enthalpies of metal hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.

    2004-01-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formedby chemical reaction between hydrogen...... and metal and for the stable hydrides this is associated with release of heat (#DELTA#H_f ). The more thermodynamically stable the hydride, the larger DHf, and the higher temperature is needed in order to desorphydrogen (reverse reaction) and vice versa. For practical application the temperature needed...

  7. Research on Metal Hydride Compressor System

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Ti-Zr series Laves phase hydrogen storage alloys with good hydrogen storage properties, such as large hydrogen capacity, rapid hydriding and dehydriding rate, high compression ratio, gentle plateau, small hysteresis, easily being activated and long cyclic stability etc. for metal hydride compressor have been investigated. In addition, a hydride compressor with special characteristics, namely, advanced filling method, good heat transfer effect and reasonable structural design etc. has also been constructed. A hydride compressor cryogenic system has been assembled coupling the compressor with a J-T micro-throttling refrigeration device and its cooling capacity can reach 0.4 W at 25 K.

  8. Thermodynamic Hydricity of Transition Metal Hydrides.

    Science.gov (United States)

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H(-)). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.

  9. Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.

    Science.gov (United States)

    Jordan, Abraham J; Lalic, Gojko; Sadighi, Joseph P

    2016-08-10

    Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

  10. Crystal structure of gold hydride

    Energy Technology Data Exchange (ETDEWEB)

    Degtyareva, Valentina F., E-mail: degtyar@issp.ac.ru

    2015-10-05

    Highlights: • Volume expansion of metal hydrides is due to the increase in the s-band filling. • AuH structure is similar to that of Hg having one more s electron compared to Au. • Structure stability of both Hg and AuH is governed by the Hume-Rothery rule. - Abstract: A number of transition metal hydrides with close-packed metal sublattices of fcc or hcp structures with hydrogen in octahedral interstitial positions were obtained by the high-pressure-hydrogen technique described by Ponyatovskii et al. (1982). In this paper we consider volume increase of metals by hydrogenation and possible crystal structure of gold hydride in relation with the structure of mercury, the nearest neighbor of Au in the Periodic table. Suggested structure of AuH has a basic tetragonal body-centered cell that is very similar to the mercury structure Hg-t I 2. The reasons of stability for this structure are discussed within the model of Fermi sphere–Brillouin zone interactions.

  11. Fundamental experiments on hydride reorientation in zircaloy

    Science.gov (United States)

    Colas, Kimberly B.

    In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and

  12. Crystal structure and switchable optical properties of yttrium hydride films covered by palladium layer

    Institute of Scientific and Technical Information of China (English)

    张文魁; 甘永平; 杨晓光; 黄辉; 余厉阳

    2003-01-01

    The palladium/yttrium films were prepared using magnetron sputtering technique.The changes of crystal structure,morphology and optical properties of the films during the hydrogen absorption/desorption process were investigated.The results of SEM and AFM analysis show that yttrium films have columnar structure,and the Pd cover layers on the surface of the yttrium films are composed of nanometer-sized Pd particles,which contain a large amount of smaller crystalline grains.During the gas hydrogen absorption/desorption process,YH3 and YH2 hydrides form on the sites of Pd grains contacting with Y grains.Upon hydrogenation,YH3 hydride forms and the switchable optical properties can be observed.The light transparency of the films increases with the increasing of hydrogen loading time and the light wavelength,and the absorption limitation occurs at λ=400 nm.Upon dehydrogenation,YH3 hydride dissociates into YH2 hydride,and the maximum transparency occurs at λ=689 nm.

  13. Kinetics of hydride front in Zircaloy-2 and H release from a fractional hydrided surface

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, M.; Gonzalez-Gonzalez, A.; Moya, J. S.; Remartinez, B.; Perez, S.; Sacedon, J. L. [Instituto de Ciencia de Materiales de Madrid (CSIC), Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain); Iberdrola, Tomas Redondo 3, 28033 Madrid (Spain); Instituto de Ciencia de Materiales de Madrid (CSIC), Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain)

    2009-07-15

    The authors study the hydriding process on commercial nuclear fuel claddings from their inner surface using an ultrahigh vacuum method. The method allows determining the incubation and failure times of the fuel claddings, as well as the dissipated energy and the partial pressure of the desorbed H{sub 2} from the outer surface of fuel claddings during the hydriding process. The correlation between the hydriding dissipated energy and the amount of zirconium hydride (formed at different stages of the hydriding process) leads to a near t{sup 1/2} potential law corresponding to the time scaling of the reaction for the majority of the tested samples. The calibrated relation between energy and hydride thickness allows one to calculate the enthalpy of the {delta}-ZrH{sub 1.5} phase. The measured H{sub 2} desorption from the external surface is in agreement with a proposed kinetic desorption model from the hydrides precipitated at the surface.

  14. Ionic conduction of lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Pilipenko, G.I.; Oparin, D.V.; Zhuravlev, N.A.; Gavrilov, F.F.

    1987-09-01

    Using the electrical-conductivity- and NMR-measurement- methods, the ionic-conduction mechanism is established in stoichiometric lithium hydride single crystals. The activation energies of migration of anion- and cation-vacancies and the formation of Schottky-pair defects are determined. They assume that the mechanisms of self-diffusion and conductivity are different in lithium hydride.

  15. Titanium tritide radioisotope heat source development : palladium-coated titanium hydriding kinetics and tritium loading tests.

    Energy Technology Data Exchange (ETDEWEB)

    Van Blarigan, Peter; Shugard, Andrew D.; Walters, R. Tom (Savannah River National Labs, Aiken, SC)

    2012-01-01

    We have found that a 180 nm palladium coating enables titanium to be loaded with hydrogen isotopes without the typical 400-500 C vacuum activation step. The hydriding kinetics of Pd coated Ti can be described by the Mintz-Bloch adherent film model, where the rate of hydrogen absorption is controlled by diffusion through an adherent metal-hydride layer. Hydriding rate constants of Pd coated and vacuum activated Ti were found to be very similar. In addition, deuterium/tritium loading experiments were done on stacks of Pd coated Ti foil in a representative-size radioisotope heat source vessel. The experiments demonstrated that such a vessel could be loaded completely, at temperatures below 300 C, in less than 10 hours, using existing department-of-energy tritium handling infrastructure.

  16. Room temperature and thermal decomposition of magnesium hydride/deuteride thin films

    Energy Technology Data Exchange (ETDEWEB)

    Ares, J.R.; Leardini, F.; Bodega, J.; Macia, M.D.; Diaz-Chao, P.; Ferrer, I.J.; Fernandez, J.F.; Sanchez, C. [Universidad Autonoma de Madrid (Spain). Lab. de Materiales de Interes en Energias Renovables

    2010-07-01

    Magnesium hydride (MgH{sub 2}) can be considered an interesting material to store hydrogen as long as two main drawbacks were solved: (i) its high stability and (ii) slow (de)hydriding kinetics. In that context, magnesium hydride films are an excellent model system to investigate the influence of structure, morphology and dimensionality on kinetic and thermodynamic properties. In the present work, we show that desorption mechanism of Pd-capped MgH{sub 2} at room temperature is controlled by a bidimensional interphase mechanism and a similar rate step limiting mechanism is observed during thermal decomposition of MgH{sub 2}. This mechanism is different to that occurring in bulk MgH{sub 2} (nucleation and growth) and obtained activation energies are lower than those reported in bulk MgH{sub 2}. We also investigated the Pd-capping properties upon H-absorption/desorption by means of RBS and isotope experiments. (orig.)

  17. Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape.

    Science.gov (United States)

    Syrenova, Svetlana; Wadell, Carl; Nugroho, Ferry A A; Gschneidtner, Tina A; Diaz Fernandez, Yuri A; Nalin, Giammarco; Świtlik, Dominika; Westerlund, Fredrik; Antosiewicz, Tomasz J; Zhdanov, Vladimir P; Moth-Poulsen, Kasper; Langhammer, Christoph

    2015-12-01

    Physicochemical properties of nanoparticles may depend on their size and shape and are traditionally assessed in ensemble-level experiments, which accordingly may be plagued by averaging effects. These effects can be eliminated in single-nanoparticle experiments. Using plasmonic nanospectroscopy, we present a comprehensive study of hydride formation thermodynamics in individual Pd nanocrystals of different size and shape, and find corresponding enthalpies and entropies to be nearly size- and shape-independent. The hysteresis observed is significantly wider than in bulk, with details depending on the specifics of individual nanoparticles. Generally, the absorption branch of the hysteresis loop is size-dependent in the sub-30 nm regime, whereas desorption is size- and shape-independent. The former is consistent with a coherent phase transition during hydride formation, influenced kinetically by the specifics of nucleation, whereas the latter implies that hydride decomposition either occurs incoherently or via different kinetic pathways.

  18. Comparison of selenium determination in liver samples by atomic absorption spectroscopy and inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Miksa, Irina Rudik; Buckley, Carol L; Carpenter, Nancy P; Poppenga, Robert H

    2005-07-01

    Selenium (Se) is an essential trace element that is often deficient in the natural diets of domestic animal species. The measurement of Se in whole blood or liver is the most accurate way to assess Se status for diagnostic purposes. This study was conducted to compare hydride generation atomic absorption spectroscopy (HG-AAS) with inductively coupled plasma-mass spectrometry (ICP-MS) for the detection and quantification of Se in liver samples. Sample digestion was accomplished with magnesium nitrate and nitric acid for HG-AAS and ICP-MS, respectively. The ICP-MS detection was optimized for 82Se with yttrium used as the internal standard and resulted in a method detection limit of 0.12 microg/g. Selenium was quantified by both methods in 310 samples from a variety of species that were submitted to the Toxicology Laboratory at New Bolton Center (Kennett Square, PA) for routine diagnostic testing. Paired measurements for each sample were evaluated by a mean difference plot method. Limits of agreement were used to describe the maximum differences likely to occur between the 2 methods. Results suggest that under the specified conditions ICP-MS can be reliably used in place of AAS for quantitation of tissue Se at or below 2 microg/g to differentiate between adequate and deficient liver Se concentrations.

  19. Recyclable decoration of amine-functionalized magnetic nanoparticles with Ni(2+) for determination of histidine by photochemical vapor generation atomic spectrometry.

    Science.gov (United States)

    Hu, Yuan; Wang, Qi; Zheng, Chengbin; Wu, Li; Hou, Xiandeng; Lv, Yi

    2014-01-07

    It is critically important to accurately determine histidine since it is an indicator for many diseases when at an abnormal level. Here, an inexpensive and simple method using an amine-functionalized magnetic nanoparticle-based Ni(2+)-histidine affinity pair system was developed for highly sensitive and selective detection of histidine in human urine by photochemical vapor generation atomic spectrometry. Ni(2+) was first bound to the amine groups of the amine-functionalized magnetic nanoparticles and then liberated to solution via the highly specific interaction between the histidine and Ni(2+) in the presence of histidine. The liberated histidine-Ni(2+) complex was exposed to UV irradiation in the presence of formic acid to form gaseous nickel tetracarbonyl, which was separated from the sample matrix and determined by atomic absorption/fluorescence spectrometry. Compared to other methods, this approach promises high sensitivity, simplicity in design, and convenient operation. The need for organic solvents, enzymatic reactions, separation processes, chemical modification, expensive instrumentations, and sophisticated and complicated pretreatment is minimized with this strategy. A limit of detection of 1 nM was obtained and provided tens-to-hundreds of fold improvements over that achieved with conventional methods. The protocol was evaluated by analysis of several urine samples with good recoveries and showed great potential for practical application.

  20. Hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S [Tampa, FL; Niemann, Michael U [Venice, FL; Goswami, D Yogi [Tampa, FL; Stefanakos, Elias K [Tampa, FL

    2012-04-10

    A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

  1. Hydride heat pump with heat regenerator

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative hydride heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system. A series of at least four canisters containing a lower temperature performing hydride and a series of at least four canisters containing a higher temperature performing hydride is provided. Each canister contains a heat conductive passageway through which a heat transfer fluid is circulated so that sensible heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  2. Hydrogen storage in complex metal hydrides

    National Research Council Canada - National Science Library

    Bogdanovic, Borislav; Felderhoff, Michael; Streukens, Guido

    2009-01-01

    ...) are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides...

  3. Method of forming metal hydride films

    Science.gov (United States)

    Steinberg, R.; Alger, D. L.; Cooper, D. W. (Inventor)

    1977-01-01

    The substrate to be coated (which may be of metal, glass or the like) is cleaned, both chemically and by off-sputtering in a vacuum chamber. In an ultra-high vacuum system, vapor deposition by a sublimator or vaporizer coats a cooled shroud disposed around the substrate with a thin film of hydride forming metal which getters any contaminant gas molecules. A shutter is then opened to allow hydride forming metal to be deposited as a film or coating on the substrate. After the hydride forming metal coating is formed, deuterium or other hydrogen isotopes are bled into the vacuum system and diffused into the metal film or coating to form a hydride of metal film. Higher substrate temperatures and pressures may be used if various parameters are appropriately adjusted.

  4. Sealed aerospace metal-hydride batteries

    Science.gov (United States)

    Coates, Dwaine

    1992-01-01

    Nickel metal hydride and silver metal hydride batteries are being developed for aerospace applications. There is a growing market for smaller, lower cost satellites which require higher energy density power sources than aerospace nickel-cadmium at a lower cost than space nickel-hydrogen. These include small LEO satellites, tactical military satellites and satellite constellation programs such as Iridium and Brilliant Pebbles. Small satellites typically do not have the spacecraft volume or the budget required for nickel-hydrogen batteries. NiCd's do not have adequate energy density as well as other problems such as overcharge capability and memory effort. Metal hydride batteries provide the ideal solution for these applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems.

  5. Probing the cerium/cerium hydride interface using nanoindentation

    Energy Technology Data Exchange (ETDEWEB)

    Brierley, Martin, E-mail: martin.brierley@awe.co.uk [Atomic Weapons Establishment, Aldermaston, Berkshire RG7 4PR (United Kingdom); University of Manchester, Manchester M13 9PL (United Kingdom); Knowles, John, E-mail: john.knowles@awe.co.uk [Atomic Weapons Establishment, Aldermaston, Berkshire RG7 4PR (United Kingdom)

    2015-10-05

    Highlights: • A disparity exists between the minimum energy and actual shape of a cerium hydride. • Cerium hydride is found to be harder than cerium metal by a ratio of 1.7:1. • A zone of material under compressive stress was identified surrounding the hydride. • No distribution of hardness was apparent within the hydride. - Abstract: A cerium hydride site was sectioned and the mechanical properties of the exposed phases (cerium metal, cerium hydride, oxidised cerium hydride) were measured using nanoindentation. An interfacial region under compressive stress was observed in the cerium metal surrounding a surface hydride that formed as a consequence of strain energy generated by the volume expansion associated with precipitation of the hydride phase.

  6. Destabilization of magnesium hydride through interface engineering

    OpenAIRE

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesium hydride is very stable, which means that hydrogen is released only at elevated temperature. Furthermore, the kinetics of hydrogen sorption is slow, which further hampers the practical use of this...

  7. Determination of the heat of hydride formation/decomposition by high-pressure differential scanning calorimetry (HP-DSC).

    Science.gov (United States)

    Rongeat, Carine; Llamas-Jansa, Isabel; Doppiu, Stefania; Deledda, Stefano; Borgschulte, Andreas; Schultz, Ludwig; Gutfleisch, Oliver

    2007-11-22

    Among the thermodynamic properties of novel materials for solid-state hydrogen storage, the heat of formation/decomposition of hydrides is the most important parameter to evaluate the stability of the compound and its temperature and pressure of operation. In this work, the desorption and absorption behaviors of three different classes of hydrides are investigated under different hydrogen pressures using high-pressure differential scanning calorimetry (HP-DSC). The HP-DSC technique is used to estimate the equilibrium pressures as a function of temperature, from which the heat of formation is derived. The relevance of this procedure is demonstrated for (i) magnesium-based compounds (Ni-doped MgH2), (ii) Mg-Co-based ternary hydrides (Mg-CoHx) and (iii) Alanate complex hydrides (Ti-doped NaAlH4). From these results, it can be concluded that HP-DSC is a powerful tool to obtain a good approximation of the thermodynamic properties of hydride compounds by a simple and fast study of desorption and absorption properties under different pressures.

  8. A comparison of simultaneous plasma, atomic absorption, and iron colorimetric determinations of major and trace constituents in acid mine waters

    Science.gov (United States)

    Ball, J.W.; Nordstrom, D.K.

    1994-01-01

    Sixty-three water samples collected during June to October 1982 from the Leviathan/Bryant Creek drainage basin were originally analyzed by simultaneous multielement direct-current plasma (DCP) atomic-emission spectrometry, flame atomic-absorption spectrometry, graphite-furnace atomic-absorption spectrometry (GFAAS) (thallium only), ultraviolet-visible spectrometry, and hydride-generation atomic-absorption spectrometry.Determinations were made for the following metallic and semi-metallic constituents: AI, As, B, Ba, Be, Bi, Cd, Ca, Cr, Co, Cu, Fe(11), Fe(total), Li, Pb, Mg, Mn, Mo, Ni, K, Sb, Se, Si, Na, Sr, TI, V, and Zn. These samples were re-analyzed later by simultaneous multielement inductively coupled plasma (ICP) atomic-emission spectrometry and Zeeman-corrected GFAAS to determine the concentrations of many of the same constituents with improved accuracy, precision, and sensitivity. The result of this analysis has been the generation of comparative concentration values for a significant subset of the solute constituents. Many of the more recently determined values replace less-than-detection values for the trace metals; others constitute duplicate analyses for the major constituents. The multiple determinations have yielded a more complete, accurate, and precise set of analytical data. They also have resulted in an opportunity to compare the performance of the plasma-emission instruments operated in their respective simultaneous multielement modes. Flame atomic-absorption spectrometry was judged best for Na and K and hydride-generation atomic-absorption spectrometry was judged best for As because of their lower detection limit and relative freedom from interelement spectral effects. Colorimetric determination using ferrozine as the color agent was judged most accurate, precise, and sensitive for Fe. Cadmium, lead, and vanadium concentrations were too low in this set of samples to enable a determination of whether ICP or DCP is a more suitable technique. Of

  9. gamma-Zr-Hydride Precipitate in Irradiated Massive delta- Zr-Hydride

    DEFF Research Database (Denmark)

    Warren, M. R.; Bhattacharya, D. K.

    1975-01-01

    During examination of A Zircaloy-2-clad fuel pin, which had been part of a test fuel assembly in a boiling water reactor, several regions of severe internal hydriding were noticed in the upper-plenum end of the pin. Examination of similar fuel pins has shown that hydride of this type is caused...

  10. Application of hafnium hydride control rod to large sodium cooled fast breeder reactor

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, Kazumi, E-mail: kazumi_ikeda@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Moriwaki, Hiroyuki, E-mail: hiroyuki_moriwaki@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Ohkubo, Yoshiyuki, E-mail: yoshiyuki_okubo@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Iwasaki, Tomohiko, E-mail: tomohiko.iwasaki@qse.tohoku.ac.jp [Department of Quantum Science and Energy Engineering, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai-shi, Miyagi-ken 980-8579 (Japan); Konashi, Kenji, E-mail: konashi@imr.tohoku.ac.jp [Institute for Materials Research, Tohoku University, Narita-cho, Oarai-machi, Higashi-Ibaraki-gun, Ibaraki-ken 311-1313 (Japan)

    2014-10-15

    Highlights: • Application of hafnium hydride control rod to large sodium cooled fast breeder reactor. • This paper treats application of an innovative hafnium hydride control rod to a large sodium cooled fast breeder reactor. • Hydrogen absorption triples the reactivity worth by neutron spectrum shift at H/Hf ratio of 1.3. • Lifetime of the control rod quadruples because produced daughters of hafnium isotopes are absorbers. • Nuclear and thermal hydraulic characteristics of the reactor are as good as or better than B-10 enriched boron carbide. - Abstract: This study treats the feasibility of long-lived hafnium hydride control rod in a large sodium-cooled fast breeder reactor by nuclear and thermal analyses. According to the nuclear calculations, it is found that hydrogen absorption of hafnium triples the reactivity by the neutron spectrum shift at the H/Hf ratio of 1.3, and a hafnium transmutation mechanism that produced daughters are absorbers quadruples the lifetime due to a low incineration rate of absorbing nuclides under irradiation. That is to say, the control rod can function well for a long time because an irradiation of 2400 EFPD reduces the reactivity by only 4%. The calculation also reveals that the hafnium hydride control rod can apply to the reactor in that nuclear and thermal characteristics become as good as or better than 80% B-10 enriched boron carbide. For example, the maximum linear heat rate becomes 3% lower. Owing to the better power distribution, the required flow rate decreases approximately by 1%. Consequently, it is concluded on desk analyses that the long lived hafnium hydride control rod is feasible in the large sodium-cooled fast breeder reactor.

  11. Electronic Principles of Hydrogen Incorporation and Dynamics in Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Ljiljana Matović

    2012-08-01

    Full Text Available An approach to various metal hydrides based on electronic principles is presented. The effective medium theory (EMT is used to illustrate fundamental aspects of metal-hydrogen interaction and clarify the most important processes taking place during the interaction. The elaboration is extended using the numerous existing results of experiment and calculations, as well as using some new material. In particular, the absorption/desorption of H in the Mg/MgH2 system is analyzed in detail, and all relevant initial structures and processes explained. Reasons for the high stability and slow sorption in this system are noted, and possible solutions proposed. The role of the transition-metal impurities in MgH2 is briefly discussed, and some interesting phenomena, observed in complex intermetallic compounds, are mentioned. The principle mechanism governing the Li-amide/imide transformation is also discussed. Latterly, some perspectives for the metal-hydrides investigation from the electronic point of view are elucidated.

  12. The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components Delayed Hydride Cracking

    CERN Document Server

    Puls, Manfred P

    2012-01-01

    By drawing together the current theoretical and experimental understanding of the phenomena of delayed hydride cracking (DHC) in zirconium alloys, The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components: Delayed Hydride Cracking provides a detailed explanation focusing on the properties of hydrogen and hydrides in these alloys. Whilst the focus lies on zirconium alloys, the combination of both the empirical and mechanistic approaches creates a solid understanding that can also be applied to other hydride forming metals.   This up-to-date reference focuses on documented research surrounding DHC, including current methodologies for design and assessment of the results of periodic in-service inspections of pressure tubes in nuclear reactors. Emphasis is placed on showing that our understanding of DHC is supported by progress across a broad range of fields. These include hysteresis associated with first-order phase transformations; phase relationships in coherent crystalline metallic...

  13. Accuracy of a method based on atomic absorption spectrometry to determine inorganic arsenic in food: Outcome of the collaborative trial IMEP-41.

    Science.gov (United States)

    Fiamegkos, I; Cordeiro, F; Robouch, P; Vélez, D; Devesa, V; Raber, G; Sloth, J J; Rasmussen, R R; Llorente-Mirandes, T; Lopez-Sanchez, J F; Rubio, R; Cubadda, F; D'Amato, M; Feldmann, J; Raab, A; Emteborg, H; de la Calle, M B

    2016-12-15

    A collaborative trial was conducted to determine the performance characteristics of an analytical method for the quantification of inorganic arsenic (iAs) in food. The method is based on (i) solubilisation of the protein matrix with concentrated hydrochloric acid to denature proteins and allow the release of all arsenic species into solution, and (ii) subsequent extraction of the inorganic arsenic present in the acid medium using chloroform followed by back-extraction to acidic medium. The final detection and quantification is done by flow injection hydride generation atomic absorption spectrometry (FI-HG-AAS). The seven test items used in this exercise were reference materials covering a broad range of matrices: mussels, cabbage, seaweed (hijiki), fish protein, rice, wheat, mushrooms, with concentrations ranging from 0.074 to 7.55mgkg(-1). The relative standard deviation for repeatability (RSDr) ranged from 4.1 to 10.3%, while the relative standard deviation for reproducibility (RSDR) ranged from 6.1 to 22.8%.

  14. Preliminary development of flaw evaluation procedures for delayed hydride cracking initiation under hydride non-ratcheting conditions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, S.; Cui, J.; Kawa, D.; Shek, G.K.; Scarth, D.A. [Kinectrics Inc., Toronto, Ontario (Canada)

    2006-07-01

    The flaw evaluation procedure for Delayed Hydride Cracking (DHC) initiation currently provided in the CSA Standard N285.8 was developed for hydride ratcheting conditions, in which flaw-tip hydrides do not completely dissolve at peak temperature. Test results have shown that hydrided regions formed under non-ratcheting conditions, in which flaw-tip hydrides completely dissolve at peak temperature, have significantly higher resistance to cracking than those formed under ratcheting conditions. This paper presents some preliminary work on the development of a procedure for the evaluation of DHC initiation for flaws under hydride non-ratcheting conditions. (author)

  15. Laboratory Rotational Spectroscopy of the Interstellar Diatomic Hydride Ion SH+ (X 3Σ-)

    Science.gov (United States)

    Halfen, DeWayne; Ziurys, Lucy M.

    2016-06-01

    Diatomic hydride are among the most common molecular species in the interstellar medium (ISM). The low molecular mass and thus moments of inertia cause their rotational spectra to lie principally in the submillimeter and far-infrared regions. Diatomic hydrides, both neutral (MH) and ionic (MH+) forms, are also basic building blocks of interstellar chemistry. In ionic form, they may be the “hidden” carriers of refractory elements in dense gas. They are therefore extremely good targets for space-borne and airborne platforms such as Herschel, SOFIA, and SAFIR. However, in order to detect these species in the ISM, their rotational spectra must first be measured in the laboratory. To date, there is very little high resolution data available for many hydride species, in particular the ionic form. Using submillimeter/THz direct absorption methods in the Ziurys laboratory, spectra of the interstellar diatomic hydride SH+ (X 3Σ-) have been recorded. Recent work has concerned measurement of all three fine structure components of the fundamental rotational transition N = 1 ← 0 in the range 345 - 683 GHz. SH+ was generated from H2S and argon in an AC discharge. The data have been analyzed, and spectroscopic constants for this species have been refined. SH+ is found in Photon Dominated Regions (PDRs) and X-ray Dominated Regions (XDRs) and is thought to trace energetic processes in the ISM. These current measurements confirm recent observations of this species at submillimeter/THz wavelengths with ALMA and other ground-based telescopes.

  16. In-situ study of hydriding kinetics in Pd-based thin film systems

    Energy Technology Data Exchange (ETDEWEB)

    Delmelle, Renaud; Proost, Joris [Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium). Div. of Materials and Process Engineering

    2010-07-01

    The hydriding kinetics of Pd thin films has been investigated in detail. The key experimental technique used in this work consists of a high resolution curvature measurement setup, which continuously monitors the reflections of multiple laser beams coming off a cantilevered sample. After mounting the sample inside a vacuum chamber, a H-containing gas mixture is introduced to instantaneously generate a given hydrogen partial pressure (p{sub H2}) inside the chamber. The resulting interaction of H with the Pd layer then leads to a volume expansion of the thin film system. This induces in turn changes in the sample curvature as a result of internal stresses developing in the Pd film during a hydriding cycle. Based on such curvature date obtained in-situ at different p{sub H2}, a two-step model for the kinetics of Pd-hydride formation has been proposed and expressions for the hydrogen adsorption and absorption velocities have been derived. The rate-limiting steps have been identified by studying the p{sub H2}-dependence of these velocities. Furthermore, from our in-situ experimental data, relevant kinetic parameters have been calculated. The effect of dry air exposure of the Pd films on the hydriding kinetics has been considered as well. (orig.)

  17. Hydriding and microstructure nanocrystallization of ZK60 Mg alloy by reaction milling in hydrogen

    Institute of Scientific and Technical Information of China (English)

    YUAN Yuan; WANG Heng; HU Lian-xi; SUN Hong-fei; FANG Wen-bin

    2009-01-01

    The hydriding of as-cast Mg-5.5%Zn-0.6%Zr (ZK60 Mg) (mass fraction) alloy was achieved by room-temperature reaction milling in hydrogen, with the mechanical energy serving as the driving force for the process. The hydriding progress during milling was examined by hydrogen absorption measurement, and the microstructure change was characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The results show that, by room-temperature reaction milling in hydrogen, the as-cast ZK60 Mg alloy can be fully hydrided to form a nanocrystalline MgH2 single-phase microstructure. In particular, the average grain size of the MgH2 phase obtained by room-temperature reaction milling in hydrogen for 16.2 h is about 8-10 nm, and the average particle size of the as-milled hydrided powders is 2-3 μm.

  18. Heavy hydrides: H2Te ultraviolet photochemistry

    Science.gov (United States)

    Underwood, J.; Chastaing, D.; Lee, S.; Wittig, C.

    2005-08-01

    The room-temperature ultraviolet absorption spectrum of H2Te has been recorded. Unlike other group-6 hydrides, it displays a long-wavelength tail that extends to 400 nm. Dissociation dynamics have been examined at photolysis wavelengths of 266 nm (which lies in the main absorption feature) and 355 nm (which lies in the long-wavelength tail) by using high-n Rydberg time-of-flight spectroscopy to obtain center-of-mass translational energy distributions for the channels that yield H atoms. Photodissociation at 355 nm yields TeH(Π1/22) selectively relative to the TeH(Π3/22) ground state. This is attributed to the role of the 3A' state, which has a shallow well at large RH-TeH and correlates to H +TeH(Π1/22). Note that the Π1/22 state is analogous to the P1/22 spin-orbit excited state of atomic iodine, which is isoelectronic with TeH. The 3A' state is crossed at large R only by 2A″, with which it does not interact. The character of 3A' at large R is influenced by a strong spin-orbit interaction in the TeH product. Namely, Π1/22 has a higher degree of spherical symmetry than does Π3/22 (recall that I(P1/22) is spherically symmetric), and consequently Π1/22 is not inclined to form either strongly bonding or antibonding orbitals with the H atom. The 3A'←X transition dipole moment dominates in the long-wavelength region and increases with R. Structure observed in the absorption spectrum in the 380-400 nm region is attributed to vibrations on 3A'. The main absorption feature that is peaked at ˜240nm might arise from several excited surfaces. On the basis of the high degree of laboratory system spatial anisotropy of the fragments from 266 nm photolysis, as well as high-level theoretical studies, the main contribution is believed to be due to the 4A″ surface. The 4A″←X transition dipole moment dominates in the Franck-Condon region, and its polarization is in accord with the experimental observations. An extensive secondary photolysis (i.e., of nascent TeH) is

  19. Pressure-induced transformations of molecular boron hydride

    CERN Document Server

    Nakano, S; Gregoryanz, E A; Goncharov, A F; Mao Ho Kwang

    2002-01-01

    Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV.

  20. High H- ionic conductivity in barium hydride

    Science.gov (United States)

    Verbraeken, Maarten C.; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T. S.

    2015-01-01

    With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H-) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm-1 at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

  1. Influence of surface contaminations on the hydrogen storage behaviour of metal hydride alloys.

    Science.gov (United States)

    Schülke, Mark; Paulus, Hubert; Lammers, Martin; Kiss, Gábor; Réti, Ferenc; Müller, Karl-Heinz

    2008-03-01

    Hydrogen storage in metal hydrides is a promising alternative to common storage methods. The surface of a metal hydride plays an important part in the absorption of hydrogen, since important partial reaction steps take place here. The development of surface contaminations and their influence on hydrogen absorption is examined by means of absorption experiments and surface analysis, using X-ray photoelectron spectroscopy (XPS), thermal desorption mass spectrometry (TDMS) and secondary neutral mass spectrometry (SNMS), in this work. All investigations were carried out on a modern AB(2) metal hydride alloy, namely Ti(0.96)Zr(0.04)Mn(1.43)V(0.45)Fe(0.08). Surface analysis (SNMS, XPS) shows that long-term air storage (several months) leads to oxide layers about 15 nm thick, with complete oxidation of all main alloy components. By means of in situ oxygen exposure at room temperature and XPS analysis, it can be shown that an oxygen dose of about 100 Langmuirs produces an oxide layer comparable to that after air storage. Manganese enrichment (segregation) is also clearly observed and is theoretically described here. This oxide layer hinders hydrogen absorption, so an activation procedure is necessary in order to use the full capacity of the metal hydride. This procedure consists of heating (T = 120 degrees C) in vacuum and hydrogen flushing at pressures like p = 18 bar. During the activation process the alloy is pulverized to particles of approximately 20 microm through lattice stretches. It is shown that this pulverization of the metal hydride (creating clean surface) during hydrogen flushing is essential for complete activation of the material. Re-activation of powder contaminated by small doses of air (p approximately 0.1 bar) does not lead to full absorption capacity. In ultrahigh vacuum, hydrogen is only taken up by the alloy after sputtering of the surface (which is done in order to remove oxide layers from it), thus creating adsorption sites for the hydrogen. This

  2. Lattice contraction in photochromic yttrium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter, E-mail: jepe@ife.no; Mongstad, Trygve T.; You, Chang Chuan; Karazhanov, Smagul

    2013-12-15

    Highlights: •Photochromic yttrium hydride films (YH:O) were prepared by reactive sputtering. •Black and transparent YH:O films were studied by time-resolved synchrotron XRD. •Both YH:O samples showed a lattice contraction upon illumination. •Also exposure to the X-ray beam itself results in a lattice contraction. -- Abstract: A strong photochromic effect was recently discovered in thin films of oxygen-containing yttrium hydride taking place at room temperature and reacting to ultraviolet and visible light. In this paper, we report on a lattice contraction upon illumination observed for thin-film samples of photochromic yttrium hydride, recorded by time-resolved X-ray diffraction using synchrotron radiation. The time dependence of the lattice contraction is consistent with the observed photochromic response of the samples.

  3. Atom probe analysis of titanium hydride precipitates.

    Science.gov (United States)

    Takahashi, J; Kawakami, K; Otsuka, H; Fujii, H

    2009-04-01

    It is expected that the three-dimensional atom probe (3DAP) will be used as a tool to visualize the atomic scale of hydrogen atoms in steel is expected, due to its high spatial resolution and very low detection limit. In this paper, the first 3DAP analysis of titanium hydride precipitates in metal titanium is reported in terms of the quantitative detection of hydrogen. FIB fabrication techniques using the lift-out method have enabled the production of needle tips of hydride precipitates, of several tens of microns in size, within a titanium matrix. The hydrogen concentration estimated from 3DAP analysis was slightly smaller than that of the hydride phase predicted from the phase diagram. We discuss the origin of the difference between the experimental and predicted values and the performance of 3DAP for the quantitative detection of hydrogen.

  4. Hydrogen storage in complex metal hydrides

    Directory of Open Access Journals (Sweden)

    BORISLAV BOGDANOVIĆ

    2009-02-01

    Full Text Available Complex metal hydrides such as sodium aluminohydride (NaAlH4 and sodium borohydride (NaBH4 are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides. The most important point for a wide application of these materials is the reversibility under moderate technical conditions. At present, only NaAlH4 has favourable thermodynamic properties and can be employed as a thermally reversible means of hydrogen storage. By contrast, NaBH4 is a typical non- -reversible complex metal hydride; it reacts with water to produce hydrogen.

  5. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    Science.gov (United States)

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

  6. Structural and magnetic transformations in NdMn{sub 2}H{sub x} hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Budziak, A., E-mail: andrzej.budziak@ifj.edu.pl [H. Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Zachariasz, P. [Faculty of Physics and Applied Computer Science, AGH, University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow (Poland); Pelka, R. [The H. Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Figiel, H.; Zukrowski, J.; Woch, M.W. [Faculty of Physics and Applied Computer Science, AGH, University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow (Poland)

    2012-06-05

    Highlights: Black-Right-Pointing-Pointer Full structural phase diagram is presented for the NdMn{sub 2}H{sub x} (2.0 {<=} x {<=} 4.0) hydrides in the temperature range of 70-385 K. Black-Right-Pointing-Pointer For samples x = 2.0, 2.5, and 4.0 a splitting into two phases with different hydrogen concentrations are observed. Black-Right-Pointing-Pointer Only for samples with x = 3.0 and 3.5 no spinodal decompositions are detected. Black-Right-Pointing-Pointer The effects of hydrogen absorption on structural properties are shown to be reflected in magnetic behavior. Black-Right-Pointing-Pointer A huge jump of magnetic ordering temperatures from {approx}104 K for host NdMn{sub 2} to above 200 K for its hydrides is observed or anticipated. - Abstract: X-ray powder diffraction and bulk magnetization measurements were used to study structural and magnetic properties of hydrides NdMn{sub 2}H{sub x} (2.0 {<=} x {<=} 4.0). The X-ray investigations performed in the temperature range 70-385 K have revealed many structural transformations at low temperatures. In particular, a transformation from the hexagonal to the monoclinic phase and spinodal decompositions were observed. The magnetic behavior of the hydrides is correlated with the structural transitions. A tentative structural diagram is presented. The obtained results are compared with the properties of other cubic and hexagonal RMn{sub 2}H{sub x} hydrides.

  7. Evidence of stress-induced hydrogen ordering in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Steuwer, A. [FaME38 at the ESRF-ILL, 6 rue J Horowitz, 38042 Grenoble (France); ESS Scandinavia, University of Lund, Stora Algatan 4, 22350 Lund (Sweden)], E-mail: steuwer@ill.fr; Santisteban, J.R. [Centro Atomico Bariloche, CNEA, San Carlos de Bariloche (Argentina); Preuss, M. [University of Manchester, Grosvenor Street, Manchester M1 7HS (United Kingdom); Peel, M.J.; Buslaps, T. [European Synchrotron Radiation Facility, 6 rue J Horowitz, 38042 Grenoble (France); Harada, M. [R and D Section, Chofu-Kita Plant, Kobe Special Tube Co, Shimonoseki 752-0953 (Japan)

    2009-01-15

    The formation of hydrides in zirconium alloys significantly affects their mechanical properties and is considered to play a critical role in their failure mechanisms, yet relatively little is known about the micromechanical behavior of hydrides in the bulk. This paper presents the result of in situ uniaxial mechanical tensioning experiments on hydrided zircaloy-2 and zircaloy-4 specimens using energy-dispersive synchrotron X-ray diffraction, which suggests that a stress-induced transformation of the {delta}-hydride to {gamma}-hydride via ordering of the hydrogen atoms occurs, akin to a Snoek-type relaxation. Subsequent annealing was found to reverse the ordering phenomenon.

  8. Mathematical Modeling of Pneumatic Artificial Muscle Actuation via Hydrogen Driving Metal Hydride-LaNi5

    Institute of Scientific and Technical Information of China (English)

    Thananchai Leephakpreeda

    2012-01-01

    Quantitative understanding of mechanical actuation of intricate Pneumatic Artificial Muscle (PAM) actuators is technically required in control system design for effective real-time implementation.This paper presents mathematical modeling of the PAM driven by hydrogen-gas pressure due to absorption and desorption of metal hydride.Empirical models of both mechanical actuation of industrial PAM and chemical reaction of the metal hydride-LaNi5 are derived systematically where their interactions comply with the continuity principle and energy balance in describing actual dynamic behaviors of the PAM actuator (PAM and hydriding/dehydriding-reaction bed).Simulation studies of mechanical actuation under various loads are conducted so as to present dynamic responses of the PAM actuators.From the promising results,it is intriguing that the heat input for the PAM actuator can be supplied to,or pumped from the reaction bed,in such a way that absorption and desorption of hydrogen gas take place,respectively,in controlling the pressure of hydrogen gas within the PAM actuator.Accordingly,this manipulation results in desired mechanical actuation of the PAM actuator in practical uses.

  9. Hydride formation on deformation twin in zirconium alloy

    Science.gov (United States)

    Kim, Ju-Seong; Kim, Sung-Dae; Yoon, Jonghun

    2016-12-01

    Hydrides deteriorate the mechanical properties of zirconium (Zr) alloys used in nuclear reactors. Intergranular hydrides that form along grain boundaries have been extensively studied due to their detrimental effects on cracking. However, it has been little concerns on formation of Zr hydrides correlated with deformation twins which is distinctive heterogeneous nucleation site in hexagonal close-packed metals. In this paper, the heterogeneous precipitation of Zr hydrides at the twin boundaries was visualized using transmission electron microscopy. It demonstrates that intragranular hydrides in the twinned region precipitates on the rotated habit plane by the twinning and intergranular hydrides precipitate along the coherent low energy twin boundaries independent of the conventional habit planes. Interestingly, dislocations around the twin boundaries play a substantial role in the nucleation of Zr hydrides by reducing the misfit strain energy.

  10. Scaling up effects of Mg hydride in a temperature and pressure-controlled hydrogen storage device

    Energy Technology Data Exchange (ETDEWEB)

    Verga, M.; Armanasco, F.; Guardamagna, C.; Valli, C. [CESI RICERCA S.p.A., Via Rubattino 54, 20134 Milano (Italy); Bianchin, A.; Lo Russo, S. [Dipartimento di Fisica, Universita di Padova, via Marzolo 8, 35131 Padova (Italy); Agresti, F.; Maddalena, A.; Principi, G. [Settore Materiali, Dipartimento di Ingegneria Meccanica, via Marzolo 9, 35131 Padova (Italy)

    2009-05-15

    A research program addressed to evaluate the magnesium hydride storage scaling up effects is being developed by CESI RICERCA, Milano, and the Hydrogen Group of Padova University. A storage device containing 500 g of magnesium hydride powder (manufactured by Venezia Tecnologie S.p.A. using high-energy ball milling) has been designed and tested in different operating conditions. A number of absorption and desorption cycles at different temperatures and pressures has been carried out in order to see if the results are comparable with laboratory data obtained on small amounts (fractions of grams) of powder samples. A sensible performance degradation that reduced the overall storage capacity of about 50% has been noticed after 20 cycles, presumably due to local powder heating, fragmentation and subsequent compaction. Further tests on a smaller tank equipped also with a porous baffle gave useful indications for the design of an improved large hydrogen reservoir. (author)

  11. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form,

  12. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  13. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  14. Automated determinations of selenium in thermal power plant wastewater by sequential hydride generation and chemiluminescence detection.

    Science.gov (United States)

    Ezoe, Kentaro; Ohyama, Seiichi; Hashem, Md Abul; Ohira, Shin-Ichi; Toda, Kei

    2016-02-01

    After the Fukushima disaster, power generation from nuclear power plants in Japan was completely stopped and old coal-based power plants were re-commissioned to compensate for the decrease in power generation capacity. Although coal is a relatively inexpensive fuel for power generation, it contains high levels (mgkg(-1)) of selenium, which could contaminate the wastewater from thermal power plants. In this work, an automated selenium monitoring system was developed based on sequential hydride generation and chemiluminescence detection. This method could be applied to control of wastewater contamination. In this method, selenium is vaporized as H2Se, which reacts with ozone to produce chemiluminescence. However, interference from arsenic is of concern because the ozone-induced chemiluminescence intensity of H2Se is much lower than that of AsH3. This problem was successfully addressed by vaporizing arsenic and selenium individually in a sequential procedure using a syringe pump equipped with an eight-port selection valve and hot and cold reactors. Oxidative decomposition of organoselenium compounds and pre-reduction of the selenium were performed in the hot reactor, and vapor generation of arsenic and selenium were performed separately in the cold reactor. Sample transfers between the reactors were carried out by a pneumatic air operation by switching with three-way solenoid valves. The detection limit for selenium was 0.008 mg L(-1) and calibration curve was linear up to 1.0 mg L(-1), which provided suitable performance for controlling selenium in wastewater to around the allowable limit (0.1 mg L(-1)). This system consumes few chemicals and is stable for more than a month without any maintenance. Wastewater samples from thermal power plants were collected, and data obtained by the proposed method were compared with those from batchwise water treatment followed by hydride generation-atomic fluorescence spectrometry.

  15. Thermodynamic diagnosis of the properties and mechanism of dihydropyridine-type compounds as hydride source in acetonitrile with "Molecule ID Card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Tan, Yue; Cao, Chao-Tun

    2010-02-11

    A series of 45 dihydropyridine-type organic compounds as hydride source were designed and synthesized. The thermodynamic driving forces (defined as enthalpy changes or redox potentials in this work) of the dihydropyridines to release hydride anions, hydrogen atoms (hydrogen for short), and electrons in acetonitrile, the thermodynamic driving forces of the radical cations of the dihydropyridines to release protons and hydrogens in acetonitrile, and the thermodynamic driving forces of the neutral pyridine-type radicals of the dihydropyridines to release electron in acetonitrile were determined by using titration calorimetry and electrochemical methods. The rates and activation parameters of hydride transfer from the dihydropyridines to acridinium perclorate, a well-known hydride acceptor, were determined by using UV-vis absorption spectroscopy technique. The relationship between the thermodynamic driving forces and kinetic rate of the hydride transfer was examined. Thermodynamic characteristic graph (TCG) of the dihydropyridines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose or predict the characteristic chemical properties of the dihydropyridines and their various reaction intermediates. The mechanism of hydride transfer from the dihydropyridines to acridinium perclorate was diagnosed and elucidated by using the determined thermodynamic parameters and the activation parameters.

  16. A review of recent advances on the effects of microstructural refinement and nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Varin, R. A.; Zbroniec, L. [University of Waterloo, Department of Mechanical and Mechatronics Engineering, Waterloo, Ontario (Canada); Polanski, M.; Bystrzycki, J. [Faculty of Advanced Technology and Chemistry, Military University of Technology, Warsaw (Poland)

    2011-07-01

    The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada) and Military University of Technology (Warsaw, Poland) are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size) induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand, the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general, catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which, in turn, act catalytically. However, these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g., enthalpy change of hydrogen sorption reactions). It is shown that a complex metal hydride, LiAlH{sub 4}, after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl{sub 2} catalytic precursor, is able to desorb relatively large quantities of hydrogen at room temperature, 40 and 80 {sup o}C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems. (authors)

  17. A Review of Recent Advances on the Effects of Microstructural Refinement and Nano-Catalytic Additives on the Hydrogen Storage Properties of Metal and Complex Hydrides

    Directory of Open Access Journals (Sweden)

    Jerzy Bystrzycki

    2010-12-01

    Full Text Available The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada and Military University of Technology (Warsaw, Poland are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand, the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general, catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which, in turn, act catalytically. However, these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g., enthalpy change of hydrogen sorption reactions. It is shown that a complex metal hydride, LiAlH4, after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl2 catalytic precursor, is able to desorb relatively large quantities of hydrogen at RT, 40 and 80 °C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems.

  18. Highly efficient bimetal synergetic catalysis by a multi-wall carbon nanotube supported palladium and nickel catalyst for the hydrogen storage of magnesium hydride.

    Science.gov (United States)

    Yuan, Jianguang; Zhu, Yunfeng; Li, Liquan

    2014-06-25

    A multi-wall carbon nanotube supported Pd and Ni catalyst efficiently catalyzes the hydrogen storage of magnesium hydride prepared by HCS + MM. Excellent hydrogen storage properties were obtained: hydrogen absorption - 6.44 wt% within 100 s at 373 K, hydrogen desorption - 6.41 wt% within 1800 s at 523 K and 6.70 wt% within 400 s at 573 K.

  19. Electrolytic hydriding of LaFe{sub 13-x}Si{sub x} alloys for energy efficient magnetic cooling

    Energy Technology Data Exchange (ETDEWEB)

    Lyubina, Julia; Hannemann, Ullrich; Ryan, Mary P. [Department of Materials, Imperial College London (United Kingdom); Cohen, Lesley F. [Department of Physics, Imperial College London (United Kingdom)

    2012-04-17

    An effective, low-temperature and readily available electrochemical method for tuning the operation temperature of LaFe{sub 13-x}Si{sub x}-type alloys is demonstrated. Electrolytically hydrided materials have the same high level magnetic properties as in high temperature gas-phase processed materials and offer an advantage of higher hydrogen absorption rate in the ferromagnetic state. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Numerical study of a magnesium hydride tank

    Science.gov (United States)

    Delhomme, Baptiste; de Rango, Patricia; Marty, Philippe

    2012-11-01

    Hydrogen storage in metal hydride tanks (MHT) is a very promising solution. Several experimental tanks, studied by different teams, have already proved the feasibility and the interesting performances of this solution. However, in much cases, an optimization of tank geometry is still needed in order to perform fast hydrogen loading. The development of efficient numerical tools is a key issue for MHT design and optimization. We propose a simple model representing a metal hydride tank exchanging its heat of reaction with a thermal fluid flow. In this model, the radial and axial discretisations have been decoupled by using Matlab® one-dimensional tools. Calculations are compared to experimental results obtained in a previous study. A good agreement is found for the loading case. The discharging case shows some discrepancies, which are discussed in this paper.

  1. A generic statistical model of hydride formation in a random alloy

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2016-09-01

    Hydride formation in metals (e.g. in Pd), accompanied by a hysteresis loop in the absorption isotherms, is one of the generic examples of first-order phase transitions (FOPTs). During the last decade, the corresponding experimental studies, driven by applications related to hydrogen storage, have shifted towards metal particles sized from a few nanometers to micrometers in general and to alloyed particles of these sizes in particular. The understanding of hydride formation in alloys is, however, still far from complete. Herein, a statistical model of hydride formation in a random alloy is presented. The model is focused on the situation when this process is favorable in metal 1 (e.g. Pd) and shows what may happen when atoms of metal 2 make it less favorable due to decrease of the hydrogen binding energy and/or attractive hydrogen-hydrogen (H-H) interaction. Random distribution of metal atoms is taken explicitly into account. The attractive H-H interaction, including its dependence on fraction of metal 2 in the alloy, is described at the mean-field level. With increasing fraction of the latter metal, the critical temperature is found to decrease linearly or nonlinearly depending on the values of the model parameters. If the decrease of the hydrogen binding energy with increasing number of nearest-neighbor (nn) atoms of metal 2 is appreciable, the model predicts up to three hysteresis loops.

  2. Nickel metal hydride LEO cycle testing

    Science.gov (United States)

    Lowery, Eric

    1995-01-01

    The George C. Marshall Space Flight Center is working to characterize aerospace AB5 Nickel Metal Hydride (NiMH) cells. The cells are being evaluated in terms of storage, low earth orbit (LEO) cycling, and response to parametric testing (high rate charge and discharge, charge retention, pulse current ability, etc.). Cells manufactured by Eagle Picher are the subjects of the evaluation. There is speculation that NiMH cells may become direct replacements for current Nickel Cadmium cells in the near future.

  3. Storing hydrogen in the form of light alloy hydrides

    Science.gov (United States)

    Freund, E.; Gillerm, C.

    1981-01-01

    Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

  4. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    Science.gov (United States)

    Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

    2014-12-23

    In this review, we discuss the evolution of localized surface plasmon resonance and surface plasmon resonance hydrogen sensors based on nanostructured metal hydrides, which has accelerated significantly during the past 5 years. We put particular focus on how, conceptually, plasmonic resonances can be used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and at the single-nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes in the quest to develop efficient solid-state hydrogen storage materials with fast response times, reasonable thermodynamics, and acceptable long-term stability. Therefore, a brief introduction to the thermodynamics of metal hydride formation is also given. However, plasmonic hydrogen sensors not only are of academic interest as research tool in materials science but also are predicted to find more practical use as all-optical gas detectors in industrial and medical applications, as well as in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier. Therefore, the wide range of different plasmonic hydrogen sensor designs already available is reviewed together with theoretical efforts to understand their fundamentals and optimize their performance in terms of sensitivity. In this context, we also highlight important challenges to be addressed in the future to take plasmonic hydrogen sensors from the laboratory to real applications in devices, including poisoning/deactivation of the active materials, sensor lifetime, and cross-sensitivity toward other gas species.

  5. Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

    Science.gov (United States)

    Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

    1993-01-01

    Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

  6. Method of making crack-free zirconium hydride

    Science.gov (United States)

    Sullivan, Richard W.

    1980-01-01

    Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

  7. Creating nanoshell on the surface of titanium hydride bead

    Directory of Open Access Journals (Sweden)

    PAVLENKO Vyacheslav Ivanovich

    2016-12-01

    Full Text Available The article presents data on the modification of titanium hydride bead by creating titanium nanoshell on its surface by ion-plasma vacuum magnetron sputtering. To apply titanium nanoshell on the titanium hydride bead vacuum coating plant of multifunctional nanocomposite coatings QVADRA 500 located in the center of high technology was used. Analysis of the micrographs of the original surface of titanium hydride bead showed that the microstructure of the surface is flat, smooth, in addition the analysis of the microstructure of material surface showed the presence of small porosity, roughness, mainly cavities, as well as shallow longitudinal cracks. The presence of oxide film in titanium hydride prevents the free release of hydrogen and fills some micro-cracks on the surface. Differential thermal analysis of both samples was conducted to determine the thermal stability of the initial titanium hydride bead and bead with applied titanium nanoshell. Hydrogen thermal desorption spectra of the samples of the initial titanium hydride bead and bead with applied titanium nanoshell show different thermal stability of compared materials in the temperature range from 550 to 860о C. Titanium nanoshells applied in this way allows increasing the heat resistance of titanium hydride bead – the temperature of starting decomposition is 695о C and temperature when decomposition finishes is more than 1000о C. Modified in this way titanium hydride bead can be used as a filler in the radiation protective materials used in the construction or upgrading biological protection of nuclear power plants.

  8. Hydrogen storage in the form of metal hydrides

    Science.gov (United States)

    Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

    1984-01-01

    Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

  9. Electrochemical and Optical Properties of Magnesium-Alloy Hydrides Reviewed

    Directory of Open Access Journals (Sweden)

    Thirugnasambandam G. Manivasagam

    2012-10-01

    Full Text Available As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase hydrogen loading, provides precise control with only moderate reaction conditions. Interestingly, the alloy composition determines the crystallographic nature of the metal-hydride: a structural change is induced from rutile to fluorite at 80 at.% of Mg in Mg-TM alloy, with ensuing improved hydrogen mobility and storage capacity. So far, 6 wt.% (equivalent to 1600 mAh/g of reversibly stored hydrogen in MgyTM(1-yHx (TM: Sc, Ti has been reported. Thin film forms of these metal-hydrides reveal interesting electrochromic properties as a function of hydrogen content. Optical switching occurs during (dehydrogenation between the reflective metal and the transparent metal hydride states. The chronological sequence of the optical improvements in optically active metal hydrides starts with the rare earth systems (YHx, followed by Mg rare earth alloy hydrides (MgyGd(1-yHx and concludes with Mg transition metal hydrides (MgyTM(1-yHx. In-situ optical characterization of gradient thin films during (dehydrogenation, denoted as hydrogenography, enables the monitoring of alloy composition gradients simultaneously.

  10. High energy density battery based on complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  11. High energy density battery based on complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  12. Synthesis, characterization and properties of some organozinc hydride complexes

    NARCIS (Netherlands)

    Koning, A.J. de; Boersma, J.; Kerk, G.J.M. van der

    1980-01-01

    The synthesis and characterization of the monopyridine complexes of ethylzinc hydride and phenylzinc hydride are described. On treatment with TMED these complexes are converted into R2Zn3H4. TMED species through a combination of ligand-exchange and disproportionation. The formation of organozinc hyd

  13. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    Energy Technology Data Exchange (ETDEWEB)

    Shek, G.K. [Ontario Hydro Technol., Ont. (Canada). Mater. Technol. Unit; Jovanovic, M.T. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Seahra, H. [Ontario Hydro Technol., Ont. (Canada). Mater. Technol. Unit; Ma, Y. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Li, D. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Eadie, R.L. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extruded pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at K{sub I} below 12 MPa {radical}m at both 200 and 250 C very large striations (>40 {mu}m at 200 and >50 {mu}m at 250 C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when K{sub I} was increased beyond about 12 MPa {radical}m for these same specimens, the striation spacing decreased below 30 {mu}m, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface. (orig.).

  14. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    Science.gov (United States)

    Shek, G. K.; Jovanoviċ, M. T.; Seahra, H.; Ma, Y.; Li, D.; Eadie, R. L.

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extrude pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at KI below 12 MPa √m at both 200 and 250°C very large striations (> 40 μ at 200 and >50 μm at 250°C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when KI was increased beyond about 12 MPa √m for these same specimens, the striation spacing decreased below 30 μ, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface.

  15. High ramp rate thermogravimetric analysis of zirconium(II) hydride and titanium(II) hydride

    Energy Technology Data Exchange (ETDEWEB)

    Licavoli, Joseph J., E-mail: jjlicavo@mtu.edu; Sanders, Paul G., E-mail: sanders@mtu.edu

    2015-09-20

    Highlights: • A unique arc image device has been proposed for high ramp rate thermogravimetry. • Powder oxidation influences decomposition kinetics at temperatures below 933 K. • Particle size has a negligible effect on TiH{sub 2} decomposition behavior. • Improvements to the device are required to conduct accurate kinetic analysis. - Abstract: Zirconium and titanium hydride are utilized in liquid phase metal foam processing techniques. This application results in immediate exposure to molten metal and almost immediate decomposition at high temperatures. Most decomposition characterization techniques utilize slow heating rates and are unable to capture the decomposition behavior of hydrides under foam processing conditions. In order to address this issue a specialized high ramp rate thermogravimetric analyzer was created from a xenon arc image refiner. In addition to thermogravimetry, complimentary techniques including X-ray diffraction and scanning electron microscopy were used to characterize hydride decomposition and compare the results to literature. Hydrides were partially oxidized and separated into particles size ranges to evaluate the influence of these factors on decomposition. Oxidizing treatments were found to decrease decomposition rate only at temperatures below 933 K (660 °C) while particle size effects appeared to be negligible. Several improvements to the unique TGA apparatus presented in the current work are suggested to allow reliable kinetic modeling and analysis.

  16. ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jy-An John [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Yan, Yong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Wang, Hong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-10-28

    A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydrides in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation tests of

  17. Growth and decomposition of Lithium and Lithium hydride on Nickel

    DEFF Research Database (Denmark)

    Engbæk, Jakob; Nielsen, Gunver; Nielsen, Jane Hvolbæk

    2006-01-01

    In this paper we have investigated the deposition, structure and decomposition of lithium and lithium-hydride films on a nickel substrate. Using surface sensitive techniques it was possible to quantify the deposited Li amount, and to optimize the deposition procedure for synthesizing lithium......-hydride films. By only making thin films of LiH it is possible to study the stability of these hydride layers and compare it directly with the stability of pure Li without having any transport phenomena or adsorbed oxygen to obscure the results. The desorption of metallic lithium takes place at a lower...... temperature than the decomposition of the lithium-hydride, confirming the high stability and sintering problems of lithium-hydride making the storage potential a challenge. (c) 2006 Elsevier B.V. All rights reserved....

  18. Helium trapping at erbium oxide precipitates in erbium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Foiles, Stephen M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Battaile, Corbett Chandler [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-02-01

    The formation of He bubbles in erbium tritides is a significant process in the aging of these materials. Due to the long-standing uncertainty about the initial nucleation process of these bubbles, there is interest in mechanisms that can lead to the localization of He in erbium hydrides. Previous work has been unable to identify nucleation sites in homogeneous erbium hydride. This work builds on the experimental observation that erbium hydrides have nano- scale erbium oxide precipitates due to the high thermodynamic stability of erbium oxide and the ubiquitous presence of oxygen during materials processing. Fundamental DFT calculations indicate that the He is energetically favored in the oxide relative to the bulk hydride. Activation energies for the motion of He in the oxide and at the oxide-hydride interface indicate that trapping is kinetically feasible. A simple kinetic Monte Carlo model is developed that demonstrates the degree of trapping of He as a function of temperature and oxide fraction.

  19. Photochromism of rare-earth metal-oxy-hydrides

    Science.gov (United States)

    Nafezarefi, F.; Schreuders, H.; Dam, B.; Cornelius, S.

    2017-09-01

    Recently, thin films of yttrium oxy-hydride (YOxHy) were reported to show an unusual color-neutral photochromic effect promising for application in smart windows. Our present work demonstrates that also oxy-hydrides based on Gd, Dy, and Er have photochromic properties and crystal structures similar to YOxHy. Compared to YOxHy, the optical bandgaps of the lanthanide based oxy-hydrides are smaller while photochromic contrast and kinetics show large variation among different cations. Based on these findings, we propose that cation alloying is a viable pathway to tailor the photochromic properties of oxy-hydride materials. Furthermore, we predict that the oxy-hydrides of the other lanthanides are also potentially photochromic.

  20. Metal hydrides for concentrating solar thermal power energy storage

    Science.gov (United States)

    Sheppard, D. A.; Paskevicius, M.; Humphries, T. D.; Felderhoff, M.; Capurso, G.; Bellosta von Colbe, J.; Dornheim, M.; Klassen, T.; Ward, P. A.; Teprovich, J. A.; Corgnale, C.; Zidan, R.; Grant, D. M.; Buckley, C. E.

    2016-04-01

    The development of alternative methods for thermal energy storage is important for improving the efficiency and decreasing the cost of concentrating solar thermal power. We focus on the underlying technology that allows metal hydrides to function as thermal energy storage (TES) systems and highlight the current state-of-the-art materials that can operate at temperatures as low as room temperature and as high as 1100 °C. The potential of metal hydrides for thermal storage is explored, while current knowledge gaps about hydride properties, such as hydride thermodynamics, intrinsic kinetics and cyclic stability, are identified. The engineering challenges associated with utilising metal hydrides for high-temperature TES are also addressed.

  1. Simultaneous determination of arsenic and antimony in water by hydride generation-atomic fluorescence spectrometry%同时测定水中砷和锑的氢化物发生-原子荧光光谱法

    Institute of Scientific and Technical Information of China (English)

    宋岳; 周虹

    2012-01-01

    目的 建立双道原子荧光光度计同时测定饮用水中砷和锑的方法,以提高工作效率.方法 选择最佳的仪器条件,进行样品处理方法及酸度、硼氢化钾浓度、检出限、线性范围、精密度、加标回收率等研究.结果 该方法线性关系:砷为0 ~ 80 μg/L,锑为O~40μg/L.检出限:砷为0.087 μg/L,锑为0.19μg/L.相对标准偏差:砷为1.93% ~ 2.55%;锑为1.97% ~3.02%.平均加标回收率:砷为95.7%;锑为96.5%.结论 该方法操作简便,灵敏度高,快速,便于推广,适用于水中砷和锑的同时测定.%[ Objective]To establish the method for simultaneous determination of arsenic and antimony in drinking water by double channel atomic fluorescence spectrometer, improve work efficiency. [Methods]Choosing optimal instrument condition, the sample treatment method, acidity, concentration of potassium borohydride, detection limit, linear range, precision and the recovery of standard addition were studied. [Results]The linear relationship of arsenic and antimony was 0-80μg/L and 0-40 μg/L respectively. The detection limit of arsenic and antimony was 0.087 μg/L and 0.19 μg/L respectively. The relative standard deviation of arsenic and antimony was 1.93% -2. 55% and 1. 97% -3. 02% respectively. The average recovery of standard addition of arsenic and antimony was 95.7% and 96.5% respectively. [ Conclusion] This method has the advantages of simple operation and high sensitivity , it is rapid and easy to spread, which is suitable for simultaneous determination of arsenic and antimony in water.

  2. Determination of arsenic in urine by wet digestion-hydride generation atomic fluorescence spectrometry%湿法消化-氢化物原子荧光法测定尿中砷

    Institute of Scientific and Technical Information of China (English)

    张克梅; 王文静

    2011-01-01

    Objective: To establish an accurate and simple determination of universal detection of arsenic in urine. Methods:Mixed acid sample digestion in the electric panel heating with thiourea, ascorbic acid to pentavalent arsenic to trivalent arsenic pre -reduction, and then potassium borohydride as reducing agent, to 5% HNO3 as the medium, with the AFS-230E direct determination of atomic fluorescence spectrometer. Results: The optimal experimental conditions, good linearity was presented within the arsenic concentration range of 0.0 μg/L ~ 20.0 μg/L; and the correlation coefficient was 0.9999, the lowest detection limit of the method was 0. 164 μg/L, relative standard deviation (RSD) was 0.4% ~ 1.2%, the recovery was 98.6% ~103.5%. Conclusion: The method is simple, precise, which high recovery rate, which is to determine a reliable method ofurinary arsenic.%目的:建立一种准确简单易于普及的测定尿中砷的检测方法.方法:样品用混合酸在电热板上加热消解后,用硫脉抗坏血酸将五价砷预还原为三价砷,再用硼氢化钾作还原剂,以5% HNO3为介质,用AF5-230E原子荧光光度计直接测定.结果:在最佳实验条件下,砷的浓度在0.0 μg/L~20.0 μg/L之间线性关系良好,相关系数r= 0.9999,方法的最低检出限为0.164 μg/L,RSD为0.4%~1.2%,加标回收率为98.6%~103.5%.结论:该方法操作简单,精密度好,回收率高,是测定尿砷含量的可靠方法.

  3. Multisyringe flow injection lab-on-valve systems coupled to hydride generation atomic fluorescence spectrometry for on-line bead-injection preconcentration and determination of total inorganic arsenic in environmental waters

    DEFF Research Database (Denmark)

    Long, Xiangbao; Miró, Manuel; Hansen, Elo Harald;

    conditions, a detection limit (3σ) of 0.02 ng mL-1 and a precision better than 6.0% at the 0.1 g L-1 level were obtained for the bead-injection mode whenever the loading sample volume was affixed at 3.0 mL. The procedure was validated by the determination of arsenic in certified reference materials...... inorganic arsenic in freshwaters. The method involves the preconcentration of arsenate(V) at pH 10 on a renewable anion exchanger, namely Q-Sepharose, packed in a LOV micro-column. The analyte species is afterwards stripped out, and concurrently pre-reduced, by a 0.25 mL of eluent containing 6 mol L-1 HCl...

  4. 尿中铅测定的氢化物发生原子荧光光谱法%Determination of lead in urine by hydride generation atomic fluorescence spectrometry

    Institute of Scientific and Technical Information of China (English)

    孙华; 任韧

    2004-01-01

    目的建立测定尿中铅的氢化物发生原子荧光光谱法.方法尿样经混合酸加热消化后,用硼氢化钾将铅还原成挥发性铅的氢化物,用AFS-2201型双道原子荧光光谱仪进行测定.结果在本方法条件下绘制标准曲线,在0.0~50.0μg/L浓度范围内线性关系良好,相对标准偏差(RSD)为3.6%,检出限为0.2μg/L,加标回收率为91.4%~97.5%.取15名铅作业工人尿样分别用本法和二硫腙比色法同时测定铅含量,结果差异无显著性(P>0.20).结论氢化物发生原子荧光光谱法具有操作简便、灵敏度高、检出限低、基体干扰少等优点,作为新一代检测手段,优于现有方法.

  5. Determination of Lead in Urine by Hydride generating Atomic Fluorescence Spectrum Method%氢化物发生原子荧光光谱法测定尿中铅

    Institute of Scientific and Technical Information of China (English)

    郑瑾; 边文耀; 高美叶

    2002-01-01

    采用AFS 230型双道原子荧光光度计测定尿中铅,对仪器条件、精密度、准确度等方面进行了探讨性实验,结果满意;方法的检出限为0.19 ng/ml,相对标准偏差为2.01%,回收率为91%~108%,线性范围0~500ng/ml.

  6. Determination on urine lead level by direct injection-hydride generation-atomic fluorescence spectrophotometry%直接进样-氢化物发生原子荧光光谱法测定尿铅水平

    Institute of Scientific and Technical Information of China (English)

    王军军; 黄灿东; 李歆; 杨雪姬

    2012-01-01

    目的 用直接进样-氢化物发生原子荧光光谱法测定尿铅水平.方法尿样加入到硝酸溶液中振摇混匀后,直接用氢化物发生原子荧光光谱法测定尿铅水平.结果 本法在0.90~300.00 μg/L线性关系良好,相对标准偏差为3.09% ~6.84%,检出限0.90 μg/L,加标回收率为93.9%~ 102.0%,平均回收率为97.4%.结论 本法准确、可靠、灵敏、操作简单快捷,适合基层单位普遍应用.

  7. Determination of Lead in Food and Feed Samples Using Hydride Generation-Atomic Fluorescence Spectrometry%氢化物发生原子荧光光谱法测定食品和饲料中的铅

    Institute of Scientific and Technical Information of China (English)

    翟毓秀; 郝林华

    2000-01-01

    应用AFS-2201型双道原子荧光光谱仪进行了氢化物发生原子荧光法测定食品和饲料中铅的研究.方法中采用高氯酸做介质,并对各种最佳分析条件进行了探讨和验证.方法的检出限为0.3 μg/L,线性范围为1.00~500 μg/L,回收率为87%~98%.用标准物质进行对照,其测定值均在给定的标准值范围之内.该方法操作简单、快速,灵敏度高,精密度和准确度好,线性范围宽,检出限低,所用试剂无毒性,且仪器性能稳定,价格低廉,便于推广应用.

  8. Determination of total arsenic in food by hydride generation atomic fluorescence spectrometry%食品中总砷的氢化物发生原子荧光测定法

    Institute of Scientific and Technical Information of China (English)

    周磊; 佘晓蕾

    2003-01-01

    目的应用AFS-230 a型原子荧光光度计进行氢化物发生原子荧光法测定食品中总砷的研究.方法采用盐酸做介质,用标准物质进行对照.结果测定值均在给定的标准范围之内,并对各种最佳分析条件进行了探究和验证.方法检出限1.27 μg/L,线性范围为0~100 μg/L,回收率83%~96%.结论该方法操作简单、快速、灵敏度高,精密度和准确度好,线性范围宽,检出限低,所用试剂无毒性,且仪器性能稳定,便于推广应用.

  9. Determination of Selenium in Apple-vinegar by Hydride Generation-Atomic Fluorescence Spectrometry%原子荧光光谱法测定苹果醋中的硒

    Institute of Scientific and Technical Information of China (English)

    曹璨

    2008-01-01

    建立了原子荧光光谱法测定苹果醋中硒的分析方法,并对HNO3-HClO4和HNO3-H2O2两种消化体系进行了比较.方法线性范围0~200 μg/L,相关系数0.999 9,检出限分别为0.134 μg/L和0.159 μg/L,回收率分别为96.0%和102.0%.

  10. Monitoring of Arsenic Content in the Blood of Arsenic Poisoning Patients by Hydride Generation Atomic Fluorescence Spectrometry%氢化物原子荧光光谱法监测砷中毒患者血液中的砷

    Institute of Scientific and Technical Information of China (English)

    丁志英

    2013-01-01

    对砷中毒患者血液中砷的监测对其临床排砷治疗有重大的指导意义.采用硝酸-高氯酸混酸消解样品,抗坏血酸-硫脲做还原剂,氢化物原子荧光光谱法测定砷中毒患者血液中的砷.运用这种方法能够快速、准确检测出砷含量,从而能够及时监测砷中毒患者血液中的砷,对临床具有重大意义.

  11. 氢化物发生-原子荧光光谱法测定钴酸锂中砷%DETERMINATION OF ARSENIC CONTENT IN LITHIUM COBALT OXIDE BY HYDRIDE GENERATION-ATOMIC FLUORESCENCE SPECTROMETRY

    Institute of Scientific and Technical Information of China (English)

    于力; 汤淑芳

    2009-01-01

    采用氢化物发生-原子荧光光谱法测定钴酸锂中砷.对样品前处理和氢化物发生条件进行了选择和优化.方法对砷的检出限为0.05mg/kg.方法的精密度(RSD,n=7)为1.93%~8.02%,回收率为99.4%~105.5%.

  12. Effect of lanthanum hydride on microstructures and hydrogen storage performances of 2LiNH2-MgH2 system

    Institute of Scientific and Technical Information of China (English)

    朱惜林; 韩树民; 赵鑫; 李媛; 刘宝忠

    2014-01-01

    Hydrogen storage properties of 2LiNH2-MgH2 system were improved by adding lanthanum hydride (LaH3), and the role of LaH3 in hydrogen sorption process of Li-Mg-N-H system was investigated. Temperature programmed sorption results showed that the addition of lanthanum hydride reduced the dehydriding/hydriding onset temperature of 2LiNH2-MgH2 system by at least 15 K. Moreover, A 0.053 wt.%/min average rate was determined for the hydrogen desorption of 2LiNH2-MgH2-0.05LaH3 composite, while it was only 0.035 wt.%/min for 2LiNH2-MgH2 system. Hydrogen absorption capacity increased from 1.62 wt.% to 2.12 wt.% within 200 min by adding LaH3 into 2LiNH2-MgH2 system at 383 K. In the dehydrogenation of 2LiNH2-MgH2-0.05LaH3 composite, LaH2 transferred to LaN phase, which reversed to LaH2 in the following hydrogen adsorption process. The reversible reaction of LaH2 ef-fectively promoted the hydrogen sorption of Li-Mg-N-H system. Moreover, the homogenous distribution of fine La hydride was fa-vorable to improving effect of lanthanum hydride.

  13. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    Science.gov (United States)

    Rico, A.; Martin-Rengel, M. A.; Ruiz-Hervias, J.; Rodriguez, J.; Gomez-Sanchez, F. J.

    2014-09-01

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young's modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young's modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found.

  14. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    Energy Technology Data Exchange (ETDEWEB)

    Rico, A., E-mail: alvaro.rico@urjc.es [DIMME, Departamento de Tecnología Mecánica, Universidad Rey Juan Carlos, c/Tulipán s/n, E-28933 Móstoles, Madrid (Spain); Martin-Rengel, M.A., E-mail: mamartin@mater.upm.es [Departamento de Ciencia de los Materiales, UPM, E.T.S.I. Caminos, Canales y Puertos, Profesor Aranguren SN, E-28040 Madrid (Spain); Ruiz-Hervias, J., E-mail: jesus.ruiz@upm.es [Departamento de Ciencia de los Materiales, UPM, E.T.S.I. Caminos, Canales y Puertos, Profesor Aranguren SN, E-28040 Madrid (Spain); Rodriguez, J. [DIMME, Departamento de Tecnología Mecánica, Universidad Rey Juan Carlos, c/Tulipán s/n, E-28933 Móstoles, Madrid (Spain); Gomez-Sanchez, F.J., E-mail: javier.gomez@amsimulation.com [Advanced Material Simulation, S.L, Madrid (Spain)

    2014-09-15

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young’s modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young’s modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found.

  15. Lithium hydride - A space age shielding material

    Science.gov (United States)

    Welch, F. H.

    1974-01-01

    Men and materials performing in the environment of an operating nuclear reactor require shielding from the escaping neutron particles and gamma rays. For efficient shielding from gamma rays, dense, high atomic number elements such as iron, lead, or tungsten are required, whereas light, low atomic number elements such as hydrogen, lithium, or beryllium are required for efficient neutron shielding. The use of lithium hydride (LiH) as a highly efficient neutron-shielding material is considered. It contains, combined into a single, stable compound, two of the elements most effective in attenuating and absorbing neutrons.

  16. Highly Concentrated Palladium Hydrides/Deuterides; Theory

    Energy Technology Data Exchange (ETDEWEB)

    Papaconstantopoulos, Dimitrios

    2013-11-26

    Accomplishments are reported in these areas: tight-binding molecular dynamics study of palladium; First-principles calculations and tight-binding molecular dynamics simulations of the palladium-hydrogen system; tight-binding studies of bulk properties and hydrogen vacancies in KBH{sub 4}; tight-binding study of boron structures; development of angular dependent potentials for Pd-H; and density functional and tight-binding calculations for the light-hydrides NaAlH4 and NaBH4

  17. Development of nickel-metal hydride cell

    Science.gov (United States)

    Kuwajima, Saburo; Kamimori, Nolimits; Nakatani, Kensuke; Yano, Yoshiaki

    1993-01-01

    National Space Development Agency of Japan (NASDA) has conducted the research and development (R&D) of battery cells for space use. A new R&D program about a Nickel-Metal Hydride (Ni-MH) cell for space use from this year, based on good results in evaluations of commercial Ni-MH cells in Tsukuba Space Center (TKSC), was started. The results of those commercial Ni-MH cell's evaluations and recent status about the development of Ni-MH cells for space use are described.

  18. Optical hydrogen sensors based on metal-hydrides

    Science.gov (United States)

    Slaman, M.; Westerwaal, R.; Schreuders, H.; Dam, B.

    2012-06-01

    For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.

  19. Investigation and characterization of ball-milled magnesium-based hydrides for hydrogen storage materials

    Science.gov (United States)

    Yang, Jing

    2011-12-01

    Three alloys are prepared through mechanical alloying and the hydrogen storage properties have been investigated systematically. In Mg-Ni and Mg-Ni-Fe alloys, the main binary alloy phase is Mg2Ni, while in Mg-Ni-Fe-Ti alloys, NiTi, FeTi are also found as the main binary phases beside Mg 2Ni. The hydrogen absorption capacities of the three alloys are 2.9wt%, 2.2wt% and 2.3wt% respectively. Absorption content increases with the increasing of milling time, which also increases the amorphous degree of the alloys. The amorphous degree increasing is unfavorable to improve hydrogen storage capacity. Longer milling time will contribute to a higher hydriding/dehydriding rate at a constant temperature. The alloys exhibit a different hydriding behavior when temperature was increased from 473K to 673K. The alloys particles became finer after long time milling, which led to a decrease in the different distance of the hydrogen atoms.

  20. Hydrides in Young Stellar Objects: Radiation tracers in a protostar-disk-outflow system

    CERN Document Server

    Benz, Arnold O; van Dishoeck, Ewine F

    2010-01-01

    Context: Hydrides of the most abundant heavier elements are fundamental molecules in cosmic chemistry. Some of them trace gas irradiated by UV or X-rays. Aims: We explore the abundances of major hydrides in W3 IRS5, a prototypical region of high-mass star formation. Methods: W3 IRS5 was observed by HIFI on the Herschel Space Observatory with deep integration (about 2500 s) in 8 spectral regions. Results: The target lines including CH, NH, H3O+, and the new molecules SH+, H2O+, and OH+ are detected. The H2O+ and OH+ J=1-0 lines are found mostly in absorption, but also appear to exhibit weak emission (P-Cyg-like). Emission requires high density, thus originates most likely near the protostar. This is corroborated by the absence of line shifts relative to the young stellar object (YSO). In addition, H2O+ and OH+ also contain strong absorption components at a velocity shifted relative to W3 IRS5, which are attributed to foreground clouds. Conclusions: The molecular column densities derived from observations corre...

  1. Nitrogen hydrides in the cold envelope of IRAS16293-2422

    CERN Document Server

    Hily-Blant, Pierre; Bacmann, Aurore; Bottinelli, Sandrine; Parise, Bérengère; Caux, Emmanuel; Faure, Alexandre

    2010-01-01

    Nitrogen is the fifth most abundant element in the Universe, yet the gas-phase chemistry of N-bearing species remains poorly understood. Nitrogen hydrides are key molecules of nitrogen chemistry. Their abundance ratios place strong constraints on the production pathways and reaction rates of nitrogen-bearing molecules. We observed the class 0 protostar IRAS16293-2422 with the heterodyne instrument HIFI, covering most of the frequency range from 0.48 to 1.78~THz at high spectral resolution. The hyperfine structure of the amidogen radical o-NH2 is resolved and seen in absorption against the continuum of the protostar. Several transitions of ammonia from 1.2 to 1.8~THz are also seen in absorption. These lines trace the low-density envelope of the protostar. Column densities and abundances are estimated for each hydride. We find that NH:NH2:NH3=5:1:300. {Dark clouds chemical models predict steady-state abundances of NH2 and NH3 in reasonable agreement with the present observations, whilst that of NH is underpredi...

  2. Characteristics of Hydrogen Storage Alloy Mg2Ni Produced by Hydriding Combustion Synthesis

    Institute of Scientific and Technical Information of China (English)

    Qian LI; Qin LIN; Lijun JIANG; Kou-chih CHOU; Feng ZHAN; Qiang ZHENG

    2004-01-01

    A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigatedby means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showedthat the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis withoutany activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp(0.1 Mpa)=3026/T+5.814 (523 K≤ T ≤623 K) for hydriding and Igp (0.1 Mpa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1 - α)]3/2 = kt and the apparent activation energy for thenucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31 kJ/(mol.H2)and 59.9±2.99 kJ/(moI.H2) respectively.

  3. NATO Advanced Study Institute on Metal Hydrides

    CERN Document Server

    1981-01-01

    In the last five years, the study of metal hydrides has ex­ panded enormously due to the potential technological importance of this class of materials in hydrogen based energy conversion schemes. The scope of this activity has been worldwide among the industrially advanced nations. There has been a consensus among researchers in both fundamental and applied areas that a more basic understanding of the properties of metal/hydrogen syster;,s is required in order to provide a rational basis for the selection of materials for specific applications. The current worldwide need for and interest in research in metal hydrides indicated the timeliness of an Advanced Study Insti­ tute to provide an in-depth view of the field for those active in its various aspects. The inclusion of speakers from non-NATO coun­ tries provided the opportunity for cross-fertilization of ideas for future research. While the emphasis of the Institute was on basic properties, there was a conscious effort to stimulate interest in the applic...

  4. Metal hydrides for lithium-ion batteries.

    Science.gov (United States)

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries.

  5. Startup and Operation of a Metal Hydride Based Isotope Separation Process

    Energy Technology Data Exchange (ETDEWEB)

    Scogin, J.H.; Poore, A.S.

    1995-02-27

    Production scale separation of tritium from other hydrogen isotopes at the Savannah River Site (SRS) in Aiken, SC, has been accomplished by several methods. These methods include thermal diffusion (1957--1986), fractional absorption (1964--1968), and cryogenic distillation (1967-present). Most recently, the Thermal Cycling Absorption Process (TCAP), a metal hydride based hydrogen isotope separation system, began production in the Replacement Tritium Facility (RTF) on April 9, 1994. TCAP has been in development at the Savannah River Technology Center since 1980. The production startup of this semi-continuous gas chromatographic separation process is a significant accomplishment for the Savannah River Site and was achieved after years of design, development, and testing.

  6. Startup and operation of a metal hydride based isotope separation process

    Energy Technology Data Exchange (ETDEWEB)

    Scogin, J.H.; Poore, A.S. [Westinghouse Savannah River Co., Aiken, SC (United States)

    1995-10-01

    Production scale separation of tritium from other hydrogen isotopes at the Savannah River Site (SRS) in Aiken, SC, USA, has been accomplished by several methods. These methods include thermal diffusion (1957-1986), fractional absorption (1964-1968), and cryogenic distillation (1967-present). Most recently, the Thermal Cycling Absorption Process (TCAP), a metal hydride based hydrogen isotope separation system, began production in the Replacement Tritium Facility (RTF) on April 9, 1994. TCAP has been in development at the Savannah River Technology Center since 1980. The production startup of this semi-continuous gas chromatographic separation process is a significant accomplishment for the Savannah River Site and was achieved after years of design, development, and testing. 2 refs., 4 figs.

  7. Discharge tube with coaxial geometry for efficient production of metal hydrides.

    Science.gov (United States)

    Bozhinova, I; Kolev, St; Dimitrova, M; Popov, Tsv; Pashov, A

    2013-09-01

    The production of metal hydrides in vapour phase is one of the problems which makes their spectroscopic investigation at high resolution difficult. The molecular densities are usually low and the absorption is often increased by the use of multipass cells or intracavity setups. In this contribution a discharge tube with coaxial geometry is investigated, which is able to produce relatively high densities of NiH (≈10(12) cm(-3)). Additional advantage of the present geometry is that the densities are very homogeneous along the discharge length, 250 mm in our case, which can be made in principle arbitrary long. As a result, reliable absorption was detected even in a single pass experiment. We also present the results of a numerical model which explains the general properties of the plasma in the tube. Based on this understanding, we discuss possible improvements and other applications of this discharge geometry.

  8. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    Science.gov (United States)

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-02

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

  9. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Science.gov (United States)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bücherl, T.; Söllradl, S.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2015-10-01

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

  10. Effect of Preparation Methods on Hydriding Properties of La1.5Mg17 Ni0.5 Composite Materials

    Institute of Scientific and Technical Information of China (English)

    Jiang Lijun; Xiao Fang; Li Qian; Lin Qin; Zhan Feng; Chou Kouchih; Lei Tingquan

    2004-01-01

    La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties of La1.5Mg17Nio.5 prepared by MA are better than that by HCS. La1.5Mg17Nio.5 prepared by MA can absorb 6.73 mass% hydrogen at 523 K within 1 min, and 4.92 mass% hydrogen at 423 K. The improvement of hydriding properties of La1.5Mg17Ni0.5alloy prepared by MA can be ascribed to the formation of nano-crystalline and defects during the mechanical alloying.

  11. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Börries, S., E-mail: stefan.boerries@hzg.de [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Metz, O.; Pranzas, P.K. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Bücherl, T. [ZTWB Radiochemie München (RCM), Technische Universität München (TUM), Walther-Meissner-Str. 3, D-85748 Garching (Germany); Söllradl, S. [Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRMII), Technische Universität München (TUM), Lichtenbergstr. 1, D-85748 Garching (Germany); Dornheim, M.; Klassen, T.; Schreyer, A. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany)

    2015-10-11

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

  12. Filiform-mode hydride corrosion of uranium surfaces

    Science.gov (United States)

    Hill, M. A.; Schulze, R. K.; Bingert, J. F.; Field, R. D.; McCabe, R. J.; Papin, P. A.

    2013-11-01

    Hydride nucleation and growth has previously been studied in uranium with an air-formed oxide. Preferred directional growth of uranium hydride has not been observed, presumably due to the constraint of the oxide layer and/or the presence of a surface layer distorted by mechanical grinding and polishing. Instead, hydrides typically first form as subsurface blisters that do not exhibit preferred growth directionality. By eliminating the strained surface layer through electropolishing, removing the natural oxide through ion sputtering, avoiding exposure of the uranium to air, and then exposing uranium to high purity hydrogen in an environmental cell, hydride growth patterns emerge that correspond to defect structures within the microstructure. These hydride growth patterns are similar to filiform corrosion, a type of corrosion that frequently forms under thin protective films. This work describes the first reported observation of filiform-like corrosion in uranium. The uranium hydride initiates at defects, but grows into filaments up to 20 μm wide, and tends to form in straight lines, largely propagating along twin boundaries. Propagation is driven by hydrogen reaction at the filament head, promoted by more efficient delivery of reactant. However, this phenomenon does not involve an electrochemical process associated with conventional filiform corrosion and is therefore described as filiform-like. Hydride growth was observed using optical microscopy for a period of nearly three years. Sample characterization included automated electron backscatter diffraction (EBSD) measurements to determine growth directions. Observation of this anomalous hydride growth provides clues as to the mechanisms operating in uranium hydriding for more conventionally prepared sample surfaces.

  13. Improving the analytical performance of hydride generation non-dispersive atomic fluorescence spectrometry. Combined effect of additives and optical filters

    Science.gov (United States)

    D'Ulivo, Alessandro; Bramanti, Emilia; Lampugnani, Leonardo; Zamboni, Roberto

    2001-10-01

    The effects of tetrahydroborate and acid concentration and the presence of L-cysteine and thiourea were investigated in the determination of As, Bi and Sn using continuous flow hydride generation atomic fluorescence spectrometry (HG AFS). The aim was to find conditions allowing the control of those effects exerting negative influence on the analytical performance of the HG AFS apparatus. The effects taken into account were: (i) the radiation scattering generated by carryover of solution from the gas-liquid separator to the atomizer; (ii) the introduction of molecular species generated by tetrahydroborate decomposition into the atomizer; and (iii) interference effects arising from other elements in the sample matrix and from different acids. The effects (i) and (ii) could be controlled using mild reaction conditions in the HG stage. The effect of HG conditions on carryover was studied by radiation scattering experiments without hydride atomization. Compromised HG conditions were found by studying the effects of tetrahydroborate (0.1-20 g l -1) and acid (0.01-7 mol l -1) concentration, and the addition of L-cysteine (10 g l -1) and thiourea (0.1 mol l -1) on the HG AFS signals. The effect of optical filters was investigated with the aim of improving the signal-to-noise ratio. Optical filters with peak wavelengths of 190 and 220 nm provided an improvement of detection limits by factors of approximately 4 and 2 for As and Te, respectively. Under optimized conditions the detection limits were 6, 5, 3, 2, 2 and 9 ng l -1 for As, Sb, Bi, Sn, Se and Te, respectively. Good tolerance to various acid compositions and sample matrices was obtained by using L-cysteine or thiourea as masking agents. Determination of arsenic in sediment and copper certified reference materials, and of bismuth in steel, sediment, soil and ore certified reference material is reported.

  14. PIE techniques for hydride reorientation test at NDC

    Energy Technology Data Exchange (ETDEWEB)

    Tsuda, Tomohiro; Shinohara, Yasunari; Yamaguchi, Yoichiro [Nuclear Development Corporation, Ibaraki (Japan)

    2008-11-15

    Dry storage of spent fuels in the interim storage facility is being planned in Japan. However, the gradual deterioration of the mechanical property of fuel cladding due to internal pressure and temperature during the storage term is known. Therefore, the integrity of stored fuel rods should be confirmed before the start of dry storage. For the last several years, NDC had a lot of experiences on the hydride reorientation test. The specimen preparation techniques on the hydride reorientation test and the mechanical testing techniques after the hydride reorientation are shown in this paper.

  15. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  16. Structural and magnetic properties of C15 HoMn{sub 2} hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Budziak, A., E-mail: andrzej.budziak@ifj.edu.pl [H.Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Zachariasz, P. [Institute of Atomic Energy POLATOM, 05-400 Otwock-Swierk (Poland); Kolwicz-Chodak, L.; Figiel, H. [Faculty of Physics and Applied Computer Science, University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland); Pacyna, A. [H.Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Zukrowski, J. [Faculty of Physics and Applied Computer Science, University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland)

    2011-02-03

    Research highlights: > Full structural and magnetic phase diagrams are presented for the HoMn{sub 2}H{sub x}(0 < x {<=} 4.3) hydrides, where x = 4.3 is a typical maximal hydrogen concentration obtained for RMn{sub 2}H{sub x} (R: rare earth) under low pressure of H{sub 2} (ca {approx} 1 bar). > For x < {approx} 1.6: (1) The spinodal decompositions into two structurally different phases are observed. The lattice parameters of one of them correspond to those of the pure host HoMn{sub 2} material, while the lattice parameters of the other phase correspond to those of HoMn{sub 2}H{sub 1.6}. (2) Abundances of both phases change with hydrogen concentration x. (3) No intermediate phase appears, which is typical for other hydrides based on the C15 Laves phase type compounds (e.g. (Tb, Gd)Mn{sub 2}). Instead of that, structural transformations to monoclinic structures are observed. > For x = 2.5 splitting into two phases with different hydrogen concentrations x (x{sub 1} {approx} 2.3 and x{sub 2} {approx} 2.8) appears again, which was observed only for hydrides based on the C14 Laves phase type compounds (e.g. in (Sm, Er, Nd)Mn{sub 2}H{sub x}) in the range 2 < x < 3. > For samples with 2 < x < 2.2 no structural transformations are detected. > The effects of hydrogen absorption on structural properties are shown to be reflected in magnetic behavior. > A huge jump of magnetic ordering temperatures from {approx}24 K for HoMn{sub 2} to {approx} (200-380) K for its hydrides is observed. - Abstract: Powder samples of cubic HoMn{sub 2}H{sub x} hydrides, with 0 {<=} x {<=} 4.3, have been investigated by X-ray diffraction and AC/DC magnetometry as a function of temperature and external magnetic field. Hydrogen is demonstrated to strongly modify structural and magnetic properties. X-ray studies revealed many structural transformations placed at low temperatures. In particular, a transformation from the cubic to the monoclinic structure was detected, which so far has not been reported

  17. Acute arsenious hydride intoxication. Four cases

    Energy Technology Data Exchange (ETDEWEB)

    Gosselin, B.; Mathieu, D.; Desprez-Nolf, M.; Cosson, A.; Goudemand, J.; Haguenoer, J.M.; Wattel, F.

    1982-02-06

    While engaged in the repair of a zinc furnace, 4 workers were accidentally exposed to arsenious hydride (AsH3) fumes. Acute intravascular haemolysis developed within a few hours. On admission, the patients immediately underwent exsanguino-transfusion; 8.2 to 10.2 l of blood were exchanged through a continuous perfusion pump at the rate of 1 l/hour. Two patients resumed diuresis during transfusion, but the other two required repeated haemodialysis. Between the 10th and 30th days, while renal function was gradually returning to normal, mildly megaloblastic anaemia developed. This was followed during the 3rd month by clinical and electric signs of polyneuritis of the lower and upper limbs, which subsequently regressed. Regular measurements of arsenic levels in the blood and urine were performed between and during exsanguino-transfusion and haemodialysis.

  18. Hydrogen desorption from nanostructured magnesium hydride composites

    Directory of Open Access Journals (Sweden)

    Brdarić Tanja P.

    2007-01-01

    Full Text Available The influence of 3d transition metal addition (Fe, Co and Ni on the desorption properties of magnesium hydride were studied. The ball milling of MgH2-3d metal blends was performed under Ar. Microstructural and morphological characterization were performed by XRD and SEM analysis, while the hydrogen desorption properties were investigated by DSC. The results show a strong correlation between the morphology and thermal stability of the composites. The complex desorption behavior (the existence of more than one desorption peak was correlated with the dispersion of the metal additive particles that appear to play the main role in the desorption. The desorption temperature can be reduced by more than 100 degrees if Fe is added as additive. The activation energy for H2 desorption from the MgH2-Fe composite is 120 kJ/mol, implying that diffusion controls the dehydration process.

  19. Review of magnesium hydride-based materials: development and optimisation

    NARCIS (Netherlands)

    Crivello, J. -C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.|info:eu-repo/dai/nl/186125372; Latroche, M.; Milanese, C.; Milcius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the

  20. Direct observation of hydrides formation in cavity-grade niobium

    Directory of Open Access Journals (Sweden)

    F. Barkov

    2012-12-01

    Full Text Available Niobium is an important technological superconductor used to make radio frequency cavities for particle accelerators. Using laser confocal microscopy we have directly investigated hydride precipitates formation in cavity-grade niobium at 77 and 140 K. We have found that large hydrides were usually formed after chemical or mechanical treatments, which are known to lead to a strong degradation of the quality factor known as Q disease. From our experiments we can conclude that hydrides causing Q disease are islands with a characteristic thickness of ≳100  nm and in-plane dimensions 1–10  μm. Our results show that mechanical polishing uploads a lot of hydrogen into bulk niobium while electropolishing leads to a mild contamination. Vacuum treatments at 600–800°C are demonstrated to preclude large hydride formation in line with the absence of Q disease in similarly treated cavities.

  1. Materials science of Mg-Ni-based new hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Orimo, S.; Fujii, H. [Hiroshima Univ. (Japan). Faculty of Integrated Arts and Sciences

    2001-02-01

    One of the advantageous functional properties of Mg alloys (or compounds) is to exhibit the reversible hydriding reaction. In this paper, we present our systematic studies regarding the relationship between nanometer- or atomistic-scale structures and the specific hydriding properties of the Mg-Ni binary system, such as(1) nanostructured (n)-Mg{sub 2}Ni, (2) a mixture of n-Mg{sub 2}Ni and amorphous (a)-MgNi,(3) pure a-MgNi, and(4) n-MgNi{sub 2}. Further studies on(5) an a-MgNi-based system for clarifying the effect of the short-range ordering on the structural and hydriding properties and(6) a MgNi{sub 2}-based system for synthesizing the new Laves phase structure are also presented. The materials science of Mg-Ni-based new hydrides will provide indispensable knowledge for practically developing the Mg alloys as hydrogen-storage materials. (orig.)

  2. Structure and bonding of second-row hydrides

    OpenAIRE

    Blinder, S. M.

    2014-01-01

    The atomic orbitals, hybridization and chemical bonding of the most common hydrides of boron, carbon, nitrogen and oxygen are described. This can be very instructive for beginning students in chemistry and chemical physics.

  3. Artificial exomuscle investigations for applications--metal hydride.

    Science.gov (United States)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bédard, Stéphane

    2007-03-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software.

  4. DETERMINATION OF METAL HYDRIDE SYSTEMS CHARACTERISTICS WHILE HEATING

    Directory of Open Access Journals (Sweden)

    Yu. Kluchka

    2012-01-01

    Full Text Available Experimental dependence of the pressure of hydrogen in the hydride cartridge when it is heated is obtained. Experimental data prove the theoretical values with an accuracy of ≈ 6%.

  5. Bipolar Nickel-Metal Hydride Battery Being Developed

    Science.gov (United States)

    Manzo, Michelle A.

    1998-01-01

    The NASA Lewis Research Center has contracted with Electro Energy, Inc., to develop a bipolar nickel-metal hydride battery design for energy storage on low-Earth-orbit satellites. The objective of the bipolar nickel-metal hydride battery development program is to approach advanced battery development from a systems level while incorporating technology advances from the lightweight nickel electrode field, hydride development, and design developments from nickel-hydrogen systems. This will result in a low-volume, simplified, less-expensive battery system that is ideal for small spacecraft applications. The goals of the program are to develop a 1-kilowatt, 28-volt (V), bipolar nickel-metal hydride battery with a specific energy of 100 watt-hours per kilogram (W-hr/kg), an energy density of 250 W-hr/liter and a 5-year life in low Earth orbit at 40-percent depth-of-discharge.

  6. High-pressure synthesis of noble metal hydrides.

    Science.gov (United States)

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-07

    The formation of hydride phases in the noble metals copper, silver, and gold was investigated by in situ x-ray diffraction at high hydrogen pressures. In the case of copper, a novel hexagonal hydride phase, Cu2H, was synthesised at pressures above 18.6 GPa. This compound exhibits an anti-CdI2-type structure, where hydrogen atoms occupy every second layer of octahedral interstitial sites. In contrast to chemically produced CuH, this phase does not show a change in compressibility compared to pure copper. Furthermore, repeated compression (after decomposition of Cu2H) led to the formation of cubic copper hydride at 12.5 GPa, a phenomenon attributed to an alteration of the microstructure during dehydrogenation. No hydrides of silver (up to 87 GPa) or gold (up to 113 GPa) were found at both room and high temperatures.

  7. Artificial exomuscle investigations for applications-metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bedard, Stephane [Victhom Human Bionics Inc., Saint-Augustin-de-Desmaures, QC (Canada)

    2007-03-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software. (review article)

  8. Out-of-pile accelerated hydriding of Zircaloy fasteners

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, J.C.

    1979-10-01

    Mechanical joints between Zircaloy and nickel-bearing alloys, mainly the Zircaloy-4/Inconel-600 combination, were exposed to water at 450/sup 0/F and 520/sup 0/F to study hydriding of Zircaloy in contact with a dissimilar metal. Accelerated hydriding of the Zircaloy occurred at both temperatures. At 450/sup 0/F the dissolved hydrogen level of the water was over ten times that at 520/sup 0/F. At 520/sup 0/F the initially high hydrogen ingress rate decreased rapidly as exposure time increased and was effectively shut off in about 25 days. Severely hydrided Zircaloy components successfully withstood thermal cycling and mechanical testing. Chromium plating of the nickel-bearing parts was found to be an effective and practical barrier in preventing nickel-alloy smearing and accelerated hydriding of Zircaloy.

  9. Hydrogen storage in sodium aluminum hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Ozolins, Vidvuds; Herberg, J.L. (Lawrence Livermore National Laboratories, Livermore, CA); McCarty, Kevin F.; Maxwell, Robert S. (Lawrence Livermore National Laboratories, Livermore, CA); Stumpf, Roland Rudolph; Majzoub, Eric H.

    2005-11-01

    Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.

  10. Hydrogen Storage Characteristics of Metal Hydro-Borate and Transition Element-Added Magnesium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Song, Myoung Youp; Kwak, Young Jun [Chonbuk National University, Jeonju (Korea, Republic of); Park, Hye Ryoung [Chonnam National University, Gwangju (Korea, Republic of)

    2016-07-15

    A metal hydro-borate Zn(BH{sub 4}){sub 2} was prepared by milling ZnCl{sub 2} and NaBH{sub 4} in a planetary ball mill in an Ar atmosphere. This sample contained NaCl. 95 wt% MgH{sub 2}-2.5 wt% Zn(BH{sub 4}){sub 2}-2.5 wt% Ni samples [named MgH{sub 2}-2.5Zn(BH{sub 4}){sub 2}-2.5Ni] were then prepared by milling in a planetary ball mill in a hydrogen atmosphere. The hydrogen absorption and release properties of the prepared samples were investigated. In particular, variations in the initial hydriding and dehydriding rates with temperature were examined. MgH{sub 2}-2.5Zn(BH{sub 4}){sub 2}-2.5Ni dehydrided at the fourth cycle contained Mg, MgO, and small amounts of β-MgH2 and Mg2Ni. The sample after hydriding-dehydriding cycling had a slightly smaller average particle size and a larger BET specific surface area than the sample after milling. Increasing the temperature from 573 K to 623 K led to a decrease in the initial hydriding rate. The initial dehydriding rate increased as the temperature increased from 573 K to 643 K. At 573 K under 12 bar H{sub 2}, the sample absorbed 3.85 wt% H for 2.5 min, 4.60 wt% H for 5 min, 4.64 wt% H for 10 min, and 4.80 wt% H for 60 min. The MgH{sub 2}-2.5Zn(BH{sub 4}){sub 2}-2.5Ni had an effective hydrogen storage capacity (the quantity of hydrogen absorbed for 60 min) of near 5 wt% (4.96 wt% at 593 K).

  11. Electronic structure of ternary hydrides based on light elements

    Energy Technology Data Exchange (ETDEWEB)

    Orgaz, E. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)]. E-mail: orgaz@eros.pquim.unam.mx; Membrillo, A. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Castaneda, R. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Aburto, A. [Departamento de Fisica, Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)

    2005-12-08

    Ternary hydrides based on light elements are interesting owing to the high available energy density. In this work we focused into the electronic structure of a series of known systems having the general formula AMH{sub 4}(A=Li,Na,M=B,Al). We computed the energy bands and the total and partial density of states using the linear-augmented plane waves method. In this report, we discuss the chemical bonding in this series of complex hydrides.

  12. Ab-Initio Study of the Group 2 Hydride Anions

    Science.gov (United States)

    Harris, Joe P.; Wright, Timothy G.; Manship, Daniel R.

    2013-06-01

    The beryllium hydride (BeH)- dimer has recently been shown to be surprisingly strongly bound, with an electronic structure which is highly dependent on internuclear separation. At the equilibrium distance, the negative charge is to be found on the beryllium atom, despite the higher electronegativity of the hydrogen. The current study expands this investigation to the other Group 2 hydrides, and attempts to explain these effects. M. Verdicchio, G. L. Bendazzoli, S. Evangelisti, T. Leininger J. Phys. Chem. A, 117, 192, (2013)

  13. Method of selective reduction of polyhalosilanes with alkyltin hydrides

    Science.gov (United States)

    Sharp, Kenneth G.; D'Errico, John J.

    1989-01-01

    The invention relates to the selective and stepwise reduction of polyhalosilanes by reacting at room temperature or below with alkyltin hydrides without the use of free radical intermediates. Alkyltin hydrides selectively and stepwise reduce the Si--Br, Si--Cl, or Si--I bonds while leaving intact any Si--F bonds. When two or more different halogens are present on the polyhalosilane, the halogen with the highest atomic weight is preferentially reduced.

  14. Method of selective reduction of halodisilanes with alkyltin hydrides

    Science.gov (United States)

    D'Errico, John J.; Sharp, Kenneth G.

    1989-01-01

    The invention relates to the selective and sequential reduction of halodisilanes by reacting these compounds at room temperature or below with trialkyltin hydrides or dialkyltin dihydrides without the use of free radical intermediates. The alkyltin hydrides selectively and sequentially reduce the Si-Cl, Si-Br or Si-I bonds while leaving intact the Si-Si and Si-F bonds present.

  15. Electronic structure and optical properties of lightweight metal hydrides

    NARCIS (Netherlands)

    Setten, van M.J.; Popa, V.A.; Wijs, de G.A.; Brocks, G.

    2007-01-01

    We study the dielectric functions of the series of simple hydrides LiH, NaH, MgH2, and AlH3, and of the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4, and Mg(AlH4)2, using first-principles density-functional theory and GW calculations. All compounds are large gap insulators with GW single-partic

  16. Optimization of Hydride Rim Formation in Unirradiated Zr 4 Cladding

    Energy Technology Data Exchange (ETDEWEB)

    Shimskey, Rick W.; Hanson, Brady D.; MacFarlan, Paul J.

    2013-09-30

    The purpose of this work is to build on the results reported in the M2 milestone M2FT 13PN0805051, document number FCRD-USED-2013-000151 (Hanson, 2013). In that work, it was demonstrated that unirradiated samples of zircaloy-4 cladding could be pre-hydrided at temperatures below 400°C in pure hydrogen gas and that the growth of hydrides on the surface could be controlled by changing the surface condition of the samples and form a desired hydride rim on the outside diameter of the cladding. The work performed at Pacific Northwest National Laboratory since the issuing of the M2 milestone has focused its efforts to optimize the formation of a hydride rim on available zircaloy-4 cladding samples by controlling temperature variation and gas flow control during pre-hydriding treatments. Surface conditioning of the outside surface was also examined as a variable. The results of test indicate that much of the variability in the hydride thickness is due to temperature variation occurring in the furnaces as well as how hydrogen gas flows across the sample surface. Efforts to examine other alloys, gas concentrations, and different surface conditioning plan to be pursed in the next FY as more cladding samples become available

  17. Mechanochemical synthesis of nanostructured chemical hydrides in hydrogen alloying mills

    Energy Technology Data Exchange (ETDEWEB)

    Wronski, Z. [CANMET' s Materials Technology Laboratory, Natural Resources Canada, Ottawa (Canada) and Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada)]. E-mail: zwronski@nrcan.gc.ca; Varin, R.A. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Chiu, C. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Czujko, T. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Calka, A. [Department of Materials Science and Engineering, University of Wollongong, NSW 2518 (Australia)

    2007-05-31

    Mechanical alloying of magnesium metal powders with hydrogen in specialized hydrogen ball mills can be used as a direct route for mechanochemical synthesis of emerging chemical hydrides and hydride mixtures for advanced solid-state hydrogen storage. In the 2Mg-Fe system, we have successfully synthesized the ternary complex hydride Mg{sub 2}FeH{sub 6} in a mixture with nanometric Fe particles. The mixture of complex magnesium-iron hydride and nano-iron released 3-4 wt.%H{sub 2} in a thermally programmed desorption experiment at the range 285-295 {sup o}C. Milling of the Mg-2Al powder mixture revealed a strong competition between formation of the Al(Mg) solid solution and the {beta}-MgH{sub 2} hydride. The former decomposes upon longer milling as the Mg atoms react with hydrogen to form the hydride phase, and drive the Al out of the solid solution. The mixture of magnesium dihydride and nano-aluminum released 2.1 wt.%H{sub 2} in the temperature range 329-340 {sup o}C in the differential scanning calorimetry experiment. The formation of MgH{sub 2} was suppressed in the Mg-B system; instead, a hydrogenated amorphous phase (Mg,B)H {sub x}, was formed in a mixture with nanometric MgB{sub 2}. Annealing of the hydrogen-stabilized amorphous mixture produced crystalline MgB{sub 2}.

  18. Metal Hydrides for High-Temperature Power Generation

    Directory of Open Access Journals (Sweden)

    Ewa C. E. Rönnebro

    2015-08-01

    Full Text Available Metal hydrides can be utilized for hydrogen storage and for thermal energy storage (TES applications. By using TES with solar technologies, heat can be stored from sun energy to be used later, which enables continuous power generation. We are developing a TES technology based on a dual-bed metal hydride system, which has a high-temperature (HT metal hydride operating reversibly at 600–800 °C to generate heat, as well as a low-temperature (LT hydride near room temperature that is used for hydrogen storage during sun hours until there is the need to produce electricity, such as during night time, a cloudy day or during peak hours. We proceeded from selecting a high-energy density HT-hydride based on performance characterization on gram-sized samples scaled up to kilogram quantities with retained performance. COMSOL Multiphysics was used to make performance predictions for cylindrical hydride beds with varying diameters and thermal conductivities. Based on experimental and modeling results, a ~200-kWh/m3 bench-scale prototype was designed and fabricated, and we demonstrated the ability to meet or exceed all performance targets.

  19. Novel fuel cell stack with coupled metal hydride containers

    Science.gov (United States)

    Liu, Zhixiang; Li, Yan; Bu, Qingyuan; Guzy, Christopher J.; Li, Qi; Chen, Weirong; Wang, Cheng

    2016-10-01

    Air-cooled, self-humidifying hydrogen fuel cells are often used for backup and portable power sources, with a metal hydride used as the hydrogen storage material. To provide a stable hydrogen flow to the fuel cell stack, heat must be provided to the metal hydride. Conventionally, the heat released from the exothermic reaction of hydrogen and oxygen in the fuel cell stack to the exhaust air is used to heat a separate metal hydride container. In this case, the heat is only partially used instead of being more closely coupled because of the heat transfer resistances in the system. To achieve better heat integration, a novel scheme is proposed whereby hydrogen storage and single fuel cells are more closely coupled. Based on this idea, metal hydride containers in the form of cooling plates were assembled between each pair of cells in the stack so that the heat could be directly transferred to a metal hydride container of much larger surface-to-volume ratio than conventional separate containers. A heat coupled fuel cell portable power source with 10 cells and 11 metal hydride containers was constructed and the experimental results show that this scheme is beneficial for the heat management of fuel cell stack.

  20. The use of metal hydrides in fuel cell applications

    Directory of Open Access Journals (Sweden)

    Mykhaylo V. Lototskyy

    2017-02-01

    Full Text Available This paper reviews state-of-the-art developments in hydrogen energy systems which integrate fuel cells with metal hydride-based hydrogen storage. The 187 reference papers included in this review provide an overview of all major publications in the field, as well as recent work by several of the authors of the review. The review contains four parts. The first part gives an overview of the existing types of fuel cells and outlines the potential of using metal hydride stores as a source of hydrogen fuel. The second part of the review considers the suitability and optimisation of different metal hydrides based on their energy efficient thermal integration with fuel cells. The performances of metal hydrides are considered from the viewpoint of the reversible heat driven interaction of the metal hydrides with gaseous H2. Efficiencies of hydrogen and heat exchange in hydrogen stores to control H2 charge/discharge flow rates are the focus of the third section of the review and are considered together with metal hydride – fuel cell system integration issues and the corresponding engineering solutions. Finally, the last section of the review describes specific hydrogen-fuelled systems presented in the available reference data.

  1. Metal hydrides based high energy density thermal battery

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zhigang Zak, E-mail: zak.fang@utah.edu [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Zhou, Chengshang; Fan, Peng [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Udell, Kent S. [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States); Bowman, Robert C. [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Vajo, John J.; Purewal, Justin J. [HRL Laboratories, LLC, 3011 Malibu Canyon Road, Malibu, CA 90265 (United States); Kekelia, Bidzina [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States)

    2015-10-05

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH{sub 2} and TiMnV as a working pair. • High energy density can be achieved by the use of MgH{sub 2} to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH{sub 2} as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV{sub 0.62}Mn{sub 1.5} alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles.

  2. Metallographic and fractographic observations of hydrides during delayed hydride cracking in Zr-2.5% Nb alloy

    Energy Technology Data Exchange (ETDEWEB)

    Jovanovic, M.T.; Eadie, R.L. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Chemical and Materials Engineering; Shek, G.K.; Seahra, H. [Ontario Hydro Technologies, Toronto, Ontario (Canada)

    1998-01-01

    Potential drop measurements, optical microscopy, and scanning electron microscopy were performed to study the mechanism of delayed hydride cracking (DHC), the relation of the fracture to the hydride morphology, and the fractography of the DHC mechanism. The material used in this study was taken from modified extrusions of the material used to manufacture Zr-2.5% Nb pressure tubes. The material was electrolytically hydrided to approximately 60 {micro}g/g before testing. Cracking tests were carried out at 250 C with an applied K{sub 1} of 12 MPa {radical}m. The number of potential jumps was strongly correlated to the number of striations on the fracture surface. The results indicate that the DHC process occurs in these samples in an intermittent fashion. Brittle fracture is the operating fracture mechanism for the hydrides that cover most of the fracture surface, but there are some regions of ductile fracture both within the fracture and at the striations.

  3. Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2011-01-01

    Trialkylborane additives promote reduction of CO(2) to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO(2) to give a formate-borane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO(2) reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate-borane adduct.

  4. Reversible storage of the hydrogen by nano structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Institut Neel et CRETA, CNRS - UJF, 38 - Grenoble (France); Marty, P. [LEGI - INPG, 38 - Grenoble (France)

    2007-07-01

    The magnesium hydride MgH{sub 2} is an excellent hydrogen storage element: low cost, abundant, high mass storage capacity up to 7,6% by weight. Meanwhile it presents slow absorption-desorption kinetics and too high thermodynamical stability. Many studies have been realized to improve these kinetics by co-milling with a transition metal. The author presents the metal transition mechanism of this process and the transfer of the production in the industry. (A.L.B.)

  5. A quantitative phase field model for hydride precipitation in zirconium alloys: Part II. Modeling of temperature dependent hydride precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Zhihua [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); PolyU Base (Shenzhen) Limited, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Hao, Mingjun [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Guo, Xianghua [State Key Laboratory of Explosion and Safety Science, Beijing Institute of Technology, Beijing 100081 (China); Tang, Guoyi [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Shi, San-Qiang, E-mail: mmsqshi@polyu.edu.hk [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); PolyU Base (Shenzhen) Limited, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China)

    2015-04-15

    A quantitative free energy functional developed in Part I (Shi and Xiao, 2014 [1]) was applied to model temperature dependent δ-hydride precipitation in zirconium in real time and real length scale. At first, the effect of external tensile load on reorientation of δ-hydrides was calibrated against experimental observations, which provides a modification factor for the strain energy in free energy formulation. Then, two types of temperature-related problems were investigated. In the first type, the effect of temperature transient was studied by cooling the Zr–H system at different cooling rates from high temperature while an external tensile stress was maintained. At the end of temperature transients, the average hydride size as a function of cooling rate was compared to experimental data. In the second type, the effect of temperature gradients was studied in a one or two dimensional temperature field. Different boundary conditions were applied. The results show that the hydride precipitation concentrated in low temperature regions and that it eventually led to the formation of hydride blisters in zirconium. A brief discussion on how to implement the hysteresis of hydrogen solid solubility on hydride precipitation and dissolution in the developed phase field scheme is also presented.

  6. EXPERIMENTAL RESULTS FOR THE ISOTOPIC EXCHANGE OF A 1600 LITER TITANIUM HYDRIDE STORAGE VESSEL

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J.

    2010-12-14

    Titanium is used as a low pressure tritium storage material. The absorption/desorption rates and temperature rise during air passivation have been reported previously for a 4400 gram prototype titanium hydride storage vessel (HSV). A desorption limit of roughly 0.25 Q/M was obtained when heating to 700 C which represents a significant residual tritium process vessel inventory. To prepare an HSV for disposal, batchwise isotopic exchange has been proposed to reduce the tritium content to acceptable levels. A prototype HSV was loaded with deuterium and exchanged with protium to determine the effectiveness of a batch-wise isotopic exchange process. A total of seven exchange cycles were performed. Gas samples were taken nominally at the beginning, middle, and end of each desorption cycle. Sample analyses showed the isotopic exchange process does not follow the standard dilution model commonly reported. Samples taken at the start of the desorption process were lower in deuterium (the gas to be removed) than those taken later in the desorption cycle. The results are explained in terms of incomplete mixing of the exchange gas in the low pressure hydride.

  7. Designing metal hydride complexes for water splitting reactions: a molecular electrostatic potential approach.

    Science.gov (United States)

    Sandhya, K S; Suresh, Cherumuttathu H

    2014-08-28

    The hydridic character of octahedral metal hydride complexes of groups VI, VII and VIII has been systematically studied using molecular electrostatic potential (MESP) topography. The absolute minimum of MESP at the hydride ligand (Vmin) and the MESP value at the hydride nucleus (VH) are found to be very good measures of the hydridic character of the hydride ligand. The increasing/decreasing electron donating feature of the ligand environment is clearly reflected in the increasing/decreasing negative character of Vmin and VH. The formation of an outer sphere metal hydride-water complex showing the HH dihydrogen interaction is supported by the location and the value of Vmin near the hydride ligand. A higher negative MESP suggested lower activation energy for H2 elimination. Thus, MESP features provided a way to fine-tune the ligand environment of a metal-hydride complex to achieve high hydridicity for the hydride ligand. The applicability of an MESP based hydridic descriptor in designing water splitting reactions is tested for group VI metal hydride model complexes of tungsten.

  8. Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

    Science.gov (United States)

    Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

    2017-06-01

    Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg2 NiH4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg2 NiH4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol(-1) ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  10. Infrared spectra of the ethynyl metal hydrides produced in reactions of laser-ablated Mn and Re atoms with acetylene.

    Science.gov (United States)

    Cho, Han-Gook; Andrews, Lester

    2011-05-19

    The ethynyl metal hydride molecules (HM-C≡CH) are identified in the matrix infrared spectra from reactions of laser-ablated Mn and Re atoms with acetylene using D and (13)C isotopic substitution and density functional computed frequencies. The assignment of strong M-H as well as C≡C bond stretching product absorptions suggests oxidative C-H insertion during reagent codeposition and subsequent photolysis. The unique linear structure calculated for HMn-C≡CH is parallel to C(3v) structures found recently for Mn complexes including CH(3)-MnF.

  11. Synthesis, properties and Moessbauer study of ZrFe{sub 2-x}Ni{sub x} hydrides (x = 0.2-0.8)

    Energy Technology Data Exchange (ETDEWEB)

    Sivov, Roman B., E-mail: rsivov@mail.ru [Department of Material Science, Lomonosov Moscow State University, Leninskie Gory 3, Moscow 119991 (Russian Federation); Zotov, Timur A., E-mail: tim.zotov@gmail.com [Chemistry Department, Lomonosov Moscow State University, Leninskie Gory 3, Moscow 119991 (Russian Federation); Verbetsky, Victor N.; Filimonov, Dmitry S.; Pokholok, Konstantin V. [Chemistry Department, Lomonosov Moscow State University, Leninskie Gory 3, Moscow 119991 (Russian Federation)

    2011-09-15

    Research highlights: > ZrFe{sub 2-x}Ni{sub x} (x = 0.2, 0.4, 0.6, and 0.8) can accumulate up to 1.7-1.8 wt.% H{sub 2} at 295 K. > H{sub 2} desorption pressures at 295 K decreased from 325 (x = 0) to 115 atm (x = 0.8). > Isomer shifts (IS) remain constant with Ni content. > Absorption of H{sub 2} results in increase in IS and hyperfine fields for all samples. > Hydride decomposition process involves formation of intermediate hydride phase. - Abstract: Interaction of ZrFe{sub 2-x}Ni{sub x} (x = 0.2, 0.4, 0.6, and 0.8) pseudobinary intermetallic compounds with hydrogen was studied. It was found that these compounds can accumulate up to 1.7-1.8 wt.% H{sub 2} at room temperature. For all investigated ZrFe{sub 2-x}Ni{sub x}-H{sub 2} systems, thermodynamic functions of the {beta}-hydride {yields} {alpha}-solution phase transition and changes of metal matrix volume during formation of hydrides were calculated. It was shown that increase in Ni content leads to reduction of both desorption pressures and starting pressures of reaction with hydrogen in the first hydrogenation cycle compared to ZrFe{sub 2}. Moessbauer investigations, which have been carried out for all alloys as well as hydrides, revealed that Curie temperatures (T{sub c}) and average hyperfine fields (HF{sub av}) of initial alloys decrease with Ni content increase, while isomer shifts (IS) remain constant. Absorption of H{sub 2} results in significant increase in IS together with some increase in T{sub c} and HF{sub av} for all samples. The decomposition of the hydride phases to intermetallic phases while heating from 78 K to room temperature was found to be a two-step process involving formation of the hydride phases with intermediate hydrogen content.

  12. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  13. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  14. Micro-scale fracture experiments on zirconium hydrides and phase boundaries

    Science.gov (United States)

    Chan, H.; Roberts, S. G.; Gong, J.

    2016-07-01

    Fracture properties of micro-scale zirconium hydrides and phase boundaries were studied using microcantilever testing methods. FIB-machined microcantilevers were milled on cross-sectional surfaces of hydrided samples, with the most highly-stressed regions within the δ-hydride film, within the α-Zr or along the Zr-hydride interface. Cantilevers were notched using the FIB and then tested in bending using a nanoindenter. Load-displacement results show that three types of cantilevers have distinct deformation properties. Zr cantilevers deformed plastically. Hydride cantilevers fractured after a small amount of plastic flow; the fracture toughness of the δ-hydride was found to be 3.3 ± 0.4 MPam1/2 and SEM examination showed transgranular cleavage on the fracture surfaces. Cantilevers notched at the Zr-hydride interface developed interfacial voids during loading, at loads considerably lower than that which initiate brittle fracture of hydrides.

  15. Investigation of Cracked Lithium Hydride Reactor Vessels

    Energy Technology Data Exchange (ETDEWEB)

    bird, e.l.; mustaleski, t.m.

    1999-06-01

    Visual examination of lithium hydride reactor vessels revealed cracks that were adjacent to welds, most of which were circumferentially located in the bottom portion of the vessels. Sections were cut from the vessels containing these cracks and examined by use of the metallograph, scanning electron microscope, and microprobe to determine the cause of cracking. Most of the cracks originated on the outer surface just outside the weld fusion line in the base material and propagated along grain boundaries. Crack depths of those examined sections ranged from {approximately}300 to 500 {micro}m. Other cracks were reported to have reached a maximum depth of 1/8 in. The primary cause of cracking was the creation of high tensile stresses associated with the differences in the coefficients of thermal expansion between the filler metal and the base metal during operation of the vessel in a thermally cyclic environment. This failure mechanism could be described as creep-type fatigue, whereby crack propagation may have been aided by the presence of brittle chromium carbides along the grain boundaries, which indicates a slightly sensitized microstructure.

  16. Transition-Metal Hydride Radical Cations.

    Science.gov (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  17. "Inverse sodium hydride": a crystalline salt that contains H(+) and Na(-).

    Science.gov (United States)

    Redko, Mikhail Y; Vlassa, Mircea; Jackson, James E; Misiolek, Andrzej W; Huang, Rui H; Dye, James L

    2002-05-29

    A crystalline salt has been synthesized that contains H(+) and Na(-) rather than the usual hydride oxidation states of H(-) and Na(+). The key is irreversible encapsulation of H(+) within the cage of 3(6)adamanzane (Adz). The internal proton is kinetically inert to reduction by Na(-) in solution in NH(3)-MeNH(2) mixtures. Synthesis of the sodide is accomplished by a metathesis reaction between Na and AdzH(+)X(-) in which X(-) is a sacrificial anion such as glycolate, isethionate, or nitrate. Reduction or deprotonation of the sacrificial anion forms insoluble byproducts and AdzH(+)Na(-) in solution. After solvent removal, the sodide is dissolved in dimethyl ether and transferred through a frit into a separate chamber for crystallization. The compound was characterized as the sodide by analysis, NMR spectra, and optical absorption spectroscopy.

  18. Electrochemical Studies on LaNi(sub 5-x)Sn(sub x) Metal Hydride Alloys

    Science.gov (United States)

    Ratnakumar, B. V.; Witham, C.; Bowman, R. C., Jr.; Hightower, A.; Fultz, B.

    1996-01-01

    Electrochemical studies were performed on LaNi(sub 5-x)Sn(sub x) with 0(less than or equal to)x(less than or equal to)0.5. We measured the effect of the Sn substituent on the kinetics of charge transfer and diffusion during hydrogen absorption and desorption, and the cyclic lifetimes of LaNi(sub 5-x)Sn(sub x) electrodes in 250 mAh laboratory test cells. We report beneficial effects of making small substitutions of Sn for Ni in LaNi(sub 5) on the performance of metal hydride alloy anode in terms of cyclic lifetime, capacity and kinetics. The optimal concentration of Sn in LaNi(sub 5-x)Sn(sub x) alloys for negative electrodes in alkaline rechargable secondary cells was found to lie in the range 0.25(less than or equal to)x(less than or equal to)0.3.

  19. Comparison of the interactions in the rare gas hydride and Group 2 metal hydride anions.

    Science.gov (United States)

    Harris, Joe P; Manship, Daniel R; Breckenridge, W H; Wright, Timothy G

    2014-02-28

    We study both the rare gas hydride anions, RG-H(-) (RG = He-Rn) and Group 2 (Group IIa) metal hydride anions, MIIaH(-) (MIIa = Be-Ra), calculating potential energy curves at the CCSD(T) level with augmented quadruple and quintuple basis sets, and extrapolating the results to the basis set limit. We report spectroscopic parameters obtained from these curves; additionally, we study the Be-He complex. While the RG-H(-) and Be-He species are weakly bound, we show that, as with the previously studied BeH(-) and MgH(-) species, the other MIIaH(-) species are strongly bound, despite the interactions nominally also being between two closed shell species: M(ns(2)) and H(-)(1s(2)). We gain insight into the interactions using contour plots of the electron density changes and population analyses. For both series, the calculated dissociation energy is significantly less than the ion/induced-dipole attraction term, confirming that electron repulsion is important in these species; this effect is more dramatic for the MIIaH(-) species than for RG-H(-). Our analyses lead us to conclude that the stronger interaction in the case of the MIIaH(-) species arises from sp and spd hybridization, which allows electron density on the MIIa atom to move away from the incoming H(-).

  20. Multidimensional simulations of hydrides during fuel rod lifecycle

    Science.gov (United States)

    Stafford, D. S.

    2015-11-01

    In light water reactor fuel rods, waterside corrosion of zirconium-alloy cladding introduces hydrogen into the cladding, where it is slightly soluble. When the solubility limit is reached, the hydrogen precipitates into crystals of zirconium hydride which decrease the ductility of the cladding and may lead to cladding failure during dry storage or transportation events. The distribution of the hydride phase and the orientation of the crystals depend on the history of the spatial temperature and stress profiles in the cladding. In this work, we have expanded the existing hydride modeling capability in the BISON fuel performance code with the goal of predicting both global and local effects on the radial, azimuthal and axial distribution of the hydride phase. We compare results from 1D simulations to published experimental data. We demonstrate the new capability by simulating in 2D a fuel rod throughout a lifecycle that includes irradiation, short-term storage in the spent fuel pool, drying, and interim storage in a dry cask. Using the 2D simulations, we present qualitative predictions of the effects of the inter-pellet gap and the drying conditions on the growth of a hydride rim.

  1. The effect of stress state on zirconium hydride reorientation

    Science.gov (United States)

    Cinbiz, Mahmut Nedim

    Prior to storage in a dry-cask facility, spent nuclear fuel must undergo a vacuum drying cycle during which the spent fuel rods are heated up to elevated temperatures of ≤ 400°C to remove moisture the canisters within the cask. As temperature increases during heating, some of the hydride particles within the cladding dissolve while the internal gas pressure in fuel rods increases generating multi-axial hoop and axial stresses in the closed-end thin-walled cladding tubes. As cool-down starts, the hydrogen in solid solution precipitates as hydride platelets, and if the multiaxial stresses are sufficiently large, the precipitating hydrides reorient from their initial circumferential orientation to radial orientation. Radial hydrides can severely embrittle the spent nuclear fuel cladding at low temperature in response to hoop stress loading. Because the cladding can experience a range of stress states during the thermo-mechanical treatment induced during vacuum drying, this study has investigated the effect of stress state on the process of hydride reorientation during controlled thermo-mechanical treatments utilizing the combination of in situ X-ray diffraction and novel mechanical testing analyzed by the combination of metallography and finite element analysis. The study used cold worked and stress relieved Zircaloy-4 sheet containing approx. 180 wt. ppm hydrogen as its material basis. The failure behavior of this material containing radial hydrides was also studied over a range of temperatures. Finally, samples from reactor-irradiated cladding tubes were examined by X-ray diffraction using synchrotron radiation. To reveal the stress state effect on hydride reorientation, the critical threshold stress to reorient hydrides was determined by designing novel mechanical test samples which produce a range of stress states from uniaxial to "near-equibiaxial" tension when a load is applied. The threshold stress was determined after thermo-mechanical treatments by

  2. Sodium-based hydrides for thermal energy applications

    Science.gov (United States)

    Sheppard, D. A.; Humphries, T. D.; Buckley, C. E.

    2016-04-01

    Concentrating solar-thermal power (CSP) with thermal energy storage (TES) represents an attractive alternative to conventional fossil fuels for base-load power generation. Sodium alanate (NaAlH4) is a well-known sodium-based complex metal hydride but, more recently, high-temperature sodium-based complex metal hydrides have been considered for TES. This review considers the current state of the art for NaH, NaMgH3- x F x , Na-based transition metal hydrides, NaBH4 and Na3AlH6 for TES and heat pumping applications. These metal hydrides have a number of advantages over other classes of heat storage materials such as high thermal energy storage capacity, low volume, relatively low cost and a wide range of operating temperatures (100 °C to more than 650 °C). Potential safety issues associated with the use of high-temperature sodium-based hydrides are also addressed.

  3. Cuantificación de arsénico por inyeccion en flujo-generación de hidruros-espectrometría de abosorcion atómica (IF-GH-EAA previa derivatzación con l-cisteína: Validación y comparación intermetodológica utilizando dos técnicas de referencia Arsenic quantitation by flow injection-hydride generation-atomicabsorption spectrometry (FI-HG-AAS after l-cysteine derivatization: Validation and inter-methodological comparison using two reference techniques

    Directory of Open Access Journals (Sweden)

    Julio A Navoni

    2010-12-01

    utilizando IF-GH-EAA, resultaron comparables al nivel basal previo al consumo. Los resultados obtenidos indican que la metodología propuesta es una alternativa válida para evaluar la exposición a As inorgánico sin necesidad de utilizar prolongados pre-tratamientos, resultando más económica y rápida y evitando la sobreestimación por medición de otras especies del arsénico de bajo impacto toxicológico.The presence of arsenic (As in drinking water is a public health concern in many regions of the world, including Argentina. Quantification of arsenic in drinking water and urine are used to assess exposure to this pollutant. This study aimed to validate a methodology for the quantification of As species [AsV + AsIII + acid monometilarsónico (MMA + dimetilarsínico acid (DMA] by flow injection-hydride generation-atomic absorption spectrometry (FI-HG-AAS, after derivatization with L-cysteine. The results were compared with those obtained using two methods of reference, hydride generation-atomic absorption spectrometry (HG-AAS for water and urine samples, and high performance liquid chromatography-hydride generation-atomic absorption spectrometry (HPLC-HG-AAS for urine samples. In addition, the selectivity of quantification by FI-HG-AAS in the presence of other chemical species of As, from fishery products intake, was evaluated through a biological assay. The As level found in water and urine samples, using the techniques of reference, showed a range from 6 to 176 μg/L and from 143 to 3312 μg/g creatinine, respectively. Pearson coefficients resulting from the comparison of data obtained by FI-HG-AAS with those achieved by the reference methods were r = 0.9976 and r = 0.9422 for water and urine, respectively. The results of the biological test showed a higher level of As, due to consumption of food fishery product, when urine samples were previously mineralized (HG-AAS, with consequent overestimation of the inorganic arsenic consumption. When these samples were analyzed

  4. Absorption spectrum, mass spectrometric properties, and electronic structure of 1,2-benzoquinone.

    Science.gov (United States)

    Albarran, Guadalupe; Boggess, William; Rassolov, Vitaly; Schuler, Robert H

    2010-07-22

    Absorption spectrophotometric and mass spectrometric properties of 1,2-benzoquinone, prepared in aqueous solution by the hexachloroiridate(IV) oxidation of catechol and isolated by HPLC, are reported. Its absorption spectrum has a broad moderately intense band in the near UV with an extinction coefficient of 1370 M(-1)cm(-1) at its 389 nm maximum. The oscillator strength of this band contrasts with those of the order-of-magnitude stronger approximately 250 nm bands of most 1,4-benzoquinones. Gaussian analysis of its absorption spectrum indicates that it also has modestly intense higher energy bands in the 250-320 nm region. In atmospheric pressure mass spectrometric studies 1,2-benzoquinone exhibits very strong positive and negative mass 109 signals that result from the addition of protons and hydride ions in APCI and ESI ion sources. It is suggested that the hydride adduct is formed as the result of the highly polar character of ortho-quinone. On energetic collision the hydride adduct loses an H atom to produce the 1,2-benzosemiquinone radical anion. The present studies also show that atmospheric pressure mass spectral patterns observed for catechol are dominated by signals of 1,2-benzoquinone resulting from oxidation of catechol in the ion sources. Computational studies of the electronic structures of 1,2-benzoquinone, its proton and hydride ion adducts, and 1,2-benzosemiquinone radical anion are reported. These computational studies show that the structures of the proton and hydride adducts are similar and indicate that the hydride adduct is the proton adduct of a doubly negatively charged 1,2-benzoquinone. The contrast between the properties of 1,2- and 1,4-benzoquinone provides the basis for considerations on the effects of conjugation in aromatic systems.

  5. Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters

    NARCIS (Netherlands)

    Intemann, J.; Sirsch, Peter; Harder, Sjoerd

    2014-01-01

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the

  6. Use of triammonium salt of aurin tricarboxylic acid as risk mitigant for aluminum hydride

    Science.gov (United States)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2017-08-08

    A process and a resulting product by process of an aluminum hydride which is modified with by physically combining in a ball milling process an aluminum hydride with a triammonium salt of aurin tricarboxylic acid. The resulting product is an aluminum hydride which is resistant to air, ambient moisture, and liquid water while maintaining useful hydrogen storage and release kinetics.

  7. Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters

    NARCIS (Netherlands)

    Intemann, J.; Sirsch, Peter; Harder, Sjoerd

    2014-01-01

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the

  8. Investigation of metal hydride materials as hydrogen reservoirs for metal-hydrogen batteries

    Science.gov (United States)

    ONISCHAK

    1976-01-01

    The performance and suitability of various metal hydride materials were examined for use as possible hydrogen storage reservoirs for secondary metal-hydrogen batteries. Lanthanum pentanickel hydride appears as a probable candidate in terms of stable hydrogen supply under feasible thermal conditions. A kinetic model describing the decomposition rate data of the hydride has been developed.

  9. Reversible hydrogen storage in nano-structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Grenoble-1 Univ. Joseph-Fourier, Institut Neel / CRETA, CNRS, 38 (France); Marty, P. [Institut National Polytechnique (INPG-LEGI), 38 - Grenoble (France)

    2007-07-01

    Magnesium hydride MgH{sub 2} is an excellent potential material for hydrogen storage: abundant and cheap, it presents a high gravimetric density (7.6% in mass of hydrogen). Nevertheless, it presents both very slow absorption/desorption kinetics and a too important thermodynamic stability leading to absorption/desorption temperatures of about 300 C. A lot of studies have been carried out to improve the reaction kinetics by co-grinding with a transition metal. The aim of this work is to explain particularly the role of the transition metal. Experimental results are presented and analyzed. (O.M.)

  10. A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

    Science.gov (United States)

    Zhou, Chengshang

    Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof

  11. Iron Hydride Detection and Intramolecular Hydride Transfer in a Synthetic Model of Mono-Iron Hydrogenase with a CNS Chelate.

    Science.gov (United States)

    Durgaprasad, Gummadi; Xie, Zhu-Lin; Rose, Michael J

    2016-01-19

    We report the identification and reactivity of an iron hydride species in a synthetic model complex of monoiron hydrogenase. The hydride complex is derived from a phosphine-free CNS chelate that includes a Fe-C(NH)(═O) bond (carbamoyl) as a mimic of the active site iron acyl. The reaction of [((O═)C(HN)N(py)S(Me))Fe(CO)2(Br)] (1) with NaHBEt3 generates the iron hydride intermediate [((O═)C(HN)N(py)S(Me))Fe(H)(CO)2] (2; δFe-H = -5.08 ppm). Above -40 °C, the hydride species extrudes CH3S(-) via intramolecular hydride transfer, which is stoichiometrically trapped in the structurally characterized dimer μ2-(CH3S)2-[((O═)C(HN)N(Ph))Fe(CO)2]2 (3). Alternately, when activated by base ((t)BuOK), 1 undergoes desulfurization to form a cyclometalated species, [((O═)C(NH)NC(Ph))Fe(CO)2] (5); derivatization of 5 with PPh3 affords the structurally characterized species [((O═)C(NH)NC)Fe(CO)(PPh3)2] (6), indicating complex 6 as the common intermediate along each pathway of desulfurization.

  12. Simultaneous determination of hydride and non-hydride forming elements by inductively coupled plasma optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Benzo, Z. [Instituto Venezolano de Investigaciones Cientificas, IVIC, Altos de Pipe, Caracas (Venezuela, Bolivarian Republic of); Matos-Reyes, M.N.; Cervera, M.L.; Guardia, M. de la, E-mail: m.luisa.cervera@uv.es [Department of Analytical Chemistry, University of Valencia, Valencia (Spain)

    2011-09-15

    The operating characteristics of a dual nebulization system were studied including instrumental and chemical conditions for the hydride generation and analytical figures of merit for both, hydride and non hydride forming elements. Analytical performance of the nebulization system was characterized by detection limits from 0.002 to 0.0026 {mu}g mL{sup -1} for the hydride forming elements and between 0.0034 and 0.0121 {mu}g mL{sup -1} for the non-hydride forming elements, relative standard deviation for 10 replicate measurements at 0.25 mg L{sup -1} level and recovery percentages between 97 and 103%. The feasibility of the system was demonstrated in the simultaneous determination of Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Zn, As, Bi, Sb, Se, and Te in the NIST 1549 (non-fat milk powder), NIST 1570a (spinach leaves), DORM-2 (dogfish muscle) and TORT-2 (lobster hepatopancreas) certified samples for trace elements. Results found were in good agreement with the certified ones. (author)

  13. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Benjamin W.; Herberg, Julie L. (Lawrence Livermore National Laboratory, Livermore, CA); Highley, Aaron M.; Grossman, Jeffrey (MIT, Cambridge, MA); Wagner, Lucas (MIT, Cambridge, MA); Bhakta, Raghu; Peaslee, D. (University of Missouri, St. Louis, MO); Allendorf, Mark D.; Liu, X. (University of Missouri, St. Louis, MO); Behrens, Richard, Jr.; Majzoub, Eric H. (University of Missouri, St. Louis, MO)

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  14. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    AI Teng; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1.

  15. A nickel metal hydride battery for electric vehicles.

    Science.gov (United States)

    Ovshinsky, S R; Fetcenko, M A; Ross, J

    1993-04-09

    Widespread use of electric vehicles can have significant impact on urban air quality, national energy independence, and international balance of trade. An efficient battery is the key technological element to the development of practical electric vehicles. The science and technology of a nickel metal hydride battery, which stores hydrogen in the solid hydride phase and has high energy density, high power, long life, tolerance to abuse, a wide range of operating temperature, quick-charge capability, and totally sealed maintenance-free operation, is described. A broad range of multi-element metal hydride materials that use structural and compositional disorder on several scales of length has been engineered for use as the negative electrode in this battery. The battery operates at ambient temperature, is made of nontoxic materials, and is recyclable. Demonstration of the manufacturing technology has been achieved.

  16. CO2 hydrogenation on a metal hydride surface.

    Science.gov (United States)

    Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

    2012-04-28

    The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface.

  17. Zirconium hydride formation in Hanford production reactor process tubes

    Energy Technology Data Exchange (ETDEWEB)

    Winegardner, W.K.; Griggs, B.

    1967-12-01

    Examination of Zircaloy-2 process tubes from Hanford Production Reactors has revealed extensive zirconium hydride formation. In general, attack is limited to the downstream portions of tubes where aluminum spacers are located. Most of the hydride platelets are contained in a case or layer on the inner surface of the tube. It is not unusual to find cases 0.004 to 0.005 in. thick. Analyses of the 0.037 in. wall tubes with such cases intact often reveal hydrogen concentrations greater than 1000 ppM. Investigation indicates that the hydriding is the result of galvanic contact between aluminum and Zircaloy-2. The galvanic couple (contact between dissimilar metals in the presence of reactor cooling water which serves as the electrolyte) results in the cathodic charging of hydrogen into the Zircaloy.

  18. NUMERICAL ANALYSIS FOR HYDRIDING IN METAL HYDRIDE HYDROGEN STORAGE TANK%金属氢化物储氢器吸氢过程的数值分析

    Institute of Scientific and Technical Information of China (English)

    叶建华; 蒋利军; 李志念; 刘晓鹏; 王树茂

    2011-01-01

    Based on the principle of hydride adsorption, a one-dimensional mathematical model for hydriding in a cylindrical metal hydride hydrogen storage tank was established. The heat and mass transfer of metal hydride beds was computed by finite difference method. The variation in temperature and hydrogen concentration at different radial positions of the hydride layer was analyzed during the process of hydriding. The effects of supply pressure, heat convection coefficient and hydride layer radial thickness on the hydriding was studied. It is shown that hydride formation initially takes place uniformly all over the metal hydride layer, but with the process of hydriding, the hydriding rate at the core region is gradually slower than one at surface region. The increase of supply pressure and heat convection coefficient can accelerate the hydriding of the hydrogen storage tank. The effect of hydride layer radial thickness is significant on the hydriding rate, and the thinner hydride layer, the higher the hydriding rate.%基于金属氢化物吸氢基本特性,建立圆柱形金属氢化物储氢器吸氢过程的-维数学物理模型.采用有限差分法对金属氢化物床体的传热传质进行计算.分别研究金属氢化物床体各处温度和氢含量在吸氢过程中的变化以及氢气压力、对流传热系数和金属氢化物床体径向厚度对金属氢化物吸氢过程的影响.计算结果表明:初始阶段金属氢化物床均匀吸氢,但随着氢化过程的进行,其中心区域的吸氢速率逐渐低于边缘区域;增加吸氢压力、提高对流传热系数均可促进储氢器的吸氢;金属氢化物床的径向厚度对吸氢速率影响很大,金属氢化物床越薄,氢化反应的速度越快.

  19. High-Spin Cobalt Hydrides for Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Patrick L. [Univ. of Rochester, NY (United States)

    2013-08-29

    Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

  20. Phase I. Lanthanum-based Start Materials for Hydride Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gschneidner, K. A. [Ames Lab., Ames, IA (United States); Schmidt, F. A. [Ames Lab., Ames, IA (United States); Frerichs, A. E. [Ames Lab., Ames, IA (United States); Ament, K. A. [Ames Lab., Ames, IA (United States)

    2013-08-20

    The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La1-xRx)(Ni1-yMy)(Siz), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

  1. Hydride formation in core-shell alloyed metal nanoparticles

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2016-07-01

    The model and analysis presented are focused on hydride formation in nanoparticles with a Pd shell and a core formed by another metal. The arrangement of metal atoms is assumed to be coherent (no dislocations). The lattice strain distribution, elastic energy, and chemical potential of hydrogen atoms are scrutinized. The slope of the chemical potential (as a function of hydrogen uptake) is demonstrated to decrease with increasing the core volume, and accordingly the critical temperature for hydride formation and the corresponding hysteresis loops are predicted to decrease as well.

  2. Hydrogen Desorption from Mg Hydride: An Ab Initio Study

    Directory of Open Access Journals (Sweden)

    Simone Giusepponi

    2012-07-01

    Full Text Available Hydrogen desorption from hydride matrix is still an open field of research. By means of accurate first-principle molecular dynamics (MD simulations an Mg–MgH2 interface is selected, studied and characterized. Electronic structure calculations are used to determine the equilibrium properties and the behavior of the surfaces in terms of structural deformations and total energy considerations. Furthermore, extensive ab-initio molecular dynamics simulations are performed at several temperatures to characterize the desorption process at the interface. The numerical model successfully reproduces the experimental desorption temperature for the hydride.

  3. Nitrogen hydrides in interstellar gas II. Analysis of Herschel/HIFI observations towards W49N and G10.6-0.4 (W31C)

    CERN Document Server

    Persson, C M; Mookerjea, B; Olofsson, A O H; Black, J H; Gerin, M; Herbst, E; Bell, T A; Coutens, A; Godard, B; Goicoechea, J R; Hassel, G E; Hily-Blant, P; Menten, K M; Muller, H S P; Pearson, J C; Yu, S; 10.1051/0004-6361/201118686

    2012-01-01

    We have used the Herschel-HIFI instrument to observe interstellar nitrogen hydrides along the sight-lines towards W49N and G10.6-0.4 in order to elucidate the production pathways leading to nitrogen-bearing species in diffuse gas. All detections show absorption by foreground material over a wide range of velocities, as well as absorption associated directly with the hot-core source itself. As in the previously published observations towards G10.6-0.4, the NH, NH2 and NH3 spectra towards W49N show strikingly similar and non-saturated absorption features. We decompose the absorption of the foreground material towards W49N into different velocity components in order to investigate whether the relative abundances vary among the velocity components, and, in addition, we re-analyse the absorption lines towards G10.6-0.4 in the same manner. Abundances, with respect to molecular hydrogen, in each velocity component are estimated using CH. The analysis points to a co-existence of the nitrogen hydrides in diffuse or tr...

  4. Hydrogen absorption of slurry system composed of different MgNi alloy and benzene

    Institute of Scientific and Technical Information of China (English)

    蔡官明; 陈长聘; 安越; 徐国华; 陈立新; 王启东

    2003-01-01

    The hydrogen absorption amount and kinetics of the slurry formed by suspending the MgNi alloy powderin liquid benzene were studied. It is discovered that hydrogen is absorbed by both the solid phase(alloy) and liquidphase(C6 H6) and the hydrogen absorption rate varies with the temperature and the content of the Mg-Ni in the slur-ry. Most hydrogen absorption curves of the slurry fall into two regions, in which the mechanism of hydriding reac-tion in the slurry system is different. In the former region, the hydriding of the alloy proceeds with hydrogen diffu-sing through C6 H6. The part in the second region is the outcome of the hydrogenation of C6 H6. At 548 K and underthe hydrogen pressure of 4.5 MPa the saturation capacity for the slurry of 80% C6 H6 (mass fraction)+20% MgNi(mass fraction) is 5.9% (mass fraction) hydrogen, which is 97% of the theoretic capacity of the slurry system.The hydride of the alloy MgNi, which is only the hydride of Mg2Ni phase, Mg2NiH4, is an efficient catalyst for thehydrogenation of C6 H6 into C6 H12 (C6 H6 +3H2→C6 H12 ) in the slurry system.

  5. Exploring "aerogen-hydride" interactions between ZOF2 (Z = Kr, Xe) and metal hydrides: An ab initio study

    Science.gov (United States)

    Esrafili, Mehdi D.; Mohammadian-Sabet, Fariba

    2016-06-01

    In this work, a new σ-hole interaction formed between ZOF2 (Z = Kr and Xe) as the Lewis acid and a series of metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CN, CH3) is reported. The nature of this interaction, called "aerogen-hydride" interaction, is unveiled by molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. Our results indicate that the aerogen-hydride interactions are quite strong and can be comparable in strength to other σ-hole bonds. An important charge-transfer interaction is also associated with the formation of OF2Z⋯HMX complexes.

  6. Uranium Hydride Nucleation and Growth Model FY'16 ESC Annual Report

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Mary Ann [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Richards, Andrew Walter [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schulze, Roland K. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-12-20

    Uranium hydride corrosion is of great interest to the nuclear industry. Uranium reacts with water and/or hydrogen to form uranium hydride which adversely affects material performance. Hydride nucleation is influenced by thermal history, mechanical defects, oxide thickness, and chemical defects. Information has been gathered from past hydride experiments to formulate a uranium hydride model to be used in a Canned Subassembly (CSA) lifetime prediction model. This multi-scale computer modeling effort started in FY’13, and the fourth generation model is now complete. Additional high-resolution experiments will be run to further test the model.

  7. Initial step of hydride formation in single crystalline gadolinium thin films and islands studied on the nm-scale

    Energy Technology Data Exchange (ETDEWEB)

    Wanjelik, Sara, E-mail: Sara.Wanjelik@hhu.de [Institute of Applied Physics, Universitätsstrasse 1, 40225 Düsseldorf (Germany); Stolboushkina, Oxana [Institute of Applied Physics, Universitätsstrasse 1, 40225 Düsseldorf (Germany); Sibirian State University of Industry, Novokuznetsk 654007 (Russian Federation); Königshofen, Samuel; Getzlaff, Mathias [Institute of Applied Physics, Universitätsstrasse 1, 40225 Düsseldorf (Germany)

    2015-10-05

    Highlights: • Hydride formation in Gd films depends on hydrogen pressure and annealing conditions. • Chain formation of disclike islands (diameter about 4 nm) in 1 0 1 0 direction appears. • A triangular shaped structure is observed together with discs. • Transformation to hydride in islands starts from the edges. • All hydrogen induced structures can be removed stepwise by annealing up to 350 °C. - Abstract: The initial steps of hydrogen absorption in gadolinium systems are investigated by means of scanning tunneling microscopy (STM) under ultra high vacuum conditions. Gadolinium is grown on a W(1 1 0) substrate. Smooth films or islands can be obtained depending on the preparation conditions. Exposure to hydrogen leads to modifications of the Gd surface. Small discs with a diameter of a few nm and a height of one atomic step appear. The discs form chains with distinct directions. A triangular shaped structure is observed together with the discs. Areas that are completely transformed to GdH{sub 2} appear, too. The absorption process in islands was also investigated and compared to the behaviour of thin films. All measurements are performed at room temperature. By increasing the temperature, changes of the different modifications can be observed up to the point at which they vanish.

  8. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  9. The influence of hydride on fracture toughness of recrystallized Zircaloy-4 cladding

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Hsiao-Hung, E-mail: 175877@mail.csc.com.tw [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China); China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chiang, Ming-Feng [China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chen, Yen-Chen [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China)

    2014-04-01

    In this work, RXA cladding tubes were hydrogen-charged to target hydrogen content levels between 150 and 800 wppm (part per million by weight). The strings of zirconium hydrides observed in the cross sections are mostly oriented in the circumferential direction. The fracture toughness of hydrided RXA Zircaloy-4 cladding was measured to evaluate its hydride embrittlement susceptibility. With increasing hydrogen content, the fracture toughness of hydrided RXA cladding decreases at both 25 °C and 300 °C. Moreover, highly localized hydrides (forming a hydride rim) aggravate the degradation of the fracture properties of RXA Zircaloy-4 cladding at both 25 °C and 300 °C. Brittle features in the form of quasi-cleavages and secondary cracks were observed on the fracture surface of the hydride rim, even for RXA cladding tested at 300 °C.

  10. On the chemical state and distribution of Zr- and V-based additives in reactive hydride composites

    Science.gov (United States)

    Bösenberg, U.; Vainio, U.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Goerigk, G.; Welter, E.; Dornheim, M.; Schreyer, A.; Bormann, R.

    2009-05-01

    Reactive hydride composites (RHCs) are very promising hydrogen storage materials for future applications due to their reduced reaction enthalpies and high gravimetric capacities. At present, the materials' functionality is limited by the reaction kinetics. A significant positive influence can be observed with addition of transition-metal-based additives. To understand the effect of these additives, the chemical state and changes during the reaction as well as the microstructural distribution were investigated using x-ray absorption near-edge structure (XANES) spectroscopy and anomalous small-angle x-ray scattering (ASAXS). In this work, zirconium- and vanadium-based additives were added to 2LiBH4-MgH2 composites and 2LiH-MgB2 composites and measured in the vicinity of the corresponding absorption edge. The measurements reveal the formation of finely distributed zirconium diboride and vanadium-based nanoparticles. The potential mechanisms for the observed influence on the reaction kinetics are discussed.

  11. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen

  12. Pore confined synthesis of magnesium boron hydride nanoparticles

    NARCIS (Netherlands)

    Au, Yuen S.; Yan, Yigang; De Jong, Krijn P.; Remhof, Arndt; De Jongh, Petra E.

    2014-01-01

    Nanostructured materials based on light elements such as Li, Mg, and Na are essential for energy storage and conversion applications, but often difficult to prepare with control over size and structure. We report a new strategy that is illustrated for the formation of magnesium boron hydrides,

  13. Novel baker's yeast catalysed hydride reduction of an epoxide moiety

    CSIR Research Space (South Africa)

    Horak, RM

    1995-02-27

    Full Text Available -4039(95)00043-7 Tetrahedron Letters, Vol. 36, No. 9, pp. 1541-1544, 1995 Elsevier Science Ltd Printed in Great Britain 0040-4039/95 $9.50+0.00 A Novel Baker's Yeast Catalysed Hydride Reduction of an Epoxide Moiety R. Marthinus Horak, Robin A...

  14. Release of hydrogen from nanoconfined hydrides by application of microwaves

    Science.gov (United States)

    Sanz-Moral, Luis Miguel; Navarrete, Alexander; Sturm, Guido; Link, Guido; Rueda, Miriam; Stefanidis, Georgios; Martín, Ángel

    2017-06-01

    The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m2/g and 1.41 cm3/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.

  15. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen stora

  16. Review of magnesium hydride-based materials: development and optimisation

    NARCIS (Netherlands)

    Crivello, J. -C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.; Latroche, M.; Milanese, C.; Milcius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    2016-01-01

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the slo

  17. Process of forming a sol-gel/metal hydride composite

    Science.gov (United States)

    Congdon, James W.

    2009-03-17

    An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

  18. Hydrogen adsorption on palladium and palladium hydride at 1 bar

    DEFF Research Database (Denmark)

    Johansson, Martin; Skulason, Egill; Nielsen, Gunver

    2010-01-01

    The dissociative sticking probability for H-2 on Pd films supported on sputtered Highly Ordered Pyrolytic Graphite (HOPG) has been derived from measurements of the rate of the H-D exchange reaction at 1 bar. The sticking probability for H-2, S. is higher on Pd hydride than on Pd (a factor of 1...

  19. Pore confined synthesis of magnesium boron hydride nanoparticles

    NARCIS (Netherlands)

    Au, Yuen S.; Yan, Yigang; De Jong, Krijn P.; Remhof, Arndt; De Jongh, Petra E.

    2014-01-01

    Nanostructured materials based on light elements such as Li, Mg, and Na are essential for energy storage and conversion applications, but often difficult to prepare with control over size and structure. We report a new strategy that is illustrated for the formation of magnesium boron hydrides, relev

  20. Superconductivity and unexpected chemistry of germanium hydrides under pressure

    Science.gov (United States)

    Davari Esfahani, M. Mahdi; Oganov, Artem R.; Niu, Haiyang; Zhang, Jin

    2017-04-01

    Following the idea that hydrogen-rich compounds might be high-Tc superconductors at high pressures, and the very recent breakthrough in predicting and synthesizing hydrogen sulfide with record-high Tc=203 K , an ab initio evolutionary algorithm for crystal structure prediction was employed to find stable germanium hydrides. In addition to the earlier structure of germane with space group Ama2, we propose a C2/m structure, which is energetically more favorable at pressures above 278 GPa (with inclusion of zero-point energy). Our calculations indicate that the C2/m phase of germane is a superconductor with Tc=67 K at 280 GPa. Germane is found to become thermodynamically unstable to decomposition to hydrogen and the compound Ge3H11 at pressures above 300 GPa. Ge3H11 with space group I 4 ¯m 2 is found to become stable at above 285 GPa with Tc=43 K . We find that the pressure-induced phase stability of germanium hydrides is distinct from analogous isoelectronic systems, e.g., Si hydrides and Sn hydrides. Superconductivity stems from large electron-phonon coupling associated with the wagging, bending, and stretching intermediate-frequency modes derived mainly from hydrogen.

  1. Structural stability of complex hydrides LiBH4 revisited

    DEFF Research Database (Denmark)

    Lodziana, Zbigniew; Vegge, Tejs

    2004-01-01

    A systematic approach to study the phase stability of LiBH4 based on ab initio calculations is presented. Three thermodynamically stable phases are identified and a new phase of Cc symmetry is proposed for the first time for a complex hydride. The x-ray diffraction pattern and vibrational spectra...

  2. Hydride encapsulation by molecular alkali-metal clusters.

    Science.gov (United States)

    Haywood, Joanna; Wheatley, Andrew E H

    2008-07-14

    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  3. Optimizing Misch-Metal Compositions In Metal Hydride Anodes

    Science.gov (United States)

    Bugga, Ratnakumar V.; Halpert, Gerald

    1995-01-01

    Electrochemical cells based on metal hydride anodes investigated experimentally in effort to find anode compositions maximizing charge/discharge-cycle performances. Experimental anodes contained misch metal alloyed with various proportions of Ni, Co, Mn, and Al, and experiments directed toward optimization of composition of misch metal.

  4. Well-defined transition metal hydrides in catalytic isomerizations.

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  5. Nanocrystalline Metal Hydrides Obtained by Severe Plastic Deformations

    Directory of Open Access Journals (Sweden)

    Jacques Huot

    2012-01-01

    Full Text Available It has recently been shown that Severe Plastic Deformation (SPD techniques could be used to obtain nanostructured metal hydrides with enhanced hydrogen sorption properties. In this paper we review the different SPD techniques used on metal hydrides and present some specific cases of the effect of cold rolling on the hydrogen storage properties and crystal structure of various types of metal hydrides such as magnesium-based alloys and body centered cubic (BCC alloys. Results show that generally cold rolling is as effective as ball milling to enhance hydrogen sorption kinetics. However, for some alloys such as TiV0.9Mn1.1 alloy ball milling and cold rolling have detrimental effect on hydrogen capacity. The exact mechanism responsible for the change in hydrogenation properties may not be the same for ball milling and cold rolling. Nevertheless, particle size reduction and texture seems to play a leading role in the hydrogen sorption enhancement of cold rolled metal hydrides.

  6. Metal hydrides for smart window and sensor applications

    NARCIS (Netherlands)

    Yoshimura, K.; Langhammer, C.; Dam, B.

    2013-01-01

    The hydrogenation of metals often leads to changes in optical properties in the visible range. This allows for fundamental studies of the hydrogenation process, as well as the exploration of various applications using these optical effects. Here, we focus on recent developments in metal hydride-base

  7. Tribochemical Decomposition of Light Ionic Hydrides at Room Temperature.

    Science.gov (United States)

    Nevshupa, Roman; Ares, Jose Ramón; Fernández, Jose Francisco; Del Campo, Adolfo; Roman, Elisa

    2015-07-16

    Tribochemical decomposition of magnesium hydride (MgH2) induced by deformation at room temperature was studied on a micrometric scale, in situ and in real time. During deformation, a near-full depletion of hydrogen in the micrometric affected zone is observed through an instantaneous (t MgH2 with reduced crystal size by mechanical deformation.

  8. KNH2-KH: a metal amide-hydride solid solution.

    Science.gov (United States)

    Santoru, Antonio; Pistidda, Claudio; Sørby, Magnus H; Chierotti, Michele R; Garroni, Sebastiano; Pinatel, Eugenio; Karimi, Fahim; Cao, Hujun; Bergemann, Nils; Le, Thi T; Puszkiel, Julián; Gobetto, Roberto; Baricco, Marcello; Hauback, Bjørn C; Klassen, Thomas; Dornheim, Martin

    2016-09-27

    We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2(-) ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

  9. On the dynamic and static manifestation of molecular absorption in thin films probed by a microcantilever

    Energy Technology Data Exchange (ETDEWEB)

    Finot, Eric [Institut CARNOT de Bourgogne; Fabre, Arnaud [French Atomic Energy Commission (CEA), Centre de Valduc, Is-sur-Tille; Passian, Ali [ORNL; Thundat, Thomas [University of Alberta, Edmonton, Canada

    2014-03-01

    Mechanical resonators shaped like microcantilevers have been demonstrated as a platform for very sensitive detection of chemical and biological analytes. However, its use as an analytical tool will require fundamental understanding of the molecular absorption-induced effects in the static and dynamic sensor response. The effect of absorption-induced surface stress on the microcantilever response is here investigated using palladium hydride formation. It is shown that the resonance and deformation states of the cantilever monitored simultaneously exhibit excellent correlation with the phase of the hydride formation. However, the associated frequency shifts and quasistatic bending are observed to be independent during solid solution phase. Importantly, absorption-induced changes in the elastic parameters of the palladium film are found to play a dominant role in the static and dynamic response. The presented results help in discerning the parameters that control the cantilever response as well as the relationships between these parameters.

  10. Thin-film metal hydrides for solar energy applications

    Energy Technology Data Exchange (ETDEWEB)

    Mongstad, Trygve Tveiteraas

    2012-11-01

    Thin-film metal hydrides may become important solar energy materials in the future. This thesis demonstrates interesting material properties of metal hydride films, relevant for applications as semiconducting materials for photovoltaic (PV) solar cells and for regulation of light using smart window technology.The work presented here has comprised an experimental study, focusing on three different materials: Magnesium hydride (MgH2), magnesium nickel hydride (Mg2NiH4) and yttrium hydride (YHx). Reactive sputter deposition was used to prepare the metal hydride film samples.This synthesis method is relatively uncommon for metal hydrides. Here,the first demonstration of reactive sputtering synthesis for YHx and Mg2NiH4 is given. Different challenges in forming singlephase, pure metal hydrides were identified: MgH2 could not be deposited without 3-16% metallic Mg present in the films, and YHx was found to react strong-ly to oxygen (O) during the deposition process. On the other hand, Mg2NiH4 films formed easily and apparently without major metallic clusters and with low O content.Mg2NiH4 is a semiconductor with an optical band gap that is suitable for PV solar cells. This study has showed that films with promising electrical and optical properties can be synthesized using reactive cosputtering of Mg and Ni. Using optical methods, the band gap for the as deposited samples was estimated to 1.54-1.76 eV, depending on the Mg-Ni composition. The asdeposited films were amorphous or nano-crystalline, but could be crystallized into the high-temperature fcc structure of Mg2NiH4 using heat treatment at 523 K. The band gap of the crystalline films was 2.1-2.2 eV, depending on the composition.A pronounced photochromic reaction to visible and UV light was observed for transparent yttrium hydride (T-YHx) samples. The optical transmission was reduced when the samples were illuminated, and the original optical transmission was restored when the samples were kept under dark conditions

  11. Synthesis of hydrides by interaction of intermetallic compounds with ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Tarasov, Boris P., E-mail: tarasov@icp.ac.ru [Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Chernogolovka 142432 (Russian Federation); Fokin, Valentin N.; Fokina, Evelina E. [Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Chernogolovka 142432 (Russian Federation); Yartys, Volodymyr A., E-mail: volodymyr.yartys@ife.no [Institute for Energy Technology, Kjeller NO 2027 (Norway); Department of Materials Science and Engineering, Norwegian University of Science and Technology, Trondheim NO 7491 (Norway)

    2015-10-05

    Highlights: • Interaction of the intermetallics A{sub 2}B, AB, AB{sub 2}, AB{sub 5} and A{sub 2}B{sub 17} with NH{sub 3} was studied. • The mechanism of interaction of the alloys with ammonia is temperature-dependent. • Hydrides, hydridonitrides, disproportionation products or metal–N–H compounds are formed. • NH{sub 4}Cl was used as an activator of the reaction between ammonia and intermetallics. • Interaction with ammonia results in the synthesis of the nanopowders. - Abstract: Interaction of intermetallic compounds with ammonia was studied as a processing route to synthesize hydrides and hydridonitrides of intermetallic compounds having various stoichiometries and types of crystal structures, including A{sub 2}B, AB, AB{sub 2}, AB{sub 5} and A{sub 2}B{sub 17} (A = Mg, Ti, Zr, Sc, Nd, Sm; B = transition metals, including Fe, Co, Ni, Ti and nontransition elements, Al and B). In presence of NH{sub 4}Cl used as an activator of the reaction between ammonia and intermetallic alloys, their interaction proceeds at rather mild P–T conditions, at temperatures 100–200 °C and at pressures of 0.6–0.8 MPa. The mechanism of interaction of the alloys with ammonia appears to be temperature-dependent and, following a rise of the interaction temperature, it leads to the formation of interstitial hydrides; interstitial hydridonitrides; disproportionation products (binary hydride; new intermetallic hydrides and binary nitrides) or new metal–nitrogen–hydrogen compounds like magnesium amide Mg(NH{sub 2}){sub 2}. The interaction results in the synthesis of the nanopowders where hydrogen and nitrogen atoms become incorporated into the crystal lattices of the intermetallic alloys. The nitrogenated materials have the smallest particle size, down to 40 nm, and a specific surface area close to 20 m{sup 2}/g.

  12. Anisotropic Azimuthal Power and Temperature distribution on FuelRod. Impact on Hydride Distribution

    Energy Technology Data Exchange (ETDEWEB)

    Motta, Arthur [Pennsylvania State Univ., State College, PA (United States); Ivanov, Kostadin [Pennsylvania State Univ., State College, PA (United States); Arramova, Maria [Pennsylvania State Univ., State College, PA (United States); Hales, Jason [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-04-29

    The degradation of the zirconium cladding may limit nuclear fuel performance. In the high temperature environment of a reactor, the zirconium in the cladding corrodes, releasing hydrogen in the process. Some of this hydrogen is absorbed by the cladding in a highly inhomogeneous manner. The distribution of the absorbed hydrogen is extremely sensitive to temperature and stress concentration gradients. The absorbed hydrogen tends to concentrate near lower temperatures. This hydrogen absorption and hydride formation can cause cladding failure. This project set out to improve the hydrogen distribution prediction capabilities of the BISON fuel performance code. The project was split into two primary sections, first was the use of a high fidelity multi-physics coupling to accurately predict temperature gradients as a function of r, θ , and z, and the second was to use experimental data to create an analytical hydrogen precipitation model. The Penn State version of thermal hydraulics code COBRA-TF (CTF) was successfully coupled to the DeCART neutronics code. This coupled system was verified by testing and validated by comparison to FRAPCON data. The hydrogen diffusion and precipitation experiments successfully calculated the heat of transport and precipitation rate constant values to be used within the hydrogen model in BISON. These values can only be determined experimentally. These values were successfully implemented in precipitation, diffusion and dissolution kernels that were implemented in the BISON code. The coupled output was fed into BISON models and the hydrogen and hydride distributions behaved as expected. Simulations were conducted in the radial, axial and azimuthal directions to showcase the full capabilities of the hydrogen model.

  13. Ti–V–Mn based metal hydrides for hydrogen compression applications

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, Lydia, E-mail: lydia.pickering@btinternet.com; Reed, Daniel; Bevan, Alexander I.; Book, David, E-mail: d.book@bham.ac.uk

    2015-10-05

    Highlights: • Ti–V–Mn based alloys were investigated as V was substituted for Nb, Cr, Mo and Ta. • The produced alloys were found to possess C14 Laves, BCC and FCC phases. • <0.2 Nb substituted for V led to small hysteresis and high dissociation pressures. • Ti{sub 0.5}–V{sub 0.45}–Nb{sub 0.05}–Mn is a suitable alloy to be used in a metal hydride compressor. - Abstract: Ti–V–Mn based alloys, consisting mainly of the hexagonal C14 Laves and BCC phases, with nominal compositions of Ti{sub 0.5}V{sub 0.4}TM{sub 0.1}Mn, where TM = Nb, Cr, Mo, Ta and Ti{sub 0.5}V{sub 0.5−x}Nb{sub x}Mn, where x = 0.05 and 0.2, were synthesised by arc melting. It was found that small amounts of Nb substituted for V (x = 0.05 and 0.1) resulted in smaller hysteresis between absorption and desorption as well as higher hydrogen dissociation pressures, compared to Ti{sub 0.5}V{sub 0.5}Mn. These findings show that Ti{sub 0.5}–V{sub 0.45}–Nb{sub 0.05}–Mn is a suitable alloy to be used in a metal hydride compressor to deliver a pressure of 650 bar in the temperature range 303–473 K.

  14. Hydride structures in Ti-aluminides subjected to high temperature and hydrogen pressure charging conditions

    Science.gov (United States)

    Legzdina, D.; Robertson, I. M.; Birnbaum, H. K.

    1991-01-01

    The distribution and chemistry of hydrides produced in single and dual phase alloys with a composition near TiAl have been investigated by using a combination of TEM and X-ray diffraction techniques. The alloys were exposed at 650 C to 13.8 MPa of gaseous H2 for 100 h. In the single-phase gamma alloy, large hydrides preferentially nucleated on the grain boundaries and matrix dislocations and a population of small hydrides was distributed throughout the matrix. X-ray and electron diffraction patterns from these hydrides indicated that they have an fcc structure with a lattice parameter of 0.45 nm. EDAX analysis of the hydrides showed that they were enriched in Ti. The hydrides were mostly removed by vacuum annealing at 800 C for 24 h. On dissolution of the hydrides, the chemistry of hydride-free regions of the grain boundary returned to the matrix composition, suggesting that Ti segregation accompanied the hydride formation rather than Ti enrichment causing the formation of the hydride.

  15. Hydriding performances and modeling of a small-scale ZrCo bed

    Energy Technology Data Exchange (ETDEWEB)

    Koo, D.; Lee, J.; Park, J.; Paek, S.; Chung, H. [KAERI-UST, Yuseong, Daejeon (Korea, Republic of); Chang, M.H.; Yun, S.H.; Cho, S.; Jung, K.J. [NFRI, Yuseong, Daejeon (Korea, Republic of)

    2015-03-15

    In order to evaluate the performance of the hydriding of a ZrCo bed, a small-scale getter bed of ZrCo was designed and fabricated. The results show that the hydriding time at room temperature was somewhat shorter than that at higher temperatures of ZrCo and that the performance of hydriding at low temperatures of ZrCo was better than that at high temperatures of ZrCo. The experimental results of the hydrogen pressure of hydriding (ZrCoH{sub 2.8}) at different temperatures were in agreement with the computed values using a numerical modeling equation but with a small difference during the first 10 minutes of the hydriding of ZrCo. The model is based on the Kozeny-Carman equation. The effect of a helium blanket on hydriding was measured and analyzed. The hydriding with no helium blanket in the primary vessel of ZrCo is much faster than that with a helium blanket. The hydriding at a helium concentration of 8% is slower than that at 0%. As the helium concentration increases, the hydriding of ZrCo decreases. The experimental results of the hydriding with 0 %, 4%, and 8% of helium concentration are in agreement with the calculated values but with minimal differences during the first 10 minutes.

  16. Dissociation potential curves of low-lying states in transition metal hydrides. 3. Hydrides of groups 6 and 7.

    Science.gov (United States)

    Koseki, Shiro; Matsushita, Takeshi; Gordon, Mark S

    2006-02-23

    The dissociation curves of low-lying spin-mixed states in monohydrides of groups 6 and 7 were calculated by using an effective core potential (ECP) approach. This approach is based on the multiconfiguration self-consistent field (MCSCF) method, followed by first-order configuration interaction (FOCI) calculations, in which the method employs an ECP basis set proposed by Stevens and co-workers (SBKJC) augmented by a set of polarization functions. Spin-orbit coupling (SOC) effects are estimated within the one-electron approximation by using effective nuclear charges, since SOC splittings obtained with the full Breit-Pauli Hamitonian are underestimated when ECP basis sets are used. The ground states of group 6 hydrides have Omega = (1)/(2)(X(6)Sigma(+)(1/2)), where Omega is the z component of the total angular momentum quantum number. Although the ground states of group 7 hydrides have Omega = 0(+), their main adiabatic components are different; the ground state in MnH originates from the lowest (7)Sigma(+), while in TcH and ReH the main component of the ground state is the lowest (5)Sigma(+). The present paper reports a comprehensive set of theoretical results including the dissociation energies, equilibrium distances, electronic transition energies, harmonic frequencies, anharmonicities, and rotational constants for several low-lying spin-mixed states in these hydrides. Transition dipole moments were also computed among the spin-mixed states and large peak positions of electronic transitions are suggested theoretically for these hydrides. The periodic trends of physical properties of metal hydrides are discussed, based on the results reported in this and other recent studies.

  17. Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.; Dedrick, Daniel E.; Reeder, Craig L.

    2012-02-01

    In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested

  18. 微波消解-高分辨连续光源原子吸收光谱法测定锁阳和韭菜籽中的重金属元素含量%Determination of Heavy Metal Elements in Cynomorium and Leek Seeds by High Resolution Continuum Source Atomic Absorption Spectrometry with Microwave Digestion

    Institute of Scientific and Technical Information of China (English)

    胡玥; 丁玉竹; 高旭东; 李西波; 邵士俊

    2016-01-01

    The contents of heavy metals ( Cu, Pb, Cd, Cr, As, Hg) in Chinese herbal medicines ( cynomorium and leek seeds) were tested using microwave digestion-high resolution continuum source atomic absorption spectrometry ( HR-CS AAS) . The samples were digested by microwave digestion, and methods were developed for the determination of the contents of Cu by flame atomic absorption spectrometry, Pb, Cd and Cr by graphite furnace atomic absorption spectrometry, As and Hg by hydride generation atomic absorption spectrometry, respectively. The recoveries were 95. 61% ~100. 1%, the relative standard deviations ( RSDs) were 0. 8% ~3. 3%, and the correlation coefficients of R2 were 0. 999. The results showed that the contents of the above-mentioned heavy metal elements in cynomorium and leek seeds were all lower than the permitted values in the standard of “medicinal plants and preparation of green import industry standard” and National food safety standard “limited quantity of pollutants in food”. The established method are simple, rapid, accurate and reliable, and are successfully applied to analyze the contents of heavy metal elements in Chinese herbal medicines.%利用微波消解-高分辨连续光源原子吸收光谱法测定锁阳、韭菜籽两种中药材中铜( Cu)、铅( Pb)、镉( Cd)、铬( Cr)、砷( As)和汞( Hg)的含量.采用微波消解进行样品前处理,火焰原子吸收法测定其中的Cu含量,石墨炉原子吸收法测定Pb、Cd和Cr含量,氢化物发生原子吸收法测定As、Hg含量.方法线性关系良好,相关系数R2大于0.999,加标回收率为95.61%~100.1%,RSD为0.8%~3.3%,测得锁阳和韭菜籽中Cu、Pb、Cd、Cr、As和Hg的含量值均低于《药用植物及制剂进口绿色行业标准》和食品安全国家标准《食品中污染物限量》( GB2762-2012)中规定的限量指标.方法分析速率快、干扰少、精密度高,适用于中药材中重金属含量的测定.

  19. Magnesium Hydride for Load Levelling Energy Storage

    DEFF Research Database (Denmark)

    Vigeholm, B.

    Some of the magnesium properties essential to the applicability of the reaction Mg+H2⇆MgH2 as a hydrogen storage system have been investigated. Three magnesium powders with particle size smaller than 50 μm average diameter were cycled, over 31, 71 and 151 cycles respectively, at 675K (400°C......) and at absorption pressures, 2-3 MPa. The powders absorbed and desorbed 60-95% of the theoretically maximal amount of hydrogen given by stoichiometric MgH2. The reaction rates changed negligibly over the extent of the experiments permitting the mentioned hydrogen exchange to be completed in less than 20 minutes...

  20. Gas atomization processing of tin and silicon modified LaNi{sub 5} for nickel-metal hydride battery applications

    Energy Technology Data Exchange (ETDEWEB)

    Ting, J.

    1999-02-12

    Numerous researchers have studied the relevant material properties of so-called AB{sub 5} alloys for battery applications. These studies involved LaNi{sub 5} substituted alloys which were prepared using conventional cast and crush alloying techniques. While valuable to the understanding of metal hydride effects, the previous work nearly ignored the potential for alternative direct powder production methods, like high pressure gas atomization (HPGA). Thus, there is a need to understand the relationship between gas atomization processes, powder particle solidification phases, and hydrogen absorption properties of ultra fine (< 25 {micro}m) atomized powders with high surface area for enhanced battery performance. Concurrently, development of a gas atomization nozzle that is more efficient than all current designs is needed to increase the yield of ultrafine AB{sub 5} alloy powder for further processing advantage. Gas atomization processing of the AB{sub 5} alloys was demonstrated to be effective in producing ultrafine spherical powders that were resilient to hydrogen cycling for the benefit of improving corrosion resistance in battery application. These ultrafine powders benefited from the rapid solidification process by having refined solute segregation in the microstructure of the gas atomized powders which enabled a rapid anneal treatment of the powders. The author has demonstrated the ability to produce high yields of ultrafine powder efficiently and cost effectively, using the new HPGA-III technology. Thus, the potential benefits of processing AB{sub 5} alloys using the new HPGA technology could reduce manufacturing cost of nickel-metal hydride powder. In the near future, the manufacture of AB{sub 5} alloy powders could become a continuous and rapid production process. The economic benefit of an improved AB{sub 5} production process may thereby encourage the use of nickel-metal hydride rechargeable batteries in electrical vehicle applications in the foreseeable

  1. The electric double layer in hydriding metals

    Directory of Open Access Journals (Sweden)

    K. Jamroziak

    2008-12-01

    Full Text Available Purpose: The effect of penetration hydrogen into fatigue load metals is widely investigated by many researchers.Hydrogen is the chemical element which plays negative role in fatigue durability of structures. It decides on fatiguebrittle cracking. In the paper authors carry out an analysis of fatigue durability. Making use of naturally coming intoexistence the electric double layer phenomenon authors discussed the model of absorbing hydrogen into fatigue gap.Design/methodology/approach: A proposed model of the mechanism of hydrogen absorption by metal wasbased on particle hydrogen and water vapor from the air.Findings: It assumes that the EDL has crucial role in intercepting of polar dipole particles of hydrogenand water’s vapor, especially in an already formed fatigue micro-gaps and gaps by effects of its electrostaticattraction force. The authors assume that the main source of hydrogen is water’s vapor, and number of hydrogendipoles is negligible.Practical implications: The problems of metals’ fragility/durability were also discussed in other papersin which author mainly tried to develop new methods of materials’ production with the consideration of assumedfatigue durability.Originality/value: Currently, in progress are works on proposing a model for hydrogen absorption by metal.Such approach to optimization in production and development of the new technologies is an essence of modernconstructions that work in all variety of mechanical stress conditions.

  2. Effect of thermo-mechanical cycling on zirconium hydride reorientation studied in situ with synchrotron X-ray diffraction

    Science.gov (United States)

    Colas, Kimberly B.; Motta, Arthur T.; Daymond, Mark R.; Almer, Jonathan D.

    2013-09-01

    The circumferential hydrides normally present in nuclear reactor fuel cladding after reactor exposure may dissolve during drying for dry storage and re-precipitate when cooled under load into a more radial orientation, which could embrittle the fuel cladding. It is necessary to study the rates and conditions under which hydride reorientation may happen in order to assess fuel integrity in dry storage. The objective of this work is to study the effect of applied stress and thermal cycling on the hydride morphology in cold-worked stress-relieved Zircaloy-4 by combining conventional metallography and in situ X-ray diffraction techniques. Metallography is used to study the evolution of hydride morphology after several thermo-mechanical cycles. In situ X-ray diffraction performed at the Advanced Photon Source synchrotron provides real-time information on the process of hydride dissolution and precipitation under stress during several thermal cycles. The detailed study of diffracted intensity, peak position and full-width at half-maximum provides information on precipitation kinetics, elastic strains and other characteristics of the hydride precipitation process. The results show that thermo-mechanical cycling significantly increases the radial hydride fraction as well as the hydride length and connectivity. The radial hydrides are observed to precipitate at a lower temperature than circumferential hydrides. Variations in the magnitude and range of hydride strains due to reorientation and cycling have also been observed. These results are discussed in light of existing models and experiments on hydride reorientation. The study of hydride elastic strains during precipitation shows marked differences between circumferential and radial hydrides, which can be used to investigate the reorientation process. Cycling under stress above the threshold stress for reorientation drastically increases both the reoriented hydride fraction and the hydride size. The reoriented hydride

  3. FEASIBILITY OF RECYCLING PLUTONIUM AND MINOR ACTINIDES IN LIGHT WATER REACTORS USING HYDRIDE FUEL

    Energy Technology Data Exchange (ETDEWEB)

    Greenspan, Ehud; Todreas, Neil; Taiwo, Temitope

    2009-03-10

    The objective of this DOE NERI program sponsored project was to assess the feasibility of improving the plutonium (Pu) and minor actinide (MA) recycling capabilities of pressurized water reactors (PWRs) by using hydride instead of oxide fuels. There are four general parts to this assessment: 1) Identifying promising hydride fuel assembly designs for recycling Pu and MAs in PWRs 2) Performing a comprehensive systems analysis that compares the fuel cycle characteristics of Pu and MA recycling in PWRs using the promising hydride fuel assembly designs identified in Part 1 versus using oxide fuel assembly designs 3) Conducting a safety analysis to assess the likelihood of licensing hydride fuel assembly designs 4) Assessing the compatibility of hydride fuel with cladding materials and water under typical PWR operating conditions Hydride fuel was found to offer promising transmutation characteristics and is recommended for further examination as a possible preferred option for recycling plutonium in PWRs.

  4. Heat transfer analysis of metal hydrides in metal-hydrogen secondary batteries

    Science.gov (United States)

    Onischak, M.; Dharia, D.; Gidaspow, D.

    1976-01-01

    The heat transfer between a metal-hydrogen secondary battery and a hydrogen-storing metal hydride was studied. Temperature profiles of the endothermic metal hydrides and the metal-hydrogen battery were obtained during discharging of the batteries assuming an adiabatic system. Two hydride materials were considered in two physical arrangements within the battery system. In one case the hydride is positioned in a thin annular region about the battery stack; in the other the hydride is held in a tube down the center of the stack. The results show that for a typical 20 ampere-hour battery system with lanthanum pentanickel hydride as the hydrogen reservoir the system could perform successfully.

  5. Molecular early main group metal hydrides: synthetic challenge, structures and applications.

    Science.gov (United States)

    Harder, Sjoerd

    2012-11-25

    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](∞) and [MH(2)](∞) salts are high, the synthesis of well-defined soluble hydride complexes is an obvious challenge. Access to molecular early main group metal hydrides, however, is rewarding: these hydrocarbon-soluble metal hydrides are highly reactive, have found use in early main group metal catalysis and are potentially also valuable molecular model systems for polar metal hydrides as a hydrogen storage material. The article focusses specifically on alkali and alkaline-earth metal hydride complexes and discusses the synthetic challenge, molecular structures, reactivity and applications.

  6. Effect of cold rolling on the hydrogen absorption and desorption kinetics of Zircaloy-4

    Energy Technology Data Exchange (ETDEWEB)

    Dupim, I.S.; Moreira, J.M.L. [CESC, Universidade Federal do ABC, Av. dos Estados 5001, CEP: 09210-580 Santo André, SP (Brazil); Huot, J. [IRH, Université du Québec à Trois Rivières, 3351 boul. des Forges, CP 500, G9Y5H7 Trois Rivières, QC (Canada); Santos, S.F., E-mail: sydney.ferreira@ufabc.edu.br [CESC, Universidade Federal do ABC, Av. dos Estados 5001, CEP: 09210-580 Santo André, SP (Brazil)

    2015-04-01

    Metal matrix composites have been considered promising candidates as nuclear fuels for pressurized water reactors and also for nuclear waste management. Among others, Zircaloy is considered an excellent alternative for metallic matrix in such composites due to its excellent mechanical properties, high thermal conductivity and high corrosion resistance at operating temperatures. For manufacturing these fuels, a necessary step is the production of Zircaloy powder to be used as raw material. A feasible route to produce powders of refractory metals and alloys like Zircaloy is the hydriding and dehydriding process. For this type of processing route, hydrogen absorption and desorption should be performed at the lowest temperature and pressure possible in order to reduce the processing costs. In this paper, we investigated the hydrogen sorption kinetics of Zircaloy and the effect of cold rolling on the reaction rate. It was found that cold rolling greatly increases the hydrogenation kinetics and drastically reduces the dehydrogenation temperature. - Highlights: • The effects of temperature and pressure on the hydrogen reaction kinetics in Zircaloy-4 are analyzed. • The incubation time during absorption measurements increased for higher H2 pressures. • Changes in hydriding reaction kinetics at 1500 kPa of H{sub 2} and 1.25 wt.% of absorption. • Cold rolling increased the hydrogen absorption kinetics and decreased the hydride decomposition temperature.

  7. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  8. Orbital-like motion of hydride ligands around low-coordinate metal centers.

    Science.gov (United States)

    Ortuño, Manuel A; Vidossich, Pietro; Conejero, Salvador; Lledós, Agustí

    2014-12-15

    Hydrogen atoms in the coordination sphere of a transition metal are highly mobile ligands. Here, a new type of dynamic process involving hydrides has been characterized by computational means. This dynamic event consists of an orbital-like motion of hydride ligands around low-coordinate metal centers containing N-heterocyclic carbenes. The hydride movement around the carbene-metal-carbene axis is the lowest energy mode connecting energy equivalent isomers. This understanding provides crucial information for the interpretation of NMR spectra.

  9. High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

    Directory of Open Access Journals (Sweden)

    Borislav Bogdanović

    2009-01-01

    Full Text Available For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

  10. High temperature metal hydrides as heat storage materials for solar and related applications.

    Science.gov (United States)

    Felderhoff, Michael; Bogdanović, Borislav

    2009-01-01

    For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 degrees C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

  11. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    Science.gov (United States)

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  12. Influence of partial substitution of cerium for lanthanum on magnetocaloric properties of La1-xCexFe11.44Si1.56 and their hydrides

    Institute of Scientific and Technical Information of China (English)

    慕利娟; 黄焦宏; 张文佳; 刘翠兰; 王高峰; 赵增祺

    2014-01-01

    The structure and magnetocaloric properties of La1–xCexFe11.44Si1.56 and their hydrides La1–xCexFe11.44Si1.56Hy (x=0, 0.1, 0.2, 0.3, 0.4) were investigated. The samples crystallized mainly in the cubic NaZn13-type structure with a small amount ofα-Fe phase as impurity. The lattice constants and Curie temperature presented the same change tendency with increasing of Ce content. For the hydrides, the influence of Ce content on lattice constants was weakened and the values of H concentration y were approximate to be 1.56. The La1–xCexFe11.44Si1.56 compounds exhibited large values of isothermal entropy change –ΔSm around the Curie tem-perature TC under a low magnetic field change of 1.5 T. The value of–ΔSm increased and then decreased with increasing Ce con-tent, reached the maximum, 26.07 J/kg·K for x=0.3. TC increased up to the vicinity of room temperature by hydrogen absorption for the Ce substituted compounds, but TC only slightly decreased with increasing Ce content. The first-order metamagnetic transi-tion was still kept in the hydrides and the maximum values of–ΔSm were lower than those of the La1–xCexFe11.44Si1.56 compounds, but still remained large values, about 10.5 J/kgK under a magnetic field change of 1.5 T. The values of–ΔSm were nearly inde-pendent of the Ce content and did not increase with increasing x for the hydrides. The La1–xCexFe11.44Si1.56Hy (x=0–0.4) hydrides exhibited large magnetic entropy changes, small hysteresis loss and effective refrigerant capacity covered the room temperature range from 305 to 317 K. These hydrides are very useful for the magnetic refrigeration applications near room temperature under low magnetic field change.

  13. Development of a novel metal hydride-air secondary battery

    Energy Technology Data Exchange (ETDEWEB)

    Gamburzev, S.; Zhang, W.; Velev, O.A.; Srinivasan, S.; Appleby, A.J. [Texas A and M University, College Station (United States). Center for Electrochemical Systems and Hydrogen Research; Visintin, A. [Universidad Nacional de La Plata (Argentina). Insituto Nacional de Investigaciones Fisicoquimica Teoricas y Applicadas

    1998-05-01

    A laboratory metal hydride/air cell was evaluated. Charging was via a bifunctional air gas-diffusion electrode. Mixed nickel and cobalt oxides, supported on carbon black and activated carbon, were used as catalysts in this electrode. At 30 mA cm{sup -2} in 6 M KOH, the air electrode potentials were -0.2 V (oxygen reduction) and +0.65 V (oxygen evolution) vs Hg/HgO. The laboratory cell was cycled for 50 cycles at the C/2 rate (10 mA cm{sup -2}). The average discharge/charge voltages of the cell were 0.65 and 1.6 V, respectively. The initial capacity of the metal hydride electrode decreased by about 15% after 50 cycles. (author)

  14. Detecting low concentrations of plutonium hydride with magnetization measurements

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Wook; Mun, E. D.; Baiardo, J. P.; Zapf, V. S.; Mielke, C. H. [National High Magnetic Field Laboratory, MPA-CMMS, Los Alamos National Laboratory (LANL), Los Alamos, New Mexico 87545 (United States); Smith, A. I.; Richmond, S.; Mitchell, J.; Schwartz, D. [Nuclear Material Science Group, MST-16, LANL, Los Alamos, New Mexico 87545 (United States)

    2015-02-07

    We report the formation of plutonium hydride in 2 at. % Ga-stabilized δ-Pu, with 1 at. % H charging. We show that magnetization measurements are a sensitive, quantitative measure of ferromagnetic plutonium hydride against the nonmagnetic background of plutonium. It was previously shown that at low hydrogen concentrations, hydrogen forms super-abundant vacancy complexes with plutonium, resulting in a bulk lattice contraction. Here, we use magnetization, X-ray, and neutron diffraction measurements to show that in addition to forming vacancy complexes, at least 30% of the H atoms bond with Pu to precipitate PuH{sub x} on the surface of the sample with x ∼ 1.9. We observe magnetic hysteresis loops below 40 K with magnetic remanence, consistent with ferromagnetic PuH{sub 1.9}.

  15. Hydrorefining distillates from coal liquefaction using intermetallic compound hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kadiev, Kh.M.; Pivovarova, N.A.; Askhabova, Kh.N.; Taramov, Kh.K.

    1986-07-01

    Investigations are discussed into hydrorefining of coal liquefaction distillate using ZrNi intermetallic compound hydride as catalyst. The paper shows that 70-75% reduction in content of unsaturated and sulfur-containing compounds takes place in the presence of this catalyst at low temperature (200-250 C) and pressure (0.1 MPa), and establishes that preliminary preparation of starting material (removal of phenols and nitrous bases) produces significant effect on hydrorefining results and product stability. Tests have also shown that although intermetallic compound hydride catalyst has fairly low stability, it is capable of recovering its catalytic properties on reduction-oxidation treatment. Description of the tests and characteristics of hydrorefining products of coal liquefaction distillate are given. 8 references.

  16. ALUMINUM HYDRIDE: A REVERSIBLE STORAGE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    One of the challenges of implementing the hydrogen economy is finding a suitable solid H{sub 2} storage material. Aluminium (alane, AlH{sub 3}) hydride has been examined as a potential hydrogen storage material because of its high weight capacity, low discharge temperature, and volumetric density. Recycling the dehydride material has however precluded AlH{sub 3} from being implemented due to the large pressures required (>10{sup 5} bar H{sub 2} at 25 C) and the thermodynamic expense of chemical synthesis. A reversible cycle to form alane electrochemically using NaAlH{sub 4} in THF been successfully demonstrated. Alane is isolated as the triethylamine (TEA) adduct and converted to unsolvated alane by heating under vacuum. To complete the cycle, the starting alanate can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride (NaH) This novel reversible cycle opens the door for alane to fuel the hydrogen economy.

  17. Irradiation effects on thermal properties of LWR hydride fuel

    Science.gov (United States)

    Terrani, Kurt; Balooch, Mehdi; Carpenter, David; Kohse, Gordon; Keiser, Dennis; Meyer, Mitchell; Olander, Donald

    2017-04-01

    Three hydride mini-fuel rods were fabricated and irradiated at the MIT nuclear reactor with a maximum burnup of 0.31% FIMA or ∼5 MWd/kgU equivalent oxide fuel burnup. Fuel rods consisted of uranium-zirconium hydride (U (30 wt%)ZrH1.6) pellets clad inside a LWR Zircaloy-2 tubing. The gap between the fuel and the cladding was filled with lead-bismuth eutectic alloy to eliminate the gas gap and the large temperature drop across it. Each mini-fuel rod was instrumented with two thermocouples with tips that are axially located halfway through the fuel centerline and cladding surface. In-pile temperature measurements enabled calculation of thermal conductivity in this fuel as a function of temperature and burnup. In-pile thermal conductivity at the beginning of test agreed well with out-of-pile measurements on unirradiated fuel and decreased rapidly with burnup.

  18. Pyrophoric behaviour of uranium hydride and uranium powders

    Energy Technology Data Exchange (ETDEWEB)

    Le Guyadec, F., E-mail: fabienne.leguyadec@cea.f [CEA Marcoule DEN/DTEC/SDTC, 30207 Bagnols sur Ceze, BP 17171 (France); Genin, X.; Bayle, J.P. [CEA Marcoule DEN/DTEC/SDTC, 30207 Bagnols sur Ceze, BP 17171 (France); Dugne, O. [DEN/DTEC/SGCS, 30207 Bagnols sur Ceze, BP 17171 (France); Duhart-Barone, A.; Ablitzer, C. [CEA Cadarache DEN/DEC/SPUA, 13108 St. Paul lez Durance (France)

    2010-01-31

    Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine powders have been studied and observed in an original and dedicated experimental device placed inside a glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide (<0.5 wt.%) was obtained by heat treatment at low temperature in flowing Ar/5%H{sub 2}. Pure uranium powder was obtained by dehydration in flowing pure argon. Those fine powders showed spontaneous ignition at room temperature in air. An in situ CCD-camera displayed ignition associated with powder temperature measurement. Characterization of powders before and after ignition was performed by XRD measurements and SEM observations. Oxidation mechanisms are proposed.

  19. Reversible metal-hydride phase transformation in epitaxial films.

    Science.gov (United States)

    Roytburd, Alexander L; Boyerinas, Brad M; Bruck, Hugh A

    2015-03-11

    Metal-hydride phase transformations in solids commonly proceed with hysteresis. The extrinsic component of hysteresis is the result of the dissipation of energy of internal stress due to plastic deformation and fracture. It can be mitigated on the nanoscale, where plastic deformation and fracture are suppressed and the transformation proceeds through formation and evolution of coherent phases. However, the phase coherency introduces intrinsic thermodynamic hysteresis, preventing reversible transformation. In this paper, it is shown that thermodynamic hysteresis of coherent metal-hydride transformation can be eliminated in epitaxial film due to substrate constraint. Film-substrate interaction leads to formation of heterophase polydomain nanostructure with variable phase fraction which can change reversibly by varying temperature in a closed system or chemical potential in an open system.

  20. Structural isotope effects in metal hydrides and deuterides.

    Science.gov (United States)

    Ting, Valeska P; Henry, Paul F; Kohlmann, Holger; Wilson, Chick C; Weller, Mark T

    2010-03-07

    Historically the extraction of high-quality crystallographic information from inorganic samples having high hydrogen contents, such as metal hydrides, has involved preparing deuterated samples prior to study using neutron powder diffraction. We demonstrate, through direct comparison of the crystal structure refinements of the binary hydrides SrH(2) and BaH(2) with their deuteride analogues at 2 K and as a function of temperature, that precise and accurate structural information can be obtained from rapid data collections from samples containing in excess of 60 at.% hydrogen using modern high-flux, medium resolution, continuous wavelength neutron powder diffraction instruments. Furthermore, observed isotope-effects in the extracted lattice parameters and atomic positions illustrate the importance of investigating compounds in their natural hydrogenous form whenever possible.

  1. Effects of metastability on hydrogen sorption in fluorine substituted hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Pinatel, E.R.; Corno, M.; Ugliengo, P.; Baricco, M., E-mail: marcello.baricco@unito.it

    2014-12-05

    Highlights: • Fluorine substitution in simple metal hydrides has been modelled. • The stability of the MH{sub (1−x)}F{sub x} solid solutions has been discussed. • Conditions for reversibility of sorption reactions have been suggested. - Abstract: In this work ab initio calculations and Calphad modelling have been coupled to describe the effect of fluorine substitution on the thermodynamics of hydrogenation–dehydrogenation in simple hydrides (NaH, AlH{sub 3} and CaH{sub 2}). These example systems have been used to discuss the conditions required for the formation of a stable hydride–fluoride solid solution necessary to obtain a reversible hydrogenation reaction.

  2. WISH VI. Constraints on UV and X-ray irradiation from a survey of hydrides in low- to high-mass YSOs

    CERN Document Server

    Benz, A O; van Dishoeck, E F; Melchior, M; Wampfler, S F; van der Tak, F; Goicoechea, J R; Indriolo, N; Kristensen, L E; Lis, D C; Mottram, J C; Bergin, E A; Caselli, P; Herpin, F; Hogerheijde, M R; Johnstone, D; Liseau, R; Nisini, B; Tafalla, M; Visser, R; Wyrowski, F

    2016-01-01

    Hydrides are simple compounds containing one or a few hydrogen atoms bonded to a heavier atom. They are fundamental precursor molecules in cosmic chemistry and many hydride ions have become observable in high quality for the first time thanks to the Herschel Space Observatory. Ionized hydrides, such as CH+ and OH+, and also HCO+ that affect the chemistry of molecules such as water, provide complementary information on irradiation by far UV (FUV) or X-rays and gas temperature. The targeted lines of CH+, OH+, H2O+, C+ and CH are detected mostly in blue-shifted absorption. H3O+ and SH+ are detected in emission and only toward some high-mass objects. The observed line parameters and correlations suggest two different origins, related to gas entrained by the outflows and to the circumstellar envelope. The column density ratios of CH+/OH+ are estimated from chemical slab models, assuming that the H2 density is given by the specific density model of each object at the beam radius. For the low-mass YSOs the observed ...

  3. Formation and characterisation of the silver hydride nanocluster cation [Ag3H2((Ph2 P)2CH2)](+) and its release of hydrogen.

    Science.gov (United States)

    Girod, Marion; Krstić, Marjan; Antoine, Rodolphe; MacAleese, Luke; Lemoine, Jérome; Zavras, Athanasios; Khairallah, George N; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2014-12-08

    Multistage mass spectrometry and density functional theory (DFT) were used to characterise the small silver hydride nanocluster, [Ag3 H2 L](+) (where L=(Ph2 P)2 CH2 ) and its gas-phase unimolecular chemistry. Collision-induced dissociation (CID) yields [Ag2 HL](+) as the major product while laser-induced dissociation (LID) proceeds via H2 formation and subsequent release from [Ag3 H2 L](+) , giving rise to [Ag3 L](+) as the major product. Deuterium labelling studies on [Ag3 D2 L](+) prove that the source of H2 is from the hydrides and not from the ligand. Comparison of TD-DFT absorption patterns obtained for the optimised structures with action spectroscopy results, allows assignment of the measured features to structures of precursors and products. Molecular dynamics "on the fly" reveal that AgH loss is favoured in the ground state, but H2 formation and loss is preferred in the first excited state S1 , in agreement with CID and LID experimental findings. This indicates favourable photo-induced formation of H2 and subsequent release from [Ag3 H2 L](+) , an important finding in context of metal hydrides as a hydrogen storage medium, which can subsequently be released by heating or irradiation with light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Characterization and Analyses of Degradation and Recovery of LaNi4.78Sn0.22 Hydrides Following Thermal Aging

    Energy Technology Data Exchange (ETDEWEB)

    Bowman Jr, Robert C [ORNL; Payzant, E Andrew [ORNL; Wilson, Philip R [Jet Propulsion Laboratory, Pasadena, CA; Pearson, David P [Jet Propulsion Laboratory, Pasadena, CA; Ledovskikh, Alexander [Eindhoven University of Technology; Danilov, Demtri [Eindhoven University of Technology; Notten, Peter [Eindhoven University of Technology; An, Ke [ORNL; Skorpenske, Harley David [ORNL; Wood III, David L [ORNL

    2013-01-01

    LaNi4.78Sn0.22Hx hydride samples were held at a hydrogen content of x > 5.0 (x is H/La atomic ratio) and temperatures above 465 K to accelerate the intrinsic degradation processes. Although Sn-substituted alloys are much more resistant to disproportionation than nearly all other LaNi5 alloys, the present test conditions did produce substantial degradation. Effects observed included reduction in hydrogen storage capacity, decreases in the plateau pressures, increased slopes of the plateaus, and smaller hysteresis ratios. A regeneration process nearly completely restored the behavior of the degraded LaNi4.78Sn0.22 hydride to its initial value. First-principles chemical reaction kinetics and statistical thermodynamics simulations have replicated experimental pressure-composition hydrogen gas absorption isotherms for both initial and degraded LaNi4.78Sn0.22 hydride. Neutron diffraction characterization of phase compositions, crystal structures, and hydrogen content have been performed on undamaged, degraded, and regenerated LaNi4.78Sn0.22 deuterides.

  5. Shielding efficiency of metal hydrides and borohydrides in fusion reactors

    OpenAIRE

    Singh Vishvanath P.; Badiger Nagappa M.; Gerward Leif

    2016-01-01

    Mass attenuation coefficients, mean free paths and exposure buildup factors have been used to characterize the shielding efficiency of metal hydrides and borohydrides, with high density of hydrogen. Gamma ray exposure buildup factors were computed using five-parameter geometric progression fitting at energies 0.015 MeV to15 MeV, and for penetration depths up to 40 mean free paths. Fast-neutron shielding efficiency has been characterized by the effective neu...

  6. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    Science.gov (United States)

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W.; Kiran, Boggavarapu; Bowen, Kit H.

    2016-10-01

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H- and CAl5-7H2- found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  7. METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

    Science.gov (United States)

    Vetrano, J.B.

    1962-01-23

    A method is given for preparing large, sound bodies of delta zirconium hydride. The method includes the steps of heating a zirconium body to a temperature of not less than l000 deg C, providing a hydrogen atmosphere for the zirconium body at a pressure not greater than one atmosphere, reducing the temperature slowly to 800 deg C at such a rate that cracks do not form while maintaining the hydrogen pressure substantially constant, and cooling in an atmosphere of hydrogen. (AEC)

  8. Aluminum Hydride as a Fuel Supplement to NanoThermites

    Science.gov (United States)

    2014-01-01

    explosives and as a hydrogen storage medium. There are as many as six crystalline phases of alane, of which α-alane is themost stable and is also the...a pure nanoaluminum-corresponding metal oxide thermite. As Fig. 2 shows, the addition ofmicron-scale aluminum hydride to a nanoaluminum–copper-oxide... hydrogen does not participate in the thermite reaction. It is quite possible that the hydrogen may react with oxygen and or the metal oxide as an

  9. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Aldridge, F.T.

    1984-05-09

    A study was made of the properties of metal hydrides which may be suitable for use in chromatographic separation of hydrogen isotopes. Sixty-five alloys were measured, with the best having a hydrogen-deuterium separation factor of 1.35 at 60/sup 0/C. Chromatographic columns using these alloys produced deuterium enrichments of up to 3.6 in a single pass, using natural abundance hydrogen as starting material. 25 references, 16 figures, 4 tables.

  10. Tin Content Determination in Canned Fruits and Vegetables by Hydride Generation Inductively Coupled Plasma Optical Emission Spectrometry

    Directory of Open Access Journals (Sweden)

    Sanda Rončević

    2012-01-01

    Full Text Available Tin content in samples of canned fruits and vegetables was determined by hydride generation inductively coupled plasma atomic emission spectrometry (HG-ICP-OES, and it was compared with results obtained by standard method of flame atomic absorption spectrometry (AAS. Selected tin emission lines intensity was measured in prepared samples after addition of tartaric acid and followed by hydride generation with sodium borohydride solution. The most favorable line at 189.991 nm showed the best detection limit (1.9 μg L−1 and limit of quantification (6.4 μg kg−1. Good linearity and sensitivity were established from time resolved analysis and calibration tests. Analytical accuracy of 98–102% was obtained by recovery study of spiked samples. Method of standard addition was applied for tin determination in samples from fully protected tinplate. Tin presence at low-concentration range was successfully determined. It was shown that tenth times less concentrations of Sn were present in protected cans than in nonprotected or partially protected tinplate.

  11. Hydriding/dehydriding behaviors of La2Mg17-10 wt.%Ni composite prepared by mechanical milling

    Institute of Scientific and Technical Information of China (English)

    LIU Jing; LI Qian

    2013-01-01

    The structure and hydriding/dehydriding behaviors of La2Mg17-10 wt.%Ni composite prepared by mechanical milling were investigated.Compared with the un-milled sample,the as-milled alloys were ready to be activated and the kinetics of hydrogen absorption was relatively fast even at environmental temperature.The composite milled for 10 h absorbed 3.16 wt.% hydrogen within 100 s at 290 K.The kinetic mechanisms of hydriding/dehydriding reactions were analyzed by using a new model.The results showed that hydrogenation processes for all composites were controlled by hydrogen diffusion and the minimum activation energy was 15.3kJ/mol H2 for the composite milled for 10 h.Mechanical milling changed the dehydriding reaction rate-controlling step from surface penetration to diffusion and reduced the activation energy from 204.6 to 87.4 kJ/mol H2.The optimum milled duration was 5 h for desorption in our trials.

  12. Synthesis of Renewable Energy Materials, Sodium Aluminum Hydride by Grignard Reagent of Al

    Directory of Open Access Journals (Sweden)

    Jun-qin Wang

    2015-01-01

    Full Text Available The research on hydrogen generation and application has attracted widespread attention around the world. This paper is to demonstrate that sodium aluminum hydride can be synthesized under simple and mild reaction condition. Being activated through organics, aluminum powder reacts with hydrogen and sodium hydride to produce sodium aluminum hydride under atmospheric pressure. The properties and composition of the sample were characterized by FTIR, XRD, SEM, and so forth. The results showed that the product through this synthesis method is sodium aluminum hydride, and it has higher purity, perfect crystal character, better stability, and good hydrogen storage property. The reaction mechanism is also discussed in detail.

  13. Pressure-driven formation and stabilization of superconductive chromium hydrides

    Science.gov (United States)

    Yu, Shuyin; Jia, Xiaojing; Frapper, Gilles; Li, Duan; Oganov, Artem R.; Zeng, Qingfeng; Zhang, Litong

    2015-01-01

    Chromium hydride is a prototype stoichiometric transition metal hydride. The phase diagram of Cr-H system at high pressures remains largely unexplored due to the challenges in dealing with the high activation barriers and complications in handing hydrogen under pressure. We have performed an extensive structural study on Cr-H system at pressure range 0 ∼ 300 GPa using an unbiased structure prediction method based on evolutionary algorithm. Upon compression, a number of hydrides are predicted to become stable in the excess hydrogen environment and these have compositions of Cr2Hn (n = 2–4, 6, 8, 16). Cr2H3, CrH2 and Cr2H5 structures are versions of the perfect anti-NiAs-type CrH with ordered tetrahedral interstitial sites filled by H atoms. CrH3 and CrH4 exhibit host-guest structural characteristics. In CrH8, H2 units are also identified. Our study unravels that CrH is a superconductor at atmospheric pressure with an estimated transition temperature (T c) of 10.6 K, and superconductivity in CrH3 is enhanced by the metallic hydrogen sublattice with T c of 37.1 K at 81 GPa, very similar to the extensively studied MgB2. PMID:26626579

  14. Metal hydride-based thermal energy storage systems

    Energy Technology Data Exchange (ETDEWEB)

    Vajo, John J.; Fang, Zhigang

    2017-10-03

    The invention provides a thermal energy storage system comprising a metal-containing first material with a thermal energy storage density of about 1300 kJ/kg to about 2200 kJ/kg based on hydrogenation; a metal-containing second material with a thermal energy storage density of about 200 kJ/kg to about 1000 kJ/kg based on hydrogenation; and a hydrogen conduit for reversibly transporting hydrogen between the first material and the second material. At a temperature of 20.degree. C. and in 1 hour, at least 90% of the metal is converted to the hydride. At a temperature of 0.degree. C. and in 1 hour, at least 90% of the metal hydride is converted to the metal and hydrogen. The disclosed metal hydride materials have a combination of thermodynamic energy storage densities and kinetic power capabilities that previously have not been demonstrated. This performance enables practical use of thermal energy storage systems for electric vehicle heating and cooling.

  15. Air passivation of metal hydride beds for waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J. E.; Hsu, R. H. [Savannah River National Laboratory, Aiken, SC 29808 (United States)

    2008-07-15

    One waste acceptance criteria for hydride bed waste disposal is that the bed be non-pyrophoric. Batch-wise air ingress tests were performed which determined the amount of air consumed by a metal hydride bed. A desorbed, 4.4 kg titanium prototype hydride storage vessel (HSV) produced a 4.4 deg.C internal temperature rise upon the first air exposure cycle and a 0.1 deg.C temperature rise upon a second air exposure. A total of 346 sec air was consumed by the bed (0.08 sec per gram Ti). A desorbed, 9.66 kg LaNi{sub 4.25}Al{sub 0.75} prototype storage bed experienced larger temperature rises over successive cycles of air ingress and evacuation. The cycles were performed over a period of days with the bed effectively passivated after the 12. cycle. Nine to ten STP-L of air reacted with the bed producing both oxidized metal and water. (authors)

  16. Investigation of long term stability in metal hydrides

    Science.gov (United States)

    Marmaro, Roger W.; Lynch, Franklin E.; Chandra, Dhanesh; Lambert, Steve; Sharma, Archana

    1991-01-01

    It is apparent from the literature and the results of this study that cyclic degradation of AB(5) type metal hydrides varies widely according to the details of how the specimens are cycled. The Rapid Cycle Apparatus (RCA) used produced less degradation in 5000 to 10000 cycles than earlier work with a Slow Cycle Apparatus (SCA) produced in 1500 cycles. Evidence is presented that the 453 K (356 F) Thermal Aging (TA) time spent in the saturated condition causes hydride degradation. But increasing the cooling (saturation) period in the RCA did not greatly increase the rate of degradation. It appears that TA type degradation is secondary at low temperatures to another degradation mechanism. If rapid cycles are less damaging than slow cycles when the saturation time is equal, the rate of hydriding/dehydriding may be an important factor. The peak temperatures in the RCA were about 30 C lower than the SCA. The difference in peak cycle temperatures (125 C in the SCA, 95 C in RCA) cannot explain the differences in degradation. TA type degradation is similar to cyclic degradation in that nickel peaks and line broadening are observed in X ray diffraction patterns after either form of degradation.

  17. Performance study of a hydrogen powered metal hydride actuator

    Science.gov (United States)

    Mainul Hossain Bhuiya, Md; Kim, Kwang J.

    2016-04-01

    A thermally driven hydrogen powered actuator integrating metal hydride hydrogen storage reactor, which is compact, noiseless, and able to generate smooth actuation, is presented in this article. To test the plausibility of a thermally driven actuator, a conventional piston type actuator was integrated with LaNi5 based hydrogen storage system. Copper encapsulation followed by compaction of particles into pellets, were adopted to improve overall thermal conductivity of the reactor. The operation of the actuator was thoroughly investigated for an array of operating temperature ranges. Temperature swing of the hydride reactor triggering smooth and noiseless actuation over several operating temperature ranges were monitored for quantification of actuator efficiency. Overall, the actuator generated smooth and consistent strokes during repeated cycles of operation. The efficiency of the actuator was found to be as high as 13.36% for operating a temperature range of 20 °C-50 °C. Stress-strain characteristics, actuation hysteresis etc were studied experimentally. Comparison of stress-strain characteristics of the proposed actuator with traditional actuators, artificial muscles and so on was made. The study suggests that design modification and use of high pressure hydride may enhance the performance and broaden the application horizon of the proposed actuator in future.

  18. Nitrogen hydrides in interstellar gas: Herschel/HIFI observations towards G10.6-0.4 (W31C)

    CERN Document Server

    Persson, C M; Cernicharo, J; Goicoechea, J R; Hassel, G E; Herbst, E; Gerin, M; De Luca, M; Bell, T A; Coutens, A; Falgarone, E; Goldsmith, P F; Gupta, H; Kazmierczak, M; Lis, D C; Mookerjea, B; Neufeld, D A; Pearson, J; Phillips, T G; Sonnentrucker, P; Stutzki, J; Vastel, C; Yu, S; Boulanger, F; Dartois, E; Encrenaz, P; Geballe, T R; Giesen, T; Godard, B; Gry, C; Hennebelle, P; Hily-Blant, P; Joblin, C; Kolos, R; Krelowski, J; Martin-Pintado, J; Menten, K; Monje, R; Perault, M; Plume, R; Salez, M; Schlemmer, S; Schmidt, M; Teyssier, D; Peron, I; Cais, P; Gaufre, P; Cros, A; Ravera, L; Morris, P; Lord, S; Planesas, P

    2010-01-01

    The HIFI instrument on board the Herschel Space Observatory has been used to observe interstellar nitrogen hydrides along the sight-line towards G10.6-0.4 in order to improve our understanding of the interstellar chemistry of nitrogen. We report observations of absorption in NH N=1-0, J=2-1 and ortho-NH2 1_1,1-0_0,0. We also observed ortho-NH3 1_0-0_0, and 2_0-1_0, para-NH3 2_1-1_1, and searched unsuccessfully for NH+. All detections show emission and absorption associated directly with the hot-core source itself as well as absorption by foreground material over a wide range of velocities. All spectra show similar, non-saturated, absorption features, which we attribute to diffuse molecular gas. Total column densities over the velocity range 11-54 km/s are estimated. The similar profiles suggest fairly uniform abundances relative to hydrogen, approximately 6*10^-9, 3*10^-9, and 3*10^-9 for NH, NH2, and NH3, respectively. These abundances are discussed with reference to models of gas-phase and surface chemistry...

  19. Characterization of Hydrogen-Storage Properties and Physical Properties of Zinc Borohydride and Transition Metals-Added Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    Young Jun KWAK

    2017-02-01

    Full Text Available In this work, 90 wt.% MgH2 + 5 wt.% Ni + 1.7 wt.% Zn(BH42 + 1.7 wt.% Ti + 1.7 wt.% Fe samples (named 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe were prepared by milling in a planetary ball mill in a hydrogen atmosphere. The fraction of additives was small (10 wt.% in order to increase hydriding and dehydriding rates without decreasing the hydrogen storage capacity much. The hydrogen absorption and release properties of the prepared samples were investigated. 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe had an effective hydrogen storage capacity of 5 wt.%. The activation of 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe was completed after 2 hydriding-dehydriding cycles. At n = 3, the sample absorbed 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min at 593 K under 12 bar H2. The sample dehydrided at the 3rd hydriding-dehydriding cycle contained Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. The BET specific surface areas of the sample after milling in a hydrogen atmosphere and after 3 hydriding-dehydriding cycles were 57.9 and 53.2 m2/g, respectively.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14878

  20. Characterization of Hydrogen-Storage Properties and Physical Properties of Zinc Borohydride and Transition Metals-Added Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    Young Jun KWAK

    2017-02-01

    Full Text Available In this work, 90 wt.% MgH2 + 5 wt.% Ni + 1.7 wt.% Zn(BH42 + 1.7 wt.% Ti + 1.7 wt.% Fe samples (named 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe were prepared by milling in a planetary ball mill in a hydrogen atmosphere. The fraction of additives was small (10 wt.% in order to increase hydriding and dehydriding rates without decreasing the hydrogen storage capacity much. The hydrogen absorption and release properties of the prepared samples were investigated. 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe had an effective hydrogen storage capacity of 5 wt.%. The activation of 90MgH2 + 5Ni + 1.7Zn(BH42 + 1.7Ti + 1.7Fe was completed after 2 hydriding-dehydriding cycles. At n = 3, the sample absorbed 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min at 593 K under 12 bar H2. The sample dehydrided at the 3rd hydriding-dehydriding cycle contained Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. The BET specific surface areas of the sample after milling in a hydrogen atmosphere and after 3 hydriding-dehydriding cycles were 57.9 and 53.2 m2/g, respectively.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14878

  1. Dual-mode chemical vapor generation for simultaneous determination of hydride-forming and non-hydride-forming elements by atomic fluorescence spectrometry.

    Science.gov (United States)

    Wang, Yu; Xu, Kailai; Jiang, Xiaoming; Hou, Xiandeng; Zheng, Chengbin

    2014-05-21

    A dual-mode chemical vapor generation integrating hydride generation and photochemical vapor generation was developed for simultaneous multi-element analysis of hydride-forming and non-hydride-forming elements by atomic fluorescence spectrometry. Four elements were selected as model elements of hydride-forming (As, Cd) and non-hydride-forming (Ni, Fe) elements to validate this proposed method. Standard or sample solutions were separately pumped to mix with tetrahydroborate, and concentrated formic acid and ammonia, and then directed to a hydride generator and a photochemical reactor to realize simultaneous hydride generation and photochemical vapor generation, respectively. Optimum conditions for dual-mode chemical vapor generation were carefully investigated. Under the optimized conditions, limits of detection of 0.05, 0.008, 0.8 and 0.1 μg L(-1) were obtained for As, Cd, Fe and Ni, respectively. The precisions were 5.0, 5.5, 4.3 and 4.5% (n = 6, RSDs) for 2 μg L(-1) of As, 1 μg L(-1) of Cd, 50 μg L(-1) of Fe and 10 μg L(-1) of Ni, respectively. This method was validated for accuracy with three certified reference water samples and applied to the simultaneous determination of these elements in a tap water sample with spike recoveries in the range of 95-99%.

  2. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  3. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  4. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  5. Carbene-metal hydrides can be much less acidic than phosphine-metal hydrides: significance in hydrogenations.

    Science.gov (United States)

    Zhu, Ye; Fan, Yubo; Burgess, Kevin

    2010-05-05

    Acidities of iridium hydride intermediates were shown to be critical in some transformations mediated by the chiral analogues of Crabtree's catalyst, 1-3. To do this, several experiments were undertaken to investigate the acidities of hydrogenation mixtures formed using these iridium-oxazoline complexes. DFT calculations indicated that the acidity difference for Ir-H intermediates in these hydrogenations were astounding; iridium hydride from the N-heterocyclic carbene catalyst 1 was calculated to be around seven pK(a) units less acidic than those from the P-based complexes 2 and 3. Consistent with this, the carbene complex 1 was shown to be more effective for hydrogenations of acid-sensitive substrates. In deuteration experiments, less "abnormal" deuteration was observed, corresponding to fewer complications from acid-mediated alkene isomerization preceding the D(2)-addition step. Finally, simple tests with pH indicators provided visual evidence that phosphine-based catalyst precursors give significantly more acidic reaction mixtures than the corresponding N-heterocyclic carbene ones. These observations indicate carbene-for-phosphine (and similar) ligand substitutions may impact the outcome of catalytic reactions by modifying the acidities of the metal hydrides formed.

  6. Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hardy, B. J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Corgnale, C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Teprovich, J. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Ward, P. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Motyka, Ted [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-01-31

    The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce very high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.

  7. Kinetics of hydrogen absorption and desorption of a mechanically milled MgH2+5at%V nanocomposite

    Institute of Scientific and Technical Information of China (English)

    Qian Li; Kuangdi Xu; Kuochih Chou; Xionggang Lu; Qin Lin

    2006-01-01

    The experimental data in the MgH2-5at%V composite was summarized and used to investigate the kinetic mechanism of hydrogen absorption and desorption using a new model. The research results indicate that a coincidence of the theoretical calculation values with the experimental data has been reached and the rate-limiting step is hydrogen diffusion through the hydride phase (β phase)with the activation energy of 47.2 kJ per mole H2 for absorption and the diffusion of hydrogen in the α solid solution (α phase) with that of 59.1 kJ per mole H2 for desorption. In addition, the hydriding rate of the MgH2-V composite is 2.9 times faster than that of MgH2powders when compared with their characteristic absorption time directly.

  8. Crack initiation at long radial hydrides in Zr-2. 5Nb pressure tube material at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Choubey, R.; Puls, M.P. (AECL Research, Pinawa, Manitoba (Canada). Whiteshell Labs.)

    1994-05-01

    Crack initiation at hydrides in smooth tensile specimens of Zr-2.5Nb pressure tube material was investigated at elevated temperatures up to 300 C using an acoustic emission (AE) technique. The test specimens contained long, radial hydride platelets. These hydrides have their plate normals oriented in the applied stress direction. Below [approximately]100 C, widespread hydride cracking was initiated at stresses close to the yield stress. An estimate of the hydride's fracture strength from this data yielded a value of [approximately]520 MPa at 100 C. Metallography showed that up to this temperature, cracking occurred along the length of the hydrides. However, at higher temperatures, there was no clear evidence of lengthwise cracking of hydrides, and fewer of the total hydride population fractured during deformation, as indicated by the AE record and the metallography. Moreover, the hydrides showed significant plasticity by-being able to flow along with the matrix material and align themselves parallel to the applied stress direction without fracturing. Near the fracture surface of the specimen, transverse cracking of the flow-reoriented hydrides had occurred at various points along the lengths of the hydrides. These fractures appear to be the result of stresses produced by large plastic strains imposed by the surrounding matrix on the less ductile hydrides.

  9. Well-Defined Molecular Magnesium Hydride Clusters : Relationship between Size and Hydrogen-Elimination Temperature

    NARCIS (Netherlands)

    Intemann, Julia; Spielmann, Jan; Sirsch, Peter; Harder, Sjoerd

    A new tetranuclear magnesium hydride cluster, [{NN-(MgH)2}2], which was based on a NN-coupled bis--diketiminate ligand (NN2-), was obtained from the reaction of [{NN-(MgnBu)2}2] with PhSiH3. Its crystal structure reveals an almost-tetrahedral arrangement of Mg atoms and two different sets of hydride

  10. Zirconium hydrides and Fe redistribution in Zr-2.5%Nb alloy under ion irradiation

    Science.gov (United States)

    Idrees, Y.; Yao, Z.; Cui, J.; Shek, G. K.; Daymond, M. R.

    2016-11-01

    Zr-2.5%Nb alloy is used to fabricate the pressure tubes of the CANDU reactor. The pressure tube is the primary pressure boundary for coolant in the CANDU design and is susceptible to delayed hydride cracking, reduction in fracture toughness upon hydride precipitation and potentially hydride blister formation. The morphology and nature of hydrides in Zr-2.5%Nb with 100 wppm hydrogen has been investigated using transmission electron microscopy. The effect of hydrides on heavy ion irradiation induced decomposition of the β phase has been reported. STEM-EDX mapping was employed to investigate the distribution of alloying elements. The results show that hydrides are present in the form of stacks of different sizes, with length scales from nano- to micro-meters. Heavy ion irradiation experiments at 250 °C on as-received and hydrided Zr-2.5%Nb alloy, show interesting effects of hydrogen on the irradiation induced redistribution of Fe. It was found that Fe is widely redistributed from the β phase into the α phase in the as-received material, however, the loss of Fe from the β phase and subsequent precipitation is retarded in the hydrided material. This preliminary work will further the current understanding of microstructural evolution of Zr based alloys in the presence of hydrogen.

  11. Arsenic speciation analysis by HPLC postcolumn hydride generation and detection by atomic fluorescence spectrometry

    OpenAIRE

    Marschner, K; Musil, S. (Stanislav); Rychlovský, P.; Dědina, J. (Jiří)

    2014-01-01

    The aim of this contribution is to present a new method of hydride generation that enables to generate arsines from iAs , iAs , MMA and DMA in a flow injection mode with the same efficiency and in the next step connection of this hydride generator with HPLC column.

  12. Pore-Confined Light Metal Hydrides for Energy Storage and Catalysis

    NARCIS (Netherlands)

    Bramwell, P.L.

    2017-01-01

    Light metal hydrides have enjoyed several decades of attention in the field of hydrogen storage, but their applications have recently begun to diversify more and more into the broader field of energy storage. For example, light metal hydrides have shown great promise as battery materials, in sensors

  13. Study on the Use of Hydride Fuel in High-Performance Light Water Reactor Concept

    Directory of Open Access Journals (Sweden)

    Haileyesus Tsige-Tamirat

    2015-01-01

    Full Text Available Hydride fuels have features which could make their use attractive in future advanced power reactors. The potential benefit of use of hydride fuel in HPLWR without introducing significant modification in the current core design concept of the high-performance light water reactor (HPLWR has been evaluated. Neutronics and thermal hydraulic analyses were performed for a single assembly model of HPLWR with oxide and hydride fuels. The hydride assembly shows higher moderation with softer neutron spectrum and slightly more uniform axial power distribution. It achieves a cycle length of 18 months with sufficient excess reactivity. At Beginning of Cycle the fuel temperature coefficient of the hydride assembly is higher whereas the moderator and void coefficients are lower. The thermal hydraulic results show that the achievable fuel temperature in the hydride assembly is well below the design limits. The potential benefits of the use of hydride fuel in the current design of the HPLWR with the achieved improvements in the core neutronics characteristics are not sufficient to justify the replacement of the oxide fuel. Therefore for a final evaluation of the use of hydride fuels in HPLWR concepts additional studies which include modification of subassembly and core layout designs are required.

  14. Theoretical study on hydrogenation catalysts containing a metal hydride as additional hydrogen supply

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, W.P.M. van

    1992-01-01

    A hypothetical hydrogenation catalyst consisting of porous, catalytically active particles embedded with metal hydride powder was evaluated. The metal hydride provides temporarily additional hydrogen if the mass transfer rate of the hydrogen to the internal of the particle is not sufficient. A numer

  15. First-principles study of superabundant vacancy formation in metal hydrides.

    Science.gov (United States)

    Zhang, Changjun; Alavi, Ali

    2005-07-13

    Recent experiments have established the generality of superabundant vacancies (SAV) formation in metal hydrides. Aiming to elucidate this intriguing phenomenon and to clarify previous interpretations, we employ density-functional theory to investigate atomic mechanisms of SAV formation in fcc hydrides of Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au. We have found that upon H insertion, vacancy formation energies reduce substantially. This is consistent with experimental suggestions. We demonstrate that the entropy effect, which has been proposed to explain SAV formation, is not the main cause. Instead, it is the drastic change of electronic structure induced by the H in the SAV hydrides, which is to a large extent responsible. Interesting trends in systems investigated are also found: ideal hydrides of 5d metals and noble metals are unstable compared to the corresponding pure metals, but the SAV hydrides are more stable than the corresponding ideal hydrides, whereas opposite results exist in the cases of Ni, Rh, and Pd. These trends of stabilities of the SAV hydrides are discussed in detail and a general understanding for SAV formation is provided. Finally, we propose an alternative reaction pathway to generate a SAV hydride from a metal alloy.

  16. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    Science.gov (United States)

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  17. Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

    2015-10-05

    Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

  18. Herschel observations of the Sgr B2 cores: Hydrides, warm CO, and cold dust

    CERN Document Server

    Etxaluze, M; Cernicharo, J; Polehampton, E T; Noriega-Crespo, A; Molinari, S; Swinyard, B M; Wu, R; Bally, J

    2013-01-01

    Sagittarius B2 (Sgr B2) is one of the most massive and luminous star-forming regions in the Galaxy and shows chemical and physical conditions similar to those in distant extragalactic starbursts. We present large-scale far-IR/submm photometric images and spectroscopic maps taken with the PACS and SPIRE instruments onboard Herschel. The spectra towards the Sgr B2 star-forming cores, B2(M) and B2(N), are characterized by strong CO line emission, emission lines from high-density tracers (HCN, HCO+, and H2S), [N II] 205 um emission from ionized gas, and absorption lines from hydride molecules (OH+, H2O+, H2O, CH+, CH, SH+, HF, NH, NH2, and NH3). The rotational population diagrams of CO suggest the presence of two gas temperature components: an extended warm component, which is associated with the extended envelope, and a hotter component, which is seen towards the B2(M) and B2(N) cores. As observed in other Galactic Center clouds, the gas temperatures are significantly higher than the dust temperatures inferred f...

  19. Electronic band structure and optical properties of the cubic, Sc, Y and La hydride systems

    Energy Technology Data Exchange (ETDEWEB)

    Peterman, D.J.

    1980-01-01

    Electronic band structure calculations are used to interpret the optical spectra of the cubic Sc, Y and La hydride systems. Self-consistent band calculations of ScH/sub 2/ and YH/sub 2/ were carried out. The respective joint densities of states are computed and compared to the dielectric functions determined from the optical measurements. Additional calculations were performed in which the Fermi level or band gap energies are rigidly shifted by a small energy increment. These calculations are then used to simulate the derivative structure in thermomodulation spectra and relate the origin of experimental interband features to the calculated energy bands. While good systematic agreement is obtained for several spectral features, the origin of low-energy interband transitions in YH/sub 2/ cannot be explained by these calculated bands. A lattice-size-dependent premature occupation of octahedral sites by hydrogen atoms in the fcc metal lattice is suggested to account for this discrepancy. Various non-self-consistent calculations are used to examine the effect of such a premature occupation. Measurements of the optical absorptivity of LaH/sub x/ with 1.6 < x < 2.9 are presented which, as expected, indicate a more premature occupation of the octahedral sites in the larger LaH/sub 2/ lattice. These experimental results also suggest that, in contrast to recent calculations, LaH/sub 3/ is a small-band-gap semiconductor.

  20. Recent advances in improving performances of the lightweight complex hydrides Li-Mg-N-H system

    Directory of Open Access Journals (Sweden)

    Bao Zhang

    2017-02-01

    Full Text Available A brief review of state-of-the art advances in improving performances of the lightweight complex hydrides Li-Mg-N-H system is reported. Among the hydrogen storage materials, Li-Mg-N-H combination systems are regarded as one of the most potential candidates for the vehicular applications owing to their high hydrogen storage capacity (>5 wt% H and a more appropriate thermodynamic properties of hydrogen absorption and desorption. In the Li-Mg-N-H systems, tremendous efforts have been devoted to improving the hydrogen storage properties by adjusting composition, revealing reaction mechanisms, adding catalysts and refining the microstructures, etc. During the studies, different mechanisms, such as the coordinated two-molecule or multimolecule reaction mechanism and the ammonia-mediated mechanism, are proposed and applied under some certain conditions. Catalysis and nanosizing are very effective in enhancing the kinetic properties and thermodynamic destabilization of Li-Mg-N-H systems. Due to nano effects, the space-confinement and nanoconfinement seems to be more effective for improving the hydrogen storage performance, and it is great significant to develop hydrogen storage materials by studying the nanoconfined effects on the Li-Mg-N-H systems.

  1. Application of metal hydride paper to simple pressure generator for use in soft actuator systems.

    Science.gov (United States)

    Ino, Shuichi; Sakaki, Kouji; Hosono, Minako; Doi, Kouki; Shimada, Shigenobu; Chikai, Manabu

    2015-01-01

    Metal hydride (MH) actuators have a simple structure and a number of features that make them attractive for use in rehabilitation engineering and assistive technology. The MH actuator provides a high power-to-weight ratio, high-strain actuation, human-compatible softness, and noiseless operation, while being environmentally benign. On the other hand, there remain technical challenges to be overcome to improve the MH actuator regarding its speed of operation and energy efficiency, given the low heat conductivity of the MH powder that is used as the pressure generator for soft actuation. To overcome the issues of low heat conductivity and the handling of MH powder, we developed an MH paper, which is a special paper incorporating MH powder and carbon fiber, for use as a new pressure-generating element for a soft MH actuator system. In addition, the basic properties and structure of the proposed MH paper were investigated through scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and several thermodynamic experiments. The results of these experiments showed that the hydrogen absorption and desorption rates of the MH paper were significantly higher than those of the MH powder around room temperature.

  2. Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

    KAUST Repository

    Werghi, Baraa

    2016-09-26

    The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

  3. A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures

    Science.gov (United States)

    Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

    2014-03-01

    Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

  4. Another Look at the Mechanisms of Hydride Transfer Enzymes with Quantum and Classical Transition Path Sampling.

    Science.gov (United States)

    Dzierlenga, Michael W; Antoniou, Dimitri; Schwartz, Steven D

    2015-04-02

    The mechanisms involved in enzymatic hydride transfer have been studied for years, but questions remain due, in part, to the difficulty of probing the effects of protein motion and hydrogen tunneling. In this study, we use transition path sampling (TPS) with normal mode centroid molecular dynamics (CMD) to calculate the barrier to hydride transfer in yeast alcohol dehydrogenase (YADH) and human heart lactate dehydrogenase (LDH). Calculation of the work applied to the hydride allowed for observation of the change in barrier height upon inclusion of quantum dynamics. Similar calculations were performed using deuterium as the transferring particle in order to approximate kinetic isotope effects (KIEs). The change in barrier height in YADH is indicative of a zero-point energy (ZPE) contribution and is evidence that catalysis occurs via a protein compression that mediates a near-barrierless hydride transfer. Calculation of the KIE using the difference in barrier height between the hydride and deuteride agreed well with experimental results.

  5. Complex rare-earth aluminum hydrides: mechanochemical preparation, crystal structure and potential for hydrogen storage.

    Science.gov (United States)

    Weidenthaler, Claudia; Pommerin, André; Felderhoff, Michael; Sun, Wenhao; Wolverton, Christopher; Bogdanović, Borislav; Schüth, Ferdi

    2009-11-25

    A novel type of complex rare-earth aluminum hydride was prepared by mechanochemical preparation. The crystal structure of the REAlH(6) (with RE = La, Ce, Pr, Nd) compounds was calculated by DFT methods and confirmed by preliminary structure refinements. The trigonal crystal structure consists of isolated [AlH(6)](3-) octahedra bridged via [12] coordinated RE cations. The investigation of the rare-earth aluminum hydrides during thermolysis shows a decrease of thermal stability with increasing atomic number of the RE element. Rare-earth hydrides (REH(x)) are formed as primary dehydrogenation products; the final products are RE-aluminum alloys. The calculated decomposition enthalpies of the rare-earth aluminum hydrides are at the lower end for reversible hydrogenation under moderate conditions. Even though these materials may require somewhat higher pressures and/or lower temperatures for rehydrogenation, they are interesting examples of low-temperature metal hydrides for which reversibility might be reached.

  6. Getting metal-hydrides to do what you want them to

    Energy Technology Data Exchange (ETDEWEB)

    Gruen, D.M.

    1981-01-01

    With the discovery of AB/sub 5/ compounds, intermetallic hydrides with unusual properties began to be developed (H dissociation pressures of one to several atmospheres, extremely rapid and reversible adsorption/desorption very large amounts of H adsorbed). This paper reviews the factors that must be controlled in order to modify these hydrides to make them useful. The system LaNi/sub 5/ + H/sub 2/ is used as example. Use of AB/sub 5/ hydrides to construct a chemical heat pumps is discussed. Results of a systematic study substituting Al for Ni are reported; the HYCSOS pump is described briefly. Use of hydrides as hydrogen getters (substituted ZrV/sub 2/) is also discussed. Finally, possible developments in intermetallic hydride research in the 1980's and the hydrogen economy are discussed. 10 figures. (DLC)

  7. Evaluation of hydride blisters in zirconium pressure tube in CANDU reactor

    Energy Technology Data Exchange (ETDEWEB)

    Cheong, Y. M.; Kim, Y. S.; Gong, U. S.; Kwon, S. C.; Kim, S. S.; Choo, K.N

    2000-09-01

    When the garter springs for maintaining the gap between the pressure tube and the calandria tube are displaced in the CANDU reactor, the sagging of pressure tube results in a contact to the calandria tube. This causes a temperature difference between the inner and outer surface of the pressure tube. The hydride can be formed at the cold spot of outer surface and the volume expansion by hydride dormation causes the blistering in the zirconium alloys. An incident of pressure tube rupture due to the hydride blisters had happened in the Canadian CANDU reactor. This report describes the theoretical development and models on the formation and growth of hydride blister and some experimental results. The evaluation methodology and non-destructive testing for hydride blister in operating reactors are also described.

  8. Assessing nanoparticle size effects on metal hydride thermodynamics using the Wulff construction.

    Science.gov (United States)

    Kim, Ki Chul; Dai, Bing; Karl Johnson, J; Sholl, David S

    2009-05-20

    The reaction thermodynamics of metal hydrides are crucial to the use of these materials for reversible hydrogen storage. In addition to altering the kinetics of metal hydride reactions, the use of nanoparticles can also change the overall reaction thermodynamics. We use density functional theory to predict the equilibrium crystal shapes of seven metals and their hydrides via the Wulff construction. These calculations allow the impact of nanoparticle size on the thermodynamics of hydrogen release from these metal hydrides to be predicted. Specifically, we study the temperature required for the hydride to generate a H(2) pressure of 1 bar as a function of the radius of the nanoparticle. In most, but not all, cases the hydrogen release temperature increases slightly as the particle size is reduced.

  9. Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides.

    Science.gov (United States)

    Schilter, David; Camara, James M; Huynh, Mioy T; Hammes-Schiffer, Sharon; Rauchfuss, Thomas B

    2016-08-10

    Hydrogenase enzymes efficiently process H2 and protons at organometallic FeFe, NiFe, or Fe active sites. Synthetic modeling of the many H2ase states has provided insight into H2ase structure and mechanism, as well as afforded catalysts for the H2 energy vector. Particularly important are hydride-bearing states, with synthetic hydride analogues now known for each hydrogenase class. These hydrides are typically prepared by protonation of low-valent cores. Examples of FeFe and NiFe hydrides derived from H2 have also been prepared. Such chemistry is more developed than mimicry of the redox-inactive monoFe enzyme, although functional models of the latter are now emerging. Advances in physical and theoretical characterization of H2ase enzymes and synthetic models have proven key to the study of hydrides in particular, and will guide modeling efforts toward more robust and active species optimized for practical applications.

  10. Microstructure-Property Correlation in Magnesium-based Hydrogen Storage Systems: The Case for Ball-milled Magnesium Hydride Powder and Magnesium-based Multilayered Composites

    Science.gov (United States)

    Danaie, Mohsen

    The main focus of this thesis is the characterization of defects and microstructure in high-energy ball milled magnesium hydride powder and magnesium-based multilayered composites. Enhancement in kinetics of hydrogen cycling in magnesium can be achieved by applying severe plastic deformation. A literature survey reveals that, due to extreme instability of alpha-MgH 2 in transmission electron microscope (TEM), the physical parameters that researchers have studied are limited to particle size and grain size. By utilizing a cryogenic TEM sample holder, we extended the stability time of the hydride phase during TEM characterization. Milling for only 30 minutes resulted in a significant enhancement in desorption kinetics. A subsequent annealing cycle under pressurized hydrogen reverted the kinetics to its initial sluggish state. Cryo-TEM analysis of the milled hydride revealed that mechanical milling induces deformation twinning in the hydride microstructure. Milling did not alter the thermodynamics of desorption. Twins can enhance the kinetics by acting as preferential locations for the heterogeneous nucleation of metallic magnesium. We also looked at the phase transformation characteristics of desorption in MgH2. By using energy-filtered TEM, we investigated the morphology of the phases in a partially desorbed state. Our observations prove that desorption phase transformation in MgH2 is of "nucleation and growth" type, with a substantial energy barrier for nucleation. This is contrary to the generally assumed "core-shell" structure in most of the simulation models for this system. We also tested the hydrogen storage cycling behavior of bulk centimeter-scale Mg-Ti and Mg-SS multilayer composites synthesized by accumulative roll-bonding. Addition of either phase (Ti or SS) allows the reversible hydrogen sorption at 350°C, whereas identically roll-bonded pure magnesium cannot be absorbed. In the composites the first cycle of absorption (also called "activation

  11. Mathematical modeling of the nickel/metal hydride battery system

    Energy Technology Data Exchange (ETDEWEB)

    Paxton, Blaine Kermit [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering

    1995-09-01

    A group of compounds referred to as metal hydrides, when used as electrode materials, is a less toxic alternative to the cadmium hydroxide electrode found in nickel/cadmium secondary battery systems. For this and other reasons, the nickel/metal hydride battery system is becoming a popular rechargeable battery for electric vehicle and consumer electronics applications. A model of this battery system is presented. Specifically the metal hydride material, LaNi{sub 5}H{sub 6}, is chosen for investigation due to the wealth of information available in the literature on this compound. The model results are compared to experiments found in the literature. Fundamental analyses as well as engineering optimizations are performed from the results of the battery model. In order to examine diffusion limitations in the nickel oxide electrode, a ``pseudo 2-D model`` is developed. This model allows for the theoretical examination of the effects of a diffusion coefficient that is a function of the state of charge of the active material. It is found using present data from the literature that diffusion in the solid phase is usually not an important limitation in the nickel oxide electrode. This finding is contrary to the conclusions reached by other authors. Although diffusion in the nickel oxide active material is treated rigorously with the pseudo 2-D model, a general methodology is presented for determining the best constant diffusion coefficient to use in a standard one-dimensional battery model. The diffusion coefficients determined by this method are shown to be able to partially capture the behavior that results from a diffusion coefficient that varies with the state of charge of the active material.

  12. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    Hydrogen storage is one of the challenges to be overcome for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods. The direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali metal alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  13. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Fewox, C; Ragaiy Zidan, R; Brenda Garcia-Diaz, B

    2008-12-31

    Hydrogen storage is one of the greatest challenges for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods; the direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  14. Effects of Ca additions on some Mg-alloy hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Lupu, D.; Biris, A.; Indrea, E.; Bucur, R.V.

    1983-01-01

    The hydrogenation of the alloy of composition CaMg/sub 1/ /sub 8/Ni/sub 0/ /sub 5/ containing CaMg/sub 2/ and MgNi/sub 2/ shows fast activation kinetics. The Mg/sub 2/Ni phase is observed in the dehydrided samples. The three plateaus on the hydrogen desorption isotherms correspond to the most stable magnesium hydrides observed up to now in Mg-alloy (..delta.. H = 20 to 24 kcal/mol H/sub 2/). The effects of Ca additions on the hydrogen storage capacity and desorption rates of some Mg-rich alloys have been studied. 16 references, 3 figures, 1 table.

  15. Alkyl and Hydride-Olefin Complexes of Niobocene

    NARCIS (Netherlands)

    Klazinga, A.H.; Teuben, J.H.

    1980-01-01

    Reactions of Cp2NbCl2 with RMgCl (R = n-C3H7, i-C3H7, n-C4H9, s-C4H9 and n-C5H11) give niobocene hydride olefin complexes Cp2Nb(H)L (L = C3H6, C4H8 and C5H10). The last step of the reaction probably proceeds via a stereospecific β-H elimination from the monoalkyl species Cp2NbR. Decomposition of n-a

  16. Geoneutrinos and Hydridic Earth (or primordially Hydrogen-Rich Planet)

    CERN Document Server

    Bezrukov, L

    2014-01-01

    Geoneutrino is a new channel of information about geochemical composition of the Earth. We alnalysed here the following problem. What statistics do we need to distinguish between predictions of Bulk Silicate Earth model and Hydridic Earth model for Th/U signal ratio? We obtained the simple formula for estimation of error of Th/U signal ratio. Our calculations show that we need more than $22 kt \\cdot year$ exposition for Gran-Sasso underground laboratory and Sudbury Neutrino Observatory. We need more than $27 kt \\cdot year$ exposition for Kamioka site in the case of stopping of all Japanese nuclear power plants.

  17. Electrochemical process and production of novel complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2013-06-25

    A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

  18. Comparison between different reactions of group IV hydride with H

    Institute of Scientific and Technical Information of China (English)

    ZHANG; Shaolong; ZHANG; Xuqiang; ZHANG; Qinggang; ZHANG; Yici

    2006-01-01

    The four-dimensional time-dependent quantum dynamics calculations for reactions of group IV hydride with H are carried out by employing the semirigid vibrating rotor target model and the time-dependent wave packet method. The reaction possibility, cross section and rate constants for reactions (H+SiH4 and H+GeH4) in different initial vibrational and rotational states are obtained. The common feature for such kind of reaction process is summarized. The theoretical result is consistent with available measurement, which indicates the credibility of this theory and the potential energy surface.

  19. Modeling of Gallium Nitride Hydride Vapor Phase Epitaxy

    Science.gov (United States)

    Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

    1997-01-01

    A reactor model for the hydride vapor phase epitaxy of GaN is presented. The governing flow, energy, and species conservation equations are solved in two dimensions to examine the growth characteristics as a function of process variables and reactor geometry. The growth rate varies with GaCl composition but independent of NH3 and H2 flow rates. A change in carrier gas for Ga source from H2 to N2 affects the growth rate and uniformity for a fixed reactor configuration. The model predictions are in general agreement with observed experimental behavior.

  20. Equilibrium composition for the reaction of plutonium hydride with air

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    There are six independent constituents with 4 chemical elements, i.e. PuH2.7(s), PuN(s), Pu2O3(s), N2, O2 and H2, therefore , the system described involves of 2 independent reactions ,both those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.

  1. Bipolar Nickel-Metal Hydride Battery Development Project

    Science.gov (United States)

    Cole, John H.

    1999-01-01

    This paper reviews the development of the Electro Energy, Inc.'s bipolar nickel metal hydride battery. The advantages of the design are that each cell is individually sealed, and that there are no external cell terminals, no electrode current collectors, it is compatible with plastic bonded electrodes, adaptable to heat transfer fins, scalable to large area, capacity and high voltage. The design will allow for automated flexible manufacturing, improved energy and power density and lower cost. The development and testing of the battery's component are described. Graphic presentation of the results of many of the tests are included.

  2. Research in Nickel/Metal Hydride Batteries 2016

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2016-10-01

    Full Text Available Nineteen papers focusing on recent research investigations in the field of nickel/metal hydride (Ni/MH batteries have been selected for this Special Issue of Batteries. These papers summarize the joint efforts in Ni/MH battery research from BASF, Wayne State University, the National Institute of Standards and Technology, Michigan State University, and FDK during 2015–2016 through reviews of basic operational concepts, previous academic publications, issued US Patent and filed Japan Patent Applications, descriptions of current research results in advanced components and cell constructions, and projections of future works.

  3. Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter

    2003-07-01

    The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and

  4. A simulation study on the hydrogen storage properties of fullerene family molecules Cx(x = 56,60,70) and their hydrides

    Science.gov (United States)

    Dai, Wei; Xiao, Ming; Chen, Mu-Qing; Xu, Jia-Jing; Tang, Yong-Jian

    2016-08-01

    Hydrogen storage is a key factor for the application of hydrogen energy. From first principle calculation, we have acquired the energy barrier for hydrogen molecules to pass through the hexagonal rings and pentagonal rings of the fullerene. Then the absorption energy and energy barrier are used to analyze the hydrogen adsorption capacity of the fullerene family and their hydrides. We have also studied the hydrogen storage properties of the fullerene family and their hydrides by grand canonical Monte Carlo method. It is found that the weight density of hydrogen storage at ambient temperature and pressure can reach 7.71 wt.%. The results show that it is difficult for hydrogen to get into the carbon cage of the fullerene because of the high energy barrier, while it is beneficial to destroy the fullerene structure for the processes of absorption and desorption. Meanwhile, fullerene hydrogenation is an effective method to improve the hydrogen storage properties. Our study facilitates the design and synthesis of hydrogen storage materials, and provides theoretical support to improve the hydrogen storage capability for materials.

  5. Investigation of Structure and Hydriding Properties of La0.6 Nd0.4 Ni4.8 Mn0.2 Cux Alloys

    Institute of Scientific and Technical Information of China (English)

    Du Ping; Cao Wei; Lü Manqi; Yang Ke

    2004-01-01

    The structure and hydriding performance of La0.6Nd0.4Ni4.8Mn0.2Cux (x = 0 ~ 0.4) alloys were investigated in order to develop suitable materials for metal hydride air conditioner. The effect of Cu addition on the crystal structure,equilibrium pressure, hydrogen capacity and hysteresis as well as hydrogen absorption/desorption kinetics were systematically studied by using the measurement of P-C isotherms, X-ray diffraction and scanning electron microscopy. As the amount of Cu increases, the plateau pressure increases and hydrogen absorption/desorption kinetics is improved, but the effective hydrogen storage capacity decreases. It is shown that variations in the basal plane parameter a can be used as an indication for the plateau pressure changes. With the increase of parameter a, the plateau pressure decreases. For La0.6 Nd0.4Ni4.8Mn0.2Cux(x = 0 ~ 0.4) alloys there is a relationship between the effective hydrogen storage capacities and the ratios of their unit cell parameters c and a. The effective hydrogen storage capacity decreases with increase of a/c.

  6. Development of a component design tool for metal hydride heat pumps

    Science.gov (United States)

    Waters, Essene L.

    Given current demands for more efficient and environmentally friendly energy sources, hydrogen based energy systems are an increasingly popular field of interest. Within the field, metal hydrides have become a prominent focus of research due to their large hydrogen storage capacity and relative system simplicity and safety. Metal hydride heat pumps constitute one such application, in which heat and hydrogen are transferred to and from metal hydrides. While a significant amount of work has been done to study such systems, the scope of materials selection has been quite limited. Typical studies compare only a few metal hydride materials and provide limited justification for the choice of those few. In this work, a metal hydride component design tool has been developed to enable the targeted down-selection of an extensive database of metal hydrides to identify the most promising materials for use in metal hydride thermal systems. The material database contains over 300 metal hydrides with various physical and thermodynamic properties included for each material. Sub-models for equilibrium pressure, thermophysical data, and default properties are used to predict the behavior of each material within the given system. For a given thermal system, this tool can be used to identify optimal materials out of over 100,000 possible hydride combinations. The selection tool described herein has been applied to a stationary combined heat and power system containing a high-temperature proton exchange membrane (PEM) fuel cell, a hot water tank, and two metal hydride beds used as a heat pump. A variety of factors can be used to select materials including efficiency, maximum and minimum system pressures, pressure difference, coefficient of performance (COP), and COP sensitivity. The targeted down-selection of metal hydrides for this system focuses on the system's COP for each potential pair. The values of COP and COP sensitivity have been used to identify pairs of highest interest for

  7. Identification and characterization of a new zirconium hydride; Identification et caracterisation d'un nouvel hydrure de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhao; Morniroli, J.P.; Legris, A.; Thuinet, L. [Universite des Sciences et Technologies de Lille, USTL, ENSCL, CNRS, 59 - Villeneuve d' Ascq (France); Zhao, Zhao; Blat-Yrieix, M.; Ambard, A.; Legras, L. [Electricite de France (EDF/RD), Centre des Renardieres, 77 - Moret sur Loing (France); Kihn, Y. [CEMES-CNRS, 31 - Toulouse (France)

    2007-07-01

    A study of hydrides characterization has been carried out in using the transmission electron microscopy technique. It has revealed the presence of small hydrides of acicular form whose length does not exceed 500 nm, among the zircaloy-4 samples hydrided by cathodic way. The electronic diffraction has shown that these small hydrides have a crystallographic structure different of those of the hydrides phases already index in literature. A more complete identification study has then been carried out. In combining the different electronic microscopy techniques (precession electronic micro diffraction and EELS) with ab initio calculations, a new hydride phase has been identified. It is called hydride {zeta}, is of trigonal structure with lattice parameters a{sub {zeta}} = a{sub {alpha}}{sub Zr} = 0.33 nm and c{sub {zeta}} 2c{sub {alpha}}{sub Zr} = 1.029 nm, its spatial group being P3m1. (O.M.)

  8. Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

    Science.gov (United States)

    Kelly, Stephen Thomas

    absorption and desorption kinetics and degrades the material texture. Cycling the films to greater hydrogen loading accelerates the changes to the kinetics and material texture. In addition to in situ XRD experiments, in situ neutron reflectivity experiments on epitaxial Mg films exposed to hydrogen gas reveal details about the microstructural development of the growing hydride layer as the film absorbs and releases hydrogen. Small (10 wt%) additions of Ti to epitaxial Mg films during growth result in metastable solid solution films of Ti in Mg that deposit epitaxially on (001) Al2O3 substrates with epitaxy similar to the pure Mg films. These metastable alloy films absorb hydrogen faster than pure Mg films under identical conditions. Subsequent film cycling results in altered reaction kinetics and a transition to a different kinetic mechanism during desorption than for pure Mg films.

  9. Thermodynamic properties of the cubic plutonium hydride solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, J M

    1981-12-01

    Pressure, temperature, and composition data for the cubic solid solution plutonium hydride phase, PuH/sub x/, have been measured by microbalance methods. Integral enthalpies and entropies of formation have been evaluated for the composition range 1.90 less than or equal to X less than or equal to 3.00. At 550/sup 0/K, ..delta..H/sup 0/ /sub f/(PuH/sub x/(s)) varies linearly from approximately (-38 +- 1) kcal mol/sup -1/ at PuH/sub 190/ to (-50 +- 1 kcal mol/sup -1/) at PuH/sub 3/ /sub 00/. Thermochemical values obtained by reevaluating tensimetric data from the literature are in excellent agreement with these results. Isotopic effects have been quantified by comparing the results for hydride and deuteride, and equations are presented for predicting ..delta..H/sup 0/ /sub f/ and ..delta..S/sup 0/ /sub f/ values for PuH/sub x/(s) and PuD/sub x/(s).

  10. Lab-size rechargeable metal hydride-air cells

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Wei-Kang; Noreus, Dag [Department of Materials and Enviromental Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm (Sweden)

    2010-09-01

    Lab-size rechargeable metal hydride-air (MH-air) cells with a gas management device were designed in order to minimize the loss of electrolyte. An AB{sub 5}-type hydrogen storage alloy was used as anode materials of the MH-air. The thickness of the metal hydride electrodes was in the range of 3.0-3.4 mm. Porous carbon-based air electrodes with Ag{sub 2}O catalysts were used as bi-functional electrodes for oxygen reduction and generation. The electrodes were first examined in half-cells to evaluate their performance and then assembled into one MH-air cell. The results showed the good cycling stability of the rechargeable MH-air cell with a capacity of 1990 mAh. The discharge voltage was 0.69 V at 0.05-0.1 C. The charge efficiency was about 90%. The specific and volumetric energy densities were about 95Wh kg{sup -1} and 140 Wh L{sup -1}, respectively. (author)

  11. Thermodynamic Calculation on the Formation of Titanium Hydride

    Institute of Scientific and Technical Information of China (English)

    Jing-wei Zhao; Hua Ding; Xue-feng Tian; Wen-juan Zhao; Hong-liang Hou

    2008-01-01

    A modified Miedema model, using interrelationship among the basic properties of elements Ti and H, is employed to calculate the standard enthalpy of formation of titanium hydride TiHx (1≤x≤2). Based on Debye theories of solid thermal capacity, the vibrational entropy, as well as electronic entropy, is acquired by quantum mechanics and statistic thermodynamics methods, and a new approach is presented to calculate the standard entropy of formation of Till2. The values of standard enthalpy of formation of TiHx decrease linearly with increase of x. The calculated results of standard enthalpy, entropy, and free energy of forma- tion of Till2 at 298.16 K are -142.39 kJ/mol, -143.0 J/(mol-K) and -99.75 k J/tool, respectively, which is consistent with the previously-reported data obtained by either experimental or theoretical calculation methods. The results show that the thermodynamic model for titanium hydride is reasonable.

  12. Effects of Alkaline Pre-Etching to Metal Hydride Alloys

    Directory of Open Access Journals (Sweden)

    Tiejun Meng

    2017-10-01

    Full Text Available The responses of one AB5, two AB2, four A2B7, and one C14-related body-centered-cubic (BCC metal hydrides to an alkaline-etch (45% KOH at 110 °C for 2 h were studied by internal resistance, X-ray diffraction, scanning electron microscope, inductively coupled plasma, and AC impedance measurements. Results show that while the etched rare earth–based AB5 and A2B7 alloys surfaces are covered with hydroxide/oxide (weight gain, the transition metal–based AB2 and BCC-C14 alloys surfaces are corroded and leach into electrolyte (weight loss. The C14-predominated AB2, La-only A2B7, and Sm-based A2B7 showed the most reduction in the internal resistance with the alkaline-etch process. Etched A2B7 alloys with high La-contents exhibited the lowest internal resistance and are suggested for use in the high-power application of nickel/metal hydride batteries.

  13. Gallium Nitride Nanowires Grown by Hydride Vapor Phase Epitaxy

    Institute of Scientific and Technical Information of China (English)

    LIU Zhan-Hui; XIU Xiang-Qan; YAN Huai-Yue; ZHANG Rong; XIE Zi-Li; HAN Ping; SHI Yi; ZHENG You-Dou

    2011-01-01

    @@ GaN nanowires are grown by hydride vapor phase epitaxy using nickel as a catalyst.The properties of the obtained GaN nanowires are characterized by scanning and transmission electron microscopy,electron diffraction,roomtemperature photoluminescence and energy dispersive spectroscopy.The results show that the nanowires are wurtzite single crystals growing along the[0001]direction and a redshift in the photoluminescence is observed due to a superposition of several effects.The Raman spectra are close to those of the bulk GaN and the significantly broadening of those modes indicates the phonon confinement effects associated with the nanoscale dimensions of the system.%GaN nanowires are grown by hydride vapor phase epitaxy using nickel as a catalyst. The properties of the obtained GaN nanowires are characterized by scanning and transmission electron microscopy, electron diffraction, room-temperature photoluminescence and energy dispersive spectroscopy. The results show that the nanowires are wurtzite single crystals growing along the [0001] direction and a redshift in the photoluminescence is observed due to a superposition of several effects. The Raman spectra are close to those of the bulk GaN and the significantly broadening of those modes indicates the phonon confinement effects associated with the nanoscale dimensions of the system.

  14. Measurement of nuclear fuel pin hydriding utilizing epithermal neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Miller, W.H. [Univ. of Missouri, Columbia, MO (United States); Farkas, D.M.; Lutz, D.R. [General Electric Co., Pleasanton, CA (United States)

    1996-12-31

    The measurement of hydrogen or zirconium hydriding in fuel cladding has long been of interest to the nuclear power industry. The detection of this hydrogen currently requires either destructive analysis (with sensitivities down to 1 {mu}g/g) or nondestructive thermal neutron radiography (with sensitivities on the order of a few weight percent). The detection of hydrogen in metals can also be determined by measuring the slowing down of neutrons as they collide and rapidly lose energy via scattering with hydrogen. This phenomenon is the basis for the {open_quotes}notched neutron spectrum{close_quotes} technique, also referred to as the Hysen method. This technique has been improved with the {open_quotes}modified{close_quotes} notched neutron spectrum technique that has demonstrated detection of hydrogen below 1 {mu}g/g in steel. The technique is nondestructive and can be used on radioactive materials. It is proposed that this technique be applied to the measurement of hydriding in zirconium fuel pins. This paper summarizes a method for such measurements.

  15. Interstellar chemistry of nitrogen hydrides in dark clouds

    CERN Document Server

    Gal, Romane Le; Faure, Alexandre; Forêts, Guillaume Pineau des; Rist, Claire; Maret, Sébastien

    2013-01-01

    The aim of the present work is to perform a comprehensive analysis of the interstellar chemistry of nitrogen, focussing on the gas-phase formation of the smallest polyatomic species and in particular nitrogen hydrides. We present a new chemical network in which the kinetic rates of critical reactions have been updated based on recent experimental and theoretical studies, including nuclear spin branching ratios. Our network thus treats the different spin symmetries of the nitrogen hydrides self-consistently together with the ortho and para forms of molecular hydrogen. This new network is used to model the time evolution of the chemical abundances in dark cloud conditions. The steady-state results are analysed, with special emphasis on the influence of the overall amounts of carbon, oxygen, and sulphur. Our calculations are also compared with Herschel/HIFI observations of NH, NH$_2$, and NH$_3$ detected towards the external envelope of the protostar IRAS 16293-2422. The observed abundances and abundance ratios ...

  16. Superconductive "sodalite"-like clathrate calcium hydride at high pressures

    CERN Document Server

    Wang, Hui; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-01-01

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H2 fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH6 a body-centred cubic structure with hydrogen that forms unusual "sodalite" cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H2 of electrons donated by Ca forming a "H4" unit as the building block in the construction of the 3-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone centre. The resultant dynamic Jahn-Teller effect helps to enhance electron-phonon coupling and leads to superconductivity of CaH6. A superconducting critical temperature (Tc) of 220-235 K at 150 GPa obtained...

  17. Electronic structure of the palladium hydride studied by compton scattering

    CERN Document Server

    Mizusaki, S; Yamaguchi, M; Hiraoka, N; Itou, M; Sakurai, Y

    2003-01-01

    The hydrogen-induced changes in the electronic structure of Pd have been investigated by Compton scattering experiments associated with theoretical calculations. Compton profiles (CPs) of single crystal of Pd and beta phase hydride PdH sub x (x=0.62-0.74) have been measured along the [100], [110] and [111] directions with a momentum resolution of 0.14-0.17 atomic units using 115 keV x-rays. The theoretical Compton profiles have been calculated from the wavefunctions obtained utilizing the full potential linearized augmented plane wave method within the local density approximation for Pd and stoichiometric PdH. The experimental and the theoretical results agreed well with respect to the difference in the CPs between PdH sub x and Pd, and the anisotropy in the CPs of Pd or PdH sub x. This study provides lines of evidence that upon hydride formation the lowest valance band of Pd is largely modified due to hybridization with H 1s-orbitals and the Fermi energy is raised into the sp-band. (author)

  18. ACCEPTABILITY ENVELOPE FOR METAL HYDRIDE-BASED HYDROGEN STORAGE SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, B.; Corgnale, C.; Tamburello, D.; Garrison, S.; Anton, D.

    2011-07-18

    The design and evaluation of media based hydrogen storage systems requires the use of detailed numerical models and experimental studies, with significant amount of time and monetary investment. Thus a scoping tool, referred to as the Acceptability Envelope, was developed to screen preliminary candidate media and storage vessel designs, identifying the range of chemical, physical and geometrical parameters for the coupled media and storage vessel system that allow it to meet performance targets. The model which underpins the analysis allows simplifying the storage system, thus resulting in one input-one output scheme, by grouping of selected quantities. Two cases have been analyzed and results are presented here. In the first application the DOE technical targets (Year 2010, Year 2015 and Ultimate) are used to determine the range of parameters required for the metal hydride media and storage vessel. In the second case the most promising metal hydrides available are compared, highlighting the potential of storage systems, utilizing them, to achieve 40% of the 2010 DOE technical target. Results show that systems based on Li-Mg media have the best potential to attain these performance targets.

  19. A deformation and thermodynamic model for hydride precipitation kinetics in spent fuel cladding

    Energy Technology Data Exchange (ETDEWEB)

    Stout, R.B.

    1989-10-01

    Hydrogen is contained in the Zircaloy cladding of spent fuel rods from nuclear reactors. All the spent fuel rods placed in a nuclear waste repository will have a temperature history that decreases toward ambient; and as a result, most all of the hydrogen in the Zircaloy will eventually precipitate as zirconium hydride platelets. A model for the density of hydride platelets is a necessary sub-part for predicting Zircaloy cladding failure rate in a nuclear waste repository. A model is developed to describe statistically the hydride platelet density, and the density function includes the orientation as a physical attribute. The model applies concepts from statistical mechanics to derive probable deformation and thermodynamic functionals for cladding material response that depend explicitly on the hydride platelet density function. From this model, hydride precipitation kinetics depend on a thermodynamic potential for hydride density change and on the inner product of a stress tensor and a tensor measure for the incremental volume change due to hydride platelets. The development of a failure response model for Zircaloy cladding exposed to the expected conditions in a nuclear waste repository is supported by the US DOE Yucca Mountain Project. 19 refs., 3 figs.

  20. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    Science.gov (United States)

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.