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Sample records for zirconium iron hydrogen

  1. Effects of titanium and zirconium on iron aluminide weldments

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    Mulac, B.L.; Edwards, G.R. [Colorado School of Mines, Golden, CO (United States). Center for Welding, Joining, and Coatings Research; Burt, R.P. [Alumax Technical Center, Golden, CO (United States); David, S.A. [Oak Ridge National Lab., TN (United States). Metals and Ceramics Div.

    1997-12-01

    When gas-tungsten arc welded, iron aluminides form a coarse fusion zone microstructure which is susceptible to hydrogen embrittlement. Titanium inoculation effectively refined the fusion zone microstructure in iron aluminide weldments, but the inoculated weldments had a reduced fracture strength despite the presence of a finer microstructure. The weldments fractured by transgranular cleavage which nucleated at cracked second phase particles. With titanium inoculation, second phase particles in the fusion zone changed shape and also became more concentrated at the grain boundaries, which increased the particle spacing in the fusion zone. The observed decrease in fracture strength with titanium inoculation was attributed to increased spacing of second phase particles in the fusion zone. Current research has focused on the weldability of zirconium- and carbon-alloyed iron aluminides. Preliminary work performed at Oak Ridge National Laboratory has shown that zirconium and carbon additions affect the weldability of the alloy as well as the mechanical properties and fracture behavior of the weldments. A sigmajig hot cracking test apparatus has been constructed and tested at Colorado School of Mines. Preliminary characterization of hot cracking of three zirconium- and carbon-alloyed iron aluminides, each containing a different total concentration of zirconium at a constant zirconium/carbon ratio of ten, is in progress. Future testing will include low zirconium alloys at zirconium/carbon ratios of five and one, as well as high zirconium alloys (1.5 to 2.0 atomic percent) at zirconium/carbon ratios of ten to forty.

  2. Hydrogen desorption kinetics from zirconium hydride and zirconium metal in vacuum

    International Nuclear Information System (INIS)

    Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.

    2014-01-01

    The kinetics of hydrogen desorption from zirconium hydride is important in many nuclear design and safety applications. In this paper, a coordinated experimental and modeling study has been used to explicitly demonstrate the applicability of existing kinetic theories for hydrogen desorption from zirconium hydride and α-zirconium. A static synthesis method was used to produce δ-zirconium hydride, and the crystallographic phases of the zirconium hydride were confirmed by X-ray diffraction (XRD). Three obvious stages, involving δ-zirconium hydride, a two-phase region, and α-zirconium, were observed in the hydrogen desorption spectra of two zirconium hydride specimens with H/Zr ratios of 1.62 and 1.64, respectively, which were obtained using thermal desorption spectroscopy (TDS). A continuous, one-dimensional, two-phase moving boundary model, coupled with the zero- and second-order kinetics of hydrogen desorption from δ-zirconium hydride and α-zirconium, respectively, has been developed to reproduce the TDS experimental results. A comparison of the modeling predictions with the experimental results indicates that a zero-order kinetic model is valid for description of hydrogen flux away from the δ-hydride phase, and that a second-order kinetic model works well for hydrogen desorption from α-Zr if the activation energy of desorption is optimized to be 70% of the value reported in the literature

  3. Determination of hydrogen in zirconium hydride and uranium-zirconium hydride by inert gas exraction-gravimetric method

    International Nuclear Information System (INIS)

    Hoshino, Akira; Iso, Shuichi

    1976-01-01

    An inert gas extraction-gravimetric method has been applied to the determination of hydrogen in zirconium hydride and uranium-zirconium hydride which are used as neutron moderator and fuel of nuclear safety research reactor (NSRR), respectively. The sample in a graphite-enclosed quartz crucible is heated inductively to 1200 0 C for 20 min in a helium stream. Hydrogen liberated from the sample is oxidized to water by copper(I) oxide-copper(II) oxide at 400 0 C, and the water is determined gravimetrically by absorption in anhydrone. The extraction curves of hydrogen for zirconium hydride and uranium-zirconium hydride samples are shown in Figs. 2 and 3. Hydrogen in the samples is extracted quantitatively by heating at (1000 -- 1250) 0 C for (10 -- 40) min. Recoveries of hydrogen in the case of zirconium hydride were examined as follows: a weighed zirconium rod (5 phi x 6 mm, hydrogen -5 Torr. After the chamber was filled with purified hydrogen to 200 Torr, the rod was heated to 400 0 C for 15 h, and again weighed to determine the increase in weight. Hydrogen in the rod was then determined by the proposed method. The results are in excellent agreement with the increase in weight as shown in Table 1. Analytical results of hydrogen in zirconium hydride samples and an uranium-zirconium hydride sample are shown in Table 2. (auth.)

  4. Removal of iron contaminant from zirconium chloride solution

    International Nuclear Information System (INIS)

    Voit, D.O.

    1992-01-01

    This patent describes a process for eliminating iron contaminant from an aqueous zirconium chloride solution that has been contaminated with FeCl 3 in a plant in which zirconium and hafnium chloride solutions are separated by a main MINK solvent extraction system and the FeCl 3 is normally removed from the zirconium chloride solution by a secondary MINK solvent extraction system

  5. Development of tantalum–zirconium alloy for hydrogen purification

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Sanjay, E-mail: sanjay.barc@gmail.com [Fusion Reactor Materials Section, MG, BARC, Mumbai 85 (India); IAMR, Hiroshima University, Higashihiroshima 739-8530 (Japan); Singh, Anamika [GSASM Hiroshima University, Higashihiroshima 739-8530 (Japan); Jain, Uttam; Dey, Gautam Kumar [Fusion Reactor Materials Section, MG, BARC, Mumbai 85 (India)

    2016-11-01

    Highlights: • Terminal solid solubility of Ta increases with Zr addition. • Increase in lattice parameters of Ta due to Zr addition may be the possible reason. • Enhance H solubility could also be explained on the change in e-DOS of Ta–Zr alloys. • Ta–Zr alloys could be possible combination for hydrogen purification membrane. - Abstract: Terminal solid solubility of hydrogen in Ta–Zr alloys has been studied in connection with the development of tantalum based metallic membrane for hydrogen/tritium purification. The alloys were prepared by vacuum arc melting technique and subsequently cold rolled to 0.2 mm thickness. The terminal solid solubility of hydrogen in these cold rolled samples was investigated in a modified Sieverts apparatus. The terminal solid solubility of hydrogen was marginally increased with zirconium content. The change in the lattices parameter of tantalum upon zirconium addition and the higher affinity of zirconium for hydrogen as compared to tantalum could be the possible reasons.

  6. Hydrogen outbreak of Zirconium Molybdate Hihydrate

    International Nuclear Information System (INIS)

    Miura, Yasuhiko; Fukuda, Kazuhiro; Ochi, Eiji

    2008-01-01

    JNFL is planning to construct a facility for enclosing the hull and end pieces produced due to reprocessing of spent fuel into stainless canisters after compressing, while those hull and end pieces enclosed into the stainless canisters are called 'compressed hulls'. Since the compressed hulls contain moisture absorbent Zirconium Molybdate Hihydrate accompanying hull and end pieces, there is a risk of outbreak of radiolysisradiolysis gas such as hydrogen, etc. by radiolysisradiolysis. This report intends to state the result of radiation irradiation experiment with the purpose of examining the volume of hydrogen outbreak from Zirconium Molybdate Hihydrate of the compressed hulls. (author)

  7. Films of double oxides of zirconium and iron

    International Nuclear Information System (INIS)

    Kozik, V.V.; Borilo, L.P.; Shul'pekov, A.M.

    2000-01-01

    Films of double oxides of zirconium and iron were prepared by the method of precipitation from film-forming alcohol solutions of zirconium oxychloride and iron chloride with subsequent thermal treatment. Using the methods of X-ray phase and differential thermal analyses, conductometry and optical spectroscopy, basic chemical processes occurring in the film-forming solutions and during thermal treatment are studied alongside with phase composition and optical characteristics of the films prepared. The composition-property diagrams of the given system in a thin-film state are plotted [ru

  8. Analysis of hydrogen in zirconium metallic

    International Nuclear Information System (INIS)

    Rodrigues, A.N.; Vega Bustillos, J.O.W.

    1991-02-01

    Determination of hydrogen in zirconium metallic have been performed using the hot vacuum extraction system and the gas chromatographic technique. The zirconium metallic samples were hydrieded by electrolitic technique at difference temperatures and times, then the samples were annealing at vacuum and eatching by fluoridric acid solution. The details of the hydrieded process, analytical technique and the data obtained are discussed. (author)

  9. Extraction and determination of hydrogen in uranium and zirconium; Extraction et dosage de l'hydrogene dans l'uranium et le zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Champeix, L; Coblence, G; Darras, R [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    The method of desorption under vacuum at high temperatures in the solid phase, which gives good results in the case of steels, has been applied to uranium and zirconium. In these two metals hydrogen is found mainly in the form of hydride. It is chiefly a question of determining the most suitable temperature and the heating time necessary to obtain an almost total extraction of hydrogen. Two considerations must be taken into account in the choice of temperature. It should be such that on the one hand the hydride decomposes rapidly and completely at the reduced pressure applied, and on the other hand the diffusion of hydrogen through the metal takes place fairly quickly. The apparatus and the method used are described; systematic tests have led to the adoption of temperatures of 650 deg. C for uranium and 1050 deg. C for zirconium. (author) [French] La methode de desorption sous vide a chaud en phase solide, methode qui donne de bons resultats dans le cas des aciers, a ete appliquee a l'uranium et au zirconium. Dans ces deux metaux, l'hydrogene se trouve surtout a l'etat d'hydrure. Il s'agit essentiellement de determiner la temperature optimum et la duree du chauffage necessaire pour obtenir une extraction d'hydrogene pratiquement complete. Deux considerations interviennent dans le choix de la temperature. Elle doit etre telle que, d'une part la decomposition de l'hydrure se fasse rapidement et completement sous la pression reduite realisee et d'autre part que la diffusion de l'hydrogene a travers le metal soit assez rapide. L'appareil et le mode operatoire utilises sont decrits des essais systematiques ont conduit a adopter une temperature de 650 deg. C pour l'uranium et de 1050 deg. C pour le zirconium. (auteur)

  10. Corrosion and hydrogen absorption of commercially pure zirconium in acid fluoride solutions

    International Nuclear Information System (INIS)

    Yokoyama, Ken’ichi; Yamada, Daisuke; Sakai, Jun’ichi

    2013-01-01

    Highlights: •Zirconium corrodes and absorbs hydrogen in acid fluoride solutions. •Hydrogen thermal desorption is observed at 300–700 °C. •The resistance to hydrogen absorption of zirconium is higher than that of titanium. -- Abstract: The corrosion and hydrogen absorption of commercially pure zirconium have been investigated in acidulated phosphate fluoride (APF) solutions. Upon immersion in 2.0% APF solution of pH 5.0 at 25 °C, a granular corrosion product (Na 3 ZrF 7 ) deposits over the entire side surface of the specimen, thereby inhibiting further corrosion. In 0.2% APF solution, marked corrosion is observed from the early stage of immersion; no deposition of the corrosion product is observed by scanning electron microscopy. A substantial amount of hydrogen absorption is confirmed in both APF solutions by hydrogen thermal desorption analysis. The amount of absorbed hydrogen of the specimen immersed in the 2.0% APF solution is smaller than that in the 0.2% APF solution in the early stage of immersion. The hydrogen absorption behavior is not always consistent with the corrosion behavior. Hydrogen thermal desorption occurs in the temperature range of 300–700 °C for the specimen without the corrosion product. Under the same immersion conditions, the amount of absorbed hydrogen in commercially pure zirconium is smaller than that in commercially pure titanium as reported previously. The present results suggest that commercially pure zirconium, compared with commercially pure titanium, is highly resistant to hydrogen absorption, although corrosion occurs in fluoride solutions

  11. The addition zirconium effect on the solubility and activity of sulfur in liquid iron

    International Nuclear Information System (INIS)

    Burylev, B.P.; Mojsov, L.P.

    1994-01-01

    Critical analysis of reference data on thermodynamic properties of zirconium sulfides is conducted for evaluation of zirconium desulfonation ability in liquid steel. Sulfur solubility dependence on zirconium concentration in liquid iron is presented. Curves of sulfur solubility in liquid iron in the presence of other elements, including titanium, manganese, vanadium and chromium are presented for comparison. It is shown that equilibrium concentration of sulfur is much lower than standard sulfur concentrations in steel, therefore zirconium appears to be the best desulfonator among the metals considered

  12. Ab initio atomic simulation of hydrogen and iodine effects in zirconium

    International Nuclear Information System (INIS)

    Domain, Ch.

    2002-03-01

    In this work we present ab initio atomic simulations concerning the effects of hydrogen and iodine in hexagonal zirconium. We first studied the point defects in the dilute Zr-H (and to a less extend Zr-H-O) systems and concluded that it is better described within the generalised gradient approximation for the exchange and correlation functional. We calculated the hydrogen thermal diffusion coefficient in solid solution that agree very well with the experimental values. The calculated formation energy of different self-interstitial configuration are rather small (around 3 eV) and close to each other indicating the high complexity of these defects. We studied the core structure of the screw dislocation that has a preferential prismatic spreading. We also calculated the gamma surface for different gliding planes. The influence of hydrogen, that induces a significant reduction of the gamma surfaces excess energies, allows to qualitatively explain experimental results regarding some hydrogen effects on hexagonal zirconium plastic deformation. We also discussed the effect of zirconium hydride stoichiometry on gamma surfaces. The results concerning the iodine and oxygen adsorption on zirconium surfaces, inducing the evaluation of the effective surface energy reduction as a function of the iodine partial pressure allow for a better description of iodine induced stress corrosion cracking of zirconium. (author)

  13. The Hydrogen Pickup Behavior for Zirconium-based Alloys in Various Out-of-pile Corrosion Test Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Aomi, M.; Etoh, Y.; Ishimoto, S.; Une, K. [Nippon Nuclear Fuel Development, Co., Ltd., 2163 Narita-cho, Oarai-machi, Ibaraki-ken, 311-1313 (Japan); Ito, K. [Global Nuclear Fuel Japan Co., Ltd., 3-1 Uchikawa 2-chome, Yokosuka-shi, Kanagawa-ken, 239-0836 (Japan)

    2009-06-15

    An acceleration of hydrogen absorption in zirconium alloy claddings at high burnups is one of the most important issues limiting the fuel performance from the viewpoint of cladding integrity. In this context, advanced cladding materials with higher corrosion resistant and lower hydrogen absorption properties have been widely searched in various organizations. In this study, four kinds of zirconium-based alloys, whose in-pile data had been acquired [1,2] were subjected to comprehensive out-of-pile corrosion tests with various temperature and atmosphere conditions in order to investigate the correlation between in-pile and out-of-pile corrosion and hydrogen pick-up behavior, i.e. Zry-2, GNF-Ziron (Zry-2-based alloy with {approx}0.25 wt % of Fe), Hi-FeNi Zircaloy (Zry-2-based alloy with {approx}0.25 wt % of Fe and {approx}0.1 wt% Ni), and VB (Zr-based alloy containing Sn, Cr, and {approx}0.5 wt % of Fe). All the alloys were annealed in RXA condition. The out-of-pile corrosion tests were carried out in three different conditions of 400 deg. C steam, 475 deg. C supercritical water, and 290 deg. C LiOH aqueous solution. In addition to these alloys, several Zry-2-based alloys with various iron contents were tested in 290 deg. C LiOH aqueous solution. Among the four corrosion conditions, the 290 deg. C LiOH aqueous solution test well screened the hydrogen pick-up behavior of the alloys. The hydrogen absorption decreased with higher iron contents in the alloys in both the out-of-pile and in-pile conditions. Especially, the distinct suppression of hydrogen absorption was observed for VB with the highest iron content. The similar dependence of iron content on the hydrogen pick-up fraction was also obtained for the Zry-2-based alloys with different iron contents, which were corroded in the 290 deg. C LiOH aqueous solution condition. As for the corrosion behavior in the 290 deg. C LiOH aqueous solution condition, the weight gains of Zry-2, GNF-Ziron and VB followed the 1

  14. Zirconium intermetallics and hydrogen uptake during corrosion

    International Nuclear Information System (INIS)

    Cox, B.

    1987-04-01

    The routes by which hydrogen can enter zirconium alloys containing second phase particles during corrosion are discussed. Both direct diffusion through the bulk of the oxide film, and migration through second phase particles that intersect the surface are considered. An examination of results for hydrogen uptake by zirconium alloys during the early stages of oxidation, when the oxide film is still coherent, suggests that for Zr, Zr-1%Cu and Zr-1%Fe the hydrogen enters by diffusing through the bulk ZrO 2 film, whereas for the Zircaloys the primary migration route may be through the intermetallics. The steps in the latter process are discussed and the evidence available on the properties of the intermetallics collated. A comparison of these data with results for hydrogen uptake by two series of ternary alloys (Zr-1%Nb - 1%X, Zr-1%Cu - 1%X) suggests that high hydrogen uptakes often correlate with intermetallics with high hydrogen solubilities and vice versa. The properties of Zr(Fe/Cr) 2+x intermetallics are examined in an attempt to understand the behaviour of the Zircaloys, and it is concluded that present data establishing composition and unit cell dimensions for such intermetallic particles are not of sufficient accuracy to permit a correlation

  15. Hydrogen content in titanium and a titanium–zirconium alloy after acid etching

    Energy Technology Data Exchange (ETDEWEB)

    Frank, Matthias J.; Walter, Martin S. [Department of Biomaterials, Institute for Clinical Dentistry, University of Oslo, P.O. Box 1109, Blindern, NO-0317 Oslo (Norway); Institute of Medical and Polymer Engineering, Chair of Medical Engineering, Technische Universität München, Boltzmannstrasse 15, 85748 Garching (Germany); Lyngstadaas, S. Petter [Department of Biomaterials, Institute for Clinical Dentistry, University of Oslo, P.O. Box 1109, Blindern, NO-0317 Oslo (Norway); Wintermantel, Erich [Institute of Medical and Polymer Engineering, Chair of Medical Engineering, Technische Universität München, Boltzmannstrasse 15, 85748 Garching (Germany); Haugen, Håvard J., E-mail: h.j.haugen@odont.uio.no [Department of Biomaterials, Institute for Clinical Dentistry, University of Oslo, P.O. Box 1109, Blindern, NO-0317 Oslo (Norway)

    2013-04-01

    Dental implant alloys made from titanium and zirconium are known for their high mechanical strength, fracture toughness and corrosion resistance in comparison with commercially pure titanium. The aim of the study was to investigate possible differences in the surface chemistry and/or surface topography of titanium and titanium–zirconium surfaces after sand blasting and acid etching. The two surfaces were compared by X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, scanning electron microscopy and profilometry. The 1.9 times greater surface hydrogen concentration of titanium zirconium compared to titanium was found to be the major difference between the two materials. Zirconium appeared to enhance hydride formation on titanium alloys when etched in acid. Surface topography revealed significant differences on the micro and nanoscale. Surface roughness was increased significantly (p < 0.01) on the titanium–zirconium alloy. High-resolution images showed nanostructures only present on titanium zirconium. - Highlights: ► TiZr alloy showed increased hydrogen levels over Ti. ► The alloying element Zr appeared to catalyze hydrogen absorption in Ti. ► Surface roughness was significantly increased for the TiZr alloy over Ti. ► TiZr alloy revealed nanostructures not observed for Ti.

  16. Moessbauer spectrometry study and metallography of paramagnetic phases from zirconium-iron system

    International Nuclear Information System (INIS)

    Freitas Brandao Bittencourt, C. de.

    1976-01-01

    Binary alloys of zirconium with 3 to 23% of iron by weight, were made by diffusion at 875 0 C of iron onto thin plates of zirconium. Moessbauer spectroscopy and optic metallography indicated the phases Zr 2 Fe and Zr 4 Fe, the bulk of which probably formed during the diffusion. These phases were confirmed by electron probe microanalysis. Moessbauer spectra showed quadrupole doublets with the same hyperfine interaction parameters in both phases, but with clearly distinct asymmetries. (author)

  17. Study on the scattering law and scattering kernel of hydrogen in zirconium hydride

    International Nuclear Information System (INIS)

    Jiang Xinbiao; Chen Wei; Chen Da; Yin Banghua; Xie Zhongsheng

    1999-01-01

    The nuclear analytical model of calculating scattering law and scattering kernel for the uranium zirconium hybrid reactor is described. In the light of the acoustic and optic model of zirconium hydride, its frequency distribution function f(ω) is given and the scattering law of hydrogen in zirconium hydride is obtained by GASKET. The scattering kernel σ l (E 0 →E) of hydrogen bound in zirconium hydride is provided by the SMP code in the standard WIMS cross section library. Along with this library, WIMS is used to calculate the thermal neutron energy spectrum of fuel cell. The results are satisfied

  18. Hydrogen charging, hydrogen content analysis and metallographic examination of hydride in zirconium alloys

    International Nuclear Information System (INIS)

    Singh, R.N.; Kishore, R.; Mukherjee, S.; Roychowdhury, S.; Srivastava, D.; Sinha, T.K.; De, P.K.; Banerjee, S.; Gopalan, B.; Kameswaran, R.; Sheelvantra, Smita S.

    2003-12-01

    Gaseous and electrolytic hydrogen charging techniques for introducing controlled amount of hydrogen in zirconium alloy is described. Zr-1wt%Nb fuel tube, zircaloy-2 pressure tube and Zr-2.5Nb pressure tube samples were charged with up to 1000 ppm of hydrogen by weight using one of the aforementioned methods. These hydrogen charged Zr-alloy samples were analyzed for estimating the total hydrogen content using inert gas fusion technique. Influence of sample surface preparation on the estimated hydrogen content is also discussed. In zirconium alloys, hydrogen in excess of the terminal solid solubility precipitates out as brittle hydride phase, which acquire platelet shaped morphology due to its accommodation in the matrix and can make the host matrix brittle. The F N number, which represents susceptibility of Zr-alloy tubes to hydride embrittlement was measured from the metallographs. The volume fraction of the hydride phase, platelet size, distribution, interplatelet spacing and orientation were examined metallographically using samples sliced along the radial-axial and radial-circumferential plane of the tubes. It was observed that hydride platelet length increases with increase in hydrogen content. Considering the metallographs generated by Materials Science Division as standard, metallographs prepared by the IAEA round robin participants for different hydrogen concentration was compared. It is felt that hydride micrographs can be used to estimate not only that approximate hydrogen concentration of the sample but also its size, distribution and orientation which significantly affect the susceptibility to hydride embrittlement of these alloys. (author)

  19. Study of the solubility of iron in zirconium by thermoelectric power measurements

    International Nuclear Information System (INIS)

    Borrelly, R.; Merle, P.; Adami, L.; Centre National de la Recherche Scientifique, 69 - Villeurbanne

    1990-01-01

    Thermoelectric power (TEP) measurements are used to determine the solubility of iron in α-zirconium. A preliminary study shows that TEP is very sensitive to elements in solid solution, to cold-working and to the texture due to rolling in a temperature range including room temperature which is choosen for thermoelectric power measurements. The solutioning of iron obtained by a homogenization treatment and water-quench leads to a decrease of thermoelectric power. The conditions of homogenization treatments such that TEP variations are only due to the variation of iron content in solid solution have been determined. From these results the solubility of iron α-zirconium as a function of temperature has been determined. Moreover, the α-domain of the Zr-rich part of the Zr-Fe diagram has been completely delimited. A micrographic study has been made to confirm these results. (orig.)

  20. Extraction and determination of hydrogen in uranium and zirconium

    International Nuclear Information System (INIS)

    Champeix, L.; Coblence, G.; Darras, R.

    1959-01-01

    The method of desorption under vacuum at high temperatures in the solid phase, which gives good results in the case of steels, has been applied to uranium and zirconium. In these two metals hydrogen is found mainly in the form of hydride. It is chiefly a question of determining the most suitable temperature and the heating time necessary to obtain an almost total extraction of hydrogen. Two considerations must be taken into account in the choice of temperature. It should be such that on the one hand the hydride decomposes rapidly and completely at the reduced pressure applied, and on the other hand the diffusion of hydrogen through the metal takes place fairly quickly. The apparatus and the method used are described; systematic tests have led to the adoption of temperatures of 650 deg. C for uranium and 1050 deg. C for zirconium. (author) [fr

  1. Hydrogen determination in magnesium, zirconium, sodium and lithium using installation, C2532

    International Nuclear Information System (INIS)

    Malikova, E.D.; Velyukhanov, V.P.; Makhinova, L.O.; Kunin, L.L.

    1980-01-01

    Techniques of hydrogen determination in magnesium, lithium, sodium and zirconium using the S 2532 installation are developed. The method of oxidizing melting using lead borate has been used for hydrogen determination in lithium and sodium and the method of vacuum extraction - for hydrogen determination in zirconium and magnesium. Zr and Mg extraction has been carried out in steel reactor at the temperatures of 1000 and 650 deg C, the time of extraction being 30 and 10 minutes respectively. A quartz reactor, temperatures of oxidizing melting of 700-800 deg C, the time of analysis 10 and 20 minutes have been used for sodium and lithium. A possibility to determine volumetric content of hydrogen in magnesium at the existing surface contaminations with hydrogen-containing compounds is shown [ru

  2. Chemical aspects of hydrogen ingress in zirconium and zircaloy pressure tubes: ageing management of Indian PHWR coolant channels - determination of hydrogen and deuterium

    International Nuclear Information System (INIS)

    Sayi, Y.S.; Shankaran, P.S.; Yadav, C.S.; Ramanjaneyulu, P.S.; Venugopal, V.; Ramakumar, K.L.; Chhapru, G.C.; Prasad, R.; Jain, H.C.; Sood, D.D.

    2009-02-01

    Pressurized heavy water reactors (PHWRs) use zirconium and zirconium based alloys as clad and coolant tubes since its beginning. The first ever zircaloy-2 pressure tube failure occurred in 1983 at Ontario Hydro's Pickering Unit 2 in Canada which necessitated a thorough examination of causes of such failure. The failure was attributed to massive hydriding at the failed spot of pressure tube. Continuous usage of zirconium alloys could result in their hydrogen and deuterium pick-up leading to hydrogen/ deuterium embrittlement. The life of the zircaloy coolant channels is dictated by hydrogen/deuterium content and hence ageing management of the pressure tubes is essential for ensuring their trouble-free usage. It is desirable to have a sound knowledge on the chemical aspects of zirconium and zirconium based alloys metallurgy, the mechanistic principles of hydrogen ingress into the pressure tubes during in reactor service, and identifying suitable analytical methodologies for precise and accurate determination of hydrogen in wafer thin sliver samples carved out from insides of pressure tubes without causing any structural damage so that it can continue to remain in service. This is desirable so that the ageing management does not result in cost-escalation. This report is divided in to three main parts. The first part deals with the chemical aspects of zirconium and zirconium based alloy metallurgy, the mechanism of hydrogen pick-up and hydride formation in zirconium matrix. The second part describes various methodologies and their limitations, available for hydrogen/deuterium determination. The third part deals in detail, about the extensive investigations carried out at Radioanalytical Chemistry Division (RACD) in Radiochemistry and Isotope Group for establishing an indigenously developed hot vacuum extraction system in combination with quadrupole mass spectrometry for precise determination of hydrogen and deuterium in wafer thin sliver sample of zircaloy. The

  3. In situ hydrogen loading on zirconium powder

    Energy Technology Data Exchange (ETDEWEB)

    Maimaitiyili, Tuerdi, E-mail: tuerdi.maimaitiyili@mah.se; Blomqvist, Jakob [Malmö University, Östra Varvsgatan 11 A, Malmö, Skane 20506 (Sweden); Steuwer, Axel [Lund University, Ole Römers väg, Lund, Skane 22100 (Sweden); Nelson Mandela Metropolitan University, Gardham Avenue, Port Elizabeth 6031 (South Africa); Bjerkén, Christina [Malmö University, Östra Varvsgatan 11 A, Malmö, Skane 20506 (Sweden); Zanellato, Olivier [Ensam - Cnam - CNRS, 151 Boulevard de l’Hôpital, Paris 75013 (France); Blackmur, Matthew S. [Materials Performance Centre, School of Materials, The University of Manchester, Manchester M1 7HS (United Kingdom); Andrieux, Jérôme [European Synchrotron Radiation Facility, 6 rue J Horowitz, Grenoble 38043 (France); Université de Lyon, 43 Bd du 11 novembre 1918, Lyon 69100 (France); Ribeiro, Fabienne [Institut de Radioprotection et Sûreté Nucléaire, IRSN, BP 3, 13115 Saint-Paul Lez Durance (France)

    2015-06-26

    Commercial-grade Zr powder loaded with hydrogen in situ and phase transformations between various Zr and ZrH{sub x} phases have been monitored in real time. For the first time, various hydride phases in a zirconium–hydrogen system have been prepared in a high-energy synchrotron X-ray radiation beamline and their transformation behaviour has been studied in situ. First, the formation and dissolution of hydrides in commercially pure zirconium powder were monitored in real time during hydrogenation and dehydrogenation, then whole pattern crystal structure analysis such as Rietveld and Pawley refinements were performed. All commonly reported low-pressure phases presented in the Zr–H phase diagram are obtained from a single experimental arrangement.

  4. In situ hydrogen loading on zirconium powder

    International Nuclear Information System (INIS)

    Maimaitiyili, Tuerdi; Blomqvist, Jakob; Steuwer, Axel; Bjerkén, Christina; Zanellato, Olivier; Blackmur, Matthew S.; Andrieux, Jérôme; Ribeiro, Fabienne

    2015-01-01

    Commercial-grade Zr powder loaded with hydrogen in situ and phase transformations between various Zr and ZrH x phases have been monitored in real time. For the first time, various hydride phases in a zirconium–hydrogen system have been prepared in a high-energy synchrotron X-ray radiation beamline and their transformation behaviour has been studied in situ. First, the formation and dissolution of hydrides in commercially pure zirconium powder were monitored in real time during hydrogenation and dehydrogenation, then whole pattern crystal structure analysis such as Rietveld and Pawley refinements were performed. All commonly reported low-pressure phases presented in the Zr–H phase diagram are obtained from a single experimental arrangement

  5. Hydrogenation and high temperature oxidation of Zirconium claddings

    International Nuclear Information System (INIS)

    Novotny, T.; Perez-Feró, E.; Horváth, M.

    2015-01-01

    In the last few years a new series of experiments started for supporting the new LOCA criteria, considering the proposals of US NRC. The effects which can cause the embrittlement of VVER fuel claddings were reviewed and evaluated in the framework of the project. The purpose of the work was to determine how the fuel cladding’s hydrogen uptake under normal operating conditions, effect the behavior of the cladding under LOCA conditions. As a first step a gas system equipment with gas valves and pressure gauge was built, in which the zirconium alloy can absorb hydrogen under controlled conditions. In this apparatus E110 (produced by electrolytic method, currently used at Paks NPP) and E110G (produced by a new technology) alloys were hydrogenated to predetermined hydrogen contents. According the results of ring compression tests the E110G alloys lose their ductility above 3200 ppm hydrogen content. This limit can be applied to determine the ductile-brittle transition of the nuclear fuel claddings. After the hydrogenation, high temperature oxidation experiments were carried out on the E110G and E110 samples at 1000 °C and 1200 °C. 16 pieces of E110G and 8 samples of E110 with 300 ppm and 600 ppm hydrogen content were tested. The oxidation of the specimens was performed in steam, under isothermal conditions. Based on the ring compression tests load-displacement curves were recorded. The main objective of the compression tests was to determine the ductile-brittle transition. These results were compared to the results of our previous experiments where the samples did not contain hydrogen. The original claddings showed more ductile behavior than the samples with hydrogen content. The higher hydrogen content resulted in a more brittle mechanical behavior. However no significant difference was observed in the oxidation kinetics of the same cladding types with different hydrogen content. The experiments showed that the normal operating hydrogen uptake of the fuel claddings

  6. Thermodynamics of hydrogen and deuterium solutions in α-zirconium

    International Nuclear Information System (INIS)

    Vinokurov, Yu.V.; Mogutnov, B.M.

    1979-01-01

    Interaction of H 2 and D 2 with α-Zr are studied in the 700-890 K temperature range using a high-temperature colorimeter. It is shown that hydrogen and deuterium partial enthalpies in zirconium do not depend on the temperature and concentration and compose -48.9+-1.0 and -46.2+-1.2 kJ/g-at. Calculated is an excess entropy of hydrogen in a solution and analyzed are contributions composing it

  7. Ligand iron catalysts for selective hydrogenation

    Science.gov (United States)

    Casey, Charles P.; Guan, Hairong

    2010-11-16

    Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

  8. Application of FEM analytical method for hydrogen migration behaviour in Zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Arioka, K; Ohta, H [Takasago Research and Development Center, Mitsubishi Heavy Industries Ltd, Hyogo-ken (Japan)

    1997-02-01

    It is well recognized that the hydriding behaviours of Zirconium alloys are very significant problems as a safety issues. Also, it is well known that the diffusion of hydrogen in Zirconium alloys are affected not only by concentration but also temperature gradient. But in actual component, especially heat transfer tube such as fuel rod, we can not avoid the temperature gradient in some degree. So, it is very useful to develop the computer code which can analyze the hydrogen diffusion and precipitation behaviours under temperature gradient as a function of the structure of fuel rod. For this objective, we have developed the computer code for hydrogen migration behaviour using FEM analytical methods. So, following items are presented and discussed. Analytical method and conditions; correlation between the computed and test results; application to designing studies. (author). 8 refs, 4 figs, 2 tabs.

  9. Determination of hydrogen in uranium-niobium-zirconium alloy by inert-gas fusion

    International Nuclear Information System (INIS)

    Carden, W.F.

    1979-12-01

    An improved method has been developed using inert-gas fusion for determining the hydrogen content in uranium-niobium-zirconium (U-7.5Nb-2.5Zr) alloy. The method is applicable to concentrations of hydrogen ranging from 1 to 250 micrograms per gram and may be adjusted for analysis of greater hydrogen concentrations. Hydrogen is determined using a hydrogen determinator. The limit of error for a single determination at the 95%-confidence level (at the 3.7-μg/g-hydrogen level) is +-1.4 micrograms per gram hydrogen

  10. Status and task of the study on the hydrogen embrittlement of zirconium alloys

    International Nuclear Information System (INIS)

    Nagase, Fumihisa; Furuta, Teruo; Seino, Shun; Komatsu, Kazushi.

    1995-08-01

    As the burnup of the LWR fuel is extended, waterside corrosion and hydrogen pickup increase in the Zircaloy cladding. Hydrogen embrittlement of Zircaloy is one of the main factors which may limit the life of the fuel rod. This report presents a review on the hydrogen embrittlement of zirconium and its alloys including the irradiated materials. Research tasks for the reduction of ductility in the high burnup fuel cladding are also discussed. Many fundamental investigations have been performed on the hydrogen embrittlement of zirconium alloys. However, the embrittlement mechanism of the high burnup fuel cladding is complicated. Especially, a coupled effect of hydrides and radiation defects are expected to be pronounced with neutron dose increase. In order to evaluate the reduction of ductility of the higher burnup fuel cladding properly, it is necessary to investigate the coupled effect of these two factors by systematic examinations. (author) 64 refs

  11. Thermodynamics of hydrogen and deuterium solutions in. cap alpha. -zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Vinokurov, Yu V; Mogutnov, B M [Tsentral' nyj Nauchno-Issledovatel' skij Inst. Chernoj Metallurgii, Moscow (USSR)

    1979-09-01

    Interaction of H/sub 2/ and D/sub 2/ with ..cap alpha..-Zr are studied in the 700-890 K temperature range using a high-temperature colorimeter. It is shown that hydrogen and deuterium partial enthalpies in zirconium do not depend on the temperature and concentration and compose -48.9+-1.0 and -46.2+-1.2 kJ/g-at. Calculated is an excess entropy of hydrogen in a solution and analyzed are contributions composing it.

  12. Effect of high hydrogen content on metallurgical and mechanical properties of zirconium alloy claddings after heat-treatment at high temperature

    International Nuclear Information System (INIS)

    Turque, Isabelle

    2016-01-01

    Under hypothetical loss-of-coolant accident conditions, fuel cladding tubes made of zirconium alloys can be exposed to steam at high temperature (HT, up 1200 C) before being cooled and then quenched in water. In some conditions, after burst occurrence the cladding can rapidly absorb a significant amount of hydrogen (secondary hydriding), up to 3000 wt.ppm locally, during steam exposition at HT. The study deals with the effect, poorly studied up to date, of high contents of hydrogen on the metallurgical and mechanical properties of two zirconium alloys, Zircaloy-4 and M5, during and after cooling from high temperatures, at which zirconium is in its β phase. A specific facility was developed to homogeneously charge in hydrogen up to ∼ 3000 wt.ppm cladding tube samples of several centimeters in length. Phase transformations, chemical element partitioning and hydrogen precipitation during cooling from the β temperature domain of zirconium were studied by using several techniques, for the materials containing up to ∼ 3000 wt.ppm of hydrogen in average: in-situ neutron diffraction upon cooling from 700 C, X-ray diffraction, μ-ERDA, EPMA and electron microscopy in particular. The results were compared to thermodynamic predictions. In order to study the effect of high hydrogen contents on the mechanical behavior of the (prior-)μ phase of zirconium, axial tensile tests were performed at various temperatures between 20 and 700 C upon cooling from the β temperature domain, on samples with mean hydrogen contents up to ∼ 3000 wt.ppm. The results show that metallurgical and mechanical properties of the (prior-)β phase of zirconium alloys strongly depend on temperature and hydrogen content. (author) [fr

  13. Hydrogen Plasma Processing of Iron Ore

    Science.gov (United States)

    Sabat, Kali Charan; Murphy, Anthony B.

    2017-06-01

    Iron is currently produced by carbothermic reduction of oxide ores. This is a multiple-stage process that requires large-scale equipment and high capital investment, and produces large amounts of CO2. An alternative to carbothermic reduction is reduction using a hydrogen plasma, which comprises vibrationally excited molecular, atomic, and ionic states of hydrogen, all of which can reduce iron oxides, even at low temperatures. Besides the thermodynamic and kinetic advantages of a hydrogen plasma, the byproduct of the reaction is water, which does not pose any environmental problems. A review of the theory and practice of iron ore reduction using a hydrogen plasma is presented. The thermodynamic and kinetic aspects are considered, with molecular, atomic and ionic hydrogen considered separately. The importance of vibrationally excited hydrogen molecules in overcoming the activation energy barriers, and in transferring energy to the iron oxide, is emphasized. Both thermal and nonthermal plasmas are considered. The thermophysical properties of hydrogen and argon-hydrogen plasmas are discussed, and their influence on the constriction and flow in the of arc plasmas is considered. The published R&D on hydrogen plasma reduction of iron oxide is reviewed, with both the reduction of molten iron ore and in-flight reduction of iron ore particles being considered. Finally, the technical and economic feasibility of the process are discussed. It is shown that hydrogen plasma processing requires less energy than carbothermic reduction, mainly because pelletization, sintering, and cokemaking are not required. Moreover, the formation of the greenhouse gas CO2 as a byproduct is avoided. In-flight reduction has the potential for a throughput at least equivalent to the blast furnace process. It is concluded that hydrogen plasma reduction of iron ore is a potentially attractive alternative to standard methods.

  14. Electroless deposition process for zirconium and zirconium alloys

    Science.gov (United States)

    Donaghy, Robert E.; Sherman, Anna H.

    1981-01-01

    A method is disclosed for preventing stress corrosion cracking or metal embrittlement of a zirconium or zirconium alloy container that is to be coated on the inside surface with a layer of a metal such as copper, a copper alloy, nickel, or iron and used for holding nuclear fuel material as a nuclear fuel element. The zirconium material is etched in an etchant solution, desmutted mechanically or ultrasonically, oxidized to form an oxide coating on the zirconium, cleaned in an aqueous alkaline cleaning solution, activated for electroless deposition of a metal layer and contacted with an electroless metal plating solution. This method provides a boundary layer of zirconium oxide between the zirconium container and the metal layer.

  15. High temperature cathodic charging of hydrogen in zirconium alloys and iron and nickel base alloys

    International Nuclear Information System (INIS)

    John, J.T.; De, P.K.; Gadiyar, H.S.

    1990-01-01

    These investigations lead to the development of a new technique for charging hydrogen into metals and alloys. In this technique a mixture of sulfates and bisulfates of sodium and potassium is kept saturated with water at 250-300degC in an open pyrex glass beaker and electrolysed using platinum anode and the material to be charged as the cathode. Most of the studies were carried out on Zr alloys. It is shown that because of the high hydrogen flux available at the surface and the high diffusivity of hydrogen in metals at these temperatures the materials pick up hydrogen faster and more uniformly than the conventional electrolytic charging at room temperature and high temperature autoclaving in LiOH solutions. Chemical analysis, metallographic examination and XRD studies confirm this. This technique has been used to charge hydrogen into many iron and nickel base austentic alloys, which are very resistant to hydrogen pick up and to H-embrittlement. Since this involved a novel method of electrolysing water, the hydrogen/deuterium isotopic ratio has been studied. At this temperatures the D/H ratio in the evolved hydrogen gas was found to be closer to the value in the liquid water, which means a smaller separation factor. This confirm the earlier observation that separation factor decreases with increase of temperature. (author). 16 refs., 21 fi gs., 6 tabs

  16. An experimental investigation of the rate of hydrogen absorption in zirconium-2.5 wt percent niobium from steam/hydrogen mixtures at elevated temperatures

    International Nuclear Information System (INIS)

    Langman, V.J.

    1984-08-01

    The test specifications for an experimental program to study the rate of hydrogen absorption in zirconium-2.5 weight percent niobium pressure tube material from steam/hydrogen mixtures at elevated temperatures are discussed

  17. In-situ electrochemical impedance spectroscopy measurements of zirconium alloy oxide conductivity: Relationship to hydrogen pickup

    International Nuclear Information System (INIS)

    Couet, Adrien; Motta, Arthur T.; Ambard, Antoine; Livigni, Didier

    2017-01-01

    Highlights: • In-situ electrochemistry on zirconium alloys in 360 °C pure water show oxide layer resistivity changes during corrosion. • A linear relationship is observed between oxide resistivity and instantaneous hydrogen pickup fraction. • The resistivity of the oxide layer formed on Zircaloy-4 (and thus its hydrogen pickup fraction) is higher than on Zr-2.5Nb. - Abstract: Hydrogen pickup during nuclear fuel cladding corrosion is a critical life-limiting degradation mechanism for nuclear fuel. Following a program dedicated to zirconium alloys, corrosion, it has been hypothesized that oxide electronic resistivity determines hydrogen pickup. In-situ electrochemical impedance spectroscopy experiments were performed on Zircaloy-4 and Zr-2.5Nb alloys in 360 °C water. The oxide resistivity was measured as function of time. The results show that as the oxide resistivity increases so does the hydrogen pickup fraction. The resistivity of the oxide layer formed on Zircaloy-4 is higher than on Zr-2.5Nb, resulting in a higher hydrogen pickup fraction of Zircaloy-4, compared to Zr-2.5Nb.

  18. Internal friction study of hydrides in zirconium at low hydrogen contents

    International Nuclear Information System (INIS)

    Peretti, H.A.; Corso, H.L.; Gonzalez, O.A.; Fernandez, L.; Ghilarducci, A.A.; Salva, H.R.

    1999-01-01

    Full text: Internal friction and shear modulus measurements were carried out on crystal bar zirconium in the as received and hydride conditions using an inverted forced pendulum. Hydriding was achieved in two ways: inside and out of the pendulum. The final hydrogen content determined by fusion analysis in the 'in situ' hydride sample was of 36 ppm. Another sample was hydride by the cathodic charge method with 25 ppm. The thermal solid solubility (TSS) phase boundary presents hysteresis between the precipitation (TSSP) and the dissolution (TSSD) temperatures for the zirconium hydrides. During the first thermal cycling the anelastic effects could be attributed to the δ, ε and metastable γ zirconium hydrides. After 'in situ' annealing at 490 K, these peaks completely disappear in the electrolytically charged sample, while in the 'in situ' hydride, the peaks remain with decreasing intensity. This effect can be understood in terms of the different surface conditions of the samples. (author)

  19. Multiscale modelling of hydrogen embrittlement in zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Majevadia, Jassel; Wenman, Mark; Balint, Daniel; Sutton, Adrian [Imperial College London (United Kingdom); Nazarov, Roman [MPIE, Dusseldorf (Germany)

    2013-07-01

    Delayed Hydride Cracking (DHC) is a commonly occurring embrittlement phenomenon in zirconium alloy fuel cladding within Pressurized Water Reactors (PWRs). DHC is caused by the accumulation of hydrogen atoms taken up by the metal, and the formation of brittle hydrides in the vicinity of crack tips. The rate of crack growth is limited by the rate of hydrogen diffusion to the crack, which can be modelled by solving a stress driven diffusion equation that incorporates the elastic interaction between defects. This of interest in the present work. The elastic interaction is calculated by combining defect forces determined through Density Functional Theory (DFT) simulations, and an exact solution for the anisotropic elastic field of an edge dislocation in Zr. making it possible to determine the interaction energy without the need to simulate directly a hydrogen atom in the presence of a crack or dislocation, which is computationally prohibitive with DFT. The result of the elastic interaction energy calculations can be utilised to determine the segregation of hydrogen to a crack tip for varying crack tip geometries, and in the presence of other crystal defects. This is done by implementing a diffusion equation for hydrogen within a discrete dislocation dynamics simulation. In the present work a model has been developed to demonstrate the effect of a single dislocation on hydrogen diffusion to create a Cottrell atmosphere.

  20. 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...

  1. Molten salt scrubbing of zirconium or hafnium tetrachloride

    International Nuclear Information System (INIS)

    Lee, E.D.; McLaughlin, D.F.

    1990-01-01

    This patent describes a continuous process for removing impurities of iron or aluminum chloride or both from vaporous zirconium or hafnium chloride or both. It comprises: introducing impure zirconium or hafnium chloride vapor or both into a middle portion of an absorbing column containing a molten salt phase, the molten salt phase absorbing the impurities of iron or aluminum chloride or both to produce chloride vapor stripped of zirconium or hafnium chloride; introducing sodium or potassium chloride or both into a top portion of the column; controlling the top portion of the column to between 300--375 degrees C.; heating a bottom portion of the column to 450--550 degrees C. To vaporize zirconium chloride or hafnium chloride or hafnium and zirconium chloride from the molten salt; withdrawing molten salt substantially free of zirconium and hafnium chloride from the bottom portion of the column; and withdrawing zirconium chloride or hafnium chloride or hafnium and zirconium chloride vapor substantially free of impurities of iron and aluminum chloride from the top of the column

  2. Effects of titanium and zirconium on iron aluminide weldments

    Energy Technology Data Exchange (ETDEWEB)

    Burt, R.P.; Edwards, G.R. [Colorado School of Mines, Golden, CO (United States); David, S.A. [Oak Ridge National Lab., TN (United States)

    1996-08-01

    Iron aluminides form a coarse fusion zone microstructure when gas-tungsten arc welded. This microstructure is susceptible to hydrogen cracking when water vapor is present in the welding environment. Because fusion zone microstructural refinement can reduce the hydrogen cracking susceptibility, titanium was used to inoculate the weld pool in iron aluminide alloy FA-129. Although the fusion zone microstructure was significantly refined by this method, the fracture stress was found to decrease with titanium additions. This decrease is attributed to an increase in inclusions at the grain boundaries.

  3. Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex.

    Science.gov (United States)

    Pool, Jaime A; Lobkovsky, Emil; Chirik, Paul J

    2004-02-05

    Molecular nitrogen is relatively inert owing to the strength of its triple bond, nonpolarity and high ionization potential. As a result, the fixation of atmospheric nitrogen to ammonia under mild conditions has remained a challenge to chemists for more than a century. Although the Haber-Bosch process produces over 100 million tons of ammonia annually for the chemical industry and agriculture, it requires high temperature and pressure, in addition to a catalyst, to induce the combination of hydrogen (H2) and nitrogen (N2). Coordination of molecular nitrogen to transition metal complexes can activate and even rupture the strong N-N bond under mild conditions, with protonation yielding ammonia in stoichiometric and even catalytic yields. But the assembly of N-H bonds directly from H2 and N2 remains challenging: adding H2 to a metal-N2 complex results in the formation of N2 and metal-hydrogen bonds or, in the case of one zirconium complex, in formation of one N-H bond and a bridging hydride. Here we extend our work on zirconium complexes containing cyclopentadienyl ligands and show that adjustment of the ligands allows direct observation of N-H bond formation from N2 and H2. Subsequent warming of the complex cleaves the N-N bond at 45 degrees C, and continued hydrogenation at 85 degrees C results in complete fixation to ammonia.

  4. Zirconium alloy barrier having improved corrosion resistance

    International Nuclear Information System (INIS)

    Adamson, R.B.; Rosenbaum, H.S.

    1983-01-01

    A nuclear fuel element for use in the core of a nuclear reactor has a composite cladding container having a substrate and a dilute zirconium alloy liner bonded to the inside surface of the substrate. The dilute zirconium alloy liner forms about 1 to about 20 percent of the thickness of the cladding and is comprised of zirconium and a metal selected from the group consisting of iron, chromium, iron plus chromium, and copper. The dilute zirconium alloy liner shields the substrate from impurities or fission products from the nuclear fuel material and protects the substrate from stress corrosion and stress cracking. The dilute zirconium alloy liner displays greater corrosion resistance, especially to oxidation by hot water or steam than unalloyed zirconium. The substrate material is selected from conventional cladding materials, and preferably is a zirconium alloy. (author)

  5. Oxygen stabilized zirconium-vanadium-iron alloy

    International Nuclear Information System (INIS)

    Gruen, D.M.; Mendelsohn, M.H.

    1982-01-01

    An oxygen stabilized intermetallic compound having the formula (Zrsub(1-x)Tisub(x))sub(2-u)(Vsub(1-y)Fesub(y))Osub(z) where x = 0.0 to 0.9, y = 0.01 to 0.9, z = 0.25 to 0.5 and u = 0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196 deg C to 200 deg C at pressures down to 10 - 6 torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices, and the iron content may be substituted by nickel, cobalt or manganese. (author)

  6. Oxygen stabilized zirconium-vanadium-iron alloy

    International Nuclear Information System (INIS)

    Gruen, D.M.; Mendelsohn, M.H.

    1982-01-01

    An oxygen stabilized intermetallic compound having the formula (Zrsub(1-x)Tisub(x))sub(2-u)(Vsub(1-y)Fesub(y))Osub(z) where x=0.0 to 0.9, y=0.01 to 0.9, z=0.25 to 0.5 and u=0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196 0 C to 200 0 C at pressures down to 10 - 6 torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices, and the iron content may be substituted by nickel, cobalt or manganese. (author)

  7. Hydrogen and deuterium trapping in iron

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, H H; Lin, R W

    1981-02-01

    The research described is directed at present almost exclusively to hydrogen transport, including both chemical and physical trapping, in iron and iron-base alloys. Some attention is directed to isotope effects. Efforts are made to clarify and understand hydrogen-related phenomena which are believed to be of direct importance to practical performance.

  8. Iron-titanium-mischmetal alloys for hydrogen storage

    Science.gov (United States)

    Sandrock, Gary Dale

    1978-01-01

    A method for the preparation of an iron-titanium-mischmetal alloy which is used for the storage of hydrogen. The alloy is prepared by air-melting an iron charge in a clay-graphite crucible, adding titanium and deoxidizing with mischmetal. The resultant alloy contains less than about 0.1% oxygen and exhibits a capability for hydrogen sorption in less than half the time required by vacuum-melted, iron-titanium alloys.

  9. Effect of the hydrogen content and cooling velocity in the hydrides precipitation in α-zirconium

    International Nuclear Information System (INIS)

    Ramanathan, L.V.

    1983-01-01

    Zirconium specimens containing 50-300 ppm hydrogen have been cooled from the hydrogen solution treatment temperature at different rates by furnace cooling, air cooling and oil quenching. Optical and electron microscopical investigations have revealed grain boundary Δ - hydrides in slowly cooled specimens. At higher cooling rates γ and Δ hydrides have been found precipitated both intergranularly and intragranularly. Grain boundary Δ hydrides have been also observed in oil quenched specimens with 300 ppm hydrogen. Quenched specimens have revealed Widmanstatten and parallel plate type hydride morphologies. (Author) [pt

  10. Absorption of dissolved hydrogen from lithiated water during accelerated corrosion of zirconium-2.5 wt% niobium alloy

    International Nuclear Information System (INIS)

    Manolescu, A.V.; Mayer, P.; Rasile, E.M.; Mummenhoff, J.W.

    1982-01-01

    A series of laboratory experiments was carried out to determine the extent of dissolved hydrogen absorption from lithiated water by zirconium-2.5 wt% niobium alloy during corrosion. The material was exposed at 340 0 C to 1 M LiOH aqueous solution containing 0 to approximately 70 cm 3 /L of dissolved hydrogen. Results indicate that dissolved hydrogen has no effect on the corrosion rate or on the amount of hydrogen absorbed by the material

  11. Experimental investigation and thermodynamic simulation of the uranium oxide-zirconium oxide-iron oxide system in air

    Czech Academy of Sciences Publication Activity Database

    Petrov, Y. B.; Udalov, Y. P.; Šubrt, Jan; Bakardjieva, Snejana; Sázavský, P.; Kiselová, M.; Selucký, P.; Bezdička, Petr; Joumeau, C.; Piluso, P.

    2011-01-01

    Roč. 37, č. 2 (2011), s. 212-229 ISSN 1087-6596 Institutional research plan: CEZ:AV0Z40320502 Keywords : uranium oxide * zirconium oxide * iron oxide * fusibility curve * oxygen partial pressure * crystallization * phase composition Subject RIV: CA - Inorganic Chemistry Impact factor: 0.492, year: 2011

  12. Immobilization of transition metal ions on zirconium phosphate monolayers

    International Nuclear Information System (INIS)

    Melezhik, A.V.; Brej, V.V.

    1998-01-01

    It is shown that ions of transition metals (copper, iron, vanadyl, titanium) are adsorbed on zirconium phosphate monolayers. The zirconium phosphate threshold capacity corresponds to substitution of all protons of hydroxyphosphate groups by equivalent amounts of copper, iron or vanadyl. Adsorption of polynuclear ions is possible in case of titanium. The layered substance with specific surface up to 300 m 2 /g, wherein ultradispersed titanium dioxide particles are intercalirated between zirconium-phosphate layers, is synthesized

  13. Hydrogen permeation through sol-gel-coated iron during galvanostatic charging

    International Nuclear Information System (INIS)

    Zakorchemna, I.; Carmona, N.; Zakroczymski, T.

    2008-01-01

    One-layer sol-gel silica-zirconia and two-layer silica-zirconia and zirconia coatings were deposited on one side of iron membranes by spin-coating, densified in air and annealed up to 800 deg. C in vacuum. Hydrogen permeation through the membranes, coated and uncoated, polarised cathodically under galvanostatic control in 0.1 M NaOH solution was studied using the electrochemical permeation technique. During the initial period, the effect of the sol-gel coatings was insignificant. However, the coatings quite efficiently prevented the iron surface become more active to hydrogen entry during a long-lasting cathodic polarisation. In addition, the electrochemical-corrosion behaviour of the coated iron and the effect of the sol-gel coatings on the effective diffusivity of hydrogen in the coated membranes were studied. On the basis of the polarisation curves and the hydrogen permeation data it was proved that the sol-gel coatings blocked the iron surface for the hydrogen evolution reaction and, consequently, for the hydrogen entry into iron. The effective coating coverage was determined by comparison of the hydrogen fluxes permeating the coated and uncoated membranes. Finally the real concentration of hydrogen beneath the uncoated iron sites and the amount of hydrogen stored in a membrane were evaluated

  14. Experimental studies of relevance on zirconium nitrate raffinate sludge for its disposal as well as zirconium recovery

    International Nuclear Information System (INIS)

    Brahmananda Reddy, G.; Narasimha Murty, B.; Ravindra, H.R.

    2013-01-01

    One of the many routes of production of nuclear grade zirconium dioxide involve separation of zirconium and hafnium by solvent extraction of zirconium nitrate using tri-n-butyl phosphate followed by precipitation of zirconium with ammonia and finally calcination of the so obtained hydrated zirconia at elevated temperature. The zirconium feed solution as is generated from digestion of zirconium washed dried frit (produced by the caustic fusion of zircon sand which is one of the beach sand heavy minerals) in nitric acid contain considerable amount of sludge material and after solvent extraction this whole sludge material rests with raffinate. This sludge material has a scope to contain considerable amounts of zirconium along with other metal ions such as hafnium, aluminium, iron, etc. besides nitric acid and it constitutes one of the important solid wastes that needs to be disposed suitably. One of the disposal means of this sludge material is to use it as a land fill for which two important criteria are to be viz the pH of 10% solid waste solution should be near to neutral pH and the loss on ignition at 550℃ on dry basis of the sludge to be below 20%. In order to study the implications of presence of varying amounts of zirconium nitrate in the sludge on the pH of 10% solution of the sludge various synthetic zirconium nitrate solid waste were prepared using the sludge material generated at the laboratory during the analysis of zirconium washed dried frit. Presence of zirconium in the sludge is expected to decrease the overall pH of the 10% solution of the sludge because zirconium is prone to hydrolyze especially locally when zirconium ion comes into contact with water according to the chemical equation Zr 4+ H 2 O → ZrO 2+ + 2H + . From this equation, it is clear that for every one mole of zirconium ions two moles of hydrogen ions are produced. This is verified experimentally using the synthetically prepared sludge materials with varying amounts of zirconium

  15. Susceptibility of cold-worked zirconium-2.5 wt% niobium alloy to delayed hydrogen cracking

    International Nuclear Information System (INIS)

    Coleman, C.E.

    1976-01-01

    Notched tensile specimens of cold-worked zirconium-2.5 wt% niobium alloy have been stressed at 350 K and 520 K. At 350 K, above a possible threshold stress of 200 MPa, specimens exhibited delayed failure which was attributed to hydride cracking. Metallography showed that hydrides accumulated at notches and tips of growing cracks. The time to failure appeared to be independent of hydrogen content over the range 7 to 100 ppm hydrogen. Crack growth rates of about 10 -10 m/s deduced from fractography were in the same range as those necessary to fracture pressure tubes. The asymptotic stress intensity for delayed failure, Ksub(1H), appeared to be about 5 MPa√m. With this low value of Ksub(1H) small surface flaws may propagate in pressure tubes which contain large residual stresses. Stress relieving and modified rolling procedures will reduce the residual stresses to such an extent that only flaws 12% of the wall thickness or greater will grow. At 520 K no failures were observed at times a factor of three greater than times to failure at 350 K. Zirconium-2.5 wt% niobium appears to be safe from delayed hydrogen cracking at the reactor operating temperature. (author)

  16. Investigation of moisture-induced embrittlement of iron aluminides. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Alven, D.A.; Stoloff, N.S. [Rensselaer Polytechnic Inst., Troy, NY (United States). Materials Engineering Dept.

    1997-06-05

    Iron-aluminum alloys with 28 at.% Al and 5 at.% Cr were shown to be susceptible to hydrogen embrittlement by exposure to both gaseous hydrogen and water vapor. This study examined the effect of the addition of zirconium and carbon on the moisture-induced hydrogen embrittlement of an Fe{sub 3}Al,Cr alloy through the evaluation of tensile properties and fatigue crack growth resistance in hydrogen gas and moisture-bearing air. Susceptibility to embrittlement was found to vary with the zirconium content while the carbon addition was found to only affect the fracture toughness. Inherent fatigue crack growth resistance and fracture toughness, as measured in an inert environment, was found to increase with the addition of 0.5 at.% Zr. The combined addition of 0.5 at.% Zr and carbon only increased the fracture toughness. The addition of 1 at.% Zr and carbon was found to have no effect on the crack growth rate when compared to the base alloy. Susceptibility to embrittlement in moisture-bearing environments was found to decrease with the addition of 0.5 at.% Zr. In gaseous hydrogen, the threshold value of the Zr-containing alloys was found to increase above that found in the inert environment while the crack growth resistance was much lower. By varying the frequency of fatigue loading, it was shown that the corrosion fatigue component of the fatigue crack growth rate in an embrittling environment displays a frequency dependence. Hydrogen transport in iron aluminides was shown to occur primarily by a dislocation-assisted transport mechanism. This mechanism, in conjunction with fractography, indicates that the zirconium-containing precipitates act as traps for the hydrogen that is carried along by the dislocations through the lattice.

  17. Diffusion of hydrogen in iron oxides

    International Nuclear Information System (INIS)

    Bruzzoni, P.

    1993-01-01

    The diffusion of hydrogen in transitions metals oxides has been recently studied at room temperature through the permeability electrochemical technique. This work studies thin oxide layers grown in air or in presence of oxidizing atmospheres at temperatures up to 200 deg C. The substrate was pure iron with different superficial treatments. It was observed that these oxides reduce up to three magnitudes orders, the hydrogen stationary flux through membranes of usual thickness in comparison with iron membranes free of oxide. (Author)

  18. Ductile zirconium powder by hydride-dehydride process

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, T S [BHABHA ATOMIC RESEARCH CENTRE, BOMBAY (INDIA); CHAUDHARY, S [NUCLEAR FUEL COMPLEX, HYDERABAD (INDIA)

    1976-09-01

    The preparation of ductile zirconium powder by the hydride-dehydride process has been described. In this process massive zirconium obtained from Kroll reduction of ZrCl/sub 4/ is first rendered brittle by hydrogenation and the hydride crushed and ground in a ball mill to the required particle size. Hydrogen is then hot vacuum extracted to yield the metal powder. The process has been successfully employed for the production of zirconium powders with low oxygen content and having hardness values in the range of 115-130 BHN, starting from a zirconium sponge of 100-120 BHN hardness. Influence of surface characteristics of the starting metal on its hydriding behaviour has been studied and the optimum hydriding-dehydriding conditions established.

  19. Preparation of complexes of zirconium and hafnium tetrachlorides with phosphorus oxychloride

    International Nuclear Information System (INIS)

    Snyder, T.S.; Stoltz, R.A.

    1989-01-01

    This patent describes an improvement in a method for separating hafnium chloride from zirconium chloride using a distillation column, with a hafnium chloride enriched vapor stream taken from the top of the column and a zirconium enriched chloride stream taken from the bottom of the column. The improvement comprising: purifying the zirconium-hafnium chloride in a molten salt purification vessel prior to or after introduction into the distillation column to substantially eliminate iron chloride from the zirconium-hafnium chloride by at least periodically removing iron chloride from the molten salt purification vessel by electrochemically plating iron onto an electrode in the molten salt purification vessel. The molten salt in the molten salt purification vessel consisting essentially of a mixture of chlorides selected from the group consisting of alkali metals, alkaline earth metals, zirconium, hafnium, aluminum, manganese, and zinc

  20. Effects of alloying elements on nodular and uniform corrosion resistance of zirconium-based alloys

    International Nuclear Information System (INIS)

    Abe, Katsuhiro

    1992-01-01

    The effects of alloying and impurity elements (tin, iron, chromium, nickel, niobium, tantalum, oxygen, aluminum, carbon, nitrogen, silicon, and phosphorus) on the nodular and uniform corrosion resistance of zirconium-based alloys were studied. The improving effect of iron, nickel and niobium in nodular corrosion resistance were observed. The uniform corrosion resistance was also improved by nickel, niobium and tantalum. The effects of impurity elements, nitrogen, aluminum and phosphorus were negligibly small but increasing the silicon content seemed to improve slightly the uniform corrosion resistance. Hydrogen pick-up fraction were not changed by alloying and impurity elements except nickel. Nickel addition increased remarkably hydrogen pick-up fraction. Although the composition of secondary precipitates changed with contents of alloying elements, the correlation of composition of secondary precipitates to corrosion resistance was not observed. (author)

  1. PROCESS FOR DISSOLVING BINARY URANIUM-ZIRCONIUM OR ZIRCONIUM-BASE ALLOYS

    Science.gov (United States)

    Jonke, A.A.; Barghusen, J.J.; Levitz, N.M.

    1962-08-14

    A process of dissolving uranium-- zirconium and zircaloy alloys, e.g. jackets of fuel elements, with an anhydrous hydrogen fluoride containing from 10 to 32% by weight of hydrogen chloride at between 400 and 450 deg C., preferably while in contact with a fluidized inert powder, such as calcium fluoride is described. (AEC)

  2. A computer model for hydride blister growth in zirconium alloys

    International Nuclear Information System (INIS)

    White, A.J.; Sawatzky, A.; Woo, C.H.

    1985-06-01

    The failure of a Zircaloy-2 pressure tube in the Pickering unit 2 reactor started at a series of zirconium hydride blisters on the outside of the pressure tube. These blisters resulted from the thermal diffusion of hydrogen to the cooler regions of the pressure tube. In this report the physics of thermal diffusion of hydrogen in zirconium is reviewed and a computer model for blister growth in two-dimensional Cartesian geometry is described. The model is used to show that the blister-growth rate in a two-phase zirconium/zirconium-hydride region does not depend on the initial hydrogen concentration nor on the hydrogen pick-up rate, and that for a fixed far-field temperature there is an optimum pressure-type/calandria-tube contact temperature for growing blisters. The model described here can also be used to study large-scale effects, such as hydrogen-depletion zones around hydride blisters

  3. Hydrogen transport in iron and steel

    International Nuclear Information System (INIS)

    Louthan, M.R. Jr.; Derrick, R.G.; Donovan, J.A.; Caskey, G.R. Jr.

    1975-01-01

    The permeabilities of protium, deuterium, and tritium in iron and T-1 steel at temperatures as low as 260 0 K are in agreement with the equation proposed by Gonzalez. However, the permeabilities of HP-9-4-20 and 4130 steel to hydrogen are typically lower than predicted. The present data also show that, within experimental accuracy, the isotope effect on the permeability of hydrogen in HP-9-4-20, 4130 and T-1 steel, and high purity iron can be estimated by an inverse square root of mass correction. Trapping effects prevent the development of diffusivity and solubility equations. (auth)

  4. Effect of residual stresses on hydrogen permeation in iron

    International Nuclear Information System (INIS)

    Mouanga, M.; Bercot, P.; Takadoum, J.

    2010-01-01

    The effect of residual stresses on electrochemical permeation in iron membrane was investigated. Four thermal and mechanical treatments were chosen to obtain different surface states in relation to the residual stresses. Residual stresses were determined by X-ray diffraction (XRD) using the Macherauch and Mueller method. The results were completed by the microhardness measurements. For all iron membranes, compressive residual stresses were obtained. Electrochemical permeation experiments using a Devanathan and Stachurski cell were employed to determine the hydrogen permeation behaviour of the various iron membranes. The latter was charged with hydrogen by galvanostatic cathodic polarization in 0.1 M NaOH at 25 deg. C. The experimental results revealed that hydrogen permeation rate increases with increasing residual stresses introduced in iron membranes.

  5. Investigation of Zirconium Oxide Films in Different Dissolved Hydrogen Concentration

    International Nuclear Information System (INIS)

    Kim, Taeho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun

    2016-01-01

    It has been reported that in pre-transition zirconium oxide, the volume fraction of tetragonal zirconium oxide increased near the oxide/metal (O/M) interface, and the sub-stoichiometric zirconium oxide layer was observed. The diffusion of oxygen ion through the oxide layer is the rate-limiting process during the pre-transition oxidation process, and this diffusion mainly occurs in the grain boundaries. The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high-temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pre-transition zirconium oxide in high-temperature water chemistry. In this study, in situ Raman and TEM analysis were conducted for investigating the phase transformation of zirconium alloy in primary water. From this study, the following conclusions are drawn: 1. The zirconium alloy was oxidized in primary water chemistry for 100 d, and Raman and TEM were measured after 30, 50, 80, and 100 d from start-up. 2. TEM and FFT analysis showed that the zirconium oxide mostly consisted of the monoclinic phase. The tetragonal zirconium oxide was just found near the O/M interface

  6. Quantitative analysis of nickel in zirconium and zircaloy; Dosage du nickel dans le zirconium et dans le zircaloy

    Energy Technology Data Exchange (ETDEWEB)

    Rastoix, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    A rapid spectrophotometric has been developed for determination of 10 to 1000 ppm of Ni in zirconium and zircaloy using dimethylglyoxime. Iron, copper, tin and chromium, do not interfere at the concentration usually present in zirconium and its alloys. (author) [French] On determine colorimetriquenent 10 a 1000 ppm de Ni dans le zirconium et le zircaloy par photo colorimetrie a 440 m{mu} de la dimethylglyoxime nickelique. Le dosage est rapide. Le fer, le cuivre, l'etain, le chrome ne genent pas aux concentrations habituellement rencontrees dans le zirconium et ses alliages. (auteur)

  7. Hydrogen effect on embrittlement of iron and steel

    International Nuclear Information System (INIS)

    Shved, M.M.

    1981-01-01

    Some existing hypothesis brittleness of metals are considered. The following explanation of reversible hydrogen brittleness is suggested: hydrogen presence in iron and steel brings about the increase in the critical shear stress and the yield stress at all stages of plastic deformation (hydrogen, blocking dislocations hinders plastic shears) and the decrease of rupture strength. Decreasing forces of interatomic interaction of the surface layer some scores interatomic distances thick, hydrogen decreases the resistance of normal stresses to its effect. Thus, whatever mechanism brings about the formation of the first cracks in the metal in the presence of absorbed hydrogen, they appear at lower outside applied stresses. In the framework of the model suggested one can explain experimentally observed changes of mechanical properties of iron and steel under hydrogen effect

  8. Theoretical Investigation of Hydrogen Adsorption and Dissociation on Iron and Iron Carbide Surfaces Using the ReaxFF Reactive Force Field Method

    Energy Technology Data Exchange (ETDEWEB)

    Zou, Chenyu; van Duin, Adri C.T.; Sorescu, Dan C.

    2012-06-01

    We have developed a ReaxFF reactive force field to describe hydrogen adsorption and dissociation on iron and iron carbide surfaces relevant for simulation of Fischer–Tropsch (FT) synthesis on iron catalysts. This force field enables large system (>>1000 atoms) simulations of hydrogen related reactions with iron. The ReaxFF force field parameters are trained against a substantial amount of structural and energetic data including the equations of state and heats of formation of iron and iron carbide related materials, as well as hydrogen interaction with iron surfaces and different phases of bulk iron. We have validated the accuracy and applicability of ReaxFF force field by carrying out molecular dynamics simulations of hydrogen adsorption, dissociation and recombination on iron and iron carbide surfaces. The barriers and reaction energies for molecular dissociation on these two types of surfaces have been compared and the effect of subsurface carbon on hydrogen interaction with iron surface is evaluated. We found that existence of carbon atoms at subsurface iron sites tends to increase the hydrogen dissociation energy barrier on the surface, and also makes the corresponding hydrogen dissociative state relatively more stable compared to that on bare iron. These properties of iron carbide will affect the dissociation rate of H{sub 2} and will retain more surface hydride species, thus influencing the dynamics of the FT synthesis process.

  9. Quantitative analysis of nickel in zirconium and zircaloy

    International Nuclear Information System (INIS)

    Rastoix, M.

    1957-01-01

    A rapid spectrophotometric has been developed for determination of 10 to 1000 ppm of Ni in zirconium and zircaloy using dimethylglyoxime. Iron, copper, tin and chromium, do not interfere at the concentration usually present in zirconium and its alloys. (author) [fr

  10. Preparation of complexes of zirconium and hafnium tetrachlorides with phosphorus oxychloride

    International Nuclear Information System (INIS)

    McLaughlin, D.F.

    1989-01-01

    This patent describes an improvement in a method for separating hafnium tetrachloride from zirconium tetrachloride where a complex of zirconium-hafnium tetrachlorides and phosphorus oxychloride is prepared from zirconium-hafnium tetrachlorides and the complex of zirconium-hafnium tetrachlorides and phosphorus oxychloride is introduced into a distillation column, which distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and where a hafnium tetrachloride enriched stream is taken from the top of the column and a zirconium enriched tetrachloride stream is taken from the bottom of the column. The improvement comprising: prepurifying the zirconium-hafnium tetrachlorides, prior to preparation of the complex and introduction of the complex into a distillation column, to substantially eliminate iron chloride from the zirconium hafnium tetrachlorides, whereby buildup or iron chloride in the distillation column and in the reboiler is substantially eliminated and the column can be operated in a continuous, stable and efficient manner

  11. Low cycle fatigue behaviour of zirconium alloys at 3000C

    International Nuclear Information System (INIS)

    Hosbons, R.R.

    1975-01-01

    The low cycle fatigue lives of two zirconium alloys, zirconium--2.5 wt percent niobium and zirconium--1.1 wt percent chromium--0.1 wt percent iron, have been determined at 300 0 C. Both annealed material and cold-worked and stress-relieved material have similar fatigue lives to annealed Zircaloy-2 but β-quenched zirconium--niobium and zirconium--chromium--iron have lower fatigue lives than annealed Zircaloy-2. An atmosphere containing a concentration of iodine lower than that required for stress corrosion cracking still significantly lowers the fatigue life. A mathematical relationship between fatigue life and short-term tensile properties was used to estimate the fatigue life of zirconium alloy fuel sheaths and it was estimated that for a strain cycle of 0.1 percent a cyclic frequency exceeding 0.116 Hz (10,000 cycles/ day) would be required to cause fatigue failure of the sheath before its design life is realized

  12. Low cycle fatigue behaviour of zirconium alloys at 3000C

    International Nuclear Information System (INIS)

    Hosbons, R.R.

    1975-01-01

    The low cycle fatigue lives of two zirconium alloys, zirconium-2.5 wt% niobium and zirconium-1.1 wt% chronium-0.1 wt% iron, have been determined at 300 0 C. Both annealed material and cold-worked and stress-relieved material have similar fatigue lives to annealed Zircaloy-2 but β-quenched zirconium-niobium and zirconium-chromium-iron have lower fatigue lives than annealed Zircaloy-2. An atmosphere containing a concentration of iodine lower than that required for stress corrosion cracking still significantly lowers the fatigue life. A mathematical relationship between fatigue life and short-term tensile properties was used to estimate the fatigue life of zirconium alloy fuel sheaths and it was estimated that for a strain cycle of 0.1 per cent a cyclic frequency exceeding 0.116 Hz (10 000 cycles/day) would be required to cause fatigue failure of the sheath before its design life is realized. (author)

  13. Solubility of hydrogen in delta iron

    International Nuclear Information System (INIS)

    Shapovalov, V.I.; Trofimenko, V.V.

    1979-01-01

    The solubility of hydrogen in iron (less than 0.002 % impurities) at temperatures of 800-1510 deg C and a pressure of 100 atm was measured. The heat of solution of hydrogen in delta-Fe, equal to 73 kJ/g-atom, is by far greater than the corresponding values for α- and γ-Fe

  14. Development of zirconium hydride highly effective moderator materials

    International Nuclear Information System (INIS)

    Yin Changgeng

    2005-10-01

    The zirconium hydride with highly content of hydrogen and low density is new efficient moderator material for space nuclear power reactor. Russia has researched it to use as new highly moderator and radiation protection materials. Japanese has located it between the top of pressure vessel and the main protection as a shelter, the work temperature is rach to 220 degree C. The zirconium hydride moderator blocks are main parts of space nuclear power reactor. Development of zirconium hydride moderator materials have strength research and apply value. Nuclear Power Research and Design Instituteoh China (NPIC) has sep up the hydrogenation device and inspect systems, and accumurate a large of experience about zirconium hydride, also set up a strict system of QA and QC. (authors)

  15. Deactivation of iron oxide used in the steam-iron process to produce hydrogen

    NARCIS (Netherlands)

    Bleeker, M.F.; Veringa, H.J.; Kersten, Sascha R.A.

    2009-01-01

    In the steam-iron process pure hydrogen can be produced from any hydrocarbon feedstock by using a redox cycle of iron oxide. One of the main problems connected to the use of the iron oxide is the inherent structural changes that take place during oxygen loading and unloading leading to severe

  16. Purification of zirconium concentrates

    International Nuclear Information System (INIS)

    Brown, A.E.P.

    1976-01-01

    A commercial grade ZrO 2 and an ammonium uranate (yellow cake) are obtained from the caldasito ore processing. This ore is found in the Pocos de Caldas Plateau, State of Minas Gerais, Brazil. Caldasito is an uranigerous zirconium ore, a mixture of zircon and baddeleyite and contains 60% ZrO 2 and 0,3% U 3 O 8 . The chemical opening of the ore was made by alkaline fusion with NaOH at controlled temperature. The zirconium-uranium separation took place by a continuous liquid-liquid extraction in TBP-varsol-HNO 3 -H 2 O system. The raffinate containing zirconium + impurities (aluminium, iron and titanium) was purified by an ion exchange operation using a strong cationic resin [pt

  17. Reverse mechanical after effect during hydrogenation of zone refined iron

    Energy Technology Data Exchange (ETDEWEB)

    Spivak, L.V.; Skryabina, N.E.; Kurmaeva, L.D.; Smirnov, L.V. (Permskij Gosudarstvennyj Univ. (USSR); AN SSSR, Sverdlovsk. Inst. Fiziki Metallov)

    1984-12-01

    The relationship between the process of hydrogenation and the reverse mechanical after effect (RMA) microplastic deformation in the zone refined iron has been studied. Metallographic investigations and mechanical testing of the samples hydrogenated under torsional strain have been performed. It is shown that in the zone refined iron the formation of voids responsible for irreversible hydrogen embrittlement does not occur, but the hydrogen-initiated RMA strain is conserved, i. e. the RMA effects are independent of the presence of discontinuities.

  18. Determination of hydrogen in zirconium and its alloys by melt extraction under carrier gas flow using thermal conductivity cell as detector

    International Nuclear Information System (INIS)

    Akhtar, J.; Ahmed, M.; Mohammad, B.; Jan, S.; Waqar, F.

    1987-06-01

    In the production of zirconium metal and its alloys the presence of hydrogen impurity affects mechanical and corrosion resistance properties of the product. Therefore, determination of hydrogen contents of the product is necessary. Conditions for its analysis by melt extraction under carrier gas stream using thermal conductivity cell as detector were studied and optimised. The method is capable of measuring hydrogen impurity in parts per million range. (author)

  19. Zirconium for nitric acid solutions

    International Nuclear Information System (INIS)

    Yau, T.L.

    1984-01-01

    The excellent corrosion resistance of zirconium in nitric acid has been known for over 30 years. Recently, there is an increasing interest in using zirconium for nitric acid services. Therefore, an extensive research effort has been carried out to achieve a better understanding of the corrosion properties of zirconium in nitric acid. Particular attention is paid to the effect of concentration, temperature, structure, solution impurities, and stress. Immersion, autoclave, U-bend, and constant strain-rate tests were used in this study. Results of this study indicate that the corrosion resistance of zirconium in nitric acid is little affected by changes in temperature and concentration, and the presence of common impurities such as seawater, sodium chloride, ferric chloride, iron, and stainless steel. Moreover, the presence of seawater, sodium chloride, ferric chloride, and stainless steel has little effect on the stress corrosion craking (SCC) susceptibility of zirconium in 70% nitric acid at room temperatures. However, zirconium could be attacked by fluoride-containing nitric acid and the vapors of chloride-containing nitric acid. Also, high sustained tensile stresses should be avoided when zirconium is used to handle 70% nitric acid at elevated temperatures or > 70% nitric acid

  20. Electrochemical measurement of tritium and hydrogen permeation through iron membranes

    International Nuclear Information System (INIS)

    Hagi, Hideki; Hayashi, Yasunori

    1987-01-01

    Permeation rates of tritium and hydrogen through iron were measured by the electro-chemical method in which an aqueous solution containing 3.7 x 10 12 Bq/m 3 tritium was used as a cathodic electrolyte. Tritium and hydrogen were introduced from one side of a specimen by cathodic polarization with a constant current density, while at the other side of the specimen the permeated tritium and hydrogen were extracted by potentiostatical ionization. Nearly all of the potentiostatic current on the extraction side is produced by the ionization of hydrogen, because the concentration of tritium in the cathodic electrolyte is very small. The amount of permeated hydrogen was obtained by integrating the potentiostatic current, and that of permeated tritium was determined by measuring the radioactivity of the electrolyte sampled from the anodic side. The separation factor for permeation obtained under steady state conditions (the ratio of permeation rates of hydrogen to tritium divided by the ratio of the concentration of hydrogen to tritium in the cathodic electrolyte) is 12 at 288 K. This value is independent of cathodic current density. Diffusion coefficients of tritium (D T ) and hydrogen (D H ) in iron were determined from the tritium and hydrogen permeation by using time lag technique. For annealed iron at 286 K, D T = 9 x 10 -10 m 2 /s and D H = 4 x 10 -9 m 2 /s, and for 9 % cold-worked iron at 284 K, D T = 3 x 10 -10 m 2 /s and D H = 4 x 10 -10 m 2 /s. (author)

  1. Changes on iron electrode surface during hydrogen permeation in borate buffer solution

    International Nuclear Information System (INIS)

    Modiano, S.; Carreno, J.A.V.; Fugivara, C.S.; Torresi, R.M.; Vivier, V.; Benedetti, A.V.; Mattos, O.R.

    2008-01-01

    Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E oc ) and in the passive region (+0.30 V ECS ) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L -1 H 3 BO 3 + 0.075 mol L -1 Na 2 B 4 O 7 (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell

  2. Influence of hydrogen absorption on magnetic ordering in some zirconium-based Laves phase compounds

    International Nuclear Information System (INIS)

    Fujii, H.; Pourarian, F.; Wallace, W.E.

    1982-01-01

    Magnetization measurements were carried out on several zirconium-based hexagonal Laves phase compounds, i.e. the ZrMnsub(2+delta), (Zr,Ti)Mn 2 , Zr(Mn,Fe) 2 and Zr(Fe,Al) 2 systems and their hydrides. The absorbed hydrogen leads to a large increase (20%-30%) in volume without a change in the crystal structure. ZrMnsub(2+delta) is a weak Pauli paramagnet but becomes a spin glass near-ferromagnet by hydriding, indicating that the manganese moments are subjected to competing ferromagnetic and antiferromagnetic coupling tendencies. In the (Zrsub(1-x)Tisub(x))Mn 2 hydrides, ferromagnetic, spin-glass-like, ferromagnetic and antiferromagnetic behaviors appear at 4.2 K in the sequence of increasing x and/or decrease in hydrogen concentration. In the Zr(Mn,Fe) 2 system, the hydrogen absorption increases both the magnetic moments and the magnetic transition temperatures, while absorbed hydrogen leads to suppression of ferromagnetism in the Zr(Fe,Al) 2 system. These varied and complex magnetic behaviors are attributed to the effects of (1) variations in the interatomic distances, (2) changes in the 3d electron concentration and (3) varying local hydrogen concentrations occurring as a result of statistical fluctuations. (Auth.)

  3. The effect of pearlite on the hydrogen-induced ductility loss in ductile cast irons

    Science.gov (United States)

    Matsuo, T.

    2017-05-01

    Hydrogen energy systems, such as a hydrogen fuel cell vehicle and a hydrogen station, are rapidly developing to solve global environmental problems and resource problems. The available structural materials used for hydrogen equipments have been limited to only a few relatively expensive metallic materials that are tolerant for hydrogen embrittlement. Therefore, for the realization of a hydrogen society, it is important to expand the range of materials available for hydrogen equipment and thereby to enable the use of inexpensive common materials. Therefore, ductile cast iron was, in this study, focused as a structural material that could contribute to cost reduction of hydrogen equipment, because it is a low-cost material having good mechanical property comparable to carbon steels in addition to good castability and machinability. The strength and ductility of common ductile cast irons with a ferritic-pearlitic matrix can be controlled by the volume fraction of pearlitic phase. In the case of carbon steels, the susceptibility to hydrogen embrittlement increases with increase in the pearlite fraction. Toward the development of ferritic-pearlitic ductile cast iron with reasonable strength for hydrogen equipment, it is necessary to figure out the effect of pearlite on the hydrogen embrittlement of this cast iron. In this study, the tensile tests were conducted using hydrogen-precharged specimens of three kinds of ferritic-pearlitic ductile cast irons, JIS-FCD400, JIS-FCD450 and JIS-FCD700. Based on the results, the role of pearlite in characterizing the hydrogen embrittlement of ductile cast iron was discussed.

  4. Manufacture of titanium and zirconium hydrides

    International Nuclear Information System (INIS)

    Mares, F.; Hanslik, T.

    1973-01-01

    A method is described of manufacturing titanium and zirconium hydrides by hydrogenation of said metals characterized by the reaction temperature ranging between 250 to 500 degC, hydrogen pressure of 20 to 300 atm and possibly by the presence of a hydride of the respective metal. (V.V.)

  5. Promotion of hydrogen entry into iron from NaOH solution by iron-oxygen species

    International Nuclear Information System (INIS)

    Flis-Kabulska, I.; Flis, J.; Zakroczymski, T.

    2007-01-01

    This study was carried out to explain reasons of the enhanced hydrogen entry into iron at low polarisations. Hydrogen permeation rate (HPR) through a 35-μm thick iron membrane was studied with the electrochemical technique in 0.1 M NaOH at 25 o C. A rotating split-ring disk electrode was used to detect soluble Fe(II) species. Enhanced hydrogen entry (HPR peaks) was observed at low cathodic and low anodic polarisations during voltammetric cycling, and also during galvanostatic anodic polarisation applied after cathodic charging. HPR peaks occurred at potentials from about -1.2 to -0.9 V (NHE) which were more cathodic than the potentials of thermodynamic stability of Fe(OH) 2 or Fe 3 O 4 , and of the formation of soluble Fe(II) species. It has been suggested that the enhanced hydrogen entry is associated with the presence of FeOH ad . In this species oxygen is bound with hydrogen (oxo-hydride), hence it can be supposed that the mechanism of its promoting effect can be similar to that of hydrides of other elements of the VIb group

  6. Fractography of hydrogen-embrittled iron-chromium-nickel alloys

    International Nuclear Information System (INIS)

    Caskey, G.R. Jr.

    1980-01-01

    Tensile specimens of iron-chromium-nickel base alloys were broken in either a hydrogen environment or in air following thermal charging with hydrogen. Fracture surfaces were examined by scanning electron microscopy. Fracture morphology of hydrogen-embrittled specimens was characterized by: changed dimple size, twin-boundary parting, transgranular cleavage, and intergranular separation. The nature and extent of the fracture mode changes induced by hydrogen varied systematically with alloy composition and test temperature. Initial microstructure developed during deformation processing and heat treating had a secondary influence on fracture mode

  7. Determination of the population of octahedral and tetrahedral interstitials in zirconium hydrides

    International Nuclear Information System (INIS)

    Fedorov, V.M.; Gogava, V.V.; Shilo, S.I.; Biryukova, E.A.

    1983-01-01

    Results of neutron investigations of ZrHsub(1.66), ZrHsub(1.75) and ZrHsub(1.98) zirconium hydrides are presented. Investigations were conducted using plane polycrystal samples by multidetector system of scattered neutron detection. Neutron diffraction method was used to determine the number of interstitial hydrogen atoms in interstitials of the lattice cell in the case of statistic atom distribution. The numbers of interstitial atoms in octahedral interstitials for zirconium hydrides were determined experimentally; the difference of potential energies of hydrogen atoms in octa- and tetrahedral interstitials was determined as well. It is shown that experimentally determined difference of potential energies of hydrogen atoms, occupying octa- and tetrahedral positions in investigated zirconium hydrides results at room temperature in the pretailing occupation of tetrahedral interstitials by hydrogen atoms (85-90%); the occupation number grows with temperature decrease and the ordering of interstitial vacancies with formation of hydrogen superstructure takes place at low temperatures

  8. Cathodic behavior of zirconium in aqueous solutions

    International Nuclear Information System (INIS)

    Hine, F.; Yasuda, M.; Sato, H.

    1977-01-01

    The electrochemical behavior of Zr was studied by polarization measurements. The surface oxide and zirconium hydride formed by cathodic polarization of Zr have been examined by X-ray, SEM, and a hardness tester. Zirconium hydride would form on Zr cathode after the surface oxide is reduced at the potential, which is several hundred mV more noble than the predicted value shown by the Pourbaix diagram. The parameters for the hydrogen evolution reaction on the hydride formed Zr cathode differs from that on the oxide covered surface, which means that hydrogen evolution takes place on both surfaces under a different mechanism, while details are still veiled at present

  9. RECOVERY OF URANIUM FROM ZIRCONIUM-URANIUM NUCLEAR FUELS

    Science.gov (United States)

    Gens, T.A.

    1962-07-10

    An improvement was made in a process of recovering uranium from a uranium-zirconium composition which was hydrochlorinated with gsseous hydrogen chloride at a temperature of from 350 to 800 deg C resulting in volatilization of the zirconium, as zirconium tetrachloride, and the formation of a uranium containing nitric acid insoluble residue. The improvement consists of reacting the nitric acid insoluble hydrochlorination residue with gaseous carbon tetrachloride at a temperature in the range 550 to 600 deg C, and thereafter recovering the resulting uranium chloride vapors. (AEC)

  10. Zirconium alloy fuel cladding resistant to PCI crack propagation

    International Nuclear Information System (INIS)

    Boyle, R.F.; Foster, J.P.

    1987-01-01

    A nuclear fuel element is described cladding tube comprising: concentric tubular layers of zirconium base alloys; the concentric tubular layers including an inner layer and outer layer; the outer layer metallurgically bonded to the inner layer; the outer layer composed of a first zirconium base alloy characterized by excellent resistance to corrosion caused by exposure to high temperature and pressure aqueous environments; the inner layer composed of a second zirconium base alloy consisting of: about 0.2 to 0.6 wt.% tin, about 0.03 to 0.11 wt.% iron, less than about 0.02 wt.% chromium, up to about 350 ppm oxygen and the remainder being zirconium and incidental impurities, and the inner layer characterized by improved resistance to crack propagation under reactor operating conditions compared to the first zirconium alloy

  11. Co-Production of Electricity and Hydrogen Using a Novel Iron-based Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hilaly, Ahmad; Georgas, Adam; Leboreiro, Jose; Arora, Salil; Head, Megann; Trembly, Jason; Turk, Brian; Gupta, Raghubir

    2011-09-30

    The primary objective of this project was to develop a hydrogen production technology for gasification applications based on a circulating fluid-bed reactor and an attrition resistant iron catalyst. The work towards achieving this objective consisted of three key activities: Development of an iron-based catalyst suitable for a circulating fluid-bed reactor; Design, construction, and operation of a bench-scale circulating fluid-bed reactor system for hydrogen production; Techno-economic analysis of the steam-iron and the pressure swing adsorption hydrogen production processes. This report describes the work completed in each of these activities during this project. The catalyst development and testing program prepared and iron-based catalysts using different support and promoters to identify catalysts that had sufficient activity for cyclic reduction with syngas and steam oxidation and attrition resistance to enable use in a circulating fluid-bed reactor system. The best performing catalyst from this catalyst development program was produced by a commercial catalyst toll manufacturer to support the bench-scale testing activities. The reactor testing systems used during material development evaluated catalysts in a single fluid-bed reactor by cycling between reduction with syngas and oxidation with steam. The prototype SIP reactor system (PSRS) consisted of two circulating fluid-bed reactors with the iron catalyst being transferred between the two reactors. This design enabled demonstration of the technical feasibility of the combination of the circulating fluid-bed reactor system and the iron-based catalyst for commercial hydrogen production. The specific activities associated with this bench-scale circulating fluid-bed reactor systems that were completed in this project included design, construction, commissioning, and operation. The experimental portion of this project focused on technical demonstration of the performance of an iron-based catalyst and a

  12. Microstructural aspects of the oxidation of zirconium alloys

    International Nuclear Information System (INIS)

    Proff, Ch.

    2011-01-01

    This thesis is focused on the microstructural characterisation of precipitates in the oxide of binary zirconium alloys (1 wt.% Fe, Cr or Ni or 0.6 wt.% Nb) under different oxidation conditions at 415 C. The samples were oxidised in autoclave in air and steam and in an environmental scanning electron microscope in water vapour. The microstructural evolution of the precipitates during oxidation was characterised using electron microscopy. The findings from the analysis are the following: -Two types of oxidation behaviour are observed for precipitates. -Pilling Bedworth ratio of precipitates is higher than that of the zirconium matrix. -Formation of pure iron oxide crystals on the surface for iron bearing precipitates close to or at the surface. From these observations it is concluded that the precipitate oxidation behaviour can be correlated to precipitate composition and oxidation tendency of the elements in the precipitates. Iron exhibits clearly different behaviour. (author)

  13. The determination of zirconium by atomic absorption spectrophotometry

    International Nuclear Information System (INIS)

    Rodriguez, E.R.; Cunha, M.T.C. da

    1975-01-01

    The interference of iron in the determination of zirconium by atomic absorption spectrophotometry was studied. Attempts were made to emininate this interference by complexing the iron with EDTA, ascorbic acid and hydrazine; also by the addition of ammonium fluoride to the solution. Some experiments were carried out in order to explain the results obtained [pt

  14. Experimental and thermodynamic study of the erbium-oxygen-zirconium and gadolinium-oxygen-zirconium systems

    International Nuclear Information System (INIS)

    Jourdan, J.

    2009-11-01

    This work is a contribution to the development of innovative concepts for fuel cladding in pressurized water nuclear reactors. This concept implies the insertion of rare earth (erbium and gadolinium) in the zirconium fuel cladding. The determination of phase equilibria in the systems is essential prior to the implementation of such a promising solution. This study consisted in an experimental determination of the erbium-zirconium phase diagram. For this, we used many different techniques in order to obtain diagram data such as solubility limits, solidus, liquidus or invariant temperatures. These data allowed us to present a new diagram, very different from the previous one available in the literature. We also assessed the diagram using the CALPHAD approach. In the gadolinium-zirconium system, we determined experimentally the solubility limits. Those limits had never been determined before, and the values we obtained showed a very good agreement with the experimental and assessed versions of the diagram. Because these alloys are subjected to oxygen diffusion throughout their life, we focused our attention on the erbium-oxygen-zirconium and gadolinium-oxygen-zirconium systems. The first system has been investigated experimentally. The alloys fabrication has been performed using powder metallurgy. In order to obtain pure raw materials, we fabricated powder from erbium and zirconium bulk metals using hydrogen absorption/desorption. The characterisation of the ternary pellets allowed the determination of two ternary isothermal sections at 800 and 1100 C. For the gadolinium-oxygen-zirconium system, we calculated the phase equilibria at temperatures ranging from 800 to 1100 C, using a homemade database compiled from literature assessments of the oxygen-zirconium, gadolinium-zirconium and gadolinia-zirconia systems. Finally, we determined the mechanical properties, in connexion with the microstructure, of industrial quality alloys in order to identify the influence of

  15. Review of zirconium-zircaloy pyrophoricity

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1984-11-01

    Massive zirconium metal scrap can be handled, shipped, and stored with no evidence of combustion or pyrophoricity hazards. Mechanically produced fine scrap such as shavings, turnings, or powders can burn but are not pyrophoric unless the particle diameter is less than 54 μm. Powders with particle diameters less than 54 μm can be both pyrophoric and explosive. Pyrophoric powders should be collected and stored underwater or under inert gas cover to reduce the flammability hazard. Opening sealed containers of zirconium stored underwater should be attempted with caution since hydrogen may be present. The factors that influence the ignition temperature have been explored in depth and recommendations are included for the safe handling, shipping, and storage of pyrophoric or flammable zirconium. 29 refs., 5 figs., 6 tabs

  16. Hydrogenation of carbon to methane in reduced sponge iron, chromium, and ferrochromium

    Energy Technology Data Exchange (ETDEWEB)

    Qayyum, M A; Reeve, D A

    1976-01-01

    Hydrogenation of excess carbon to methane in reduced sponge iron, chromium and ferrochromium under isothermal and temperature-programmed conditions indicates that it is possible to control the residual carbon content of the metallized products which may be an advantage if further processing of the products is contemplated. Hydrogenation starts above 800/sup 0/C and a shrinking-core kinetic model fits the experimental data. The mean apparent activation energy for the hydrogenation of residual carbon to methane in sponge iron, chromium and ferrochromium is 21 kcal/mole.

  17. Electrocnecical behaviour of zirconium during its anodic polarization in nitrate solutions

    International Nuclear Information System (INIS)

    Stabrovskij, A.I.; Karasev, A.F.

    1983-01-01

    Electrochemical behaviour of zirconium during its anodic polarization in nitrate solutions is investigated in detail to find the method of its complete dissolution. A study has been made of the influence of varioUs factors: current density electric potential, composition and temperature of the solution, anodic polarization duration on the Zr anodic polarization in nitric acid, on the maximum permissible current density and on the zirconium yield to the solution. The zirconium polarization decreases with an acid concentration and temperature increase and increases with the current density. Iron nitrate additions to nitric acid decrease, while ammonium fluoride additions increase zirconium yield into the solution

  18. A half-century of changes in zirconium alloys

    International Nuclear Information System (INIS)

    Mardon, J.P.; Barberis, P.; Hoffmann, P.B.

    2008-01-01

    This article presents the history of zirconium alloys for PWR and BWR technologies. For more than 20 years zirconium alloys have evolved to cope with demands of the reactor operators concerning the burn-up extension and new safety margins. The poor properties of Zircaloy-1 concerning corrosion have led researchers to add elements like iron by developing Zircaloy-3A and Zircaloy-3C, and resulting in Zircaloy-4 with tin addition (from 1.30% to 1.50%). Zircaloy-4 is now outdated for PWR and new zirconium alloys with niobium are used (M5, ZIRLO...) they present a better resistance to corrosion, to hydridation, to creep and they are less prone to dimensional changes under irradiation. (A.C.)

  19. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Science.gov (United States)

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Iron-chrome-aluminum alloy cladding for increasing safety in nuclear power plants

    Science.gov (United States)

    Rebak, Raul B.

    2017-12-01

    After a tsunami caused plant black out at Fukushima, followed by hydrogen explosions, the US Department of Energy partnered with fuel vendors to study safer alternatives to the current UO2-zirconium alloy system. This accident tolerant fuel alternative should better tolerate loss of cooling in the core for a considerably longer time while maintaining or improving the fuel performance during normal operation conditions. General electric, Oak ridge national laboratory, and their partners are proposing to replace zirconium alloy cladding in current commercial light water power reactors with an iron-chromium-aluminum (FeCrAl) cladding such as APMT or C26M. Extensive testing and evaluation is being conducted to determine the suitability of FeCrAl under normal operation conditions and under severe accident conditions. Results show that FeCrAl has excellent corrosion resistance under normal operation conditions and FeCrAl is several orders of magnitude more resistant than zirconium alloys to degradation by superheated steam under accident conditions, generating less heat of oxidation and lower amount of combustible hydrogen gas. Higher neutron absorption and tritium release effects can be minimized by design changes. The implementation of FeCrAl cladding is a near term solution to enhance the safety of the current fleet of commercial light water power reactors.

  1. Electrochemical permeation tests on the kinetics of the hydrogen absorption of palladium and iron

    International Nuclear Information System (INIS)

    Dafft, E.G.

    1977-01-01

    Electrochemical permeation tests were performed to investigate the kinetics of the hydrogen development and hydrogen absorption. The cathode side of the samples was galvanostatically cathodically polarized in different electrolyte solutions with and without additions. THe hydrogen atoms diffusing out of the opposite side for iron and α-palladium were oxidized with potentiostatic, sufficiently anodic polarization. The thus registered stationary current is proportional to the hydrogen activity on the cathode side. Test apparatus and conditions are described. The measurements on iron are discussed. (orig./HPOE) [de

  2. Enhanced hydrogen entry into iron from 0.1 M NaOH at definite potentials

    International Nuclear Information System (INIS)

    Flis-Kabulska, I.; Flis, J.; Zakroczymski, T.

    2008-01-01

    This work aimed at explaining the enhancement of hydrogen entry into iron from alkaline solution occurring at definite potentials. Hydrogen permeation rate (HPR) through a 35-μm thick iron membrane was measured with the electrochemical technique in 0.1 M NaOH at 25 deg. C during cathodic and anodic polarizations. Enhanced HPR was observed at potentials of oxide reduction or iron oxidation, and potentials more cathodic than about -1.65 V NHE during prolonged galvanostatic polarization. XPS analysis showed that after the polarization, surface layers contained hydrated iron oxides and that amount of these products increased with the polarization time. It is suggested that the enhanced hydrogen entry can be explained by acidification of the near-metal solution due to iron oxidation and/or oxide reduction, and probably by a promoting effect of some Fe-O species. It is proposed that these effects are associated with surface layers. They can affect hydrogen entry as a source of protons in the oxide reduction, as a diffusion barrier making the near-metal acidification possible, and as a resistance causing an IR drop. Strong enhancement of HPR after prolonged galvanostatic polarizations can be associated with the formation of thick surface layers with IR drop enabling anodic oxidation of iron under these layers

  3. Solubility of Hydrogen and Nitrogen in liquid cast iron during melting and mold filling

    OpenAIRE

    Diószegi, Attila; Elfsberg, Jessica; Diószegi, Zoltán

    2016-01-01

    Defect formation like gas- and shrinkage porosity at cast iron component production is related to the content of gaseous elements in the liquid metal. The present work investigate the solubility of hydrogen and nitrogen in liquid iron aimed for production of lamellar and compacted graphite cast iron. The used methods and instruments are a combination of commercial measuring devices and novel experimental assemblies for measuring solubility of hydrogen and nitrogen during melting and mold fill...

  4. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    Energy Technology Data Exchange (ETDEWEB)

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  5. Electrochemical measurement of tritium and hydrogen permeation through iron membranes

    International Nuclear Information System (INIS)

    Hagi, Hideki; Hayashi, Yasunori

    1988-01-01

    Permeation rates of tritium and hydrogen through iron were measured by the electrochemical method in which an aqueous solution containing 3.7 x 10 12 Bq/m 3 tritium was used as a cathodic electrolyte. Tritium and hydrogen were introduced from one side of a specimen by cathodic polarization with a constant current density, while at the other side of the specimen the permeated tritium and hydrogen were extracted by potentiostatical ionization. Nearly all of the potentiostatic current of the extraction side stands for the ionization of hydrogen, because the concentration of tritium in the cathodic electrolyte is very small. The amount of permeated hydrogen was obtained by integrating the anodic current, and that of tritium was determined by measuring the radioactivity of the electrolyte sampled from the extraction side. The separation factor for permeation obtained under steady state conditions (the ratio of permeation rates of hydrogen to tritium divided by the ratio of the concentration of hydrogen to tritium in the charging electrolyte) is 12 at 288 K. This value is independent of cathodic current density. Diffusion coefficients of tritium (D T ) and hydrogen (D H ) in iron were determined from the time lag of tritium and hydrogen permeation. For annealed specimens at 286 K, D T = 9 x 10 -10 m 2 /s and D H = 4 x 10 -9 m 2 /s, and for 9% cold-worked specimens at 284 K, D T = 3 x 10 -10 m 2 /s and D H = 4 x 10 -10 m 2 /s. (author)

  6. Computer simulation of hydrogen diffusion and hydride precipitation at Ta/Zr bond interface. Hydrogen embrittlement in SUS304ULC/Ta/Zr explosive bonded joint

    International Nuclear Information System (INIS)

    Saida, Kazuyoshi; Fujimoto, Tetsuya; Nishimoto, Kazutoshi

    2010-01-01

    The concentration of hydrogen and precipitation of zirconium hydrides in Ta/Zr explosive bonded joint were analysed by computer simulation. Numerical model of hydride precipitation under hydrogen diffusion was simplified by the alternate model coupled the macroscopic hydrogen diffusion with the microscopic hydride precipitation. Effects of the initial hydrogen content in Ta, working degree of Zr and post-bond heat treatment on the hydrogen diffusion and hydride precipitation were investigated. Hydrogen was rapidly diffused from Ta substrate into Zr after explosive bonding and temporarily concentrated at Ta/Zr bond interface. Zirconium hydrides were precipitated and grew at Ta/Zr bond interface, and the precipitation zone of hydrides was enlarged with the lapse of time. The precipitation of zirconium hydrides was promoted when the initial hydrogen content in Ta and working degree of Zr were increased. The concentration of hydrogen and precipitation of hydrides at the bond interface were reduced and diminished by post-bond heat treatment at 373 K. It was deduced that hydrogen embrittlement in Ta/Zr explosive bonded joint was caused by the precipitation of zirconium hydrides and concentration of hydrogen at Ta/Zr bond interface during the diffusion of hydrogen containing in Ta substrate. (author)

  7. The effect of water on the stability of iron oxide and iron carbide nanoparticles in hydrogen and syngas followed by in situ X-ray absorption spectroscopy

    NARCIS (Netherlands)

    Thuene, P.C.; Moodley - Gengan, P.; Scheijen, F.J.E.; Fredriksson, H.O.A.; Lancee, R.J.; Kropf, J.; Miller, J.T.; Niemantsverdriet, J.W.

    2012-01-01

    The effect of water on iron-based nanoparticles under hydrogen and syngas was investigated by in situ X-ray absorption spectroscopy. The iron oxide (¿-Fe2O3) nanoparticles, dispersed as a monolayer on flat silica surfaces, were readily converted into metallic iron in dry hydrogen at 350 °C and into

  8. Hydrogen concentration determination in pressure tube samples using differential scanning calorimetry (dsc)

    International Nuclear Information System (INIS)

    Marinescu, R.; Mincu, M.

    2015-01-01

    Zirconium alloys are widely used as a structural material in nuclear reactors. It is known that zirconium based cladding alloys absorb hydrogen as a result of service in a pressurized water reactor. Hydrogen absorbed (during operation of the reactor) in the zirconium alloy, out of which the pressure tube is made, is one of the major factors determining the life time of the pressure tube. For monitoring the hydrides, samples of the pressure tube are periodically taken and analyzed. At normal reactor operating temperature, hydrogen has limited solubility in the zirconium lattice and precipitates out of solid solution as zirconium hydride when the solid solubility is exceeded. As a consequences material characterization of Zr-2.5Nb CANDU pressure tubes is required after manufacturing but also during the operation to assess its structural integrity and to predict its behavior until the next in-service inspection. Hydrogen and deuterium concentration determination is one of the most important parameters to be evaluated during the experimental tests. Hydrogen present in zirconium alloys has a strong effect of weakening. Following the zirconium-hydrogen reaction, the resulting zirconium hydride precipitates in the mass of material. Weakening of the material, due to the presence of 10 ppm of precipitated hydrogen significantly affects some of its properties. The concentration of hydrogen in a sample can be determined by several methods, one of them being the differential scanning calorimetry (DSC). The principle of the method consists in measuring the difference between the amount of heat required to raise the temperature of a sample and a reference to a certain value. The experiments were made using a TA Instruments DSC Q2000 calorimeter. This paper contains experimental work for hydrogen concentration determination by Differential Scanning Calorimetry (DSC) method. Also, the reproducibility and accuracy of the method used at INR Pitesti are presented. (authors)

  9. Interrelationship between structure and corrosion behaviour of zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, T [Bayer A.G., Leverkusen (Germany, F.R.)

    1979-05-01

    Due to plant failures caused by the break-down of zirconium grade 702 subjected to sulphuric acid the structure and corrosion behaviour of welded and as delivered specimens were tested for various heat treatments. It was shown by structure investigations and electron microprobe analysis that the corrosion behaviour of zirconium (in boiling 65 pct sulphuric acid) is strongly infuenced by the structure, which in its turn is dependent on the grade of purity and the prehistory of the material. Type, amount, and distribution of residual elements or precipitations caused by them are responsible for the corrosion resistance. This is valid particularly for the element iron. The plant failures mentioned here coincided with the examination results. Measures to improve the chemical resistance of pure zirconium subjected to extremely aggressive media were derived.

  10. Performance of magnetic zirconium-iron oxide nanoparticle in the removal of phosphate from aqueous solution

    International Nuclear Information System (INIS)

    Zhang, Chang; Li, Yongqiu; Wang, Fenghua; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Ma, Chi; Li, Zihao; Xu, ZiYi; Zeng, Guangming

    2017-01-01

    Highlights: • Magnetic zirconium-iron oxide nanoparticle (MZION) was successfully synthesized. • The removal of phosphate could be effectively fulfilled using MZION. • MZION could be conveniently separated by magnet after adsorption. • The Fe/Zr molar ratios played a key role in adsorption capacity and magnetic separation. - Abstract: In this study, magnetic zirconium-iron oxide nanoparticles (MZION) of different Fe/Zr molar ratios were successfully prepared using the co-precipitation method, and their performance for phosphate removal was systematically evaluated. The as-obtained adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Zeta potential analyzer, Fourier transform infrared spectroscopy (FT-IR) and Brunauer Emmett Teller (BET) specific surface area analysis. The effects of pH, ionic strength, and co-existing ions (including Cl − , SO 4 2− , NO 3 − and HCO 3 − ) were measured to evaluate the adsorption performance in batch experiments. The results showed that decreasing the Fe/Zr molar ratios increased the specific surface area that was propitious to adsorption process, but the adsorption capacity enhanced with the decrease of Fe/Zr molar ratios. Phosphate adsorption on MZION could be well described by the Freundlich equilibrium model and pseudo-second-order kinetics. The adsorption of phosphate was highly pH dependent and decreased with increasing pH from 1.5 to 10.0. The adsorption was slightly affected by ionic strength. With the exception of HCO 3 − , co-existing anions showed minimum or no effect on their adsorption performance. After adsorption, phosphate on these MZION could be easily desorbed by 0.1 M NaOH solution. The phosphate adsorption mechanism of MZION followed the inner-sphere complexing mechanism, and the surface −OH groups played a significant role in the phosphate adsorption. Additionally, the main advantages of MZION consisted in its

  11. Performance of magnetic zirconium-iron oxide nanoparticle in the removal of phosphate from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chang, E-mail: zhangchang@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Li, Yongqiu [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Wang, Fenghua, E-mail: 952157786@qq.com [Institute of Physical Education, Xinjiang Normal University, Urumqi 830054 (China); Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Ma, Chi; Li, Zihao; Xu, ZiYi; Zeng, Guangming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China)

    2017-02-28

    Highlights: • Magnetic zirconium-iron oxide nanoparticle (MZION) was successfully synthesized. • The removal of phosphate could be effectively fulfilled using MZION. • MZION could be conveniently separated by magnet after adsorption. • The Fe/Zr molar ratios played a key role in adsorption capacity and magnetic separation. - Abstract: In this study, magnetic zirconium-iron oxide nanoparticles (MZION) of different Fe/Zr molar ratios were successfully prepared using the co-precipitation method, and their performance for phosphate removal was systematically evaluated. The as-obtained adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Zeta potential analyzer, Fourier transform infrared spectroscopy (FT-IR) and Brunauer Emmett Teller (BET) specific surface area analysis. The effects of pH, ionic strength, and co-existing ions (including Cl{sup −}, SO{sub 4}{sup 2−}, NO{sub 3}{sup −} and HCO{sub 3}{sup −}) were measured to evaluate the adsorption performance in batch experiments. The results showed that decreasing the Fe/Zr molar ratios increased the specific surface area that was propitious to adsorption process, but the adsorption capacity enhanced with the decrease of Fe/Zr molar ratios. Phosphate adsorption on MZION could be well described by the Freundlich equilibrium model and pseudo-second-order kinetics. The adsorption of phosphate was highly pH dependent and decreased with increasing pH from 1.5 to 10.0. The adsorption was slightly affected by ionic strength. With the exception of HCO{sub 3}{sup −}, co-existing anions showed minimum or no effect on their adsorption performance. After adsorption, phosphate on these MZION could be easily desorbed by 0.1 M NaOH solution. The phosphate adsorption mechanism of MZION followed the inner-sphere complexing mechanism, and the surface −OH groups played a significant role in the phosphate adsorption. Additionally, the main

  12. Oxide characterization and hydrogen behaviors of Zr-based alloys

    International Nuclear Information System (INIS)

    Kim, Y. S.; Kim, D. J.; Kwon, S. H.; Lee, H. S.; Oh, S. J.; Yim, B. J.; Son, S. B.; Yun, S. P.

    2006-03-01

    The work scope and contents of the research are as follows : basic properties of zirconium alloys, hydrogen pick-up mechanism of zirconium alloy, effects of hydride on the corrosion behaviors of zirconium alloys, estimation on stress of oxide layer in the zirconium alloy, microstructure and characteristic of oxide in pre-hydrided zirconium alloys

  13. Low temperature internal friction in pure iron charged with hydrogen or deuterium

    International Nuclear Information System (INIS)

    Moser, P.; Dufresne, J.F.; Ritchie, I.G.

    1977-01-01

    The search for the elusive hydrogen Snoek-peak in pure iron has been continued with specimens charged with either hydrogen or deuterium. The peaks observed are attributed to deformation produced during charging and can be classified as an α-type peak and a Snoek-Koester type peak. The detailed behavior of these peaks during systematic outgassing of hydrogen or deuterium is described

  14. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

    A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.

  15. Hydrogen absorption-desorption at metal surfaces

    International Nuclear Information System (INIS)

    Ward, C.A.; Pataki, L.

    1991-04-01

    On the basis of experimental studies, it has been proposed that when zirconium oxide (ZrO 2 ) is exposed to hydrogen at 300 degrees C or higher, a reaction occurs to produce metallic zirconium and water, thereby increasing the electrical conductivity of the oxide film and its permeability to hydrogen. A series of experiments has been performed in which specimens of zirconium and zirconium-2.5% niobium were either hydrided or deuterided in a furnace at a temperature between 300 degrees C and 800 degrees C and in an atmosphere that consisted primarily of either hydrogen (H 2 ) or deuterium (D 2 ). After cooling a specimen to room temperature, it was placed in a thermogravimetric analyzer that was equipped with a mass spectrometer, TGA-MS. Each specimen was then heated to 1200 degrees C at a controlled rate in a primarily helium atmosphere monitored with the mass spectrometer. Light water (H 2 O) evolved from the hydrided specimens and heavy water (D 2 0) from the deuterided ones and there was a weight loss of the specimens that accompanied the water evolution. The specimens having approximately the same amount of hydride but more oxide also evolved more H 2 O, and that the H 2 O did not come from reactions between impurity H 2 and oxygen (O 2 ) in the TGA-MS. Heating a zirconium or zirconium alloy specimen that contains a hydride or deuteride phase within and an oxide layer on its surface causes the hydrogen to diffuse toward the surface and when it encounters the oxide a reaction follows that produces water. The conventional mechanism for the dissipation of the imperviousness of ZrO 2 to H 2 that results from the oxide being exposed to a reducing atmosphere will not explain the water production observed in these experiments. However, the existence of the proposed reaction can account for the elevated hydrogen concentration in an oxide film that has been observed to accompany the aqueous corrosion of zirconium and the effects on both the electrical conductivity and

  16. Hydrogen-Bonding Interactions Trigger a Spin-Flip in Iron(III) Porphyrin Complexes**

    Science.gov (United States)

    Sahoo, Dipankar; Quesne, Matthew G; de Visser, Sam P; Rath, Sankar Prasad

    2015-01-01

    A key step in cytochrome P450 catalysis includes the spin-state crossing from low spin to high spin upon substrate binding and subsequent reduction of the heme. Clearly, a weak perturbation in P450 enzymes triggers a spin-state crossing. However, the origin of the process whereby enzymes reorganize their active site through external perturbations, such as hydrogen bonding, is still poorly understood. We have thus studied the impact of hydrogen-bonding interactions on the electronic structure of a five-coordinate iron(III) octaethyltetraarylporphyrin chloride. The spin state of the metal was found to switch reversibly between high (S=5/2) and intermediate spin (S=3/2) with hydrogen bonding. Our study highlights the possible effects and importance of hydrogen-bonding interactions in heme proteins. This is the first example of a synthetic iron(III) complex that can reversibly change its spin state between a high and an intermediate state through weak external perturbations. PMID:26109743

  17. Fluorometric determination of zirconium in minerals

    Science.gov (United States)

    Alford, W.C.; Shapiro, L.; White, C.E.

    1951-01-01

    The increasing use of zirconium in alloys and in the ceramics industry has created renewed interest in methods for its determination. It is a common constituent of many minerals, but is usually present in very small amounts. Published methods tend to be tedious, time-consuming, and uncertain as to accuracy. A new fluorometric procedure, which overcomes these objections to a large extent, is based on the blue fluorescence given by zirconium and flavonol in sulfuric acid solution. Hafnium is the only element that interferes. The sample is fused with borax glass and sodium carbonate and extracted with water. The residue is dissolved in sulfuric acid, made alkaline with sodium hydroxide to separate aluminum, and filtered. The precipitate is dissolved in sulfuric acid and electrolysed in a Melaven cell to remove iron. Flavonol is then added and the fluorescence intensity is measured with a photo-fluorometer. Analysis of seven standard mineral samples shows excellent results. The method is especially useful for minerals containing less than 0.25% zirconium oxide.

  18. Well-defined single-site monohydride silica-supported zirconium from azazirconacyclopropane

    KAUST Repository

    Hamzaoui, Bilel

    2015-01-13

    The silica-supported azazirconacyclopropane ≡SiOZr(HNMe2)(η2-NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150°C) to the single-site monopodal monohydride silica-supported zirconium species ≡SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by contacting compound 2 with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200°C revealed alkene hydrogenation.

  19. Well-defined single-site monohydride silica-supported zirconium from azazirconacyclopropane

    KAUST Repository

    Hamzaoui, Bilel; El Eter, Mohamad; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Basset, Jean-Marie

    2015-01-01

    The silica-supported azazirconacyclopropane ≡SiOZr(HNMe2)(η2-NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150°C) to the single-site monopodal monohydride silica-supported zirconium species ≡SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by contacting compound 2 with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200°C revealed alkene hydrogenation.

  20. Study of the microstructural and mechanical properties of titanium-niobium-zirconium based alloys processed with hydrogen and powder metallurgy for use in dental implants

    International Nuclear Information System (INIS)

    Duvaizem, Jose Helio

    2009-01-01

    Hydrogen has been used as pulverization agent in alloys based on rare earth and transition metals due to its extremely high diffusion rate even on low temperatures. Such materials are used on hydrogen storage dispositives, generation of electricity or magnetic fields, and are produced by a process which the first step is the transformation of the alloy in fine powder by miling. Besides those, hydrogenium is also being used to obtain alloys based on titanium - niobium - zirconium in the pulverization. Powder metallurgy is utilized on the production of these alloys, making it possible to obtain structures with porous surface as result, requirement for its application as biomaterials. Other advantages of powder metallurgy usage include better surface finish and better microstructural homogeneity. In this work samples were prepared in the Ti-13Nb-13Zr composition. The hydrogenation was performed at 700 degree C, 600 degree C, and 500 degree C for titanium, niobium and zirconium respectively. After hydrogenation, the milling stage was carried out on high energy planetary ball milling with 200rpm during 90 minutes, and also in conventional ball milling for 30 hours. Samples were pressed in uniaxial press, followed by isostatic cold press, and then sintered at 1150 degree C for 7-13 hours. Microstructural properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and x-ray diffraction. Mechanical and structural properties determined were density, microhardness and moduli of elasticity. The sample sintered at 1150 degree C for 7h, hydrogenated using 10.000 mbar and produced by milling on high energy planetary ball milling presented the best mechanical properties and microstructural homogeneity. (author)

  1. Application of cylinder symmetry to iron and titanium oxidation by oxygen or hydrogen-water vapour mixes

    International Nuclear Information System (INIS)

    Raynaud, Pierre

    1980-01-01

    This research thesis addresses the study of the oxidation reaction in the case of corrosion of iron by oxygen, hydrogen sulphide or hydrogen-water vapour mixes, and in the case of oxidation of titanium and of titanium nitride by hydrogen-water vapour mixes. It first addresses the corrosion of iron by oxygen with an experiment performed in cylinder symmetry: description of operational conditions, discussion of kinetic curves, development of a law of generation of multiple layers in cylinder symmetry, analytical exploitation of experimental results. The second part addresses the oxidation of iron by hydrogen-water vapour mixes: experimental conditions, influence of temperature on kinetics, micrographic study (oxide morphology, coating morphology, interpretation of differences with the case of plane symmetry), discussion of the influence of cylinder symmetry on oxidation kinetics. The third part addresses the oxidation of titanium by hydrogen-water vapour mixes: global kinetic evolution, reaction products and micrographic examination, morphology and texture studies, discussion of the oxidation mechanism and of cylinder symmetry [fr

  2. An iron-57 Moessbauer spectroscopic study of titania-supported iron- and iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1992-01-01

    57 Fe Moessbauer spectroscopy shows that titania-supported iron is reduced by treatment in hydrogen at significantly lower temperatures than corresponding silica- and alumina-supported catalysts. The metallic iron formed under hydrogen at 600deg C is partially converted to carbide by treatment in carbon monoxide and hydrogen. In contrast to its alumina- and silica-supported counterparts, the remainder of the titania-supported iron is unchanged by this gaseous mixture. The 57 Fe Moessbauer spectra of EXAFS show that iron and iridium in the titania-supported iron-iridium catalysts are reduced in hydrogen at even lower temperatures and, after treatment at 600deg C, are predominantly present as the iron-iridium alloy. The treatment of these reduced catalysts in carbon monoxide and hydrogen is shown by Moessbauer spectroscopy and EXAFS to induce the segregation of iron from the iron-iridium alloy and its conversion to iron oxide. (orig.)

  3. Development of Zirconium alloys (for pressure tubes)

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kwon, Sang Chul; Choo, Ki Nam; Jung, Chung Hwan; Yim, Kyong Soo; Kim, Sung Soo; Baek, Jong Hyuk; Jeong, Yong Hwan; Kim, Kyong Ho; Cho, Hae Dong [Korea Atomic Energy Research Inst., Daeduk (Korea, Republic of); Hwang, S. K.; Kim, M. H. [Inha Univ., Incheon (Korea, Republic of); Kwon, S. I [Korea Univ., Seoul (Korea, Republic of); Kim, I. S. [Korea Advanced Inst. of Science and Technology, Taejon (Korea, Republic of)

    1997-09-01

    The objective of this research is to set up the basic technologies for the evaluation of pressure tube integrity and to develop improved zirconium alloys to prevent pressure tube failures due to DHC and hydride blister caused by excessive creep-down of pressure tubes. The experimental procedure and facilities for characterization of pressure tubes were developed. The basic research related to a better understanding of the in-reactor performances of pressure tubes leads to noticeable findings for the first time : the microstructural effect on corrosion and hydrogen pick-up behavior of Zr-2.5Nb pressure tubes, texture effect on strength and DHC resistance and enhanced recrystallization by Fe in zirconium alloys and etc. Analytical methodology for the assessment of pressure tubes with surface flaws was set up. A joint research is being under way with AECL to determine the fracture toughness of O-8 at the EOL (End of Life) that had been quadruple melted and was taken out of the Wolsung Unit-1 after 10 year operation. In addition, pressure tube with texture controlled is being made along with VNINM in Russia as a joint project between KAERI and Russia. Finally, we succeeded in developing 4 different kinds of zirconium alloys with better corrosion resistance, low hydrogen pickup fraction and higher creep strength. (author). 121 refs., 65 tabs., 260 figs

  4. Highly corrosion resistant zirconium based alloy for reactor structural material

    International Nuclear Information System (INIS)

    Ito, Yoichi.

    1996-01-01

    The alloy of the present invention is a zirconium based alloy comprising tin (Sn), chromium (Cr), nickel (Ni) and iron (Fe) in zirconium (Zr). The amount of silicon (Si) as an impurity is not more than 60ppm. It is preferred that Sn is from 0.9 to 1.5wt%, that of Cr is from 0.05 to 0.15wt%, and (Fe + Ni) is from 0.17 to 0.5wt%. If not less than 0.12wt% of Fe is added, resistance against nodular corrosion is improved. The upper limit of Fe is preferably 0.40wt% from a view point of uniform suppression for the corrosion. The nodular corrosion can be suppressed by reducing the amount of Si-rich deposition product in the zirconium based alloy. Accordingly, a highly corrosion resistant zirconium based alloy improved for the corrosion resistance of zircaloy-2 and usable for a fuel cladding tube of a BWR type reactor can be obtained. (I.N.)

  5. Fretting wear behavior of zirconium alloy in B-Li water at 300 °C

    Science.gov (United States)

    Zhang, Lefu; Lai, Ping; Liu, Qingdong; Zeng, Qifeng; Lu, Junqiang; Guo, Xianglong

    2018-02-01

    The tangential fretting wear of three kinds of zirconium alloys tube mated with 304 stainless steel (SS) plate was investigated. The tests were conducted in an autoclave containing 300 °C pressurized B-Li water for tube-on-plate contact configuration. The worn surfaces were examined with scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and 3D microscopy. The cross-section of wear scar was examined with transmission electron microscope (TEM). The results indicated that the dominant wear mechanism of zirconium alloys in this test condition was delamination and oxidation. The oxide layer on the fretted area consists of outer oxide layer composed of iron oxide and zirconium oxide and inner oxide layer composed of zirconium oxide.

  6. Out-of-pile test of zirconium cladding simulating reactivity initiated accident

    Energy Technology Data Exchange (ETDEWEB)

    Kim, J. H.; Lee, M. H.; Choi, B. K.; Bang, J. K.; Jung, Y. H. [KAERI, Taejon (Korea, Republic of)

    2004-07-01

    Mechanical properties of zirconium cladding such as Zircaloy-4 and advanced cladding were evaluated by ring tension test to simulate Reactivity-Initiated Accident (RIA) as an out-pile test. Cladding was hydrided by means of charging hydrogen up to 1000ppm to simulate high-burnup situation, finally fabricated to circumferential tensile specimen. Ring tension test was carried out from 0.01 to 1/sec to keep pace with actual RIA event. The results showed that mechanical strength of zirconium cladding increased at the value of 7.8% but ductility decreased at the 34% as applied strain rate and absorbed hydrogen increased. Further activities regarding out-of-pile testing plans for simulated high-burnup cladding were discussed in this paper.

  7. Hydrogen-bearing iron peroxide and the origin of ultralow-velocity zones

    Science.gov (United States)

    Liu, Jin; Hu, Qingyang; Young Kim, Duck; Wu, Zhongqing; Wang, Wenzhong; Xiao, Yuming; Chow, Paul; Meng, Yue; Prakapenka, Vitali B.; Mao, Ho-Kwang; Mao, Wendy L.

    2017-11-01

    Ultralow-velocity zones (ULVZs) at Earth’s core-mantle boundary region have important implications for the chemical composition and thermal structure of our planet, but their origin has long been debated. Hydrogen-bearing iron peroxide (FeO2Hx) in the pyrite-type crystal structure was recently found to be stable under the conditions of the lowermost mantle. Using high-pressure experiments and theoretical calculations, we find that iron peroxide with a varying amount of hydrogen has a high density and high Poisson ratio as well as extremely low sound velocities consistent with ULVZs. Here we also report a reaction between iron and water at 86 gigapascals and 2,200 kelvin that produces FeO2Hx. This would provide a mechanism for generating the observed volume occupied by ULVZs through the reaction of about one-tenth the mass of Earth’s ocean water in subducted hydrous minerals with the effectively unlimited reservoir of iron in Earth’s core. Unlike other candidates for the composition of ULVZs, FeO2Hx synthesized from the superoxidation of iron by water would not require an extra transportation mechanism to migrate to the core-mantle boundary. These dense FeO2Hx-rich domains would be expected to form directly in the core-mantle boundary region and their properties would provide an explanation for the many enigmatic seismic features that are observed in ULVZs.

  8. Experiments on interactions between zirconium-containing melt and water (ZREX). Hydrogen generation and chemical augmentation of energetics

    Energy Technology Data Exchange (ETDEWEB)

    Cho, D.H.; Armstrong, D.R.; Gunther, W.H. [Argonne National Lab., IL (United States); Basu, S.

    1998-01-01

    The results of the first data series of experiments on interactions between zirconium-containing melt and water are described. These experiments involved dropping 1-kg batches of pure zirconium or zirconium-zirconium dioxide mixture melt into a column of water. A total of nine tests were conducted, including four with pure zirconium melt and five with Zr-ZrO{sub 2} mixture melt. Explosions took place only in those tests which were externally triggered. While the extent of zirconium oxidation in the triggered experiments was quite extensive, the estimated explosion energetics were found to be very small compared to the combined thermal and chemical energy available. (author)

  9. Formation of zirconium dioxide layers on microelectrode of zirconium. Inhibition of the hydrogen evolution reaction

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Lubomír; Fanelli, N.; Hromadová, Magdaléna

    2017-01-01

    Roč. 49, C (2017), s. 128-133 ISSN 0324-1130 R&D Projects: GA ČR(CZ) GA16-03085S Institutional support: RVO:61388955 Keywords : zirconium * ZrO2 * corrosion Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 0.238, year: 2016

  10. Hydrogen-bearing iron peroxide and its implications to the deep Earth

    Science.gov (United States)

    Liu, J.; Hu, Q.; Kim, D. Y.; Wu, Z.; Wang, W.; Alp, E. E.; Yang, L.; Xiao, Y.; Meng, Y.; Chow, P.; Greenberg, E.; Prakapenka, V. B.; Mao, H. K.; Mao, W. L.

    2017-12-01

    Hydrous materials subducted into the deep mantle may play a significant role in the geophysical and geochemical processes of the lower mantle through geological time, but their roles have not become clear yet in the region. Hydrogen-bearing iron peroxide (FeO2Hx) was recently discovered to form through dehydrogenation of goethite (e.g., FeOOH) and the reaction between hematite (Fe2O3) and water under deep lower mantle conditions. We conducted synchrotron Mössbauer, X-ray absorption, and X-ray emission spectroscopy measurements to investigate the electronic spin and valence states of iron in hydrogen-bearing iron peroxide (FeO2Hx) in-situ at high pressures. Combined with theoretical calculations and other high-pressure experiments (i.e., nuclear resonant inelastic x-ray scattering spectroscopy and X-ray diffraction coupled with laser-heated diamond-anvil cell techniques), we find that the intriguing properties of FeO2Hx could shed light on the origin of a number of the observed geochemical and geophysical anomalies in the deep Earth.

  11. Hydrogen solubility in iron, platinum and their alloys under pressure up to 67 kbars

    International Nuclear Information System (INIS)

    Belash, I.T.; Antonov, V.E.; Ponyatovskij, E.G.

    1979-01-01

    The solubility of hydrogen was studied in iron, nickel and Fe-Pt-H alloy at a high pressure. It was shown that at T=250 deg C and psub(Hsub(2))=67 kbar, the solubility hy of hydrogen in α-iron and platinum is below the sensitivity threshold of the employed method of chemical analysis, deltasub(n) approximately 0.05 (n - atomic ratio hydrogen metal). At this pressure and at a temperature of T=150 deg C, the equilibrium concentration of hydrogen in non-ordered Fe-Pt alloys with a FCC lattice, containing 25 and 32 at. % Pt, attains, respectively, n = (5+-2)x10 -2 and (2+-5)x10 -2 . Ordering of the alloy with 25 at. % Pt produces no substantial change in the solubility of hydrogen. In a hydrogen atmosphere, the dependence of the Curie point Tsub(c)(psub(Hsub(2)) deviates from Tsub(c)(p). In an inert medium, at p=67 kbar, ΔTsub(c)=Tsub(c)(psub(Hsub(2)) - Tsub(c)(p) = 35+-10 deg C

  12. Hydrogen-bearing iron peroxide and the origin of ultralow-velocity zones

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jin; Hu, Qingyang; Kim, Duck Young; Wu, Zhongqing; Wang, Wenzhong; Xiao, Yuming; Chow, Paul; Meng, Yue; Prakapenka, Vitali B.; Mao, Ho-Kwang; Mao, Wendy L. (Stanford); (UST - China); (CIW); (UC); (CHPSTAR- China)

    2017-11-22

    Ultralow-velocity zones (ULVZs) at Earth’s core–mantle boundary region have important implications for the chemical composition and thermal structure of our planet, but their origin has long been debated1,2,3. Hydrogen-bearing iron peroxide (FeO2Hx) in the pyrite-type crystal structure was recently found to be stable under the conditions of the lowermost mantle4,5,6. Using high-pressure experiments and theoretical calculations, we find that iron peroxide with a varying amount of hydrogen has a high density and high Poisson ratio as well as extremely low sound velocities consistent with ULVZs. Here we also report a reaction between iron and water at 86 gigapascals and 2,200 kelvin that produces FeO2Hx. This would provide a mechanism for generating the observed volume occupied by ULVZs through the reaction of about one-tenth the mass of Earth’s ocean water in subducted hydrous minerals with the effectively unlimited reservoir of iron in Earth’s core. Unlike other candidates for the composition of ULVZs7,8,9,10,11,12, FeO2Hx synthesized from the superoxidation of iron by water would not require an extra transportation mechanism to migrate to the core–mantle boundary. These dense FeO2Hx-rich domains would be expected to form directly in the core–mantle boundary region and their properties would provide an explanation for the many enigmatic seismic features that are observed in ULVZs.

  13. Preliminary radiation-oxidizing treatment influence on radiation-catalytic activity of zirconium during water decomposition process

    International Nuclear Information System (INIS)

    Garibov, A.A.; Aliyev, A.G.; Agayev, T.N.; Aliyev, S.M.; Velibekova, G.Z.

    2004-01-01

    The study of physical-chemical processes proceeding in contact of metal constructional materials nuclear reactors with water at simultaneous influence of temperature and radiation represents the large interest at the decision of problems material authority and safety of work of nuclear -power installations [1-2]. One of the widely widespread materials of active zone nuclear reactors is metal zirconium and its alloys. The influence of preliminary radiation processing on radiation, radiation -thermal and thermal processes of accumulation of molecular hydrogen and oxidation zirconium in contact with water is investigated at T=673 K and ρ=5mg/sm 3 [3-4]. Initial samples zirconium previously has been exposed by an irradiation in medium H 2 O 2 at D=20-410 kGy. The contribution of radiation processes in these contacts in process thermo-radiation decomposition of water and oxidation of materials of zirconium is revealed. It is established that the interaction of Zr metal, preliminary treated by radiation, with water at radiation -heterogeneous processes leads to passivity of a surface. The rate meanings of thermal, radiation -thermal processes and radiation-chemical yields of hydrogen are determined. It is revealed, that at radiation-heterogeneous processes in system Zr +H 2 O (ρ =5mg/sm 3 T=673 K) the increase of the absorbed doze up to 123 kGy results to reduction of a radiation -chemical yield of molecular hydrogen. The further increase of the absorbed doze results to increase of a radiation -chemical yield of hydrogen. The observable effect at the preliminary radiation of zirconium is connected to formation of oxide phase on a surface. The mechanism of radiation -heterogeneous processes proceeding in system Zr+H 2 O is suggested. (author)

  14. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama

    2016-09-29

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  15. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama; Alandini, Nurtalya; Rueping, Magnus

    2016-01-01

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  16. Hydride precipitation, fracture and plasticity mechanisms in pure zirconium and Zircaloy-4 at temperatures typical for the postulated loss-of-coolant accident

    International Nuclear Information System (INIS)

    Pshenichnikov, Anton; Stuckert, Juri; Walter, Mario

    2016-01-01

    Highlights: • All δ-hydrides in Zr and Zircaloy-4 have basal or pyramidal types of habit planes. • Seven orientation relationships for δ-hydrides in Zr matrix were detected. • Decohesion fracture mechanism of hydrogenated Zr was investigated by fractography. - Abstract: The results of investigations of samples of zirconium and its alloy Zircaloy-4, hydrogenated at temperatures 900–1200 K (typical temperatures for loss-of-coolant accidents) are presented. The analyses, based on a range of complementary techniques (X-ray diffraction, scanning electron microscopy, electron backscatter diffraction) reveals the direct interrelation of internal structure transformation and hydride distribution with the degradation of mechanical properties. Formation of small-scale zirconium hydrides and their bulk distribution in zirconium and Zircaloy-4 were investigated. Fractographical analysis was performed on the ruptured samples tested in a tensile machine at room temperature. The already-known hydrogen embrittlement mechanisms based on hydride formation and hydrogen-enhanced decohesion and the applicability of them in the case of zirconium and its alloys is discussed.

  17. Accelerated irradiation growth of zirconium alloys

    International Nuclear Information System (INIS)

    Griffiths, M.; Gilbert, R.W.; Fidleris, V.

    1989-01-01

    This paper discusses how sponge zirconium and Zr-2.5 wt% Nb, Zircaloy, or Excel alloys all exhibit accelerated irradiation growth compared with high-purity crystal-bar zirconium for irradiation temperatures between 550 to 710 K and fluences between 0.1 to 10 x 10 25 n · m -2 (E > 1 MeV). There is generally an incubation period or fluence before the onset of accelerated or breakaway growth, which is dependent on the particular material being irradiated, its metallurgical condition before irradiation, and the irradiation temperature. Transmission electron microscopy has shown that there is a correlation between accelerated irradiation growth and the appearance of c-component vacancy loops on basal planes. Measurements in some specimens indicate that a significant fraction of the strain can be directly attributed to the loops themselves. There is considerable evidence to show that their formation is dependent both on the specimen purity and on the irradiation temperature. Materials that have a high interstitial-solute content contain c-component loops and exhibit high growth rates even at low fluences ( 2 :5 n · m -2 , E > 1 MeV). For sponge zirconium and the Zircaloys, c-component loop formation and the associated acceleration of growth (breakaway) during irradiation occurs because the intrinsic interstitial solute (mainly, oxygen, carbon and nitrogen) in the zirconium matrix is supplemented by interstitial iron, chromium, and nickel from the radiation-induced dissolution of precipitates. (author)

  18. Waterside corrosion of zirconium alloys in nuclear power plants

    International Nuclear Information System (INIS)

    1998-01-01

    Technically the study of corrosion of zirconium alloys in nuclear power reactors is a very active field and both experimental work and understanding of the mechanisms involved are going through rapid changes. As a result, the lifetime of any publication in this area is short. Because of this it has been decided to revise IAEA-TECDOC-684 - Corrosion of Zirconium Alloys in Nuclear Power Plants - published in 1993. This updated, revised and enlarged version includes major changes to incorporate some of the comments received about the first version. Since this review deals exclusively with the corrosion of zirconium and zirconium based alloys in water, and another separate publication is planned to deal with the fuel-side corrosion of zirconium based fuel cladding alloys, i.e. stress corrosion cracking, it was decided to change the original title to Waterside Corrosion of Zirconium Alloys in Nuclear Power Plants. The rapid changes in the field have again necessitated a cut-off date for incorporating new data. This edition incorporates data up to the end of 1995; including results presented at the 11 International Symposium on Zirconium in the Nuclear Industry held in Garmisch-Partenkirchen, Germany, in September 1995. The revised format of the review now includes: Introductory chapters on basic zirconium metallurgy and oxidation theory; A revised chapter discussing the present extent of our knowledge of the corrosion mechanism based on laboratory experiments; a separate and revised chapter discussing hydrogen uptake; a completely reorganized chapter summarizing the phenomenological observations of zirconium alloy corrosion in reactors; a new chapter on modelling in-reactor corrosion; a revised chapter devoted exclusively to the manner in which irradiation might influence the corrosion process; finally, a summary of our present understanding of the corrosion mechanisms operating in reactor

  19. Neutron-induced hydrogen and helium production in iron

    Energy Technology Data Exchange (ETDEWEB)

    Haight, Robert C.

    2004-01-01

    In support of the Advanced Fuel Cycle Initiative, cross sections for hydrogen and helium production by neutrons are being investigated on structural materials from threshold to 100 MeV with the continuous-in-energy spallation neutron source at the Los Alamos Neutron Science Center (LANSCE). The present measurements are for elemental iron. The results are compared with values from the ENDF/B-VI library and its extension with LA150 evaluations. For designs in the Advanced Fuel Cycle Initiative, structural materials will be subjected to very large fluences of neutrons, and the selection of these materials will be guided by their resistance to radiation damage. The macroscopic effects of radiation damage result both from displacement of atoms in the materials as well as nuclear transmutation. We are studying the production of hydrogen and helium by neutrons, because these gases can lead to significant changes in materials properties such as embrittlement and swelling. Our experiments span the full range from threshold to 100 MeV. The lower neutron energies are those characteristic of fission neutrons, whereas the higher energies are relevant for accelerator-based irradiation test facilities. Results for the nickel isotopes, {sup 58,60}Ni, have been reported previously. The present studies are on natural iron.

  20. Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

    Science.gov (United States)

    Khan, M. N.; Shamim, T.

    2017-08-01

    Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

  1. Preparation of highly-oxidized starch using hydrogen peroxide and its application as a novel ligand for zirconium tanning of leather.

    Science.gov (United States)

    Yu, Yue; Wang, Ya-Nan; Ding, Wei; Zhou, Jianfei; Shi, Bi

    2017-10-15

    A series of highly-oxidized starch (HOS) were prepared using H 2 O 2 and a copper-iron catalyst as a desired ligand for zirconium tanning of leather. The effects of catalyst and H 2 O 2 dosages, and reaction temperature on the oxidation degree (OD, represented as the amount of carbonyl and carboxyl groups derived) of starch were investigated. The OD reached 76.2% when oxidation was conducted using 60% H 2 O 2 and 0.015% catalyst at 98°C for 2h. 13 C NMR and FT-IR illustrated carbonyl and carboxyl groups were formed in HOS after oxidation. GPC and laser particle size analyses indicated the decrease of HOS molecular size with increasing H 2 O 2 dosage and OD. HOS with moderate OD and molecular weight was able to coordinate with zirconium and remarkably improve tanning process. Leather tanned by Zr complexes using HOS-60 (60% H 2 O 2 , Mn 3516g/mol) as ligand presented considerably better physical and organoleptic properties than those of traditional Zr-tanned leather. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Methods for determination of zirconium in titanium alloys

    International Nuclear Information System (INIS)

    1985-01-01

    Two methods for determining zirconium content in titanium alloys are specified in this standard. One is the ion-exchange/mandelic acid gravimetry for Zr content below 20 % down to 1 % while the other is the mandelic acid gravimetry for Zr content below 20 % down to 0.5 %. In the former, a specimen is decomposed by hydrochloric acid and hydrofluoric acid. After substances such as titanium are oxidized by adding nitric acid, the liquid is adjusted into a 4N hydrochloric acid - gN hydrofluoric acid solution, which is them passed through an ion-exchange column. The niobium and tantalum contents are absorbed while the titanium and zirconium contents flow out. Perchloric acid and sulfuric acid are poured in the solution to remove hydrofluoric acid. Aqueous ammonia is added to produce hydroxide of titanium and zirconium, which is then filtered out. The hydroxyde is dissolved in hydrochloric acid, and mandelic acid is poured to precipitate the zirconium content. The precipitate is ignited and the weight of the oxide formed is measured. The coprecipitated titanium content is determined by the absorptiometric method using hydrogen peroxide. Finally, the weight of the oxide is corrected. In the latter determination method, on the other hand, only several steps of the above procedure are used, namely, decomposition by hydrochloric acid, precipitation of zirconium, ignition of precipitate, measurement of oxide weight and weight correction. (Nogami, K.)

  3. Investigation of Hydrogen and Nitrogen Content in Compacted Graphite Iron Production

    OpenAIRE

    Siafakas, Dimitrios

    2013-01-01

    The aim of this research, part of a wider program called SPOFIC, is to investigate how the casting procedure affects the concentration of hydrogen and nitrogen gases in Compacted Graphite Iron used for the production of truck cylinder blocks. Hydris equipment was used for the Hydrogen measurements and the Optical Emission Spectroscopy and combustion analysis methods were used for the nitrogen measurements. The experiment was performed in one of the cooperating foundries. It was found that Hyd...

  4. The Effect of Hydrogen on the Mechanical Properties of Cast Irons and ADI with Various Carbon Equivalent and Graphite Morphology

    International Nuclear Information System (INIS)

    Cho, Yong Gi; Lee, Kyung Sub

    1989-01-01

    The effect of hydrogen on the mechanical properties of cast irons, flake, CV graphite cast iron ductile iron and ADI have been investigated. The effects of various carbon equivalent, graphite morphology and matrix have been analyzed to determine the predominant factor which influences on the hydrogen embrittlement. The effect of various carbon equivalent on the embrittlement was little in the similar graphite morphology. The embrittlement of ferrite matrix changed by heat treatment was less than that of pearlite matrix. In the case of ADI, the tendency of hydrogen embrittlement of lower bainite matrix was less remarkable than that of upper banite matrix. As the result of hydrogen charging, the tendency of interface decohesion between matrix-graphite was increased in flake G.C.I., and the trend from ductile fracture mode to brittle fracture mode was observed in CV G.C.I and ductile iron. Lower bainite in ADI showed the ductile fracture mode. Hydrogen solubility of lower bainite was higher than that of upper bainite

  5. A microstuctural study on accelerated zirconium alloy oxidation

    International Nuclear Information System (INIS)

    Sohn, Seung Bum; Oh, Seung Jun; Jang, Jung Nam; Kim, Yong Soo; Jung, Yong Hwan; Baek, Jong Hyuk; Park, Jung Yong

    2005-01-01

    It has been reported that the effect of thermal redistribution of hydrides across the zirconium metaloxide interface, coupled with thermal feedback on the metal-oxide interface, is a dominating factor in the accelerated oxidation in zirconium alloys cladding PWR fuel. Basically this influence determines characteristic of oxide layer. Influence estimation for corrosion oxide layer due to hydrogen / hydride carried out because of investigation on the kinetic on accelerated oxidation due to hydride precipitation was preceded. Generally, it is known that ZrO 2 tetragonal layer structures play an important role as a barrier layer. So analysing the ZrO 2 monoclinic and tetragonal structure distribution is our main aim. Especially, this study focused on the hydride effects. In other words, the difference of crystal structure distribution between pre-hydrided and without hydrided specimen is just expected results. Experimental results of microstructure at zirconium metal-oxide interface through TEM and EBSD analysis was confirmed

  6. The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

    Science.gov (United States)

    Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

    2013-04-28

    The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

  7. Long-time corrosion and high-temperature oxidation of zirconium alloys applied on NPP like fuel elements cover

    International Nuclear Information System (INIS)

    Vrtilkova, V.; Novotny, L.; Lingart, S.; Doukha, R.; Yarosh, Ya.; Kolenchik, Ya.

    2007-01-01

    Zirconium is applying in nuclear energy since 50-th of last century in capacity of material for cover production for fuel elements, reactor fuel and structural parts, and mainly due to both corrosion stability and low effective cross section for thermal neutrons capture. Impurities in doping elements form and alloy production technology has influence on mechanical and corrosion properties of finite alloy. Long-time corrosion tests for several zirconium alloys in forcing autoclave under different reaction conditions were carried out. After that process kinetics was studied, mass increase, hydrogen formation, zirconium hydride forming morphology, zirconium oxide layer thickness have been determined as well

  8. Storage and characterization of the hydrogen in mixed oxides on base of cerium-nickel and zirconium or the aluminium

    International Nuclear Information System (INIS)

    Debeusscher, S.

    2008-12-01

    The mixed oxides based on cerium-nickel and zirconium or aluminium are able to store large quantities of hydrogen, To determine nature, reactivity and properties of hydrogen species (spill-over, direct desorption), the solid were studied by different physicochemical techniques in the dried, calcined and partially reduced states: XRD, porosity, TGA, TPR, TPA, TPD, chemical titration and inelastic neutron scattering (INS). Solids are mainly meso-porous with a common pore size at 4 nm, They are constituted of CeO 2 phase, Ce-Ni or Ce-Ni-Zr solid solution and of Ni(OH) 2 in the dried state and NiO in the calcined state. The Ni species are in various environments and the strong interactions between the cations in solid solution and at different particles interface influence their reducibility and the creation of anionic vacancies. Activation in H 2 in temperature is determining for hydrogen storage in the solid while calcination step is not necessary. INS Analyses evidence that the hydrogen species inserted during treatment in H 2 are H + (OH - ), hydride H - and H * (metallic nickel) species, present in various chemical environments, in particular for hydride species. All kinds of hydrogen species participate to the reaction during the chemical titration in agreement with the proposed hydrogenation mechanism. The study of the adsorption of hydrogen shows that this step is fast and in quantity of the same order as that measured by chemical titration. The direct desorption of H 2 is very low, linked to the presence of hydrogen in interaction with metallic nickel (H *- .). Desorption of water is also observed, in parallel, corresponding to the elimination of groups. The hydride species are not desorbed. These various observations allow connecting hydrogen species properties with their localization in the structure and to model active sites. (author)

  9. The solubility and diffusivity of hydrogen in well-annealed and deformed iron

    International Nuclear Information System (INIS)

    Kiuchi, K.; McLellan, R.B.

    1983-01-01

    It has been shown that a large volume of data for the solubility of hydrogen in iron is affected by spurious surface conditions. Arrhenius plots of solubility data in the temperature range 300-1750 K, which are free of such effects, exhibit a temperature variation which, despite the low H-solubility in the entire temperature range, is not consistent with regular mixing statistics. This departure from regular behavior is consistent with the thermal activation of H atoms into energetically less favorable octahedral sites as the temperature is increased. The enhancement in H-solubility caused by the cold deformation of iron can be understood in terms of a simple Maxwell-Boltzmann distribution of H atoms between ''normal'' lattice sites and ''trapping'' sites of depth 34 kJ/mol. The 62 currently existing sets of data for the diffusivity of hydrogen through b.c.c. iron exhibit a large degree of mutual inconsistency. Exhaustive statistical analysis of this large data mass has shown that only those data obtained by electrochemical methods and H 2 -gas equilibration methods using UHV techniques and Pd-coated membranes are reliable. The problem of H-diffusion in deformed iron has been analysed using a semi-quantitative model in which the retarding effect of trapping sites on the diffusivity is partially compensated by a ''pipe'' diffusion contribution along dislocations. It is shown that this model is in accord with the diffusivities measured in deformed iron when data not encumbered by spurious surface effects are considered

  10. Experimental study and modelling of iron ore reduction by hydrogen

    International Nuclear Information System (INIS)

    Wagner, D.

    2008-01-01

    In an effort to find new ways to drastically reduce the CO 2 emissions from the steel industry (ULCOS project), the reduction of iron ore by pure hydrogen in a shaft furnace was investigated. The work consisted of literature, experimental, and modelling studies. The chemical reaction and its kinetics were analysed on the basis of thermogravimetric experiments and physicochemical characterizations of partially reduced samples. A specific kinetic model was designed, which simulates the successive reactions, the different steps of mass transport, and possible iron sintering, at the particle scale. Finally, a 2-dimensional numerical model of a shaft furnace was developed. It depicts the variation of the solid and gas temperatures and compositions throughout the reactor. One original feature of the model is using the law of additive characteristic times for calculating the reaction rates. This allowed us to handle both the particle and the reactor scale, while keeping reasonable calculation time. From the simulation results, the influence of the process parameters was assessed. Optimal operating conditions were concluded, which reveal the efficiency of the hydrogen process. (author)

  11. Hydrogen diffusion in the elastic fields of dislocations in iron

    Energy Technology Data Exchange (ETDEWEB)

    Sivak, A. B., E-mail: Sivak-AB@nrcki.ru; Sivak, P. A. [National Research Centre Kurchatov Institute (Russian Federation); Romanov, V. A.; Chernov, V. M. [National Research Tomsk State University (Russian Federation)

    2016-12-15

    The effect of dislocation stress fields on the sink efficiency thereof is studied for hydrogen interstitial atoms at temperatures of 293 and 600 K and at a dislocation density of 3 × 10{sup 14} m{sup –2} in bcc iron crystal. Rectilinear full screw and edge dislocations in basic slip systems 〈111〉(110), 〈111〉(112), 〈100〉(100), and 〈100〉(110) are considered. Diffusion of defects is simulated by means of the object kinetic Monte Carlo method. The energy of interaction between defects and dislocations is calculated using the anisotropic theory of elasticity. The elastic fields of dislocations result in a less than 25% change of the sink efficiency as compared to the noninteracting linear sink efficiency at a room temperature. The elastic fields of edge dislocations increase the dislocation sink efficiency, whereas the elastic fields of screw dislocations either decrease this parameter (in the case of dislocations with the Burgers vector being 1/2〈111〉) or do not affect it (in the case of dislocations with the Burgers vector being 〈100〉). At temperatures above 600 K, the dislocations affect the behavior of hydrogen in bcc iron mainly owing to a high binding energy between the hydrogen atom and dislocation cores.

  12. On the mechanism of ion exchange in zirconium phosphates

    International Nuclear Information System (INIS)

    Clearfield, A.; Kalnins, J.M.

    1978-01-01

    The exchange of transition metal (M 2+ ) ions from manganese through cobalt, nickel, copper to zinc with γ-zirconium phosphate was examined. By using acetate salts the hydrogen ion concentration is kept low enough to achieve high loadings. The fully loaded solids have the composition ZrM(PO 4 ) 2 .4H 2 O. Near quantitative uptakes are achieved at 100 0 C. The interlayer spacings change very little with loading indicating that γ-zirconium phosphate is able to accommodate cations and water molecules without appreciable increase in volume. The copper exchanged phase readily forms an acetylacetonate when shaken with 2,4-pentanedione. (author)

  13. Identification of the zirconium hydrides metallography in zircaloy-2

    International Nuclear Information System (INIS)

    Garcia Gonzalez, F.

    1968-01-01

    Technique for the Identification of the zirconium hydrides in metallographic specimens have been developed. Microhardness, quantitative estimation and relative orientation of the present hydrides as well as grain size determination of the different Zircaloy-2 tube specimens have also been made. The specimens used were corrosion- tested in water during various periods of time at 300 degree castrating, prior to the metallographic examination. Reference specimens, as received, and heavily hydride specimens in a hydrogen atmosphere at 800 degree centigrees, have been used in the previous stages of the work. No difficulties have been met in this early stage of acquaintanceship with the zirconium hydrides. (Author) 5 refs

  14. Dependency of Delayed Hydride Crack Velocity on the Direction of an Approach to Test Temperatures in Zirconium Alloys

    International Nuclear Information System (INIS)

    Kim, Young Suk; Kim, Kang Soo; Im, Kyung Soo; Ahn, Sang Bok; Cheong, Yong Moo

    2005-01-01

    Recently, Kim proposed a new DHC model where a driving force for the DHC is a supersaturated hydrogen concentration as a result of a hysteresis of the terminal solid solubility (TSS) of hydrogen in zirconium alloys upon a heating and a cooling. This model was demonstrated to be valid through a model experiment where the prior plastic deformation facilitated nucleation of the reoriented hydrides, thus reducing the supersaturated hydrogen concentration at the plastic zone ahead of the crack tip and causing hydrogen to move to the crack tip from the bulk region. Thus, an approach to the test temperature by a cooling is required to create a supersaturation of hydrogen, which is a driving force for the DHC of zirconium alloys. However, despite the absence of the supersaturation of hydrogen due to an approach to the test temperature by a heating, DHC is observed to occur in zirconium alloys at the test temperatures below 180 .deg. C. As to this DHC phenomenon, Kim proposed that stress-induced transformation from γ-hydrides to δ-hydrides is likely to be a cause of this, based on Root's observation that the γ-hydride is a stable phase at temperatures lower than 180 .deg. C. In other words, the hydrides formed at the crack tip would be δ-hydrides due to the stressinduced transformation while the bulk region still maintains the initial hydride phase or γ-hydrides. It should be noted that Ambler has also assumed the crack tip hydrides to be δ-hydrides. When the δ-hydrides or ZrH1.66 are precipitated at the crack tip due to the transformation of the γ-hydrides or ZrH, the crack tip will have a decreased concentration of dissolved hydrogen in zirconium, considering the atomic ratio of hydrogen and zirconium in the γ- and δ-hydrides. In contrast, due to no stress-induced transformation of hydrides, the bulk region maintains the initial concentration of dissolved hydrogen. Hence, there develops a difference in the hydrogen concentration or .C between the bulk and the

  15. Dependency of Delayed Hydride Crack Velocity on the Direction of an Approach to Test Temperatures in Zirconium Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kim, Kang Soo; Im, Kyung Soo; Ahn, Sang Bok; Cheong, Yong Moo [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2005-07-01

    Recently, Kim proposed a new DHC model where a driving force for the DHC is a supersaturated hydrogen concentration as a result of a hysteresis of the terminal solid solubility (TSS) of hydrogen in zirconium alloys upon a heating and a cooling. This model was demonstrated to be valid through a model experiment where the prior plastic deformation facilitated nucleation of the reoriented hydrides, thus reducing the supersaturated hydrogen concentration at the plastic zone ahead of the crack tip and causing hydrogen to move to the crack tip from the bulk region. Thus, an approach to the test temperature by a cooling is required to create a supersaturation of hydrogen, which is a driving force for the DHC of zirconium alloys. However, despite the absence of the supersaturation of hydrogen due to an approach to the test temperature by a heating, DHC is observed to occur in zirconium alloys at the test temperatures below 180 .deg. C. As to this DHC phenomenon, Kim proposed that stress-induced transformation from {gamma}-hydrides to {delta}-hydrides is likely to be a cause of this, based on Root's observation that the {gamma}-hydride is a stable phase at temperatures lower than 180 .deg. C. In other words, the hydrides formed at the crack tip would be {delta}-hydrides due to the stressinduced transformation while the bulk region still maintains the initial hydride phase or {gamma}-hydrides. It should be noted that Ambler has also assumed the crack tip hydrides to be {delta}-hydrides. When the {delta}-hydrides or ZrH1.66 are precipitated at the crack tip due to the transformation of the {gamma}-hydrides or ZrH, the crack tip will have a decreased concentration of dissolved hydrogen in zirconium, considering the atomic ratio of hydrogen and zirconium in the {gamma}- and {delta}-hydrides. In contrast, due to no stress-induced transformation of hydrides, the bulk region maintains the initial concentration of dissolved hydrogen. Hence, there develops a difference in the

  16. Embrittlement of nickel-, cobalt-, and iron-base superalloys by exposure to hydrogen

    Science.gov (United States)

    Gray, H. R.

    1975-01-01

    Five nickel-base alloys (Inconel 718, Udimet 700, Rene 41, Hastelloy X, and TD-NiCr), one cobalt-base alloy (L-605), and an iron-base alloy (A-286) were exposed in hydrogen at 0.1 MN/sq m (15 psi) at several temperatures in the range from 430 to 980 C for as long as 1000 hours. These alloys were embrittled to varying degrees by such exposures in hydrogen. Embrittlement was found to be: (1) sensitive to strain rate, (2) reversible, (3) caused by large concentrations of absorbed hydrogen, and (4) not associated with any detectable microstructural changes in the alloys. These observations are consistent with a mechanism of internal reversible hydrogen embrittlement.

  17. Prevention of delayed hydride cracking in zirconium alloys

    International Nuclear Information System (INIS)

    Cheadle, B.A.; Coleman, C.E.; Ambler, J.F.R.

    1987-01-01

    Zirconium alloys are susceptible to a mechanism for crack initiation and propagation called delayed hydride cracking. From a review of component failures and experimental results, we have developed the requirements for preventing this cracking. The important parameters for cracking are hydrogen concentration, flaws, and stress; each should be minimized. At the design and construction stages hydrogen pickup has to be controlled, quality assurance needs to be at a high enough level to ensure the absence of flaws, and residual stresses must be eliminated by careful fabrication and heat treatment

  18. N₂reduction and hydrogenation to ammonia by a molecular iron-potassium complex.

    Science.gov (United States)

    Rodriguez, Meghan M; Bill, Eckhard; Brennessel, William W; Holland, Patrick L

    2011-11-11

    The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N(2)) to ammonia (NH(3)) is an iron surface promoted with potassium cations (K(+)), but soluble iron complexes have neither reduced the N-N bond of N(2) to nitride (N(3-)) nor produced large amounts of NH(3) from N(2). We report a molecular iron complex that reacts with N(2) and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe(3)N(2) core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H(2) to give substantial yields of N(2)-derived ammonia. These reactions, although not yet catalytic, give structural and spectroscopic insight into N(2) cleavage and N-H bond-forming reactions of iron.

  19. RF plasma-driven hydrogen permeation through a biased iron membrane

    International Nuclear Information System (INIS)

    Banno, T.; Waelbroeck, F.; Winter, J.

    1984-01-01

    The steady-state RF plasma-driven hydrogen permeation through an electrically biased iron membrane has been investigated as a function of the bias potential Vsub(M) for membrane temperatures in the range of 150-400 0 C. Vsub(M) has been gradually increased positively from the floating potential of the membrane. The permeation flux decreases when Vsub(M) increases at low voltages: positive hydrogen ions are repelled. The membrane temperature does not influence this effect measurably. The permeation flux starts to increase when Vsub(M) is raised higher, i.e. when energetic electrons strike the surface. This phenomenon shows a pronounced temperature dependence - the enhancement is largest for the lowest temperatures. The effect is interpreted in terms of an electron-induced dissociation of hydrogen molecules on the membrane surface. (orig.)

  20. Atomic-scale investigation of point defects and hydrogen-solute atmospheres on the edge dislocation mobility in alpha iron

    Energy Technology Data Exchange (ETDEWEB)

    Bhatia, M. A.; Solanki, K. N., E-mail: kiran.solanki@asu.edu [School for Engineering of Matter, Transport, and Energy, Arizona State University, Tempe, Arizona 85287 (United States); Groh, S. [Institute of Mechanics and Fluid Dynamics, TU Bergakademie Freiberg, Freiberg 09556 (Germany)

    2014-08-14

    In this study, we present atomistic mechanisms of 1/2 [111](11{sup ¯}0) edge dislocation interactions with point defects (hydrogen and vacancies) and hydrogen solute atmospheres in body centered cubic (bcc) iron. In metals such as iron, increases in hydrogen concentration can increase dislocation mobility and/or cleavage-type decohesion. Here, we first investigate the dislocation mobility in the presence of various point defects, i.e., change in the frictional stress as the edge dislocation interacts with (a) vacancy, (b) substitutional hydrogen, (c) one substitutional and one interstitial hydrogen, (d) interstitial hydrogen, (e) vacancy and interstitial hydrogen, and (f) two interstitial hydrogen. Second, we examine the role of a hydrogen-solute atmosphere on the rate of local dislocation velocity. The edge dislocation simulation with a vacancy in the compression side of the dislocation and an interstitial hydrogen atom at the tension side exhibit the strongest mechanical response, suggesting a higher potential barrier and hence, the higher frictional stress (i.e., ∼83% higher than the pure iron Peierls stress). In the case of a dislocation interacting with a vacancy on the compressive side, the vacancy binds with the edge dislocation, resulting in an increase in the friction stress of about 28% when compared with the Peierls stress of an edge dislocation in pure iron. Furthermore, as the applied strain increases, the vacancy migrates through a dislocation transportation mechanism by attaining a velocity of the same order as the dislocation velocity. For the case of the edge dislocation interacting with interstitial hydrogen on the tension side, the hydrogen atom jumps through one layer perpendicular to the glide plane during the pinning-unpinning process. Finally, our simulation of dislocation interactions with hydrogen show first an increase in the local dislocation velocity followed by a pinning of the dislocation core in the atmosphere, resulting in

  1. Iron-57 and iridium-193 Moessbauer spectroscopic studies of supported iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1988-01-01

    57 Fe and 193 Ir Moessbauer spectroscopy shows that silica- and alumina-supported iron-iridium catalysts formed by calcination in air contain mixtures of small particle iron(III) oxide and iridium(IV) oxide. The iridium dioxide in both supported catalysts is reduced in hydrogen to metallic iridium. The α-Fe 2 O 3 in the silica supported materials is predominantly reduced in hydrogen to an iron-iridium alloy whilst in the alumina-supported catalyst the iron is stabilised by treatment in hydrogen as iron(II). Treatment of a hydrogen-reduced silica-supported iron catalyst in hydrogen and carbon monoxide is accompanied by the formation of iron carbides. Carbide formation is not observed when the iron-iridium catalysts are treated in similar atmospheres. The results from the bimetallic catalysts are discussed in terms of the hydrogenation of associatively adsorbed carbon monoxide and the selectivity of supported iron-iridium catalysts to methanol formation. (orig.)

  2. The effects of zirconium and carbon on the hot cracking resistance of iron aluminides. Topical report

    Energy Technology Data Exchange (ETDEWEB)

    Mulac, B.L.; Edwards, G.R. [Colorado School of Mines, Golden, CO (United States). Dept. of Metallurgical and Materials Engineering; David, S.A. [Oak Ridge National Lab., TN (United States)

    1998-02-01

    Iron aluminides have been of interest for about 60 years because of their good high temperature strengths (below 600{degrees}C) and excellent oxidation and sulfidation resistance, as well as their relatively low cost and conservation of strategic elements. These advantageous properties have driven the development of iron aluminides as potential structural materials. However, the industrial application of iron aluminides has been inhibited because of a sharp reduction in strength at temperatures higher than 600{degrees}C and low ductility at ambient temperatures due to hydrogen embrittlement. Oak Ridge National Laboratory has shown in recent years that room temperature properties of alloys containing 28% Al (all compositions are in atomic percent unless otherwise noted) can be improved through thermomechanical processing and alloying. Iron aluminides must have good weldability if they are to be used as structural materials. A coarse fusion zone microstructure is formed when iron aluminides are welded, increasing their susceptibility to cold cracking in water vapor. A recent study at Colorado School of Mines has shown that refining the fusion zone microstructure by weld pool oscillation effectively reduces cold cracking. Weld pool inoculation has been shown to refine fusion zone microstructures, but coarse carbide distribution caused this approach to reducing cold cracking to be ineffective.

  3. Modelling zirconium hydrides using the special quasirandom structure approach

    KAUST Repository

    Wang, Hao; Chroneos, Alexander I.; Jiang, Chao; Schwingenschlö gl, Udo

    2013-01-01

    The study of the structure and properties of zirconium hydrides is important for understanding the embrittlement of zirconium alloys used as cladding in light water nuclear reactors. Simulation of the defect processes is complicated due to the random distribution of the hydrogen atoms. We propose the use of the special quasirandom structure approach as a computationally efficient way to describe this random distribution. We have generated six special quasirandom structure cells based on face centered cubic and face centered tetragonal unit cells to describe ZrH2-x (x = 0.25-0.5). Using density functional theory calculations we investigate the mechanical properties, stability, and electronic structure of the alloys. © the Owner Societies 2013.

  4. SOLUBILITY OF IRON IN METALLIC HYDROGEN AND STABILITY OF DENSE CORES IN GIANT PLANETS

    International Nuclear Information System (INIS)

    Wahl, Sean M.; Wilson, Hugh F.; Militzer, Burkhard

    2013-01-01

    The formation of the giant planets in our solar system, and likely a majority of giant exoplanets, is most commonly explained by the accretion of nebular hydrogen and helium onto a large core of terrestrial-like composition. The fate of this core has important consequences for the evolution of the interior structure of the planet. It has recently been shown that H 2 O, MgO, and SiO 2 dissolve in liquid metallic hydrogen at high temperature and pressure. In this study, we perform ab initio calculations to study the solubility of an innermost metallic core. We find dissolution of iron to be strongly favored above 2000 K over the entire pressure range (0.4-4 TPa) considered. We compare with and summarize the results for solubilities on other probable core constituents. The calculations imply that giant planet cores are in thermodynamic disequilibrium with surrounding layers, promoting erosion and redistribution of heavy elements. Differences in solubility behavior between iron and rock may influence evolution of interiors, particularly for Saturn-mass planets. Understanding the distribution of iron and other heavy elements in gas giants may be relevant in understanding mass-radius relationships, as well as deviations in transport properties from pure hydrogen-helium mixtures

  5. Quantification of the distribution of hydrogen by nuclear microprobe at the Laboratory Pierre Sue in the width of zirconium alloy fuel clad of PWR reactors

    International Nuclear Information System (INIS)

    Raepsaet, C.; Bossis, Ph.; Hamon, D.; Bechade, J.L.; Brachet, J.C.

    2007-01-01

    Among the analysis techniques by ions beams, the micro ERDA (Elastic Detection Analysis) is an interesting technique which allows the quantitative distribution of the hydrogen in materials. In particular, this analysis has been used for hydride zirconium alloys, with the nuclear microprobe of the Laboratory Pierre Sue. This probe allows the characterization of radioactive materials. The technique principles are recalled and then two examples are provided to illustrate the fuel clad behavior in PWR reactors. (A.L.B.)

  6. Influence of hydride on the mechanical behavior under irradiation of zirconium and Zircaloy-4

    International Nuclear Information System (INIS)

    Vazquez, Carolina A.

    2006-01-01

    In the present work the radiation hardening law for zirconium with different thermal treatments and with two hydrogen contents, and Zircaloy-4 with low hydrogen content was studied. The irradiations were made at room temperature to a neutron fluences lower than those where the dislocation channeling and deformation inhomogeneities are expected. For zirconium with hydrogen contents lower than 20 ppm and with 100 ppm, irradiated to a neutron dose of 0.0008 dpa (3.6 x 10 17 n/cm 2 ), a behavior according to the Seeger's model was observed. The model predicts the lineal dependence of the yield stress with the square root of the neutron fluence. At this dose range and at room temperature, the hardening due the hydrogen content and the irradiation hardening are additive. Isochronal annealings to determine the hardening recovery temperature were carried out. Values for this temperature above 425 C degrees were found, which are circa 100 C degrees higher than those corresponding to Stage V of radiation damage in Zr and Zry without hydrogen. This suggests that there is a synergistic effect of radiation damage and hydrogen uptake on the mechanical properties; it is possible to think in a probable and severe ductility reduction, even at low neutron fluences. (author) [es

  7. Self-assembled monolayers of n-alkanethiols suppress hydrogen evolution and increase the efficiency of rechargeable iron battery electrodes.

    Science.gov (United States)

    Malkhandi, Souradip; Yang, Bo; Manohar, Aswin K; Prakash, G K Surya; Narayanan, S R

    2013-01-09

    Iron-based rechargeable batteries, because of their low cost, eco-friendliness, and durability, are extremely attractive for large-scale energy storage. A principal challenge in the deployment of these batteries is their relatively low electrical efficiency. The low efficiency is due to parasitic hydrogen evolution that occurs on the iron electrode during charging and idle stand. In this study, we demonstrate for the first time that linear alkanethiols are very effective in suppressing hydrogen evolution on alkaline iron battery electrodes. The alkanethiols form self-assembled monolayers on the iron electrodes. The degree of suppression of hydrogen evolution by the alkanethiols was found to be greater than 90%, and the effectiveness of the alkanethiol increased with the chain length. Through steady-state potentiostatic polarization studies and impedance measurements on high-purity iron disk electrodes, we show that the self-assembly of alkanethiols suppressed the parasitic reaction by reducing the interfacial area available for the electrochemical reaction. We have modeled the effect of chain length of the alkanethiol on the surface coverage, charge-transfer resistance, and double-layer capacitance of the interface using a simple model that also yields a value for the interchain interaction energy. We have verified the improvement in charging efficiency resulting from the use of the alkanethiols in practical rechargeable iron battery electrodes. The results of battery tests indicate that alkanethiols yield among the highest faradaic efficiencies reported for the rechargeable iron electrodes, enabling the prospect of a large-scale energy storage solution based on low-cost iron-based rechargeable batteries.

  8. Self-Assembled Monolayers of n-Alkanethiols Suppress Hydrogen Evolution and Increase the Efficiency of Rechargeable Iron Battery Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Malkhandi, S; Yang, B; Manohar, AK; Prakash, GKS; Narayanan, SR

    2013-01-09

    Iron-based rechargeable batteries, because of their low cost, eco-friendliness, and durability, are extremely attractive for large-scale energy storage. A principal challenge in the deployment of these batteries is their relatively low electrical efficiency. The low efficiency is due to parasitic hydrogen evolution that occurs on the iron electrode during charging and idle stand. In this study, we demonstrate for the first time that linear alkanethiols are very effective in suppressing hydrogen evolution on alkaline iron battery electrodes. The alkanethiols form self-assembled monolayers on the iron electrodes. The degree of suppression of hydrogen evolution by the alkanethiols was found to be greater than 90%, and the effectiveness of the alkanethiol increased with the chain length. Through steady-state potentiostatic polarization studies and impedance measurements on high-purity iron disk electrodes, we show that the self-assembly of alkanethiols suppressed the parasitic reaction by reducing the interfacial area available for the electrochemical reaction. We have modeled the effect of chain length of the alkanethiol on the surface coverage, charge-transfer resistance, and double-layer capacitance of the interface using a simple model that also yields a value for the interchain interaction energy. We have verified the improvement in charging efficiency resulting from the use of the alkanethiols in practical rechargeable iron battery electrodes. The results of battery tests indicate that alkanethiols yield among the highest faradaic efficiencies reported for the rechargeable iron electrodes, enabling the prospect of a large-scale energy storage solution based on low-cost iron-based rechargeable batteries.

  9. N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex

    Science.gov (United States)

    Rodriguez, Meghan M.; Bill, Eckhard; Brennessel, William W.; Holland, Patrick L.

    2011-01-01

    The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N2) to ammonia is an iron surface promoted with K+, but soluble iron complexes have neither reduced the N-N bond of N2 to nitride nor produced large amounts of NH3 from N2. We report a molecular iron complex that reacts with N2 and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe3N2 core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H2 to give substantial yields of N2-derived ammonia. These reactions, though not yet catalytic, give structural and spectroscopic insight into N2 cleavage and N-H bond-forming reactions of iron. PMID:22076372

  10. Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods

    Science.gov (United States)

    Mariani, Robert Dominick

    2014-09-09

    Zirconium-based metal alloy compositions comprise zirconium, a first additive in which the permeability of hydrogen decreases with increasing temperatures at least over a temperature range extending from 350.degree. C. to 750.degree. C., and a second additive having a solubility in zirconium over the temperature range extending from 350.degree. C. to 750.degree. C. At least one of a solubility of the first additive in the second additive over the temperature range extending from 350.degree. C. to 750.degree. C. and a solubility of the second additive in the first additive over the temperature range extending from 350.degree. C. to 750.degree. C. is higher than the solubility of the second additive in zirconium over the temperature range extending from 350.degree. C. to 750.degree. C. Nuclear fuel rods include a cladding material comprising such metal alloy compositions, and nuclear reactors include such fuel rods. Methods are used to fabricate such zirconium-based metal alloy compositions.

  11. Selective Precipitation of Thorium lodate from a Tartaric Acid-Hydrogen Peroxide Medium Application to Rapid Spectrophotometric Determination of Thorium in Silicate Rocks and in Ores

    Science.gov (United States)

    Grimaldi, F.S.

    1957-01-01

    This paper presents a selective iodate separation of thorium from nitric acid medium containing d-tartaric acid and hydrogen peroxide. The catalytic decomposition of hydrogen peroxide is prevented by the use of 8quinolinol. A few micrograms of thorium are separated sufficiently clean from 30 mg. of such oxides as cerium, zirconium, titanium, niobium, tantalum, scandium, or iron with one iodate precipitation to allow an accurate determination of thorium with the thoronmesotartaric acid spectrophotometric method. The method is successful for the determination of 0.001% or more of thorium dioxide in silicate rocks and for 0.01% or more in black sand, monazite, thorite, thorianite, eschynite, euxenite, and zircon.

  12. Capture and storage of hydrogen gas by zero-valent iron.

    Science.gov (United States)

    Reardon, Eric J

    2014-02-01

    Granular Fe(o), used to reductively degrade a variety of contaminants in groundwater, corrodes in water to produce H2(g). A portion enters the Fe(o) lattice where it is stored in trapping sites such as lattice defects and microcracks. The balance is dissolved by the groundwater where it may exsolve as a gas if its solubility is exceeded. Gas exsolution can reduce the effectiveness of the Fe(o) treatment zone by reducing contact of the contaminant with iron surfaces or by diverting groundwater flow. It also represents a lost electron resource that otherwise could be involved in reductive degradation of contaminants. It is advantageous to select an iron for remediation purposes that captures a large proportion of the H2(g) it generates. This study examines various aspects of the H2(g) uptake process and has found 1) H2(g) does not have to be generated at the water/iron interface to enter the lattice. It can enter directly from the gas/water phases, 2) exposure of granular sponge iron to H2(g) reduces the dormant period for the onset of iron corrosion, 3) the large quantities of H2(g) generated by nano-Fe(o) injected into a reactive barrier of an appropriate granular iron can be captured in the lattice of that iron, and 4) lattice-bound hydrogen represents an additional electron resource to Fe(o) for remediation purposes and may be accessible using physical or chemical means. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Li4FeH6: Iron-containing complex hydride with high gravimetric hydrogen density

    Directory of Open Access Journals (Sweden)

    Hiroyuki Saitoh

    2014-07-01

    Full Text Available Li4FeH6, which has the highest gravimetric hydrogen density of iron-containing complex hydrides reported so far, is synthesized by hydrogenation of a powder mixture of iron and LiH above 6.1 GPa at 900 °C. In situ synchrotron radiation X-ray diffraction measurements reveal that while kinetics require high temperature and thus high pressure for the synthesis, Li4FeH6 is expected to be thermodynamically stable slightly below room temperature at ambient pressure; further synthetic studies to suppress the kinetic effects may enable us to synthesize Li4FeH6 at moderate pressures. Li4FeH6 can be recovered at ambient conditions where Li4FeH6 is metastable.

  14. First-principles calculation for the effect of hydrogen atoms on the mobility of a screw dislocation in BCC iron

    International Nuclear Information System (INIS)

    Itakura, Mitsuhiro; Kaburaki, Hideo; Yamaguchi, Masatake; Endo, Tatsuro; Higuchi, Kenji; Ogata, Shigenobu; Kimizuka, Hajime

    2012-01-01

    Effect of hydrogen atoms on the mobility of a screw dislocation in BCC iron has been evaluated using the first-principles calculation. The stable position of a hydrogen atom is found to be near the screw dislocation core and inside the core respectively when the dislocation is at the easy-core or hard-core configuration in BCC iron. The intrinsically unstable hard-core configuration of the screw dislocation is stabilized when a hydrogen atom is trapped inside the core. On the basis of this first-principles result, an elastic string model of a dislocation is developed to predict the kink motion in the presence of a hydrogen atom. It is found that a double-kink formation is facilitated when a hydrogen atom is located near a dislocation line, however, a kink motion is retarded when a hydrogen atom is behind the kink. (author)

  15. Quantification of the distribution of hydrogen by nuclear microprobe at the Laboratory Pierre Sue in the width of zirconium alloy fuel clad of PWR reactors; Quantification de la repartition de l'hydrogene a la microsonde nucleaire du Laboratoire Pierre Sue dans l'epaisseur de tubes de gainage du combustible des REP en alliage de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Raepsaet, C. [CEA Saclay, Dept. de Recherche sur l' Etat Condense, les Atomes et les Molecules (DSM/DRECAM/LPS-CNRS) UMR9956, 91 - Gif sur Yvette (France); Bossis, Ph. [CEA Saclay, Dept. des Materiaux pour le Nucleaire (DEN/DANS/DMN/SEMULM2E), 91 - Gif-sur-Yvette (France); Hamon, D.; Bechade, J.L.; Brachet, J.C. [CEA Saclay, Dept. des Materiaux pour le Nucleaire (DEN/DANS/DMN/SRMALA2M), 91 - Gif-sur-Yvette (France)

    2007-07-01

    Among the analysis techniques by ions beams, the micro ERDA (Elastic Detection Analysis) is an interesting technique which allows the quantitative distribution of the hydrogen in materials. In particular, this analysis has been used for hydride zirconium alloys, with the nuclear microprobe of the Laboratory Pierre Sue. This probe allows the characterization of radioactive materials. The technique principles are recalled and then two examples are provided to illustrate the fuel clad behavior in PWR reactors. (A.L.B.)

  16. Sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides

    Directory of Open Access Journals (Sweden)

    R.V. Smotraiev

    2016-05-01

    Full Text Available The actual problem of water supply in the world and in Ukraine, in particular, is a high level of pollution in water resources and an insufficient level of drinking water purification. With industrial wastewater, a significant amount of pollutants falls into water bodies, including suspended particles, sulfates, iron compounds, heavy metals, etc. Aim: The aim of this work is to determine the impact of aluminum and manganese ions additives on surface and sorption properties of zirconium oxyhydroxide based sorbents during their production process. Materials and Methods: The sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides were prepared by sol-gel method during the hydrolysis of metal chlorides (zirconium oxychloride ZrOCl2, aluminum chloride AlCl3 and manganese chloride MnCl2 with carbamide. Results: The surface and sorption properties of sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides were investigated. X-ray amorphous structure and evolved hydroxyl-hydrate cover mainly characterize the obtained xerogels. The composite sorbents based on xerogels of zirconium oxyhydroxide doped with aluminum oxyhydroxide (aS = 537 m2/g and manganese oxyhydroxide (aS = 356 m2/g have more developed specific surface area than single-component xerogels of zirconium oxyhydroxide (aS = 236 m2/g and aluminum oxyhydroxide (aS = 327 m2/g. The sorbent based on the xerogel of zirconium and manganese oxyhydroxides have the maximum SO42--ions sorption capacity. It absorbs 1.5 times more SO42–-ions than the industrial anion exchanger AN-221. The sorbents based on xerogels of zirconium oxyhydroxide has the sorption capacity of Fe3+-ions that is 1.5…2 times greater than the capacity of the industrial cation exchanger KU-2-8. The Na+-ions absorption capacity is 1.47…1.56 mmol/g for each sorbent. Conclusions: Based on these data it can be concluded that the proposed method is effective for sorbents production based on

  17. Delayed hydrogen cracking test design for pressure tubes

    International Nuclear Information System (INIS)

    Haddad, Roberto; Loberse, Antonio N.; Yawny, Alejandro A.; Riquelme, Pablo

    1999-01-01

    CANDU nuclear power stations pressure tubes of alloy Zr-2,5 % Nb present a cracking phenomenon known as delayed hydrogen cracking (DHC). This is a brittle fracture of zirconium hydrides that are developed by hydrogen due to aqueous corrosion on the metal surface. This hydrogen diffuses to the crack tip where brittle zirconium hydrides develops and promotes the crack propagation. A direct current potential decay (DCPD) technique has been developed to measure crack propagation rates on compact test (CT) samples machined from a non irradiated pressure tube. Those test samples were hydrogen charged by cathodic polarization in an acid solution and then pre cracked in a fatigue machine. This technique proved to be useful to measure crack propagation rates with at least 1% accuracy for DHC in pressure tubes. (author)

  18. Precipitation of γ-zirconium hydride in zirconium

    International Nuclear Information System (INIS)

    Carpenter, G.J.C.

    1978-01-01

    A mechanism for the precipitation of γ-zirconium hydride in zirconium is presented which does not require the diffusion of zirconium. The transformation is completed by shears caused by 1/3 (10 anti 10) Shockley partial dislocations on alternate zirconium basal planes, either by homogeneous nucleation or at lattice imperfections. Homogeneous nucleation is considered least likely in view of the large nucleation barrier involved. Hydrides may form at dislocations by the generation of partials by means of either a pole or ratchet mechanism. The former requires dislocations with a component of Burgers vector along the c-axis, but contrast experiments show that these are not normally observed in annealed zirconium. It is therefore most likely that intragranular hydrides form at the regular 1/3 (11 anti 20) dislocations, possibly by means of a ratchet mechanism. Contrast experiments in the electron microscope show that the precipitates have a shear character consistent with the mechanism suggested. The possibility that the shear dislocations associated with the hydrides are emissary dislocations is considered and a model suggested in which this function is satisfied together with the partial relief of misfit stresses. The large shear strains associated with the precipitation mechanism may play an important role in the preferential orientation of hydrides under stress

  19. A hydrogen-ferric ion rebalance cell operating at low hydrogen concentrations for capacity restoration of iron-chromium redox flow batteries

    Science.gov (United States)

    Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Zou, J.; Ren, Y. X.

    2017-06-01

    To eliminate the adverse impacts of hydrogen evolution on the capacity of iron-chromium redox flow batteries (ICRFBs) during the long-term operation and ensure the safe operation of the battery, a rebalance cell that reduces the excessive Fe(III) ions at the positive electrolyte by using the hydrogen evolved from the negative electrolyte is designed, fabricated and tested. The effects of the flow field, hydrogen concentration and H2/N2 mixture gas flow rate on the performance of the hydrogen-ferric ion rebalance cell have been investigated. Results show that: i) an interdigitated flow field based rebalance cell delivers higher limiting current densities than serpentine flow field based one does; ii) the hydrogen utilization can approach 100% at low hydrogen concentrations (≤5%); iii) the apparent exchange current density of hydrogen oxidation reaction in the rebalance cell is proportional to the square root of the hydrogen concentration at the hydrogen concentration from 1.3% to 50%; iv) a continuous rebalance process is demonstrated at the current density of 60 mA cm-2 and hydrogen concentration of 2.5%. Moreover, the cost analysis shows that the rebalance cell is just approximately 1% of an ICRFB system cost.

  20. Hydrogen sulphide improves adaptation of Zea mays seedlings to iron deficiency.

    Science.gov (United States)

    Chen, Juan; Wu, Fei-Hua; Shang, Yu-Ting; Wang, Wen-Hua; Hu, Wen-Jun; Simon, Martin; Liu, Xiang; Shangguan, Zhou-Ping; Zheng, Hai-Lei

    2015-11-01

    Hydrogen sulphide (H2S) is emerging as a potential molecule involved in physiological regulation in plants. However, whether H2S regulates iron-shortage responses in plants is largely unknown. Here, the role of H2S in modulating iron availability in maize (Zea mays L. cv Canner) seedlings grown in iron-deficient culture solution is reported. The main results are as follows: Firstly, NaHS, a donor of H2S, completely prevented leaf interveinal chlorosis in maize seedlings grown in iron-deficient culture solution. Secondly, electron micrographs of mesophyll cells from iron-deficient maize seedlings revealed plastids with few photosynthetic lamellae and rudimentary grana. On the contrary, mesophyll chloroplasts appeared completely developed in H2S-treated maize seedlings. Thirdly, H2S treatment increased iron accumulation in maize seedlings by changing the expression levels of iron homeostasis- and sulphur metabolism-related genes. Fourthly, phytosiderophore (PS) accumulation and secretion were enhanced by H2S treatment in seedlings grown in iron-deficient solution. Indeed, the gene expression of ferric-phytosiderophore transporter (ZmYS1) was specifically induced by iron deficiency in maize leaves and roots, whereas their abundance was decreased by NaHS treatment. Lastly, H2S significantly enhanced photosynthesis through promoting the protein expression of ribulose-1,5-bisphosphate carboxylase large subunit (RuBISCO LSU) and phosphoenolpyruvate carboxylase (PEPC) and the expression of genes encoding RuBISCO large subunit (RBCL), small subunit (RBCS), D1 protein (psbA), and PEPC in maize seedlings grown in iron-deficient solution. These results indicate that H2S is closely related to iron uptake, transport, and accumulation, and consequently increases chlorophyll biosynthesis, chloroplast development, and photosynthesis in plants. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  1. Phase transformations in intermetallic phases in zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Filippov, V. P., E-mail: vpfilippov@mephi.ru [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) (Russian Federation); Kirichenko, V. G. [Kharkiv National Karazin University (Ukraine); Salomasov, V. A. [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) (Russian Federation); Khasanov, A. M. [University of North Carolina – Asheville, Chemistry Department (United States)

    2017-11-15

    Phase change was analyzed in intermetallic compounds of zirconium alloys (Zr – 1.03 at.% Fe; Zr – 0.51 at.% Fe; Zr – 0.51 at.% Fe – M(M = Nb, Sn). Mössbauer spectroscopy on {sup 57}Fe nuclei in backscattering geometry with the registration of the internal conversion electrons and XRD were used. Four types of iron bearing intermetallic compounds with Nb were detected. A relationship was found between the growth process of intermetallic inclusions and segregation of these phases. The growth kinetics of inclusions possibly is not controlled by bulk diffusion, and a lower value of the iron atom’s activation energy of migration can be attributed to the existence of enhanced diffusion paths and interface boundaries.

  2. Automatic measuring system of zirconium thickness for zirconium liner cladding tubes

    International Nuclear Information System (INIS)

    Matsui, K.; Yamaguchi, H.; Hiroshima, T.; Sakamoto, T.; Murayama, R.

    1985-01-01

    An automatic system of pure zirconium liner thickness for zirconium-zircaloy cladding tubes has been successfully developed. The system consists of three parts. (1) An ultrasonic thickness measuring method for mother tubes before cold rolling. (2) An electromagnetic thickness measuring method for the manufactured tubes. (3) An image processing method for the cross sectional view of the manufactured cut tube samples. In Japanese nuclear industry, zirconium-zircaloy cladding tubes have been tested in order to realize load following operation in the atomic power plant. In order to provide for the practical use in the near future, Sumitomo Metal Industries, Ltd. has been studied and established the practical manufacturing process of the zirconium liner cladding tubes. The zirconium-liner cladding tube is a duplex tube comprising an inner layer of pure zirconium bonded to zircaloy metallurgically. The thickness of the pure zirconium is about 10 % of the total wall thickness. Several types of the automatic thickness measuring methods have been investigated instead of the usual microscopic viewing method in which the liner thickness is measured by the microscopic cross sectional view of the cut tube samples

  3. Zirconium and hafnium

    Science.gov (United States)

    Jones, James V.; Piatak, Nadine M.; Bedinger, George M.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Zirconium and hafnium are corrosion-resistant metals that are widely used in the chemical and nuclear industries. Most zirconium is consumed in the form of the main ore mineral zircon (ZrSiO4, or as zirconium oxide or other zirconium chemicals. Zirconium and hafnium are both refractory lithophile elements that have nearly identical charge, ionic radii, and ionic potentials. As a result, their geochemical behavior is generally similar. Both elements are classified as incompatible because they have physical and crystallochemical properties that exclude them from the crystal lattices of most rock-forming minerals. Zircon and another, less common, ore mineral, baddeleyite (ZrO2), form primarily as accessory minerals in igneous rocks. The presence and abundance of these ore minerals in igneous rocks are largely controlled by the element concentrations in the magma source and by the processes of melt generation and evolution. The world’s largest primary deposits of zirconium and hafnium are associated with alkaline igneous rocks, and, in one locality on the Kola Peninsula of Murmanskaya Oblast, Russia, baddeleyite is recovered as a byproduct of apatite and magnetite mining. Otherwise, there are few primary igneous deposits of zirconium- and hafnium-bearing minerals with economic value at present. The main ore deposits worldwide are heavy-mineral sands produced by the weathering and erosion of preexisting rocks and the concentration of zircon and other economically important heavy minerals, such as ilmenite and rutile (for titanium), chromite (for chromium), and monazite (for rare-earth elements) in sedimentary systems, particularly in coastal environments. In coastal deposits, heavy-mineral enrichment occurs where sediment is repeatedly reworked by wind, waves, currents, and tidal processes. The resulting heavy-mineral-sand deposits, called placers or paleoplacers, preferentially form at relatively low latitudes on passive continental margins and supply 100 percent of

  4. White Paper Summary of 2nd ASTM International Workshop on Hydrides in Zirconium Alloy Cladding

    Energy Technology Data Exchange (ETDEWEB)

    Sindelar, R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Louthan, M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); PNNL, B. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-05-29

    This white paper recommends that ASTM International develop standards to address the potential impact of hydrides on the long term performance of irradiated zirconium alloys. The need for such standards was apparent during the 2nd ASTM International Workshop on Hydrides in Zirconium Alloy Cladding and Assembly Components, sponsored by ASTM International Committee C26.13 and held on June 10-12, 2014, in Jackson, Wyoming. The potentially adverse impacts of hydrogen and hydrides on the long term performance of irradiated zirconium-alloy cladding on used fuel were shown to depend on multiple factors such as alloy chemistry and processing, irradiation and post irradiation history, residual and applied stresses and stress states, and the service environment. These factors determine the hydrogen content and hydride morphology in the alloy, which, in turn, influence the response of the alloy to the thermo-mechanical conditions imposed (and anticipated) during storage, transport and disposal of used nuclear fuel. Workshop presentations and discussions showed that although hydrogen/hydride induced degradation of zirconium alloys may be of concern, the potential for occurrence and the extent of anticipated degradation vary throughout the nuclear industry because of the variations in hydrogen content, hydride morphology, alloy chemistry and irradiation conditions. The tools and techniques used to characterize hydrides and hydride morphologies and their impacts on material performance also vary. Such variations make site-to-site comparisons of test results and observations difficult. There is no consensus that a single material or system characteristic (e.g., reactor type, burnup, hydrogen content, end-of life stress, alloy type, drying temperature, etc.) is an effective predictor of material response during long term storage or of performance after long term storage. Multi-variable correlations made for one alloy may not represent the behavior of another alloy exposed to

  5. Separation of zirconium through extraction in hydrochloric medium with tri-n-octilamine and its spectrophotometric determination with chloroanilic acid

    International Nuclear Information System (INIS)

    Floh, B.; Abrao, A.; Federgruen, L.

    1976-01-01

    A procedure is outlined for the spectrophotometric determination of zirconium using its complex with chloroanilic acid in HC10 4 2M. Interfering elements like Fe, Zn, U, Cy, Cd, Sb, Co, Pb, Hg, Tl, Pt, Au, Pd, Ga, In, Mo and W are previously extracted with tri-n-octylamine 7,5%-benzene from 4 M HCL. Then, the acid content of the solution is ascertained to 10 M HCL and zirconium is extracted with the amine. Nb is a strong interference, being extracted by the amine as well as zirconium and absorbing at the same region as zirconium chloroanilate. Zirconium is stripped from the organic phase with Na 2 CO 3 . The colour development is done with chloroanilic acid in 2 M HC10 4 and the measurements at 340 nm. The method allows the determination of 5 micrograms of Zr. The work curve covers the 0.2 - 2.0 μg Zr/mL range. The procedure is being applied to the determination of zirconium in several alloys and in samples containing zinc, magnesium, iron, aluminium, uranium and thorium [pt

  6. Radiochemical neutron activation analysis of zirconium and zirconium-niobium alloys

    International Nuclear Information System (INIS)

    Tashimova, F.A.; Sadikov, I.I.; Salimov, M.

    2004-01-01

    Full text: Zirconium and zirconium-niobium alloys are used on nuclear technology, as fuel cladding of nuclear reactors. Their nuclear-physical, mechanical and thermophysical properties are influenced them matrix and impurity composition, therefore determination of matrix and impurity content of these materials is a very important task. Neutron activation analysis is one from multielemental and high sensible techniques that are widely applied in analysis of high purity materials. Investigation of nuclear-physical characteristics of zirconium has shown that instrumental variant NAA is unusable for analysis due to high radioactivity of a matrix. Therefore it is necessary carrying out radiochemical separation of impurity radionuclides from matrix. Study of the literature datum have shown, that zirconium and niobium are very well extracted from muriatic solution with 5% tributyl phosphineoxide (TBPO) solution in toluene and 0,75 M solution of di-2-ethyl hexyl phosphoric acid (HDEHP) in cyclohexanone. Investigation of these elements extraction in these systems has shown that more effective and selective separation of matrix radionuclides is achieved in HDEHP-3M HCI system. This system is also extracted and hafnium, witch is an accompanying element of zirconium and its high content prevented determination of other impurity elements in sample. Therefore we used extraction system HDEHP-3M HCl for analysis of zirconium and zirconium-niobium alloys in chromatographic variant. By measurement of distribution profile of a matrix and of elution curve of determined elements is established, that for effective separation of impurity and matrix radionuclides there is enough chromatographic column with diameter 1 cm and height of a sorbent layer 7 cm, thus volume of elute, necessary for complete elution of determinate elements is 35-40 ml. On the basis of the carried out researches the technique of radiochemical NAA of high purity zirconium and zirconium-niobium alloy, which allows to

  7. Iron ore catalysts for methane decomposition to make CO x free hydrogen and carbon nano material

    KAUST Repository

    Zhou, Lu; Enakonda, Linga Reddy; Li, Sheng; Gary, Daniel; Del-Gallo, Pascal; Mennemann, Christina; Basset, Jean-Marie

    2018-01-01

    In this work, for the first time, iron ores with 91.7%–96.2% FeO, 1.3%–2.3% AlO, 1.2%–4.5% SiO, 1.3%–3.9% NaO, were studied directly as bulk catalysts for methane decomposition. By hydrogen pre-reduction at 850 °C, FeO species on iron ores were

  8. Catalyzed borohydrides for hydrogen storage

    Science.gov (United States)

    Au, Ming [Augusta, GA

    2012-02-28

    A hydrogen storage material and process is provided in which alkali borohydride materials are created which contain effective amounts of catalyst(s) which include transition metal oxides, halides, and chlorides of titanium, zirconium, tin, and combinations of the various catalysts. When the catalysts are added to an alkali borodydride such as a lithium borohydride, the initial hydrogen release point of the resulting mixture is substantially lowered. Additionally, the hydrogen storage material may be rehydrided with weight percent values of hydrogen at least about 9 percent.

  9. Ternary cobalt-molybdenum-zirconium coatings for alternative energies

    Science.gov (United States)

    Yar-Mukhamedova, Gulmira; Ved', Maryna; Sakhnenko, Nikolay; Koziar, Maryna

    2017-11-01

    Consistent patterns for electrodeposition of Co-Mo-Zr coatings from polyligand citrate-pyrophosphate bath were investigated. The effect of both current density amplitude and pulse on/off time on the quality, composition and surface morphology of the galvanic alloys were determined. It was established the coating Co-Mo-Zr enrichment by molybdenum with current density increasing up to 8 A dm-2 as well as the rising of pulse time and pause duration promotes the content of molybdenum because of subsequent chemical reduction of its intermediate oxides by hydrogen ad-atoms. It was found that the content of the alloying metals in the coating Co-Mo-Zr depends on the current density and on/off times extremely and maximum Mo and Zr content corresponds to the current density interval 4-6 A dm-2, on-/off-time 2-10 ms. Chemical resistance of binary and ternary coatings based on cobalt is caused by the increased tendency to passivity and high resistance to pitting corrosion in the presence of molybdenum and zirconium, as well as the acid nature of their oxides. Binary coating with molybdenum content not less than 20 at.% and ternary ones with zirconium content in terms of corrosion deep index are in a group ;very proof;. It was shown that Co-Mo-Zr alloys exhibits the greatest level of catalytic properties as cathode material for hydrogen electrolytic production from acidic media which is not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2-4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for red-ox processes activating by oxygen as well as electrode materials for red-ox batteries.

  10. Study of the behaviour of some heavy elements in solvents containing hydrogen fluoride

    International Nuclear Information System (INIS)

    Tarnero, M.

    1967-01-01

    The anhydrous liquid mixtures: dinitrogen tetroxide-hydrogen fluoride and antimony pentafluoride-hydrogen fluoride were studied as solvents for heavy elements interesting nuclear energy: uranium, thorium, zirconium and for some of their compounds. For N 2 O 4 -HF mixtures, electric conductivity measurements and liquid phase infrared spectra were also obtained. Uranium and zirconium tetrafluoride are much more soluble in N 2 O 4 -HF mixtures than in pure hydrogen fluoride. Uranium dissolved in these mixtures is pentavalent. In SbF 5 -HF mixtures, uranium dissolves with hydrogen evolution and becomes trivalent. The solid compound resulting from the dissolution is a fluoro-antimonate: U(SbF 6 ) 3 . (author) [fr

  11. In situ Raman Spectroscopy of Oxide Films on Zirconium Alloy in Simulated PWR Primary Water Condition

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Tae Ho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun [UNIST, Ulsan (Korea, Republic of)

    2016-05-15

    The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pretransition zirconium oxide in high-temperature water chemistry. In this work, Raman spectroscopy was used for in situ investigations for characterizing the phase of zirconium oxide. In situ Raman spectroscopy is a well-suited technique for investigating in detail the characteristics of oxide films in a high-temperature corrosion environment. In previous studies, an in situ Raman system was developed for investigating the oxides on nickel-based alloys and low alloy steels in high-temperature water environment. Also, the early stage oxidation behavior of zirconium alloy with different dissolved hydrogen concentration environments in high temperature water was treated in the authors' previous study. In this study, a specific zirconium alloy was oxidized and investigated with in situ Raman spectroscopy for 100 d oxidation, which is close to the first transition time of the zirconium alloy oxidation. The ex situ investigation methods such as transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were used to further characterize the zirconium oxide structure. As oxidation time increased, the Raman peaks of tetragonal zirconium oxide were merged or became weaker. However, the monoclinic zirconium oxide peaks became distinct. The tetragonal zirconium oxide was just found near the O/M interface and this could explain the Raman spectra difference between the 30 d result and others.

  12. Method of reducing zirconium

    International Nuclear Information System (INIS)

    Megy, J.A.

    1980-01-01

    A method was developed for making nuclear-grade zirconium from a zirconium compound, which ismore economical than previous methods since it uses aluminum as the reductant metal rather than the more expensive magnesium. A fused salt phase containing the zirconium compound to be reduced is first prepared. The fused salt phase is then contacted with a molten metal phase which contains aluminum and zinc. The reduction is effected by mutual displacment. Aluminum is transported from the molten metal phase to the fused salt phase, replacing zirconium in the salt. Zirconium is transported from the fused salt phase to the molten metal phase. The fused salt phase and the molten metal phase are then separated, and the solvent metal and zirconium are separated by distillation or other means. (DN)

  13. Hydrogen embrittlement and stress corrosion cracking in metals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Cheong, Yong Mu; Im, Kyung Soo

    2004-10-15

    The objective of this report is to elucidate the mechanism for hydrogen embrittlement (HE) and stress corrosion cracking (SCC) in metals. To this end, we investigate the common features between delayed hydride cracking (DHC) in zirconium alloys and HE in metals with no precipitation of hydrides including Fe base alloys, Nickel base alloys, Cu alloys and Al alloys. Surprisingly, as with the crack growth pattern for the DHC in zirconium alloy, the metals mentioned above show a discontinuous crack growth, striation lines and a strong dependence of yield strength when exposed to hydrogen internally and externally. This study, for the first time, analyzes the driving force for the HE in metals in viewpoints of Kim's DHC model that a driving force for the DHC in zirconium alloys is a supersaturated hydrogen concentration coming from a hysteresis of the terminal solid solubility of hydrogen, not by the stress gradient, As with the crack growing only along the hydride habit plane during the DHC in zirconium alloys, the metals exposed to hydrogen seem to have the crack growing by invoking the dislocation slip along the preferential planes as a result of some interactions of the dislocations with hydrogen. Therefore, it seems that the hydrogen plays a role in inducing the slip only on the preferential planes so as to cause a strain localization at the crack tip. Sulfur in metals is detrimental in causing a intergranular cracking due to a segregation of the hydrogens at the grain boundaries. In contrast, boron in excess of 500 ppm added to the Ni3Al intermetallic compound is found to be beneficial in suppressing the HE even though further details of the mechanism for the roles of boron and sulfur are required. Carbon, carbides precipitating semi-continuously along the grain boundaries and the CSL (coherent site lattice) boundaries is found to suppress the intergranular stress corrosion cracking (IGSCC) in Alloy 600. The higher the volume fraction of twin boundaries, the

  14. Hydrogen embrittlement and stress corrosion cracking in metals

    International Nuclear Information System (INIS)

    Kim, Young Suk; Cheong, Yong Mu; Im, Kyung Soo

    2004-10-01

    The objective of this report is to elucidate the mechanism for hydrogen embrittlement (HE) and stress corrosion cracking (SCC) in metals. To this end, we investigate the common features between delayed hydride cracking (DHC) in zirconium alloys and HE in metals with no precipitation of hydrides including Fe base alloys, Nickel base alloys, Cu alloys and Al alloys. Surprisingly, as with the crack growth pattern for the DHC in zirconium alloy, the metals mentioned above show a discontinuous crack growth, striation lines and a strong dependence of yield strength when exposed to hydrogen internally and externally. This study, for the first time, analyzes the driving force for the HE in metals in viewpoints of Kim's DHC model that a driving force for the DHC in zirconium alloys is a supersaturated hydrogen concentration coming from a hysteresis of the terminal solid solubility of hydrogen, not by the stress gradient, As with the crack growing only along the hydride habit plane during the DHC in zirconium alloys, the metals exposed to hydrogen seem to have the crack growing by invoking the dislocation slip along the preferential planes as a result of some interactions of the dislocations with hydrogen. Therefore, it seems that the hydrogen plays a role in inducing the slip only on the preferential planes so as to cause a strain localization at the crack tip. Sulfur in metals is detrimental in causing a intergranular cracking due to a segregation of the hydrogens at the grain boundaries. In contrast, boron in excess of 500 ppm added to the Ni3Al intermetallic compound is found to be beneficial in suppressing the HE even though further details of the mechanism for the roles of boron and sulfur are required. Carbon, carbides precipitating semi-continuously along the grain boundaries and the CSL (coherent site lattice) boundaries is found to suppress the intergranular stress corrosion cracking (IGSCC) in Alloy 600. The higher the volume fraction of twin boundaries, the more

  15. Effect of the hydrogen concentration on the ductility of Zry-4

    International Nuclear Information System (INIS)

    Domizzi, G.; Ovejero Garcia, J.

    1996-01-01

    After many years in service, zirconium alloys employed in nuclear reactors may reach high contents of hydride particles, exceeding the hydrogen solid solubility at the service temperature. The brittle character of zirconium hydride promotes the alloy embrittlement. In order to predict the critical hydrogen concentration which causes a ductile-brittle transition in a Zry-4 foil, 0.02mm thick, tensile test specimens were hydride by gaseous charging. To obtain uniform hydride distribution the specimens were electroplated with a film of copper prior to gaseous charge. In absence of oxide film, the foils retained its ductility up to high hydrogen concentration (950 Og/g). The critical hydrogen concentration was attained at 2900-3100 Og/g. (author). 4 refs., 2 figs., 1 tab

  16. Rapid radiochemical separation of zirconium-95 and niobium-95

    International Nuclear Information System (INIS)

    Downey, D.M.; McLaughlin, C.L.

    1983-01-01

    A rapid method for the quantitative separation of 95 Zr and 95 Nb has been developed. The method is based on the ion flotation of cationic zirconium complex ions with sodium lauryl sulfate (NaLS) from niobium which is masked with hydrogen peroxide. The separation was applied to mixtures of 95 Zr and 95 Nb initially in oxalic acid solution and quantitative recoveries of the radiochemically pure radioisotopes were obtained. (orig.)

  17. PLUTONIUM-ZIRCONIUM ALLOYS

    Science.gov (United States)

    Schonfeld, F.W.; Waber, J.T.

    1960-08-30

    A series of nuclear reactor fuel alloys consisting of from about 5 to about 50 at.% zirconium (or higher zirconium alloys such as Zircaloy), balance plutonium, and having the structural composition of a plutonium are described. Zirconium is a satisfactory diluent because it alloys readily with plutonium and has desirable nuclear properties. Additional advantages are corrosion resistance, excellent fabrication propenties, an isotropie structure, and initial softness.

  18. ZIRCONIUM-CLADDING OF THORIUM

    Science.gov (United States)

    Beaver, R.J.

    1961-11-21

    A method of cladding thorium with zirconium is described. The quality of the bond achieved between thorium and zirconium by hot-rolling is improved by inserting and melting a thorium-zirconium alloy foil between the two materials prior to rolling. (AEC)

  19. Mecanical Properties Degradation by Hydrogen Embrittlement

    International Nuclear Information System (INIS)

    Bertolino, G; Meyer, G; Perez Ipina J

    2001-01-01

    The presence of hydrogen-rich media during nuclear plant operation motivates the study of the zirconium alloys degradation of their mechanical properties influenced by hydrogen content and temperature.In this work we study samples with a microstructure of equiaxial grains resulted from hot-rolled, and with different homogeneous hydrogen content obtained by electrochemical charge and a thermal treatment.The influence of hydrogen content and temperature was analyzed from the results of fracture-mechanical tests on CT (compact test) probes using the J-criteria

  20. Peculiarities of formation of zirconium aluminides in hydride cycle mode

    International Nuclear Information System (INIS)

    Muradyan, G.N.

    2016-01-01

    The zirconium aluminides are promising structural materials in aerospace, mechanical engineering, chemical industry, etc. They are promising for manufacturing of heat-resistant wires, that will improve the reliability and efficiency of electrical networks. In the present work, the results of study of zirconium aluminides formation in the Hydride Cycle (HC) mode, developed in the Laboratory of high-temperature synthesis of the Institute of Chemical Physics of NAS RA, are described. The formation of zirconium aluminides in HC proceeded according to the reaction xZrH_2+(1-x)Al → alloy Zr_xAl(1-x)+H_2↑. The samples were certified using: chemical analysis to determine the content of hydrogen (pyrolysis method); differential thermal analysis (DTA, derivatograph Q-1500, T_heating = 1000°C, rate 20°C/min); X-ray analysis (XRD, diffractometer DRON-0.5). The influences of the ratio of powders ZrH_2/Al in the reaction mixture, compacting pressure, temperature and heating velocity on the characteristics of the synthesized aluminides were determined. In HC, the solid solutions of Al in Zr, single phase ZrAl_2 and ZrAl_3 aluminides and Zr_3AlH_4.49 hydride were synthesized. Formation of aluminides in HC mode took place by the solid-phase mechanism, without melting of aluminum. During processing, the heating of the initial charge up to 540°C resulted in the decomposition of zirconium hydride (ZrH_2) to HCC ZrH_1.5, that interacted with aluminum at 630°C forming FCC alumohydride of zirconium. Further increase of the temperature up to 800°C led to complete decomposition of the formed alumohydride of zirconium. The final formation of the zirconium aluminide occurred at 1000-1100°C in the end of HC process. Conclusion: in the synthesis of zirconium aluminides, the HC mode has several significant advantages over the conventional modes: lower operating temperatures (1000°C instead of 1800°C); shorter duration (1.5-2 hours instead of tens of hours); the availability of

  1. Dissolution of anodic zirconium dioxide films in aqueous media

    International Nuclear Information System (INIS)

    Merati, A.; Cox, B.

    1999-01-01

    Zirconium with a low thermal neutron cross section, good corrosion resistance in high-temperature water, and high thermal conductivity is an ideal material for nuclear reactors. Its good resistance to water and steam at reactor temperatures is of the greatest interest to nuclear fuel designers. Dissolution of zirconium dioxide (ZrO 2 ) films in aggressive media was investigated. The extent of uniform and localized dissolution was measured by ultraviolet-visible (UV-VIS) spectrometry and an alternating current (AC) impedance test, respectively. Scanning electron microscopy (SEM) showed the extent of dissolution of ZrO 2 was a function only of the fluoride ion content and pH of the medium. Cathodic polarization was used to identify the preferred sites for localized dissolution of the oxide film. In 0.1 M potassium bifluoride (KHF 2 ), both uniform thinning and local breakdown of the oxide were observed. Within the limits of the investigating techniques, no evidence of dissolution was observed in the other solutions tested: 0.5 M sulfuric acid (H 2 SO 4 ). 1.0 M nitric acid (HNO 3 ), 5 M hydrochloric acid (HCl), or 0.1 M potassium fluoride (KF). In areas around iron-containing particles, fine cracks in the anodic oxide at prior metal grain boundaries and arrays of cracks in the oxide associated with residual scratches from the initial specimen preparation were the preferred spots for localized dissolution of the oxide film. Iron precipitates immediately below the surface of the oxide layer increased the local electrical conductivity. Enrichment of iron in the oxide matrix around these precipitates during the anodization process appeared to cause prospective spots, acting as anodic sites for pH formation

  2. Rapid radiochemical separation of zirconium-95 and niobium-95

    Energy Technology Data Exchange (ETDEWEB)

    Downey, D.M.; McLaughlin, C.L.

    1983-01-01

    A rapid method for the quantitative separation of /sup 95/Zr and /sup 95/Nb has been developed. The method is based on the ion flotation of cationic zirconium complex ions with sodium lauryl sulfate (NaLS) from niobium which is masked with hydrogen peroxide. The separation was applied to mixtures of /sup 95/Zr and /sup 95/Nb initially in oxalic acid solution and quantitative recoveries of the radiochemically pure radioisotopes were obtained.

  3. Metallurgy of zirconium and hafnium

    International Nuclear Information System (INIS)

    Baryshnikov, N.V.; Geger, V.Eh.; Denisova, N.D.; Kazajn, A.A.; Kozhemyakin, V.A.; Nekhamkin, L.G.; Rodyakin, V.V.; Tsylov, Yu.A.

    1979-01-01

    Considered are those properties of zirconium and of hafnium, which are of practical interest for the manufacture of these elements. Systematized are the theoretical and the practical data on the procedures for thermal decomposition of zirconia and for obtaining zirconium dioxide and hafnium dioxide by a thermal decomposition of compounds and on the hydrometallurgical methods for extracting zirconium and hafnium. Zirconium and hafnium fluorides and chlorides production procedures are described. Considered are the iodide and the electrolytic methods of refining zirconium and hafnium

  4. Environmentally-induced cracking of zirconium alloys - a review

    International Nuclear Information System (INIS)

    Cox, B.

    1990-01-01

    The general field of environmentally-induced cracking of zirconium alloys has been reviewed and the phenomena that are observed and the progress in understanding the mechanisms are summarized. The details of the industrially important pellet-clad interaction failures of nuclear reactor fuel have been left for a companion review, and only observations on the mechanism are summarized briefly here. It is concluded that in the zirconium alloy system, by virtue of the physical peculiarities of the system, it is easier to reach unambiguous conclusions about the environmental cracking mechanisms that are operating than with other systems. Thus, chemical dissolution in either liquid or vapour phase is thought to be the principal mechanism for intergranular cracking, while adsorption-induced embrittlement is thought to be the most common transgranular quasi-cleavage process. Hydrogen embrittlement in this system can be identified because it requires precipitated hydride that gives characteristic fractography when cracked. Only in a few instances does stress-corrosion cracking appear to proceed by a hydride cracking mechanism. (orig.)

  5. Synthesis of zirconium by zirconium tetrachloride reduction by magnesio-thermia. Experimental study and modelling; Elaboration de zirconium par reduction de tetrachlorure de zirconium par magnesothermie. Etude experimentale et modelisation

    Energy Technology Data Exchange (ETDEWEB)

    Basin, N

    2001-01-01

    This work deals with the synthesis of zirconium. The ore is carbo-chlorinated to obtain the tetrachloride which is then purified by selective condensation and extractive distillation. Zirconium tetrachloride is then reduced by magnesium and the pseudo-alloy is obtained according to the global following reaction (Kroll process): ZrCl{sub 4} + 2 Mg = 2 MgCl{sub 2}. By thermodynamics, it has been shown that the volatilization of magnesium chloride and the formation of zirconium sub-chlorides are minimized when the combined effects of temperature and of dilution with argon are limited. With these conditions, the products, essentially zirconium and magnesium chloride, are obtained in equivalence ratio in the magnesio-thermia reaction. The global kinetics of the reduction process has been studied by a thermal gravimetric method. A thermo-balance device has been developed specially for this kinetics study. It runs under a controlled atmosphere and is coupled to a vapor tetrachloride feed unit. The transformation is modelled supposing that the zirconium and magnesium chloride formation result: 1)of the evaporation of magnesium from its liquid phase 2)of the transfer of magnesium and zirconium tetrachloride vapors towards the front of the reaction located in the gaseous phase 3)of the chemical reaction. In the studied conditions, the diffusion is supposed to be the limiting process. The influence of the following parameters: geometry of the reactive zone, temperature, scanning rate of the argon-zirconium tetrachloride mixture, composition of the argon-zirconium tetrachloride mixture has been experimentally studied and confronted with success to the model. (O.M.)

  6. Zirconium - an imported mineral commodity

    International Nuclear Information System (INIS)

    1983-10-01

    This report examines Canada's position in regard to the principal zirconium materials: zircon; fusion-cast zirconium-bearing refractory products; zirconium-bearing chemicals; and zirconium metal, master alloys, and alloys. None of these is produced in Canada except fused alumina-zirconia and certain magnesium-zirconium alloys and zirconium-bearing steels. Most of the 3 000-4 000 tonnes of the various forms of zircon believed to be consumed in Canada each year is for foundry applications. Other minerals, notably chromite, olivine and silica sand are also used for these purposes and, if necessary, could be substituted for zircon. Zirconium's key role in Canada is in CANDU nuclear power reactors, where zirconium alloys are essential in the cladding for fuel bundles and in capital equipment such as pressure tubes, calandria tubes and reactivity control mechanisms. If zirconium alloys were to become unavailable, the Canadian nuclear power industry would collapse. As a contingency measure, Ontario Hydro maintains at least nine months' stocks of nuclear fuel bundles. Canada's vulnerability to short-term disruptions to supplies of nuclear fuel is diminished further by the availability of more expensive electricity from non-nuclear sources and, given time, from mothballed thermal plants. Zirconium minerals are present in many countries, notably Australia, the Republic of South Africa and the United States. Australia is Canada's principal source of zircon imports; South Africa is its sole source of baddeleyite. At this time, there are no shortages of either material. Canada has untapped zirconium resources in the Athabasca Oil Sands (zircon) and at Strange Lake along the ill-defined border between Quebec and Newfoundland (gittinsite). Adequate metal and alloy production facilities exist in France, Japan and the United States. No action by the federal government in regard to zirconium supplies is called for at this time

  7. Influence of redox condition in iron, silicon and hydrogen contents of leached glass surface

    International Nuclear Information System (INIS)

    Manara, A.; Lanza, F.; Della Mea, G.; Rossi, C.; Salvagno, G.

    1984-01-01

    Surface analysis has been conducted on samples leached in a Sochlet apparatus at 100 0 C in the presence and in the absence of air. The XPS technique was applied to analyze the content of iron and silicon while the nuclear reaction method was utilized to analyze the content of hydrogen. Samples leached in argon atmosphere have shown a smaller content of iron and silicon with respect to the samples leached in air atmosphere. The H concentration has shown the same behavior. The results are discussed in terms of possible formation of iron compounds in the different redox condition and of their different stabilities and in terms of their efficiency in reducing exchange between Na + and H + ions. 11 references, 3 figures, 1 table

  8. Process for purifying zirconium sponge

    International Nuclear Information System (INIS)

    Abodishish, H.A.M.; Kimball, L.S.

    1992-01-01

    This patent describes a Kroll reduction process wherein a zirconium sponge contaminated with unreacted magnesium and by-product magnesium chloride is produced as a regulus, a process for purifying the zirconium sponge. It comprises: distilling magnesium and magnesium chloride from: a regulus containing a zirconium sponge and magnesium and magnesium chloride at a temperature above about 800 degrees C and at an absolute pressure less than about 10 mmHg in a distillation vessel to purify the zirconium sponge; condensing the magnesium and the magnesium chloride distilled from the zirconium sponge in a condenser; and then backfilling the vessel containing the zirconium sponge and the condenser containing the magnesium and the magnesium chloride with a gas; recirculating the gas between the vessel and the condenser to cool the zirconium sponge from above about 800 degrees C to below about 300 degrees C; and cooling the recirculating gas in the condenser containing the condensed magnesium and the condensed magnesium chloride as the gas cools the zirconium sponge to below about 300 degrees C

  9. Reaction path sampling of the reaction between iron(II) and hydrogen peroxide in aqueous solution

    NARCIS (Netherlands)

    Ensing, B.; Baerends, E.J.

    2002-01-01

    Previously, we have studied the coordination and dissociation of hydrogen peroxide with iron(II) in aqueous solution by Car-Parrinello molecular dynamics at room temperature. We presented a few illustrative reaction events, in which the ferryl ion ([Fe(IV)O

  10. Gadolinium-hydrogen ion exchange of zirconium phosphate

    Science.gov (United States)

    Liu, D. C.; Power, J. L.

    1972-01-01

    The Gd(+3)/H(+) ion exchange on a commercial zirconium phosphate ion exchanger was investigated in chloride, sulfate, and phosphate solutions of Gd(+3) at gadolinium concentrations of 0.001 to 1 millimole per cc and in the pH range of 0 to 3.5. Relatively low Gd(+3) capacities, in the range of 0.01 to 0.1 millimole per g of ion exchanger were found at room temperature. A significant difference in Gd(+3) sorption was observed, depending on whether the ion exchanger was converted from initial conditions of greater or lesser Gd(+3) sorption than the specific final conditions. Correlations were found between decrease in Gd(+3) capacity and loss of exchanger phosphate groups due to hydrolysis during washing and between increase in capacity and treatment with H3PO4. Fitting of the experimental data to ideal ion exchange equilibrium expressions indicated that each Gd(+3) ion is sorbed on only one site of the ion exchanger. The selectivity quotient was determined to be 2.5 + or - 0.4 at room temperature on gadolinium desorption in chloride solutions.

  11. Contribution to the study of zirconium self-diffusion in zirconium carbide

    International Nuclear Information System (INIS)

    An, Chul

    1972-01-01

    The objective of this research thesis is to determine experimental conditions allowing the measurement of the self-diffusion coefficient of zirconium in zirconium carbide. The author reports the development of a method of preparation of zirconium carbide samples. He reports the use of ion implantation as technique to obtain a radio-tracer coating. The obtained results give evidence of the impossibility to use sintered samples with small grains because of the demonstrated importance of intergranular diffusion. The self-diffusion coefficient is obtained in the case of zirconium carbide with grains having a diameter of few millimetres. The presence of 95 Nb from the disintegration of 95 Zr indicates that these both metallic elements have very close diffusion coefficients at 2.600 C [fr

  12. Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts.

    Science.gov (United States)

    Li, Jiang; Liu, Jun-Ling; Zhou, Hong-Jun; Fu, Yao

    2016-06-08

    Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen-iron species, the presence of crystallized Fe2 O3 phase, and the pore structure change were the main reasons for catalyst deactivation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Artefacts in multimodal imaging of titanium, zirconium and binary titanium-zirconium alloy dental implants: an in vitro study.

    Science.gov (United States)

    Smeets, Ralf; Schöllchen, Maximilian; Gauer, Tobias; Aarabi, Ghazal; Assaf, Alexandre T; Rendenbach, Carsten; Beck-Broichsitter, Benedicta; Semmusch, Jan; Sedlacik, Jan; Heiland, Max; Fiehler, Jens; Siemonsen, Susanne

    2017-02-01

    To analyze and evaluate imaging artefacts induced by zirconium, titanium and titanium-zirconium alloy dental implants. Zirconium, titanium and titanium-zirconium alloy implants were embedded in gelatin and MRI, CT and CBCT were performed. Standard protocols were used for each modality. For MRI, line-distance profiles were plotted to quantify the accuracy of size determination. For CT and CBCT, six shells surrounding the implant were defined every 0.5 cm from the implant surface and histogram parameters were determined for each shell. While titanium and titanium-zirconium alloy induced extensive signal voids in MRI owing to strong susceptibility, zirconium implants were clearly definable with only minor distortion artefacts. For titanium and titanium-zirconium alloy, the MR signal was attenuated up to 14.1 mm from the implant. In CT, titanium and titanium-zirconium alloy resulted in less streak artefacts in comparison with zirconium. In CBCT, titanium-zirconium alloy induced more severe artefacts than zirconium and titanium. MRI allows for an excellent image contrast and limited artefacts in patients with zirconium implants. CT and CBCT examinations are less affected by artefacts from titanium and titanium-zirconium alloy implants compared with MRI. The knowledge about differences of artefacts through different implant materials and image modalities might help support clinical decisions for the choice of implant material or imaging device in the clinical setting.

  14. Artefacts in multimodal imaging of titanium, zirconium and binary titanium–zirconium alloy dental implants: an in vitro study

    Science.gov (United States)

    Schöllchen, Maximilian; Aarabi, Ghazal; Assaf, Alexandre T; Rendenbach, Carsten; Beck-Broichsitter, Benedicta; Semmusch, Jan; Sedlacik, Jan; Heiland, Max; Fiehler, Jens; Siemonsen, Susanne

    2017-01-01

    Objectives: To analyze and evaluate imaging artefacts induced by zirconium, titanium and titanium–zirconium alloy dental implants. Methods: Zirconium, titanium and titanium–zirconium alloy implants were embedded in gelatin and MRI, CT and CBCT were performed. Standard protocols were used for each modality. For MRI, line–distance profiles were plotted to quantify the accuracy of size determination. For CT and CBCT, six shells surrounding the implant were defined every 0.5 cm from the implant surface and histogram parameters were determined for each shell. Results: While titanium and titanium–zirconium alloy induced extensive signal voids in MRI owing to strong susceptibility, zirconium implants were clearly definable with only minor distortion artefacts. For titanium and titanium–zirconium alloy, the MR signal was attenuated up to 14.1 mm from the implant. In CT, titanium and titanium–zirconium alloy resulted in less streak artefacts in comparison with zirconium. In CBCT, titanium–zirconium alloy induced more severe artefacts than zirconium and titanium. Conclusions: MRI allows for an excellent image contrast and limited artefacts in patients with zirconium implants. CT and CBCT examinations are less affected by artefacts from titanium and titanium–zirconium alloy implants compared with MRI. The knowledge about differences of artefacts through different implant materials and image modalities might help support clinical decisions for the choice of implant material or imaging device in the clinical setting. PMID:27910719

  15. Method of separating hafnium from zirconium

    International Nuclear Information System (INIS)

    Megy, J.A.

    1980-01-01

    English. A new anhydrous method was developed for separating zirconium and hafnium, which gives higher separation factors and is more economical than previous methods. A molten phase, comprising a solution of unseparated zirconium and hafnium and a solvent metal, is first prepared. The molten metal phase is contacted with a fused salt phase which includes a zirconium salt. Zirconium and hafnium separation is effected by mutual displacement with hafnium being transported from the molten metal phase to the fused salt phase, while zirconium is transported from the fused salt phase to the molten metal phase. The solvent metal is less electropositive than zirconium. Zinc was chosen as the solvent metal, from a group which also included cadmium, lead, bismuth, copper, and tin. The fused salt phase cations are more electropositive than zirconium and were selected from a group comprising the alkali elements, the alkaline earth elements, the rare earth elements, and aluminum. A portion of the zirconium in the molten metal phase was oxidized by injecting an oxidizing agent, chlorine, to form zirconium tetrachlorid

  16. Valorizing waste iron powder in biogas production: Hydrogen sulfide control and process performances.

    Science.gov (United States)

    Andriamanohiarisoamanana, Fetra J; Shirai, Tomoya; Yamashiro, Takaki; Yasui, Seiichi; Iwasaki, Masahiro; Ihara, Ikko; Nishida, Takehiro; Tangtaweewipat, Suchon; Umetsu, Kazutaka

    2018-02-15

    Biogas is composed of different gases including hydrogen sulfide (H 2 S), which is a hazardous gas that damages pipes and generators in anaerobic digestion system. The objective of this study was to control H 2 S by waste iron powder produced by laser cutting machine in a steel and iron industry. Waste iron powder was mixed with dairy manure at a concentration between 2.0 and 20.0 g/L in batch experiments, while the concentration was varied between 1.0 and 4.0 g/L in bench experiment. In batch experiment, a reduction of up to 93% of H 2 S was observed at waste iron powder of 2.0 g/L (T1), while the reduction was of more than 99% at waste iron powder beyond 8.0 g/L (T4 ∼ T6). The total sulfide concentration (S T ) increased together with waste iron powder concentration and was fitted with a quadratic equation with a maximum S T of 208.0 mg/L at waste iron powder of 20.2 g/L. Waste iron powder did not have significant effect on methane yield in batch and bench experiments. However, hydrolysis rate constant was increased by almost 100%, while the lag-phase period was reduced to half in test digesters compared to that in control digester. In bench experiment, H 2 S concentration was reduced by 89% at 2.0 g/L, while 50% at 1.0 g/L. Therefore, waste iron powder was effectively removed H 2 S and did not affect negatively anaerobic digestion process. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Zirconium-barrier cladding attributes

    International Nuclear Information System (INIS)

    Rosenbaum, H.S.; Rand, R.A.; Tucker, R.P.; Cheng, B.; Adamson, R.B.; Davies, J.H.; Armijo, J.S.; Wisner, S.B.

    1987-01-01

    This metallurgical study of Zr-barrier fuel cladding evaluates the importance of three salient attributes: (1) metallurgical bond between the zirconium liner and the Zircaloy substrate, (2) liner thickness (roughly 10% of the total cladding wall), and (3) softness (purity). The effect that each of these attributes has on the pellet-cladding interaction (PCI) resistance of the Zr-barrier fuel was studied by a combination of analytical model calculations and laboratory experiments using an expanding mandrel technique. Each of the attributes is shown to contribute to PCI resistance. The effect of the zirconium liner on fuel behavior during off-normal events in which steam comes in contact with the zirconium surface was studied experimentally. Simulations of loss-of-coolant accident (LOCA) showed that the behavior of Zr-barrier cladding is virtually indistinguishable from that of conventional Zircaloy cladding. If steam contacts the zirconium liner surface through a cladding perforation and the fuel rod is operated under normal power conditions, the zirconium liner is oxidized more rapidly than is Zircaloy, but the oxidation rate returns to the rate of Zircaloy oxidation when the oxide phase reaches the zirconium-Zircaloy metallurgical bond

  18. Influence of preliminary radiation-oxidizing treatment on the corrosion resistance of zirconium in conditions of action of ionizing radiation

    International Nuclear Information System (INIS)

    Garibov, A. A.; Aliyev, A. G.; Agayev, T. N.; Velibekova, G. Z.

    2004-01-01

    Today mainly water-cooled nuclear reactors predominate in atomic energetics. For safe work of nuclear reactors detection of accumulation process of explosives, formed during radiation and temperature influence on heat-carriers in contact with materials of nuclear reactors in normal and emergency regimes of work is of great importance. The main sources of molecular hydrogen formation in normal and emergency regimes are the processes of liquid and vaporous water in vapo metallic reaction [1-5]. At the result of these processes molecular hydrogen concentration in heat-carrier composition always exceeds theoretically expected concentration. One of the main ways to solve the problem of water-cooled reactors safety is detection of possibilities to raise material resistance of fuel elements and heat carrier to joint action of ionizing radiation and temperature. The second way is inhibition of radiation-catalytic activity of construction materials' surface during the process of water decomposition. It's been established, that one of the ways to raise resistance of zirconium materials to the influence of ionizing radiation is formation of thin oxide film on the surface of metals. In the given work the influence of preliminary oxidizing treatment of zirconium surface on its radiation-catalytic activity during the process of water decomposition. With this aim zirconium is exposed to preliminary influence of gamma-quantum in contact with hydrogen peroxide at different meanings of absorbed radiation dose

  19. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral iron

    Science.gov (United States)

    Barklem, P. S.

    2018-05-01

    Data for inelastic processes due to hydrogen atom collisions with iron are needed for accurate modelling of the iron spectrum in late-type stars. Excitation and charge transfer in low-energy Fe+H collisions is studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multi-channel Landau-Zener model. An extensive calculation including 166 covalent states and 25 ionic states is presented and rate coefficients are calculated for temperatures in the range 1000-20 000 K. The largest rates are found for charge transfer processes to and from two clusters of states around 6.3 and 6.6 eV excitation, corresponding in both cases to active 4d and 5p electrons undergoing transfer. Excitation and de-excitation processes among these two sets of states are also significant. Full Tables and rate coefficient data are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/612/A90

  20. Localized deformation of zirconium-liner tube

    International Nuclear Information System (INIS)

    Nagase, Fumihisa; Uchida, Masaaki

    1988-03-01

    Zirconium-liner tube has come to be used in BWR. Zirconium liner mitigates the localized stress produced by the pellet-cladding interaction (PCI). In this study, simulating the ridging, stresses were applied to the inner surfaces of zirconium-liner tubes and Zircaloy-2 tubes, and, to investigate the mechanism and the extent of the effect, the behavior of zirconium liner was examined. As the result of examination, stress was concentrated especially at the edge of the deformed region, where zirconium liner was highly deformed. Even after high stress was applied, the deformation of Zircaloy part was small, since almost the concentrated stress was mitigated by the deformation of zirconium liner. In addition, stress and strain distributions in the cross section of specimen were calculated with a computer code FEMAXI-III. The results also showed that zirconium liner mitigated the localized stress in Zircaloy, although the affected zone was restricted to the region near the boundary between zirconium liner and Zircaloy. (author)

  1. Zirconium isotope separation process

    International Nuclear Information System (INIS)

    Peterson, S.H.; Lahoda, E.J.

    1988-01-01

    A process is described for reducing the amount of zirconium 91 isotope in zirconium comprising: forming a first solution of (a) a first solvent, (b) a scavenger, and (c) a zirconium compound which is soluble in the first solvent and reacts with the scavenger when exposed to light of a wavelength of 220 to 600 nm; irradiating the first solution with light at the wavelength for a time sufficient to photoreact a disproportionate amount of the zirconium compound containing the zirconium 91 isotope with the scavenger to form a reaction product in the first solution; contacting the first solution, while effecting the irradiation, with a second solvent which is immiscible with the first solvent, which the second solvent is a preferential solvent for the reaction product relative to the first solvent, such that at least a portion of the reaction product is transferred to the second solvent to form a second solution; and separating the second solution from the first solution after the contacting

  2. Solvent extraction of titanium(IV), zirconium(IV) and hafnium(IV) salicylates using liquid ion exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Sundaramurthi, N M; Shinde, V M

    1989-02-01

    A solvent extraction method is proposed for the extraction of quadrivalent titanium, zirconium an hafnium from salicylate media using liquid ion exchangers such as Aliquat 336 and trioctylamine dissolved in xylene. The optimum conditions were evaluated from a critical study of the following: pH, salicylate concentration, amine concentration, diluent and period of equilibration. The method allows the separation of titanium, zirconium and hafnium from binary mixtures containing commonly associated metal ions and is applicable to the analysis of real samples such as BCS-CRM 387 nimonic 901, BCS-CRM 243/4 ferro-titanium, BCS-CRM 307 magnesium alloy and BCS-CRM 388 zircon. Titanium is determined either with hydrogen peroxide or by atomic absorption spectrometry whereas zirconium and hafnium are determined spectrophotometrically with Alizarin Red S and Zylenol Orange, respectively. The results of both separation and analysis are reported. The method is precise, accurate and fast.

  3. Process for etching zirconium metallic objects

    International Nuclear Information System (INIS)

    Panson, A.J.

    1988-01-01

    In a process for etching of zirconium metallic articles formed from zirconium or a zirconium alloy, wherein the zirconium metallic article is contacted with an aqueous hydrofluoric acid-nitric acid etching bath having an initial ratio of hydrofluoric acid to nitric acid and an initial concentration of hydrofluoric and nitric acids, the improvement, is described comprising: after etching of zirconium metallic articles in the bath for a period of time such that the etching rate has diminished from an initial rate to a lesser rate, adding hydrofluoric acid and nitric acid to the exhausted bath to adjust the concentration and ratio of hydrofluoric acid to nitric acid therein to a value substantially that of the initial concentration and ratio and thereby regenerate the etching solution without removal of dissolved zirconium therefrom; and etching further zirconium metallic articles in the regenerated etching bath

  4. Components made of corrosion-resistent zirconium alloy and method for its production

    International Nuclear Information System (INIS)

    Hanneman, R.E.; Urquhart, A.W.; Vermilyea, D.A.

    1977-01-01

    The invention deals with a method to increase the resistance of zirconium alloys to blister corrosion which mainly occurs in boiling-water nuclear reactors. According to the method described, the surface of the alloy body is coated with a thin film of a suitable electronically conducting material. Gold, silver, platinum, nickel, chromium, iron and niobium are suitable as coating materials. The invention is more closely explained by means of examples. (GSC) [de

  5. Zirconium and cast zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Krone, K

    1977-04-01

    A survey is given on the occurence of zirconium, production of Zr sponge and semi-finished products, on physical and mechanical properties, production of Zr cast, composition of the commercial grades and reactor grades qualities, metal cutting, welding, corrosion behavior and use.

  6. Synthesis of zirconium by zirconium tetrachloride reduction by magnesio-thermia. Experimental study and modelling

    International Nuclear Information System (INIS)

    Basin, N.

    2001-01-01

    This work deals with the synthesis of zirconium. The ore is carbo-chlorinated to obtain the tetrachloride which is then purified by selective condensation and extractive distillation. Zirconium tetrachloride is then reduced by magnesium and the pseudo-alloy is obtained according to the global following reaction (Kroll process): ZrCl 4 + 2 Mg = 2 MgCl 2 . By thermodynamics, it has been shown that the volatilization of magnesium chloride and the formation of zirconium sub-chlorides are minimized when the combined effects of temperature and of dilution with argon are limited. With these conditions, the products, essentially zirconium and magnesium chloride, are obtained in equivalence ratio in the magnesio-thermia reaction. The global kinetics of the reduction process has been studied by a thermal gravimetric method. A thermo-balance device has been developed specially for this kinetics study. It runs under a controlled atmosphere and is coupled to a vapor tetrachloride feed unit. The transformation is modelled supposing that the zirconium and magnesium chloride formation result: 1)of the evaporation of magnesium from its liquid phase 2)of the transfer of magnesium and zirconium tetrachloride vapors towards the front of the reaction located in the gaseous phase 3)of the chemical reaction. In the studied conditions, the diffusion is supposed to be the limiting process. The influence of the following parameters: geometry of the reactive zone, temperature, scanning rate of the argon-zirconium tetrachloride mixture, composition of the argon-zirconium tetrachloride mixture has been experimentally studied and confronted with success to the model. (O.M.)

  7. Acid-Base Bifunctional Zirconium N-Alkyltriphosphate Nanohybrid for Hydrogen Transfer of Biomass-Derived Carboxides

    DEFF Research Database (Denmark)

    Li, Hu; He, Jian; Riisager, Anders

    2016-01-01

    sites, and their catalytic activity in converting biomass-derived carbonyl compounds to corresponding alcohols in 2-propanol. Particularly, a quantitative yield of furfuryl alcohol (FFA) was obtained from furfural (FUR) over organotriphosphate-zirconium hybrid (ZrPN) under mild conditions. The presence...

  8. Spectrophotometric determination of zirconium in nickel-base alloys with Arsenazo III after separation by froth flotation

    International Nuclear Information System (INIS)

    Sekine, K.; Onishi, H.

    1977-01-01

    0.02-0.1% of zirconium can be determined in nickel alloys by spectrophotometry with Arsenazo III after its separation from the sample solution by means of froth flotation using Arsenazo III and Zephiramine. Nickel, chromium and iron do not interfere. Analysis of standard alloys yielded a standard deviation of 2.2%. (orig.) [de

  9. Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

    Science.gov (United States)

    Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

    2016-07-01

    The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

  10. Removal of Reactive Red 198 by Nanoparticle Zero Valent Iron in the Presence of Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Siroos Shojaei

    2017-04-01

    Full Text Available Although dyes are widely used in textile industries, they are carcinogenic, teratogenic and mutagenic. Industries discharge their wastewater containing a variety of colors into water resources and make harmful effect on the environment. The present study aims to Evaluate removal of reactive red 198 by nanoparticle zero valent iron (NZVI in the presence of hydrogen peroxide from aqueous solution. The effective parameters on the removal of dye such as the hydrogen peroxide concentration of NZVI, contact time, pH and dye concentration were investigated and optimized. According to the results, the combination of NZVI with hydrogen peroxide is more effective than single hydrogen peroxide. At pH = 4, contact time= 40 min, 200 M of hydrogen peroxide, dye concentration= 75 mg/L and concentration of NZVI 2g/L, color removal was achieved 91% approximately. Based on the results of experiments, using hydrogen peroxide- NZVI has high efficiency in removal of azo dye type.

  11. Review of theoretical conceptions on regimes of oxidation and hydrogen pickup in Zr-alloys

    International Nuclear Information System (INIS)

    Likhanskii, V.; Evdokimov, I.

    2008-01-01

    In this paper the following issues are presented: 1) Experimental observations published in the journals on corrosion regimes of zirconium alloys of various compositions both for ex-pile oxidation experiments and for in-pile operating conditions of the materials. Factors experimentally stated on the effect of alloying composition, microstructure and texture on the rate of uniform corrosion and susceptibility of alloys to nodular corrosion. 2) Phenomenological models existing in publications, which describe conditions of uniform and nodular corrosion for Zr-alloys of various composition and microstructures, effect of irradiation and oxidizing medium; 3) Experimental data and phenomenological models describing regimes of hydrogen absorption in zirconium alloys; 4) Examples of application of physical models in explaining regimes, peculiarities of oxidation and hydrogen pickup for zirconium claddings of various alloying composition and microstructure

  12. Hydrogen terminal solubility in Zircaloy-4

    International Nuclear Information System (INIS)

    Vizcaino, Pablo; Banchik, Abrahan D.

    1999-01-01

    Terminal solubility temperature of hydrogen in zirconium and its alloys is an important parameter because hydrides precipitation embrittled these materials making them susceptible to the phenomenon known as retarded hydrogen cracking. This work continues the study presented in the 25 AATN Meeting. Within this framework, a study focused on determining these curves in recrystallized Zircaloy-4, using scanning differential calorimetric technique. Terminal solubility curves for Zircaloy-4 were constructed within a concentration range from 40 to 640 ppm in hydrogen weight and comparisons with results obtained by other authors were made. (author)

  13. Neutron activation of chlorine in zirconium and zirconium alloys use of the matrix as comparator

    International Nuclear Information System (INIS)

    Cohen, I.M.; Gomez, C.D.; Mila, M.I.

    1981-01-01

    A procedure is described for neutron activation analysis of chlorine in zirconium and zirconium alloys. Calculation of chlorine concentration is performed relative to zirconium concentration in the matrix in order to minimize effects of differences in irradiation and counting geometry. Principles of the method and the results obtained are discussed. (author)

  14. Hot vacuum extraction-isotopic dilution mass spectrometry for determination of hydrogen isotopes in zircaloys

    International Nuclear Information System (INIS)

    Shi, Y.; Leeson, P.K.; Wilkin, D.; Britton, A.; Macleod, R.

    2016-01-01

    A hot vacuum extraction-isotope dilution mass spectrometry (HVE-IDMS) was studied for determination of hydrogen isotopes in zirconium metal and alloys as nuclear reactor materials. A theoretical assessment of the completeness of the extraction of hydrogen isotopes under the chosen condition was carried out based on the hydrogen and deuterium solubility data for zirconium. The optimal isotopic spiking condition for conventional IDMS was further explored for the special case IDMS where the isotope abundance of the samples is varied and non-natural. Applying the optimal conditions, the accurate IDMS determination was realized. The agreement between the measured values and the certified or prepared values of standard reference materials and homemade standard materials validate the method developed. (author)

  15. Extraction of zirconium from raffinate stream of Zirconium Oxide Plant raffinate

    International Nuclear Information System (INIS)

    Pandey, Garima; Chinchale, R.; Renjith, A.U.; Mukhopadhyay, S.; Shenoy, K.T.; Ghosh, S.K.

    2013-01-01

    Recovery of metals from dilute streams is a major task in nuclear industry in the view of environmental remediation and value recovery. Presently solvent extraction process is employed on the commercial scale to recover nuclear pure zirconium using TBP as extractant. The waste stream of TBP extraction process contains about 1.2 gpl of Zirconium in nitrate form. At present there is no process to recover Zirconium from this raffinate stream. Hence, under the present study recovery of zirconium from the raffinate stream of Zirconium Oxide Plant Raffinate has been investigated. TBP, which is the most commonly used solvent in the nuclear industry is not suitable for the extraction of zirconium from lean solution at low acidity as its distribution coefficient is less than one. In search of a suitable extractant Mixed Alkyl Phosphine Oxide (MAPO) was investigated as potential carrier. Parametric batch studies for various equilibrium data like extractant concentration, strippant concentration, solvent reusability, equilibration time, acidity etc. were done to optimize the process condition. For the distribution studies, equal volumes of the raffinate and organic phase were shaken at room temperature in digital wrist action shaker for 10 minutes to ensure complete equilibrium. It was found that 0.1 M MAPO in 80:20 dodecane: isodecanol is suitable for extraction of Zr at 2 N acidity. 0.1 M MAPO gives distribution coefficient in the range of 12-15 for Zr. The slope of log-log plot between MAPO concentration and K, suggests involvement of 3 molecules of MAPO in the formation of extracting species. 0.2 M Oxalic acid was able to completely back extract Zr from the organic phase into aqueous phase. Also good regeneration capacity of MAPO projects its potential to be used as extractant for the process. Based on the equilibrium studies, Dispersion Liquid Membrane configuration in hollow fiber contactor was explored for the extraction of Zirconium from Zirconium Nitrate Pure

  16. INR participation in the IAEA research project investigating the influence of hydrogen absorption on zirconium alloy behavior

    International Nuclear Information System (INIS)

    Roth, Maria; Radu, Vasile; Dobrea, Dumitru; Pitigoi, Vasile

    2003-01-01

    The paper summarizes the results obtained at INR Pitesti from its participation in the research project coordinated by IAEA Vienna in cooperation with Chalk River and AECL Canada, titled 'Hydrogen and Hydride Induced Degradation of the Mechanical and Physical Properties of Zirconium-based Alloys'. Evidenced is the contribution of INR Pitesti in the works of this project as well as the benefits of this participation for Romania as owner of CANDU type reactor. In the frame this project new results concerning the propagation rate of DHC type cracks in pressure tubes in CANDU reactors were obtained. The same method used to investigate the DHC project was adapted for determination of other quantities of interest related to structural integrity of the materials. The methodology was applied for testing the pressure tubes in Cernavoda NPP Unit 1. The contribution of INR team to statistical processing of data obtained in all the laboratories participating in this project is also highlighted. Opportunity afforded by IAEA to INR Pitesti to bring its contribution to the development of this project of international cooperation together with other well-known institutions and the support from RAAN are acknowledged. These opened ways for other fruitful international cooperation

  17. Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Wael Ahmed Abou Taleb Sayed

    2011-01-13

    stability was reported for a reaction time of 10 hours. The results showed that the reaction route, the product distribution and hydrogen selectivity strongly depend on the iron oxide phase. The {alpha}-Fe{sub 2}O{sub 3} phase showed high hydrogen selectivity with the highest stability. Over {alpha}-Fe{sub 2}O{sub 3}/SiC supported catalysts acetaldehyde, water and CO{sub 2} were the main products. The product distributions strongly depended on the catalyst iron content. With increasing sample iron content, more CO{sub 2} and water was produced. The catalyst with an iron content of 1.9% showed the highest acetaldehyde yield. This is attributed to the low iron oxide content at active sites which lead to a dehydrogenation of ethanol to acetaldehyde. In contrast, at higher iron content more active sites were provided hence the acetaldehyde re-adsorbed and further oxidised to CO{sub 2}. All supported catalysts showed a good stability for 10 hours. In this time, the ethanol conversion was decreased by 9% with constant acetaldehyde yield. These results provide evidence that the reaction occurs over the iron oxide surface and iron oxide-support interface but not over the SiC particles. These results were supported by carrying out the ethanol oxidation over pure {alpha}-Fe{sub 2}O{sub 3} nanoparticles with different surface areas. Those surface areas were chosen depending on the surface areas measured for the pure {alpha}-Fe{sub 2}O{sub 3} and surface area calculated for iron oxide in the supported samples. The investigation showed that with a large catalyst surface areas hydrogen with a high selectivity may be produced, whereas with a small surface area only acetaldehyde, water and CO{sub 2} can be produced. The characterisation of the used catalyst showed a small variation of the iron oxide particle size and large surface area. This proved that the SiC support avoids a hot spot formation and prevents iron oxide particles from being sintered. (orig.)

  18. Proceedings of the second Alfred O. Nier symposium on inorganic mass spectrometry

    International Nuclear Information System (INIS)

    Green, L.W.

    1996-01-01

    The proceedings are organized under the following headings: thermal ionization mass spectrometry, applications and instrumentation; inductively coupled plasma and glow discharge mass spectrometry; gases; laser resonance ionization; general. Topics of nuclear significance include: determination of trace iron in zirconium; characterization of uranium in surface waters; subpicogram quantities of technetium; measurement of isotope ratios; determination of hydrogen and deuterium in zirconium and its alloys; Kr and Xe isotopic measurements; Kr-85 detection; SIMS study of zirconium corrosion; isotopes at CEA (Commissariat a l'Energie Atomique). All the papers have been abstracted separately for INIS

  19. Irradiation induced effects in zirconium (A review)

    International Nuclear Information System (INIS)

    Madden, P.K.

    1975-06-01

    Irradiation creep in zirconium and its alloys is comprehensively discussed. The main theories are outlined and the gaps between them and the observed creep behaviour, indicated. Although irradiation induced point defects play an important role, effects due to irradiation induced dislocation loops seem insignificant. The experimental results suggest that microstructural variations due to prior cold-working or hydrogen injection perturb the irradiation growth and the irradiation creep of zircaloy. Further investigations into these areas are required. One disadvantage of creep experiments lies in their duration. The possibility of accelerated experiments using ion implantation or electron irradiation is examined in the final section, and its possible advantages and disadvantages are outlined. (author)

  20. Interpretation of acoustic parameters obtained by EMAR measurement for non-destructive hydrogen concentration measurement in Zr alloy

    International Nuclear Information System (INIS)

    Nakatsuka, Masafumi; Uchida, Katsuya; Miyazaki, Akihiro; Ishii, Yoshiaki

    2007-01-01

    An obvious quantitative relation between hydrogen concentrations in zirconium alloy and acoustic anisotropy parameters obtained by the electromagnetic acoustic resonance (EMAR) method was reported. To elucidate the mechanism, the acoustic parameters were calculated based on the elastic theory and the equation of motion. The acoustic parameters of obtained by the EMAR method were interpreted quantitatively using the anisotropic elastic constants of the specimen, and value calculated from texture data for non-hydrogen charged specimens showed good agreement with those obtained by the EMAR method. Calculated temperature dependence of the acoustic anisotropy for the non-hydrogen charged specimen also agreed well with that by the EMAR method. The consistencies demonstrated that the absolute values of the acoustic parameters for non-hydrogen charged specimen can be calculated from both the texture data of (0002) pole figure and the elastic constants of the specimen. Hydrogen addition up to approximately 650ppm was found not to change the original (0002) pole figure and, correspondingly, no hydrogen concentration dependence of the acoustic parameters was obtained from the calculation. These results implied that the zirconium hydride itself played an important role for the change in the acoustic parameters of the hydrogen charged specimens, and the importance of obtaining the information on the elastic constants of the zirconium hydride was pointed out. (author)

  1. Hydrogen-induced cracking: 2

    International Nuclear Information System (INIS)

    Puls, M.P.

    1984-12-01

    There is a strong motivation for understanding the factors controlling zirconium hydride reorientation under stress because of the important role this plays in hydrogen-induced crack growth and/or crack initiation in zirconium and its alloys, particularly under thermal cycling conditions. Following an approach developed by Sauthoff, an analysis of the orienting effect of external stress on the nucleation, growth and coarsening of γ- and delta-zirconium hydride precipitates in zirconium and its alloys is presented. The analysis is based on a previous theoretical study of some of the factors affecting hydride solubility in stressed and unstressed solids. Expressions are derived for the effect of stress on nucleation, growth and coarsening. We conclude, on the basis of these that the preferential orientation of hydride precipitates under stress is most efficient during the nucleation stage. The reason for this is that the overall driving force for nucleation, for the chosen parameters and the usual experimental conditions, is fairly small. Therefore, the driving force for orientating under stress can be a substantial fraction of the overall driving force. The analysis shows that hydride growth is unlikely to play a role in preferential orientation, but coarsening could be important under carefully chosen experimental conditions, which may be relevant to the hydride-cracking process

  2. Modification in band gap of zirconium complexes

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Mayank, E-mail: mayank30134@gmail.com; Singh, J.; Chouhan, S. [Department of Physics, ISLE, IPS Academy, Indore (M.P.) (India); Mishra, A. [School of Physics, Devi Ahilya Vishwavidyalaya, Indore (M.P.) (India); Shrivastava, B. D. [Govt. P. G. College, Biora (M.P.) (India)

    2016-05-06

    The optical properties of zirconium complexes with amino acid based Schiff bases are reported here. The zirconium complexes show interesting stereo chemical features, which are applicable in organometallic and organic synthesis as well as in catalysis. The band gaps of both Schiff bases and zirconium complexes were obtained by UV-Visible spectroscopy. It was found that the band gap of zirconium complexes has been modified after adding zirconium compound to the Schiff bases.

  3. Hydrogenation Properties of TiFe Doped with Zirconium

    Directory of Open Access Journals (Sweden)

    Catherine Gosselin

    2015-11-01

    Full Text Available The goal of this study was to optimize the activation behaviour of hydrogen storage alloy TiFe. We found that the addition of a small amount of Zr in TiFe alloy greatly reduces the hydrogenation activation time. Two different procedural synthesis methods were applied: co-melt, where the TiFe was melted and afterward re-melted with the addition of Zr, and single-melt, where Ti, Fe and Zr were melted together in one single operation. The co-melted sample absorbed hydrogen at its maximum capacity in less than three hours without any pre-treatment. The single-melted alloy absorbed its maximum capacity in less than seven hours, also without pre-treatment. The reason for discrepancies between co-melt and single-melt alloys was found to be the different microstructure. The effect of air exposure was also investigated. We found that the air-exposed samples had the same maximum capacity as the argon protected samples but with a slightly longer incubation time, which is probably due to the presence of a dense surface oxide layer. Scanning electron microscopy revealed the presence of a rich Zr intergranular phase in the TiFe matrix, which is responsible for the enhanced hydrogenation properties of these Zr-doped TiFe alloys.

  4. Plasma arc melting of zirconium

    International Nuclear Information System (INIS)

    Tubesing, P.K.; Korzekwa, D.R.; Dunn, P.S.

    1997-01-01

    Zirconium, like some other refractory metals, has an undesirable sensitivity to interstitials such as oxygen. Traditionally, zirconium is processed by electron beam melting to maintain minimum interstitial contamination. Electron beam melted zirconium, however, does not respond positively to mechanical processing due to its large grain size. The authors undertook a study to determine if plasma arc melting (PAM) technology could be utilized to maintain low interstitial concentrations and improve the response of zirconium to subsequent mechanical processing. The PAM process enabled them to control and maintain low interstitial levels of oxygen and carbon, produce a more favorable grain structure, and with supplementary off-gassing, improve the response to mechanical forming

  5. Deformation mechanisms and irradiation effects in zirconium alloys. A multi-scale study

    International Nuclear Information System (INIS)

    Onimus, Fabien

    2015-01-01

    occurs at high doses, the nucleation and growth of loops, has been particularly studied. The effects of the hydrogen pick up and of an external applied stress on loops have been characterized by TEM. This work, which already contributes to a better understanding of deformation mechanisms and mechanical behavior of zirconium alloys, should improve, in a future prospect, the reliability and performance of pressurized water reactors fuel assemblies. (author) [fr

  6. Hydrogen permeation in FeCrAl alloys for LWR cladding application

    Science.gov (United States)

    Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.; Snead, Lance L.

    2015-06-01

    FeCrAl, an advanced oxidation-resistant iron-based alloy class, is a highly prevalent candidate as an accident-tolerant fuel cladding material. Compared with traditional zirconium alloy fuel cladding, increased tritium permeation through FeCrAl fuel cladding to the primary coolant is expected, raising potential safety concerns. In this study, the hydrogen permeability of several FeCrAl alloys was obtained using a static permeation test station, which was calibrated and validated using 304 stainless steel. The high hydrogen permeability of FeCrAl alloys leads to concerns with respect to potentially significant tritium release when used for fuel cladding in LWRs. The total tritium inventory inside the primary coolant of a light water reactor was quantified by applying a 1-dimensional steady state tritium diffusion model to demonstrate the dependence of tritium inventory on fuel cladding type. Furthermore, potential mitigation strategies for tritium release from FeCrAl fuel cladding were discussed and indicate the potential for application of an alumina layer on the inner clad surface to serve as a tritium barrier. More effort is required to develop a robust, economical mitigation strategy for tritium permeation in reactors using FeCrAl clad fuel assemblies.

  7. Tritium permeation through iron

    International Nuclear Information System (INIS)

    Hagi, Hideki; Hayashi, Yasunori

    1989-01-01

    An experimental method for measuring diffusion coefficients and permeation rates of tritium in metals around room temperature has been established, and their values in iron have been obtained by using the method. Permeation rates of tritium and hydrogen through iron were measured by the electrochemical method in which a tritiated aqueous solution was used as a cathodic electrolyte. Tritium and hydrogen were introduced from one side of a membrane specimen by cathodic polarization, while at the other side of the specimen the permeating tritium and hydrogen were extracted by potentiostatical ionization. The amount of permeated hydrogen was obtained by integrating the anodic current, and that of tritium was determined by measuring the radioactivity of the electrolyte sampled from the extraction side. Diffusion coefficients of tritium (D T ) and hydrogen (D H ) were determined from the time lag of tritium and hydrogen permeation. D T =9x10 -10 m 2 /s and D H =4x10 -9 m 2 /s at 286 K for annealed iron specimens. These values of D T and D H were compared with the previous data of the diffusion coefficients of hydrogen and deuterium, and the isotope effect in diffusion was discussed. (orig.)

  8. Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

    Science.gov (United States)

    Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

    2018-05-01

    The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.

  9. Zirconium mediated hydrogen outdiffusion from p-GaN

    Energy Technology Data Exchange (ETDEWEB)

    Kaminska, E.; Piotrowska, A.; Barcz, A.; Jasinski, J.; Zielinski, M.; Golaszewska, K.; Davis, R.F.; Goldys, E.; Tomsia, K.

    2000-07-01

    The authors have shown that Zr-based metallization can effectively remove hydrogen from the p-type GaN subsurface, which eventually leads to the formation of an ohmic contact. As the release of hydrogen starts at {approximately}900 C, the thermal stability of the contact system is of particular importance. The remarkable thermal behavior of the ZrN/ZrB{sub 2} metallization is associated to the microstructure of each individual Zr-based compound, as well as to the interfacial crystalline accommodation.

  10. Modeling of Some Physical Properties of Zirconium Alloys for Nuclear Applications in Support of UFD Campaign

    Energy Technology Data Exchange (ETDEWEB)

    Michael V. Glazoff

    2013-08-01

    Zirconium-based alloys Zircaloy-2 and Zircaloy-4 are widely used in the nuclear industry as cladding materials for light water reactor (LWR) fuels. These materials display a very good combination of properties such as low neutron absorption, creep behavior, stress-corrosion cracking resistance, reduced hydrogen uptake, corrosion and/or oxidation, especially in the case of Zircaloy-4. However, over the last couple of years, in the post-Fukushima Daiichi world, energetic efforts have been undertaken to improve fuel clad oxidation resistance during off-normal temperature excursions. Efforts have also been made to improve upon the already achieved levels of mechanical behavior and reduce hydrogen uptake. In order to facilitate the development of such novel materials, it is very important to achieve not only engineering control, but also a scientific understanding of the underlying material degradation mechanisms, both in working conditions and in storage of used nuclear fuel. This report strives to contribute to these efforts by constructing the thermodynamic models of both alloys; constructing of the respective phase diagrams, and oxidation mechanisms. A special emphasis was placed upon the role of zirconium suboxides in hydrogen uptake reduction and the atomic mechanisms of oxidation. To that end, computational thermodynamics calculations were conducted concurrently with first-principles atomistic modeling.

  11. Application of sorption method on hydroxides for purification of some reactive from iron(III) markings

    International Nuclear Information System (INIS)

    Rakhmonberdiev, A.D.; Khamidov, B.O.

    1986-01-01

    The method of purification of solutions of citric acid, tartaric acid and their salts, potassium hydroxide, potassium nitrate and chloride, sodium perchlorate from iron (III) impurities by means of sorption method on zirconium hydroxide is elaborated. The control of iron(III) content in solutions is conducted by inversion voltammetry method with mercury-graphite electrode. It is defined that complete sorption of iron (III) ions achieves at ph =4÷14.

  12. First-Principles and Thermodynamic Simulation of Elastic Stress Effect on Energy of Hydrogen Dissolution in Alpha Iron

    Science.gov (United States)

    Rakitin, M. S.; Mirzoev, A. A.; Mirzaev, D. A.

    2018-04-01

    Mobile hydrogen, when dissolving in metals, redistributes due to the density gradients and elastic stresses, and enables destruction processes or phase transformations in local volumes of a solvent metal. It is rather important in solid state physics to investigate these interactions. The first-principle calculations performed in terms of the density functional theory, are used for thermodynamic simulation of the elastic stress effect on the energy of hydrogen dissolution in α-Fe crystal lattice. The paper presents investigations of the total energy of Fe-H system depending on the lattice parameter. As a result, the relation is obtained between the hydrogen dissolution energy and stress. A good agreement is shown between the existing data and simulation results. The extended equation is suggested for the chemical potential of hydrogen atom in iron within the local stress field. Two parameters affecting the hydrogen distribution are compared, namely local stress and phase transformations.

  13. The dissolution of organic ion exchange resins using iron-catalysed hydrogen peroxide

    International Nuclear Information System (INIS)

    Hawkings, N.; Horton, K.D.; Snelling, K.W.

    1980-10-01

    Feasibility studies have been made of the dissolution/partial decomposition of radioactive waste resins by means of iron-catalysed hydrogen peroxide. They have shown that the procedure is limited in its application and successfully treats only polystyrene/divinylbenzene-based resins. Evaporation of the final solution produces a solid residue which is difficult to handle and results in only a relatively small reduction in volume. It is concluded that the method could be used to dissolve specific waste resins for easier handling and disposal, but is not of general applicability. (author)

  14. Oxidation kinetics and auger microprobe analysis of some oxidized zirconium alloys

    International Nuclear Information System (INIS)

    Ploc, R.A.

    1989-01-01

    Oxidation kinetics at 300 o C in dry oxygen of 0.5 wt% binary alloys of iron, nickel, and chromium in zirconium were determined for several surface preparations. Further, chemical profiles of the oxides as they existed on the matrix and on the precipitates were obtained by sputtering and Auger electron analysis. The appearance of 'breakaway' oxidation was controlled by the surface finish of the alloy, a variable that could be used to eliminate the phenomenon for all alloys except the Zr/Ni binary, which required β-quenching to accomplish the same purpose. (author)

  15. Zirconium behaviour in purex process solutions

    International Nuclear Information System (INIS)

    Shu, J.

    1982-01-01

    The extraction behaviour of zirconium, as fission product, in TBP/diluent- HNO 3 -H 2 O systems, simulating Purex solutions, is studied. The main purpose is to attain an increasing in the zirconium decontamination factor by adjusting the extraction parameters. Equilibrium diagram, TBP concentration, aqueous:organic ratio, salting-out effects and, uranium loading in the organic phase were the main factors studied. All these experiments had been made with zirconium in the 10 - 2 - 10 - 3 concentration range. The extractant degradation products influence uppon the zirconium behaviour was also verified. With the obtained data it was possible to introduce some modification in the standard Purex flow-sheet in order to obtain the uranium product with higher zirconium decontamination. (Author) [pt

  16. A new mechanism of hydrogen absorption in water-water reactor core materials

    International Nuclear Information System (INIS)

    Gann, V.V.; Gann, A.V.

    2012-01-01

    The spectrum of fast protons, generated in water by fast neutrons of WWER-1000 reactor core, has been calculated using the code MCNPX. The main mechanism of fast proton generation in the moderator is found to be elastic scattering of fast neutrons on hydrogen nuclei. Fast protons with mean energy 1 MeV flow towards the surface of cladding material at flux density ∼ 0.1 μA/cm 2 . Proton range distribution profile in cladding material is calculated. The range of fast protons in zirconium averages 20 μm, the maximal proton range is larger than 200 μm. The rate of hydrogen deposition in 40 μm layer amounts to 5 x 10 -5 H/n/μ. A role of the suggested mechanism in process of zirconium clad hydrogenation during reactor irradiation is discussed.

  17. Atomistic modeling of zirconium hydride precipitation: methodology for deriving a tight-binding potential

    International Nuclear Information System (INIS)

    Dufresne, Alice

    2014-01-01

    The zirconium-hydrogen system is of nuclear safety interest, as the hydride precipitation leads to the cladding embrittlement, which is made of zirconium-based alloys. The cladding is the first safety barrier confining the radioactive products: its integrity shall be kept during the entire fuel-assemblies life, in reactor, including accidental situation, and post-operation (transport and storage). Many uncertainties remain regarding the hydrides precipitation kinetics and the local stress impact on their precipitation. The atomic scale modeling of this system would bring clarifications on the relevant mechanisms. The usual atomistic modeling methods are based on thermo-statistic approaches, whose precision and reliability depend on the interatomic potential used. However, there was no potential allowing a rigorous study of the Zr-H system. The present work has indeed addressed this issue: a new tight-binding potential for zirconium hydrides modeling is now available. Moreover, this thesis provides a detailed manual for deriving such potentials accounting for spd hybridization, and fitted here on DFT results. This guidebook has be written in light of modeling a pure transition metal followed by a metal-covalent coupling (metallic carbides, nitrides and silicides). (author)

  18. Adsorption of phosphate from aqueous solution using iron-zirconium modified activated carbon nanofiber: Performance and mechanism.

    Science.gov (United States)

    Xiong, Weiping; Tong, Jing; Yang, Zhaohui; Zeng, Guangming; Zhou, Yaoyu; Wang, Dongbo; Song, Peipei; Xu, Rui; Zhang, Chen; Cheng, Min

    2017-05-01

    Phosphate (P) removal is significant for the prevention of eutrophication in natural waters. In this paper, a novel adsorbent for the removal of P from aqueous solution was synthesized by loading zirconium oxide and iron oxide onto activated carbon nanofiber (ACF-ZrFe) simultaneously. The adsorbent was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The results showed that P adsorption was highly pH dependent and the optimum pH was found to be 4.0. The isotherm of adsorption could be well described by the Langmuir model and the maximum P adsorption capacity was estimated to be 26.3mgP/g at 25°C. The kinetic data were well fitted to the pseudo-second-order equation, indicating that chemical sorption was the rate-limiting step. Moreover, co-existing ions including sulfate (SO 4 2- ), chloride (Cl - ), nitrate (NO 3 - ) and fluoride (F - ) exhibited a distinct effect on P adsorption with the order of F - >NO 3 - >Cl - >SO 4 2- . Further investigations by FT-IR spectroscopy and pH variations associated with the adsorption process revealed that ligands exchange and electrostatic interactions were the dominant mechanisms for P adsorption. The findings reported in this work highlight the potential of using ACF-ZrFe as an effective adsorbent for the removal of P in natural waters. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Non-enzymatic hydrogen peroxide sensor using an electrode modified with iron pentacyanonitrosylferrate nanoparticles

    International Nuclear Information System (INIS)

    Razmi, H.; Mohammad-Rezaei, R.

    2010-01-01

    An electrochemical sensor was developed for determination of hydrogen peroxide (HP) based on a carbon ceramic electrode modified with iron pentacyanonitrosylferrate (FePCNF). The surface of an iron-doped CCE was derivatized in a solution of PCNF by cycling the electrode potential between -0. 2 and +1. 3 V for about 60 times. The morphology and the composition of the resulting electrode were characterized by scanning electron microscopy and Fourier transform infrared techniques. The electrode displayed excellent response to the electro-oxidation of HP which is linearly related to its concentration in the range from 0. 5 μM to 1300 μM. The detection limit is 0. 4 μM, and the sensitivity is 849 A M -1 cm -2 . The modified electrode was used to determination of HP in hair coloring creams as real samples. (author)

  20. Anisotropy of mechanical properties of zirconium and zirconium alloys

    International Nuclear Information System (INIS)

    Medrano, R.E.

    1975-01-01

    In studies of technological applications of zirconium to fuel elements of nuclear reactor, it was found that the use of plasticity equations for isotropic materials is not in agreement with experimental results, because of the strong anisotropy of zirconium. The present review describes recent progress on the knowledge of the influence of anisotropy on mechanical properties, after Douglass' review in 1971. The review was written to be selfconsistent, changing drastically the presentation of some of the referenced papers. It is also suggested some particular experiments to improve developments in this area

  1. Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

    International Nuclear Information System (INIS)

    Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

    2005-01-01

    The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  2. New solvent extraction process for zirconium and hafnium

    International Nuclear Information System (INIS)

    Takahashi, M.; Katoh, Y.; Miyazaki, H.

    1984-01-01

    The authors' company developed a new solvent extraction process for zirconium and hafnium separation, and started production of zirconium sponge by this new process in September 1979. The process utilizes selective extraction of zirconium oxysulfate using high-molecular alkyl amine, and has the following advantages: 1. This extraction system has a separation factor as high as 10 to 20 for zirconium and hafnium in the range of suitable acid concentration. 2. In the scrubbing section, removal of all the hafnium that coexists with zirconium in the organic solvent can be effectively accomplished by using scrubbing solution containing hafnium-free zirconium sulfate. Consequently, hafnium in the zirconium sponge obtained is reduced to less than 50 ppm. 3. The extractant undergoes no chemical changes but is very stable for a long period. In particular, its solubility in water is small, about 20 ppm maximum, posing no environmental pollution problems such as are often caused by other process raffinates. At the present time, the zirconium and hafnium separation operation is very stable, and zirconium sponge made by this process can be applied satisfactorily to nuclear reactors

  3. At the frontier between heterogeneous and homogeneous catalysis : hydrogenation of olefins and alkynes with soluble iron nanoparticles

    NARCIS (Netherlands)

    Rangheard, Claudine; Julián Fernández, César de; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; Vries, Johannes G. de

    2010-01-01

    The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C–C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl3 reduced by 3

  4. Fine-grained zirconium-base material

    Science.gov (United States)

    Van Houten, G.R.

    1974-01-01

    A method is described for making zirconium with inhibited grain growth characteristics, by the process of vacuum melting the zirconium, adding 0.3 to 0.5% carbon, stirring, homogenizing, and cooling. (Official Gazette)

  5. Microhardness and microplasticity of zirconium nitride

    International Nuclear Information System (INIS)

    Neshpor, V.S.; Eron'yan, M.A.; Petrov, A.N.; Kravchik, A.E.

    1978-01-01

    To experimentally check the concentration dependence of microhardness of 4 group nitrides, microhardness of zirconium nitride compact samples was measured. The samples were obtained either by bulk saturation of zirconium iodide plates or by chemical precipitation from gas. As nitrogen content decreased within the limits of homogeneity of zirconium nitride samples where the concentration of admixed oxygen was low, the microhardness grew from 1500+-100 kg/mm 2 for ZrNsub(1.0) to 27000+-100 kg/mm 2 for ZrNsub(0.78). Microplasticity of zirconium nitride (resistance to fracture) decreased, as the concentration of nitrogen vacancies was growing

  6. Experimental study and modelling of iron ore reduction by hydrogen; Etude experimentale et modelisation de la reduction du minerai de fer par l'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, D

    2008-01-15

    In an effort to find new ways to drastically reduce the CO{sub 2} emissions from the steel industry (ULCOS project), the reduction of iron ore by pure hydrogen in a shaft furnace was investigated. The work consisted of literature, experimental, and modelling studies. The chemical reaction and its kinetics were analysed on the basis of thermogravimetric experiments and physicochemical characterizations of partially reduced samples. A specific kinetic model was designed, which simulates the successive reactions, the different steps of mass transport, and possible iron sintering, at the particle scale. Finally, a 2-dimensional numerical model of a shaft furnace was developed. It depicts the variation of the solid and gas temperatures and compositions throughout the reactor. One original feature of the model is using the law of additive characteristic times for calculating the reaction rates. This allowed us to handle both the particle and the reactor scale, while keeping reasonable calculation time. From the simulation results, the influence of the process parameters was assessed. Optimal operating conditions were concluded, which reveal the efficiency of the hydrogen process. (author)

  7. SEPARATION OF HAFNIUM FROM ZIRCONIUM

    Science.gov (United States)

    Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

    1960-05-31

    The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

  8. Zirconium

    Science.gov (United States)

    Bedinger, G.M.

    2013-01-01

    Zirconium is the 20th most abundant element in the Earth’s crust. It occurs in a variety of rock types and geologic environments but most often in igneous rocks in the form of zircon (ZrSiO4). Zircon is recovered as a coproduct of the mining and processing of heavy mineral sands for the titanium minerals ilmenite and rutile. The sands are formed by the weathering and erosion of rock containing zircon and titanium heavy minerals and their subsequent concentration in sedimentary systems, particularly in coastal environments. A small quantity of zirconium, less than 10 kt/a (11,000 stpy), compared with total world production of 1.4 Mt (1.5 million st) in 2012, was derived from the mineral baddeleyite (ZrO2), produced from a single source in Kovdor, Russia.

  9. Extractive metallurgy of zirconium--1945 to the present

    International Nuclear Information System (INIS)

    Franklin, D.G.; Adamson, R.B.

    1984-01-01

    Although the history of the reduction of zirconium dates from 1824 and the first ductile zirconium metal was produced in the laboratory in 1914, modern reduction practice was pioneered by the U.S. Bureau of Mines starting in 1945. This paper reviews the history of the extractive metallurgy of zirconium from the early work of W. J. Kroll and co-workers at the Bureau of Mines in Albany, Ore., through the commercial development of the production of reactor-grade zirconium metal which was spurred by the requirements of the Naval Reactor Program and the development of commercial nuclear power. Technical subjects covered include processes for opening the ore, zirconium-hafnium separation, chlorination of zirconium oxide, reduction processes, and electrowinning of zirconium metal. Proposed new processes and process modifications are reviewed

  10. Solvent extraction of zirconium

    International Nuclear Information System (INIS)

    Kim, S.S.; Yoon, J.H.

    1981-01-01

    The extraction of zirconium(VI) from an aqueous solution of constant ionic strength with versatic acid-10 dissolved in benzen was studied as a function of pH and the concentration of zirconium(VI) and organic acid. The effects of sulphate and chlorine ions on the extraction of the zirconium(VI) were briefly examined. It was revealed that (ZrOR 2 .2RH) is the predominant species of extracted zirconium(VI) in the versatic acid-10. The chemical equation and the apparent equilibrium constants thereof have been determined as follows. (ZrOsup(2+))aq+ 2(R 2 H 2 )sub(org) = (ZrOR 2 .2RH)sub(org)+2(H + )aq Ksub(Zr) = (ZrOR 2 .2RH)sub(org)(H + ) 2 /(ZrOsup(2+))sub(aq)(R 2 H 2 )sup(2)sub(org) = 3.3 x 10 -7 . The synergistic effects of TBP and D2EHPA were also studied. In the mixed solvent with 0.1M TBP, the synergistic effect was observed, while the mixed solvent with D2EHPA showed the antisynergistic effect. (Author)

  11. Determination of zirconium by fluoride ion selective electrode

    International Nuclear Information System (INIS)

    Mahanty, B.N.; Sonar, V.R.; Gaikwad, R.; Raul, S.; Das, D.K.; Prakash, A.; Afzal, Md.; Panakkal, J.P.

    2010-01-01

    Full text: Zirconium is used in a wide range of applications including nuclear clad, catalytic converters, surgical appliances, metallurgical furnaces, superconductors, ceramics, lamp filaments, anti corrosive alloys and photographical purposes. Irradiation testing of U-Zr and U-Pu-Zr fuel pins has also demonstrated their feasibility as fuel in liquid metal reactors. Different methods that are employed for the determination of zirconium are spectrophotometry, potentiometry, neutron activation analysis and mass spectrometry. Ion-selective electrode (ISE), selective to zirconium ion has been studied for the direct potentiometric measurements of zirconium ions in various samples. In the present work, an indirect method has been employed for the determination of zirconium in zirconium nitrate sample using fluoride ion selective electrode. This method is based on the addition of known excess amount of fluoride ion to react with the zirconium ion to produce zirconium tetra fluoride at about pH 2-3, followed by determination of residual fluoride ion selective electrode. The residual fluoride ion concentrations were determined from the electrode potential data using calibration plot. Subsequently, zirconium ion concentrations were determined from the concentration of consumed fluoride ions. A precision of about 2% (RSD) with the mean recovery of more than 94% has been achieved for the determination of zirconium at the concentration of 4.40 X 10 -3 moles lit -1

  12. Solute redistribution studies in oxidised zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Khera, S K; Kale, G B; Gadiyar, H S [Bhabha Atomic Research Centre, Bombay (India). Metallurgy Div.

    1977-01-01

    Electron microprobe studies on solute distribution in oxide layers and in the regions near oxide metal interface have been carried out in the case of zircaloy-2 and zirconium binary alloys containing niobium, tin, iron, copper, chromium and nickel and oxidised in steam at 550 deg C. In the case of alloys having higher oxidation rates, the oxide of solute element was found to dissolve in ZrO/sub 2/ without any composition variation. However, for solute addition with limited solubility like Cr, Cu and Fe, solute enrichment at metal/oxide interface and depletion of the same matrix has been observed. The intensity profiles for nickel distribution were also found to be identical to Fe or Cr distribution. The mode of solute distribution has been discussed in relation to oxidation behaviour of these alloys.

  13. Thermofluency in zirconium alloys

    International Nuclear Information System (INIS)

    Orozco M, E.A.

    1976-01-01

    A summary is presented about the theoretical and experimental results obtained at present in thermofluency under radiation in zirconium alloys. The phenomenon of thermofluency is presented in a general form, underlining the thermofluency at high temperature because this phenomenon is similar to the thermofluency under radiation, which ocurrs in zirconium alloys into the operating reactor. (author)

  14. Effect of hydrogen and oxygen content on the embrittlement of Zr alloys

    International Nuclear Information System (INIS)

    Griger, A.; Hozer, Z.; Matus, L.; Vasaros, L.; Horvath, M.

    2001-01-01

    An experimental study is carried out in the KFKI Atomic Energy Research Institute in order to clear up the role of oxidation and hydrogen uptake in the embrittlement process. Russian E110 type Zr1%Nb and Zircaloy-4 claddings are used as test materials. The differences between the properties of two alloys are examined. The sample preparation covered the following cases: oxidation in Ar+O 2 atmosphere; hydrogen uptake of as received and pre-oxidised samples (in Ar+O 2 atmosphere); oxidation in steam. The oxidation in Ar+O 2 and the subsequent hydrogen uptake procedure make possible the production of samples with well-characterized hydrogen and oxygen content. Corrosion treated ring samples of 8 mm height are examined in ring compression tests. The force-deformation curves are recorded and the crushing force and deformation are determined. The relative deformation is used for the characterisation of embrittlement level. The results of experiments provide detailed information about the effect of hydrogen and oxygen content on the embrittlement of zirconium alloys. The conclusions are: 1) hydrogen seems to play a more important role in the embrittlement of zirconium alloys than oxygen; 2) the Zircaloy-4 alloy becomes brittle at lower hydrogen content than the Zr1%Nb; 3) under steam oxidation conditions the Zr1%Nb alloy takes up much more hydrogen and becomes more brittle than the Zircaloy-4

  15. Production of a carbon reducing agent and hydrogen by the thermocatalytic decomposition of hydrocarbons on the surface of iron

    Energy Technology Data Exchange (ETDEWEB)

    Borok, B A; Kel' tsev, V V

    1973-01-01

    In a series of laboratory experiments, natural gas containing 98.7% methane and 1.3% nitrogen was passed through a tube packed with particles of a reduced material containing 62% iron. At 900/sup 0/C and 25 vol/vol/hr space velocity, conversion was 99%, and the exit gas contained 98.4% hydrogen. The solid product, called sooty iron, obtained in the experiments contained 20 to 60% carbon; the volume of sponge iron treated with methane at 900/sup 0/C increased when the carbon content reached 30%. Runs with natural gas at a range of temperatures and constant space velocity or at 900/sup 0/C and increasing space velocity, runs with propane feed instead of methane, and the activity of the iron-carbon complex are discussed.

  16. 40 CFR 721.9973 - Zirconium dichlorides (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs P...

  17. Advances in zirconium technology for nuclear reactor application

    International Nuclear Information System (INIS)

    Ganguly, C.

    2002-01-01

    Zirconium alloys are extensively used as a material for cladding nuclear fuels and for making core structurals of water-cooled nuclear power reactors all over the world for generation of nearly 16 percent of the worlds electricity. Only four countries in the world, namely France, USA, Russia and India, have large zirconium industry and capability to manufacture reactor grade zirconium sponge, a number of zirconium alloys and a wide variety of structural components for water cooled nuclear reactor. The present paper summarises the status of zirconium technology and highlights the achievement of Nuclear Fuel Complex during the last ten years in developing a wide variety of zirconium alloys and components for water-cooled nuclear power programme

  18. Zirconium - ab initio modelling of point defects diffusion

    International Nuclear Information System (INIS)

    Gasca, Petrica

    2010-01-01

    Zirconium is the main element of the cladding found in pressurized water reactors, under an alloy form. Under irradiation, the cladding elongate significantly, phenomena attributed to the vacancy dislocation loops growth in the basal planes of the hexagonal compact structure. The understanding of the atomic scale mechanisms originating this process motivated this work. Using the ab initio atomic modeling technique we studied the structure and mobility of point defects in Zirconium. This led us to find four interstitial point defects with formation energies in an interval of 0.11 eV. The migration paths study allowed the discovery of activation energies, used as entry parameters for a kinetic Monte Carlo code. This code was developed for calculating the diffusion coefficient of the interstitial point defect. Our results suggest a migration parallel to the basal plane twice as fast as one parallel to the c direction, with an activation energy of 0.08 eV, independent of the direction. The vacancy diffusion coefficient, estimated with a two-jump model, is also anisotropic, with a faster process in the basal planes than perpendicular to them. Hydrogen influence on the vacancy dislocation loops nucleation was also studied, due to recent experimental observations of cladding growth acceleration in the presence of this element [fr

  19. Microwave-assisted modulated synthesis of zirconium-based metal–organic framework (Zr-MOF) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2014-05-01

    Full Text Available Zirconium-based metal–organic framework (Zr-MOF) was synthesized using a microwave-assisted modulated method in a short reaction time of 5 min. The Zr-MOF material was highly crystalline with well-defined octahedral shaped crystals, and it exhibited...

  20. Iron-Air Rechargeable Battery

    Science.gov (United States)

    Narayan, Sri R. (Inventor); Prakash, G.K. Surya (Inventor); Kindler, Andrew (Inventor)

    2014-01-01

    Embodiments include an iron-air rechargeable battery having a composite electrode including an iron electrode and a hydrogen electrode integrated therewith. An air electrode is spaced from the iron electrode and an electrolyte is provided in contact with the air electrode and the iron electrodes. Various additives and catalysts are disclosed with respect to the iron electrode, air electrode, and electrolyte for increasing battery efficiency and cycle life.

  1. Modelling of zirconium alloys corrosion in LWRs

    International Nuclear Information System (INIS)

    Kritskij, V.G.; Berezina, I.G.; Kritskij, A.V.; Stjagkin, P.S.

    1999-01-01

    Chemical parameters, that exerted effect on Zr+1%Nb alloy corrosion and deserved consideration during reactor operation, were defined and a model was developed to describe the influence of physical and chemical parameters on zirconium alloys corrosion in nuclear power plants. The model is based on the correlation between the zirconium oxide solubility in high-temperature water under the influence of the chemical parameters and the measured values of fuel cladding corrosion under LWR conditions. The intensity of fuel cladding corrosion in the primary circuits depends on the coolant water quality, growth of iron oxide deposits and vaporization portion. Mathematically, the oxidation rate can be expressed as a sum of heat and radiation components. The temperature dependence on the oxidation rate can be described by the Arrenius equation. The radiation component of Zr uniform corrosion equation is a function of several factors such as neutron fluency, the temperature the metallurgical composition and et. We assume that the main factor is the changing of water chemistry and the H 2 O 2 concentration play the determinative role. Probably, the influence of H 2 O 2 is based on the formation of unstable compound ZrO 3 ·nH 2 O and Zr(OH) 4 with high solubility. The validity of the used formulae was confirmed by corrosion measurements on WWER and RBMK fuel cladding. The model can be applied for calculating the reliability of nuclear fuel operation. (author)

  2. A mechanism for the hydrogen uptake process in zirconium alloys

    International Nuclear Information System (INIS)

    Cox, B.

    1999-01-01

    Hydrogen uptake data for thin Zircaloy-2 specimens in steam at 300-400 C have been analysed to show that there is a decrease in the rate of uptake with respect to the rate of oxidation when the terminal solid solubility (TSS) of hydrogen in the metal is exceeded. In order for TSS to be reached during pre-transition oxidation a very thin 0.125 mm Zircaloy sheet was used. The specimens had been pickled initially removing all Zr 2 (Fe/Ni) particles from the initial surfaces, yet the initial hydrogen uptake rates were still much higher than for Zircaloy-4 or a binary Zr/Fe alloy that did not contain phases that dissolve readily during pickling. Cathodic polarisation at room temperature in CuSO 4 solution showed that small cracks or pores formed the cathodic sites in pre-transition oxide films. Some were at pits resulting from the initial dissolution of the Zr 2 (Fe/Ni) phase; others were not; none were at the remaining intermetallics in the original surface. These small cracks are thought to provide the ingress routes for hydrogen. A microscopic steam starvation process at the bottoms of these small cracks or pores, leading to the accumulation of hydrogen adjacent to the oxide/metal interface, and causing breakdown of the passive oxide forming at the bottom of the flaw, is thought to provide the mechanism for the hydrogen uptake process during both pre-transition and post-transition oxidation. (orig.)

  3. Applications for zirconium and columbium alloys

    International Nuclear Information System (INIS)

    Condliff, A.F.

    1986-01-01

    Currently, zirconium and columbium are used in a wide range of applications, overlapping only in the field of corrosion control. As a construction material, zirconium is primarily used by the nuclear power industry. The use of zirconium in the chemical processing industry (CPI) is, however, increasing steadily. Columbian alloys are primarily applied as superconducting alloys for research particle accelerators and fusion generators as well as in magnetic resonance imaging for medical diagnosis

  4. Hydrogen peroxide-enhanced iron-mediated aeration for the treatment of mature landfill leachate.

    Science.gov (United States)

    Deng, Yang; Englehardt, James D

    2008-05-01

    Municipal landfill leachate is being disallowed for biological treatment by some sewer authorities due to its recalcitrance and corrosiveness, and therefore physicochemical treatment may be needed. In this paper, hydrogen peroxide-enhanced iron (Fe(0))-mediated aeration (IMA) was studied as an alternative for the treatment of mature landfill leachate. Bench-scale Taguchi array screening tests and full factorial tests were conducted. Iron grade, initial pH, H(2)O(2) addition rate, and aeration rate significantly influenced both overall chemical oxygen demand (COD) removal and iron consumption. In the enhanced IMA-treated leachate at an initial pH of 8.2, COD was reduced by 50% due to oxidation and coagulation, a level almost equivalent to those obtained by Fenton treatment. Meanwhile, the 5-day biochemical oxygen demand (BOD(5))/COD ratio was increased from 0.02 to 0.17. In particular, the effect of initial pH became minor at H(2)O(2) addition rate greater than the theoretical demand for complete oxidation of organics by H(2)O(2). In addition, 83% of 300 mg/L ammonia nitrogen and 38% of 8.30 mS/cm electrical conductivity were removed when the initial pH was not adjusted. Based on these results, the process appears suitable for treatment of mature leachate.

  5. The development of zirconium alloy and its manufacturing

    International Nuclear Information System (INIS)

    Yuan Gaihuan; Yue Qiang

    2015-01-01

    Nuclear power which acts as one of low-carbon energy resources is the most realistic in large-scale application. It is also the preferred choice for many countries to develop energy resources and optimize its structure. Zirconium alloy is a key structural material for nuclear power plant fuel assemblies and cladding tubes of zirconium alloy are often referred as the first safeguard to nuclear power safety. With the development of nuclear power, three kinds of zirconium alloys Zr-Sn, Zr-Nb, Zr-Sn-Nb and with the representative products of Zr-4, M5, Zirlo respectively are developed and widely applied. Because of its severe operating environment and influence to nuclear safety, the requirements to zirconium alloys for physical and chemical properties, nuclear capability, tolerance and surface quality are very strict. The in-depth research and its manufacture capability become one of the main barriers for many countries who are developing the nuclear energy. In recent years, a stated-owned company, State Nuclear Bao Ti Zirconium Industry Company ('SNZ' for short) as well as National R and D Center for Nuclear Grade Zirconium material, is founded to meet the requirement of the rapid development of China's nuclear power industry. SNZ is dedicated for the fabrication and the research of nuclear grade zirconium products. After the successful completion of technology transfer of manufacturing for production chain and fully grasped of the manufacturing technology for the nuclear grade zirconium sponge through zirconium alloy tube, rod and strip products. National R and D Center for Nuclear Grade Zirconium material is cooperating with universities, nuclear energy research and design institutes and the owners of nuclear power plant to develop new zirconium alloy of self-owned brand. Through the selection of components, in-process testing and product inspection, four kinds of new zirconium alloys owns better performance than currently commercialized M5, Zirlo etc

  6. At the frontier between heterogeneous and homogeneous catalysis: hydrogenation of olefins and alkynes with soluble iron nanoparticles.

    Science.gov (United States)

    Rangheard, Claudine; de Julián Fernández, César; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; de Vries, Johannes G

    2010-09-28

    The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C-C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl(3) reduced by 3 equivalents of EtMgCl forms an active catalyst for the hydrogenation of a range of olefins and alkynes. Olefin hydrogenation is relatively fast at 5 bar using 5 mol% of catalyst. The catalyst is also active for terminal olefins and 1,1' and 1,2-cis disubstituted olefins while trans-olefins react much slower. 1-Octyne is hydrogenated to mixtures of 1-octene and octane. Kinetic studies led us to propose a mechanism for this latter transformation where octane is obtained by two different pathways. Characterization of the nanoparticles via TEM, magnetic measurements and poisoning experiments were undertaken to understand the true nature of our catalyst.

  7. 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.

  8. Oxidized zirconium on ceramic; Catastrophic coupling.

    Science.gov (United States)

    Ozden, V E; Saglam, N; Dikmen, G; Tozun, I R

    2017-02-01

    Oxidized zirconium (Oxinium™; Smith & Nephew, Memphis, TN, USA) articulated with polyethylene in total hip arthroplasty (THA) appeared to have the potential to reduce wear dramatically. The thermally oxidized metal zirconium surface is transformed into ceramic-like hard surface that is resistant to abrasion. The exposure of soft zirconium metal under hard coverage surface after the damage of oxidized zirconium femoral head has been described. It occurred following joint dislocation or in situ succeeding disengagement of polyethylene liner. We reported three cases of misuse of Oxinium™ (Smith & Nephew, Memphis, TN, USA) heads. These three cases resulted in catastrophic in situ wear and inevitable failure although there was no advice, indication or recommendation for this use from the manufacturer. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  9. Delayed Hydride Cracking Mechanism in Zirconium Alloys and Technical Requirements for In-Service Evaluation of Zr-2.5Nb Tubes with Flaws

    International Nuclear Information System (INIS)

    Kim, Young Suk

    2007-01-01

    In association with periodic inspection of CANDU nuclear power plant components, Canadian Standards Association issued CSA N285.8 in 2005 as technical requirements for in-service evaluation of zirconium alloy pressure tubes in CANDU reactors. This first version, CSA N285.8 involves procedures for, firstly, the evaluation of pressure tube flaws, secondly, the evaluation of pressure tube to calandria tube contact and, thirdly, the assessment of a reactor core, and material properties and derived quantities. The evaluation of pressure tube flaws includes delayed hydride cracking evaluation the procedures of which are stipulated based on the existing delayed hydride cracking models. For example, the evaluation of flaw-tip hydride precipitation during reactor cooldown involves a procedure to calculate the equilibrium hydrogen equivalent concentration in solution at the flaw tip, Htipas follows: Htip=Hfexp[- (VH delta no.)/RT], where Hf is the total bulk hydrogen equivalent concentration, VH partial molar volume of hydrogen in zirconium, δ a difference in hydrostatic stress between the bulk and the crack tip. When Htip ≥TSSP at temperature, then flaw-tip hydride is predicted to precipitate. Eq. (1) suggests that hydrogen concentration at the crack tip would increase due to an work energy given by the difference in the hydrostatic stress

  10. Degradation of the Mechanical Properties of Zirconium-base alloys due to Interaction with Hydrogen

    International Nuclear Information System (INIS)

    Bertolino, Graciela

    2001-01-01

    Security aspects and the purpose to extend the nuclear power plants lifetime motivate the renovated interest on the influence of the environment and radiation on the mechanical properties of in-reactor materials.Zirconium based alloys are the family of alloys most extensively used in nuclear core components.A consequence of the interaction of the in-reactor environment with these alloys is the formation of brittle phase Zr hydride, a process that greatly affects the component integrity.In this work we present a experimental study of the hydrogen influence on the Z ry-4 mechanical properties at different temperatures.As a complement we also present results of a finite elements simulations of the fracture process.We performed standard metallurgical and mechanical characterization in commercial Z ry-4 samples to obtain their basic properties. Different hydrogen pickup techniques were applied to obtain H concentration of charged samples between 10 and 2000 ppm, homogeneous or mainly localized at the crack tip zone.To obtain the fracture toughness of the alloys specimens were tested using elastoplastic fracture mechanics techniques.Specifically we implement J-integral methodology with partial unloading compliance measurements.Tests were performed in a temperature range of 20 to 200 o C.The negative influence of the H content on material toughness probed to be important even at very small concentrations, with an effect that decreases when temperature increases.While there was observed no change in the fracture mechanism in homogeneous charged samples, specimens charged under a superimposed stress field fractured by brittle mode when were tested at 20 to 70 o C. SEM observations of the crack growth, the fracture surface morphology and precipitates content showed the influence of the precipitates on fracture at different H concentrations.At least three stages with different fracture behavior depending on H content were identified.Complementary to the experimental work we

  11. Electrochemical-metallothermic reduction of zirconium in molten salt solutions

    International Nuclear Information System (INIS)

    McLaughlin, D.F.; Talko, F.

    1990-01-01

    This patent describes a method for separating hafnium from zirconium of the type wherein a feed containing zirconium and hafnium chlorides is prepared from zirconium-hafnium chloride and the feed is introduced into a distillation column, which distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and wherein a hafnium chloride enriched stream is taken from the top of the column and a zirconium enriched chloride stream is taken from the bottom of the column. It comprises: reducing the zirconium enriched chloride stream taken from the distillation column to metal by electrochemically reducing an alkaline earth metal in a molten salt bath with the molten salt in the molten salt bath consisting essentially of a mixture of at least one alkali metal chloride and at least one alkaline earth metal chloride and zirconium chloride, with the reduced alkaline earth metal reacting with the zirconium chloride to produce zirconium metal and alkaline earth metal chloride

  12. Study of diffusion processes in the oxide layer of zirconium alloys

    Directory of Open Access Journals (Sweden)

    Sialini P.

    2016-03-01

    Full Text Available In the active zone of a nuclear reactor where zirconium alloys are used as a coating material, this material is subject to various harmful impacts. During water decomposition reactions, hydrogen and oxygen are evolved that may diffuse through the oxidic layer either through zirconium dioxide (ZrO2 crystals or along ZrO2 grains. The diffusion mechanism can be studied using the Ion Beam Analysis (IBA method where nuclear reaction 18O(p,α15N is used. A tube made of zirconium alloy E110 (with 1 wt. % of Nb was used for making samples that were pre-exposed in UJP PRAHA a.s. and subsequently exposed to isotopically cleansed environment of H2 18O medium in an autoclave. The samples were analysed with gravimetric methods and IBA methods performed at the electrostatic particle accelerator Tandetron 4130 MC in the Nucler Physics Institute of the CAS, Řež. With IBA methods, the overall thicknesses of corrosion layers on the samples, element composition of the alloy and distribution of oxygen isotope 18O in the corrosion layer and its penetration in the alloy were identified. The retrieved data shows at the oxygen diffusion along ZrO2 grains because there are two peaks of 18O isotope concentrations in the corrosion layer. These peaks occur at the environment-oxide and oxide-metal interface. The element analysis identified the presence of undesirable hafnium.

  13. Investigation of behaviour of iron (3) microimpurity in ammonium tungstate solutions

    International Nuclear Information System (INIS)

    Vasil'ev, M.A.; Taushkanov, V.P.; Rumyantsev, V.K.; Andronov, E.A.

    1978-01-01

    To determine the purification optimum conditions of ammonium tungstate concentrated solutions from iron(3) microimpurities the behaviour of iron(3) with 10 -5 -10 -4 mol/l concentration in these solutions is studied. Concentration of hydrolyzed iron forms has been determined by spectrophotometric and radiometric methods. It is stated, that the processes of hydrolysis and aggregation of dispersed-colloid iron particles in tungstate solutions is generally over during the first 50 hours. It is shown, that a part of iron hydroxide particles of dimension less than 200 A increases with ammonium tungstate concentration increasing. Residual iron concentration also increases under the same conditions. The increasing of efficiency of solution purification is due to decreasing of carbon dispersion, applied for this purpose, and also modification of their surface by hydroxides of multivalent metas as zirconium for example

  14. The behaviour of zirconium alloys in Santowax OM organic coolant at high temperatures

    International Nuclear Information System (INIS)

    Sawatzky, A.

    1964-10-01

    Zirconium alloys have been exposed to Santowax OM at temperatures of 320 to 400 o C for times as long as 5000 hours. Short-term experiments (less than 2 weeks) were done in stainless-steel bombs and small out-of-pile loops. The X-7 organic loop in the NRX reactor was used to study long-term oxidation and hydriding both in-flux and out-of-flux. The results obtained lead to several tentative conclusions: Aluminum cladding serves as an effective hydrogen barrier; Considerable protection against hydriding is given by zirconium oxide, provided impurities in the organic are carefully controlled; Hydriding is greatly enhanced by the presence of chlorine in the coolant; and, Hydriding is somewhat enhanced by neutron irradiation. Of considerable significance is the fact that a Zircaloy-4 in-reactor test section of the X-7 loop was exposed to Santowax OM at 320 to 400 o C for more than 5000 hours without excessive hydriding. (author)

  15. Problems of zirconium metal production in Czechoslovakia

    International Nuclear Information System (INIS)

    Vareka, J.; Vaclavik, E.

    1975-01-01

    The problems are summed up of the production and quality control of zirconium sponge. A survey is given of industrial applications of zirconium in form of pure metal or alloys in nuclear power production, ferrous and non-ferrous metallurgy, chemical engineering and electrical engineering. A survey is also presented of the manufacture of zirconium metal in advanced capitalist countries. (J.B.)

  16. Effect of the hydrogen concentration on the ductility of Zry-4; Efecto de la concentracion de hidrogeno sobre la ductilidad de Zry-4

    Energy Technology Data Exchange (ETDEWEB)

    Domizzi, G; Ovejero Garcia, J [Comision Nacional de Energia Atomica, San Martin (Argentina). Unidad de Actividad Materiales

    1997-12-31

    After many years in service, zirconium alloys employed in nuclear reactors may reach high contents of hydride particles, exceeding the hydrogen solid solubility at the service temperature. The brittle character of zirconium hydride promotes the alloy embrittlement. In order to predict the critical hydrogen concentration which causes a ductile-brittle transition in a Zry-4 foil, 0.02mm thick, tensile test specimens were hydride by gaseous charging. To obtain uniform hydride distribution the specimens were electroplated with a film of copper prior to gaseous charge. In absence of oxide film, the foils retained its ductility up to high hydrogen concentration (950 Og/g). The critical hydrogen concentration was attained at 2900-3100 Og/g. (author). 4 refs., 2 figs., 1 tab.

  17. Container for hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    1976-01-12

    A container is described for storage, shipping and and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same. The container is compact, safe against fracture or accident, and is reusable. It consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and is retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates.

  18. Container for hydrogen isotopes

    International Nuclear Information System (INIS)

    1976-01-01

    A container is described for storage, shipping and and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same. The container is compact, safe against fracture or accident, and is reusable. It consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and is retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates

  19. Container for hydrogen isotopes

    International Nuclear Information System (INIS)

    Solomon, D.E.

    1977-01-01

    A container for the storage, shipping and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same which has compactness, which is safe against fracture or accident, and which is reusable is described. The container consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example, of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and will be retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates

  20. Phase Transformations in a Uranium-Zirconium Alloy containing 2 weight per cent Zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Lagerberg, G

    1961-04-15

    The phase transformations in a uranium-zirconium alloy containing 2 weight percent zirconium have been examined metallographically after heat treatments involving isothermal transformation of y and cooling from the -y-range at different rates. Transformations on heating and cooling have also been studied in uranium-zirconium alloys with 0.5, 2 and 5 weight per cent zirconium by means of differential thermal analysis. The results are compatible with the phase diagram given by Howlett and Knapton. On quenching from the {gamma}-range the {gamma} phase transforms martensitically to supersaturated a the M{sub S} temperature being about 490 C. During isothermal transformation of {gamma} in the temperature range 735 to 700 C {beta}-phase is precipitated as Widmanstaetten plates and the equilibrium structure consists of {beta} and {gamma}{sub 1}. Below 700 C {gamma} transforms completely to Widmanstaetten plates which consist of {beta} above 660 C and of a at lower temperatures. Secondary phases, {gamma}{sub 2} above 610 C and {delta} below this temperature, are precipitated from the initially supersaturated Widmanstaetten plates during the isothermal treatments. At and slightly below 700 C the cooperative growth of |3 and {gamma}{sub 2} is observed. The results of isothermal transformation are summarized in a TTTdiagram.

  1. Evaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Ozden, Adnan; Ercelik, Mustafa; Devrim, Yilser; Colpan, C. Ozgur; Hamdullahpur, Feridun

    2017-01-01

    Highlights: •Very thin SPSf/ZrP composite membranes were prepared by solution casting method. •The viability of SPSf/ZrP membranes for DMFCs was investigated for the first time. •Superior proton conductivity over Nafion ® 115 was achieved between 45–80 °C. •Desired membrane characteristics, along with low manufacturing cost were achieved. •Single cell DMFC performance was improved up to 13%. -- Abstract: Direct methanol fuel cell (DMFC) technology has advanced perceivably, but technical challenges remain that must be overcome for further performance improvements. Thus, in this study, sulfonated polysulfone/zirconium hydrogen phosphate (SPSf/ZrP) composite membranes with various sulfonation degrees (20%, 35%, and 42%) and a constant concentration of ZrP (2.5%) were prepared to mitigate the technical challenges associated with the use of conventional Nafion ® membranes in DMFCs. The composite membranes were investigated through Scanning Electron Microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), Thermogravimetric Analysis (TGA), oxidative stability and water uptake measurements, and single cell testing. Comparison was also made with Nafion ® 115. Single cell tests were performed under various methanol concentrations and cell temperatures. Stability characteristics of the DMFCs under charging and discharging conditions were investigated via 1200 min short-term stability tests. The response characteristics of the DMFCs under dynamic conditions were determined at the start-up and shut-down stages. Composite membranes with sulfonation degrees of 35% and 42% were found to be highly promising due to their advanced characteristics with respect to proton conductivity, water uptake, thermal resistance, oxidative stability, and methanol suppression. For the whole range of parameters studied, the maximum power density obtained for SPSf/ZrP-42 (119 mW cm −2 ) was found to be 13% higher than that obtained for Nafion ® 115 (105 mW cm −2 ).

  2. The fluorimetric titration of zirconium in the ppm-range

    International Nuclear Information System (INIS)

    Linden, W.E. von der; Boef, G. den; Ozinga, W.

    1976-01-01

    A fluorimetric titration of zirconium(IV) with EDTA is proposed. The fluorescence intensity of the zirconium-morin complex is used to indicate the end-point. More than twenty other cations were investigated and it was found that they did not interfere, neither did common anions. Mercury(II) can only be tolerated in amount not exceeding that of zirconium. Bismuth(III) interferes and hafnium(IV0 is titrated together with zirconium. The relative standard deviation of the titration of 10ml of a solution containing 1 ppm of zirconium does not exceed 1.5%

  3. Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Meier, R. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Heidelberg University, Institute of Physical Chemistry, Im Neuenheimer Feld 253, Heidelberg 69120 (Germany); Souček, P., E-mail: Pavel.Soucek@ec.europa.eu [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Fanghänel, Th. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Heidelberg University, Institute of Physical Chemistry, Im Neuenheimer Feld 253, Heidelberg 69120 (Germany)

    2016-04-15

    A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An–Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An–Al alloys using a LiCl–KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions. - Highlights: • Recovery of actinides was shown by electrorefining of U/Pu–Zr alloys in LiCl–KCl. • Constant current density of 20 mA/cm{sup 2} is applied. • Most of the actinides were dissolved avoiding zirconium co-dissolution. • Deterioration of the deposit quality by a small amount of co-deposited Zr is not observed.

  4. The Addition of Oxygen or Hydrogen Peroxide to Feedwater in Steam Power Plant. Thermodynamics and Morphology of Oxide-films on Iron in Neutral Aqueous Solution at Elevated Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ahrnbom, Lars [AB Energikonsult/Aangpannefoereningen, S-104 20 Stockholm (SE); Lewis, Derek [AB Atomenergi, Nykoeping (Sweden)

    1977-07-01

    A study is reported of the oxidation of iron at temperatures up to 350 deg C in aqueous systems containing oxygen and hydrogen peroxide and in the region of acid-base neutrality. New theoretical data have been obtained for the iron-water system at elevated temperatures, these are presented in the form of pe(pH){sub T}-diagrams. They show that when pe (redox potential) is controlled by the couple O{sub 2}-H{sub 2}O{sub 2}, the thermodynamically stable form of iron at pH-values near 1/2log{sub T}K{sub W} is expected to be alpha-Fe{sub 3}O{sub 4}. Measurements have been made with oxygen and hydrogen peroxide electrodes. The results are consistent with the theoretical data. They also show that only when hydrogen peroxide is present is the redox potential buffered (poised) by a well-characterised electrode reaction with a relatively large exchange current. Adequate redox-buffering is essential if the nature of the oxide-film on iron is to be closely controlled. In experiments with mechanically polished iron-foil (99.99 % Fe), a thin film of a single spinel-phase forms on specimens exposed to dilute solutions of hydrogen peroxide in rigorously deionised water. The X-ray diffraction characteristics of this phase (a = 8.390 +- 0.003 A) are not, however, consistent with those of alpha-Fe{sub 3}O{sub 4} (a = 8.398 A) or of the defect spinel-type material designated gamma-Fe{sub 2}O{sub 3} (a = 8.381 to 8.399 A). These results are consistent with the view, advanced in other work, that the primary surface film formed on iron in water under conditions close to absolute neutrality is a defect spinel-phase stabilized by incorporated protons. This phase may correspond stoichiometrically to HFe{sub 5}O{sub 8}

  5. SEPARATING HAFNIUM FROM ZIRCONIUM

    Science.gov (United States)

    Lister, B.A.J.; Duncan, J.F.

    1956-08-21

    A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

  6. Sonochemically synthesized biocompatible zirconium phosphate nanoparticles for pH sensitive drug delivery application

    Energy Technology Data Exchange (ETDEWEB)

    Kalita, Himani, E-mail: hkalita74@gmail.com [Department of Chemistry, Indian Institute of Technology Kharagpur, West Bengal 721302 (India); Prashanth Kumar, B.N., E-mail: prasanthkumar999@gmail.com [School of Medical Science and Technology, Indian Institute of Technology Kharagpur, West Bengal 721302 (India); Konar, Suraj, E-mail: suraj.konar@gmail.com [Department of Chemistry, Indian Institute of Technology Kharagpur, West Bengal 721302 (India); Tantubay, Sangeeta, E-mail: sang.chem2@gmail.com [Department of Chemistry, Indian Institute of Technology Kharagpur, West Bengal 721302 (India); Mahto, Madhusudan Kr., E-mail: mahtomk0@gmail.com [Department of Chemistry, Indian Institute of Technology Kharagpur, West Bengal 721302 (India); Mandal, Mahitosh, E-mail: mahitosh@smst.iitkgp.ernet.in [School of Medical Science and Technology, Indian Institute of Technology Kharagpur, West Bengal 721302 (India); Pathak, Amita, E-mail: ami@chem.iitkgp.ernet.in [Department of Chemistry, Indian Institute of Technology Kharagpur, West Bengal 721302 (India)

    2016-03-01

    The present work reports the synthesis of biocompatible zirconium phosphate (ZP) nanoparticles as nanocarrier for drug delivery application. The ZP nanoparticles were synthesized via a simple sonochemical method in the presence of cetyltrimethylammonium bromide and their efficacy for the delivery of drugs has been tested through various in-vitro experiments. The particle size and BET surface area of the nanoparticles were found to be ~ 48 nm and 206.51 m{sup 2}/g respectively. The conventional MTT assay and cellular localization studies of the particles, performed on MDA-MB-231 cell lines, demonstrate their excellent biocompatibility and cellular internalization behavior. The loading of curcumin, an antitumor drug, onto the ZP nanoparticles shows the rapid drug uptake ability of the particles, while the drug release study, performed at two different pH values (at 7.4 and 5) depicts pH sensitive release-profile. The MTT assay and cellular localization studies revealed higher cellular inhibition and better bioavailability of the nanoformulated curcumin compared to free curcumin. - Highlights: • Biocompatible zirconium phosphate nanoparticles were synthesized by a simple sonochemical approach. • Curcumin was rapidly loaded onto the particles by the aid by hydrogen bond formation. • The curcumin loaded zirconium phosphate nanoparticles depict pH triggered drug release phenomenon. • The nanoformulated curcumin showed enhanced anti-tumor activity as compared to the native curcumin.

  7. Sonochemically synthesized biocompatible zirconium phosphate nanoparticles for pH sensitive drug delivery application

    International Nuclear Information System (INIS)

    Kalita, Himani; Prashanth Kumar, B.N.; Konar, Suraj; Tantubay, Sangeeta; Mahto, Madhusudan Kr.; Mandal, Mahitosh; Pathak, Amita

    2016-01-01

    The present work reports the synthesis of biocompatible zirconium phosphate (ZP) nanoparticles as nanocarrier for drug delivery application. The ZP nanoparticles were synthesized via a simple sonochemical method in the presence of cetyltrimethylammonium bromide and their efficacy for the delivery of drugs has been tested through various in-vitro experiments. The particle size and BET surface area of the nanoparticles were found to be ~ 48 nm and 206.51 m"2/g respectively. The conventional MTT assay and cellular localization studies of the particles, performed on MDA-MB-231 cell lines, demonstrate their excellent biocompatibility and cellular internalization behavior. The loading of curcumin, an antitumor drug, onto the ZP nanoparticles shows the rapid drug uptake ability of the particles, while the drug release study, performed at two different pH values (at 7.4 and 5) depicts pH sensitive release-profile. The MTT assay and cellular localization studies revealed higher cellular inhibition and better bioavailability of the nanoformulated curcumin compared to free curcumin. - Highlights: • Biocompatible zirconium phosphate nanoparticles were synthesized by a simple sonochemical approach. • Curcumin was rapidly loaded onto the particles by the aid by hydrogen bond formation. • The curcumin loaded zirconium phosphate nanoparticles depict pH triggered drug release phenomenon. • The nanoformulated curcumin showed enhanced anti-tumor activity as compared to the native curcumin.

  8. Zirconium cladding - the long way towards a mechanistic understanding of processing and performance

    International Nuclear Information System (INIS)

    Preuss, Michael

    2011-01-01

    Zirconium alloys are the material of choice to encapsulate nuclear fuel in light and heavy water-cooled reactors due to their low neutron absorption, excellent corrosion resistance and sufficient mechanical properties. Despite these advantageous physical and mechanical properties a more physically based understanding of microstructure and texture evolution during processing is highly desirable in order to improve our understanding of formability during thermomechanical processing and performance variability of cladding material. In addition, the purely empirical understanding of aqueous zirconium corrosion, hydrogen pick up, hydride precipitation as well as irradiation growth and creep limits the accuracy of life predictions and therefore the level of burnup that is obtained from current fuel assemblies. The presentation aims at giving examples of new research strategies that will enable the development of a new physical understanding of processing and performance aspects in zirconium cladding material, which is required to develop new predictive models. Particular emphasis will be placed on using novel research tools and large-scale research facilities such as neutron spallation and synchrotron radiation sources to undertake very detailed and often in-situ studies of deformation mechanisms and microstructure evolution as well as determining stress states in grain families, oxides and hydrides. The results will be presented in the view of how they might help us to improve our understanding and enable the development of better predictive models

  9. Spectrophotometric titration of zirconium in siliceous materials

    International Nuclear Information System (INIS)

    Sugawara, K.F.; Su, Y.-S.; Strzegowski, W.R.

    1978-01-01

    An accurate and selective complexometric titration procedure based upon a spectrophotometrically detected end-point has been developed for the determination of zirconium in glasses, glass-ceramics and refractories. A p-bromomandelic acid separation step for zirconium imparts excellent selectivity to the procedure. The method is particularly important for the 1 to 5% concentration range where a simple, accurate and selective method for the determination of zirconium has been lacking. (author)

  10. Wear and chemistry of zirconium-silicate, aluminium-silicate and zirconium-aluminium-silicate glasses in alkaline medium

    International Nuclear Information System (INIS)

    Rouse, C.G.; Lemos Guenaga, C.M. de

    1984-01-01

    A study of the chemical durability, in alkaline solutions, of zirconium silicate, aluminium silicate, zirconium/aluminium silicate glasses as a function of glass composition is carried out. The glasses were tested using standard DIN-52322 method, where the glass samples are prepared in small polished pieces and attacked for 3 hours in a 800 ml solution of 1N (NaOH + NA 2 CO 3 ) at 97 0 C. The results show that the presence of ZrO 2 in the glass composition increases its chemical durability to alkaline attack. Glasses of the aluminium/zirconium silicate series were melted with and without TiO 2 . It was shown experimentally that for this series of glasses, the presence of both TiO 2 and ZrO 2 gave better chemical durability results. However, the best overall results were obtained from the simpler zirconium silicate glasses, where it was possible to make glasses with higher values of ZrO 2 . (Author) [pt

  11. Study for the chlorination of zirconium oxide

    International Nuclear Information System (INIS)

    Seo, E.S.M.; Takiishi, H.; Paschoal, J.O.A.; Andreoli, M.

    1990-12-01

    In the development of new ceramic and metallic materials the chlorination process constitutes step in the formation of several intermediate compounds, such as metallic chlorides, used for the production of high, purity raw materials. Chlorination studies with the aim of fabrication special zirconium-base alloys have been carried out at IPEN. Within this program the chlorination technique has been used for zirconium tetrachloride production from zirconium oxide. In this paper some relevant parameters such as: time and temperature of reaction, flow rate of chloride gas and percentage of the reducing agent which influence the efficiency of chlorination of zirconium oxide are evaluated. Thermodynamical aspects about the reactions involved in the process are also presented. (author)

  12. Joint titrimetric determination of zirconium and hafnium

    International Nuclear Information System (INIS)

    Vazquez, Cristina; Botbol, Moises; Bianco de Salas, G.N.; Cornell de Casas, M.I.

    1980-01-01

    A method for the joint titrimetric determination of zirconium and hafnium, which are elements of similar chemical behaviour, is described. The disodic salt of the ethylendiaminetetracetic acid (EDTA) is used for titration, while xilenol orange serves as final point indicator. Prior to titration it is important to evaporate with sulfuric acid, the solution resulting from the zirconium depolymerization process, to adjust the acidity and to eliminate any interferences. The method, that allows the quick and precise determination of zirconium and hafnium in quantities comprised between 0.01 and mg, was applied to the analysis of raw materials and of intermediate and final products in the fabrication of zirconium sponge and zircaloy. (M.E.L.) [es

  13. Voltammetric determination of zirconium using azo compounds

    International Nuclear Information System (INIS)

    Orshulyak, O.O.; Levitskaya, G.D.

    2008-01-01

    The optimum conditions for zirconium complexation with azo compounds are found. The applicability of Eriochrome Red B, Calcon, and Calcion to the voltammetric determination of zirconium, total Zr(IV) and Hf(IV), and Zr(IV) in the presence of Zn(II), Cu(II), Cd(II), Ni(II), or Ti(IV) is demonstrated. The developed procedures are used to determine zirconium in a terbium alloy and in an alloy for airplane wheel drums [ru

  14. Iron ore catalysts for methane decomposition to make CO x free hydrogen and carbon nano material

    KAUST Repository

    Zhou, Lu

    2018-03-27

    In this work, for the first time, iron ores with 91.7%–96.2% FeO, 1.3%–2.3% AlO, 1.2%–4.5% SiO, 1.3%–3.9% NaO, were studied directly as bulk catalysts for methane decomposition. By hydrogen pre-reduction at 850 °C, FeO species on iron ores were gradually reduced into FeO, FeO and then finally into Fe species. After reduction of 1.6 g of iron ore catalysts of 50 µm particle size with 100 mL/min pure H for 3.5 h at 850 °C, CMD life testing was conducted at 850 °C and GHSV of 3.75 L/g h and the catalyst showed a stable methane conversion for 5 h. When methane decomposition proceeded on Fe sites, FeC species would be formed to deposit graphite around themselves to finally form carbon nano onions. This carbon nano onions material showed excellent application for wastewater purification. All samples were fully characterized with XRF, XRD, H-TPR, TEM and Raman.

  15. Hydrogen charging/discharging system with liquid organic compounds: a lacunar oxide catalyst to hydrogenate the unsaturated organic compound

    International Nuclear Information System (INIS)

    Jalowiecki-Duhamel, L.; Carpentier, J.; Payen, E.; Heurtaux, F.

    2006-01-01

    Lacunar mixed oxides based on cerium nickel and aluminium or zirconium CeM 0.5 Ni x O y s (M = Zr or Al), able to store high quantities of hydrogen, have been analysed in the hydrogenation of toluene into methyl-cyclohexane (MCH). When these solids present very good toluene hydrogenation activity and selectivity towards MCH in presence of H 2 , in absence of gaseous hydrogen, the reactive hydrogen species stored in the solid can hydrogenate toluene into MCH. The hydrogenation activity under helium + toluene flow decreases as a function of time and becomes nil. The integration of the curve obtained allows to determine the extractable hydrogen content of the solid used, and a value of 1.2 wt % is obtained at 80 C on a CeAl 0.5 Ni 3 O y compound pre-treated in H 2 at 300 C. To optimise the system, different parameters have been analysed, such as the catalyst formulation, the metal content, the pre-reducing conditions as well as the reaction conditions under helium + toluene. (authors)

  16. Influence of Zircaloy cladding composition on hydride formation during aqueous hydrogen charging

    Energy Technology Data Exchange (ETDEWEB)

    Rajasekhara, S. [Intel Corporation, 2501 NW 229th Av., Hillsboro, OR 97124 (United States); Kotula, P.G.; Enos, D.G.; Doyle, B.L. [Sandia National Laboratories, Albuquerque, NM, 87185 (United States); Clark, B.G., E-mail: blyclar@sandia.gov [Sandia National Laboratories, Albuquerque, NM, 87185 (United States)

    2017-06-15

    Although hydrogen uptake in Zirconium (Zr) based claddings has been a topic of many studies, hydrogen uptake as a function of alloy composition has received little attention. In this work, commercial Zr-based cladding alloys (Zircaloy-2, Zircaloy-4 and ZIRLO™), differing in composition but with similar initial textures, grain sizes, and surface roughness, were aqueously charged with hydrogen for 100, 300, and 1000 s at nominally 90 °C to produce hydride layers of varying thicknesses. Transmission electron microscope characterization following aqueous charging showed hydride phase and orientation relationship were identical in all three alloys. However, elastic recoil detection measurements confirmed that surface hydride layers in Zircaloy-2 and Zircaloy-4 were an order of magnitude thicker relative to ZIRLO™. - Highlights: •Aqueous charging was performed to produce a layer of zirconium hydride for three different Zr-alloy claddings. •Hydride thicknesses were analyzed by elastic recoil detection and transmission electron microscopy. •Zircaloy-2 and Zircaloy-4 formed thicker hydride layers than ZIRLO™ for the same charging durations.

  17. URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

    Science.gov (United States)

    Vogler, S.; Beederman, M.

    1961-05-01

    A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

  18. Identification of the zirconium hydrides metallography in zircaloy-2; Contribucion al estudio por metalografia de los hidruros de circonio en Zircaloy-2

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Gonzalez, F

    1968-07-01

    Technique for the Identification of the zirconium hydrides in metallographic specimens have been developed. Microhardness, quantitative estimation and relative orientation of the present hydrides as well as grain size determination of the different Zircaloy-2 tube specimens have also been made. The specimens used were corrosion- tested in water during various periods of time at 300 degree castrating, prior to the metallographic examination. Reference specimens, as received, and heavily hydride specimens in a hydrogen atmosphere at 800 degree centigrees, have been used in the previous stages of the work. No difficulties have been met in this early stage of acquaintanceship with the zirconium hydrides. (Author) 5 refs.

  19. Iron on mixed zirconia-titania substrate F-T catalyst

    International Nuclear Information System (INIS)

    Dyer, P.N.; Nordquist, A.F.; Pierantozzi, R.

    1988-01-01

    This patent deals with a Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized

  20. Production of nuclear grade zirconium: A review

    Energy Technology Data Exchange (ETDEWEB)

    Xu, L., E-mail: L.Xu-2@tudelft.nl [School of Materials Science and Metallurgy, Northeastern University, Shenyang 110004 (China); Department of Materials Science and Engineering, Delft University of Technology, Delft 2628 CD (Netherlands); Xiao, Y. [Department of Metallurgical Engineering, Anhui University of Technology, Ma' anshan 243002 (China); Zr-Hf-Ti Metallurgie B.V., Den Haag 2582 SB (Netherlands); Sandwijk, A. van [Zr-Hf-Ti Metallurgie B.V., Den Haag 2582 SB (Netherlands); Xu, Q. [School of Materials Science and Metallurgy, Northeastern University, Shenyang 110004 (China); Yang, Y. [Department of Materials Science and Engineering, Delft University of Technology, Delft 2628 CD (Netherlands)

    2015-11-15

    Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium as a fuel cladding material. This paper provides an overview of the processes for nuclear grade zirconium production with emphasis on the methods of Zr–Hf separation. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The known pyrometallurgical Zr–Hf separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt–metal equilibrium. In the present paper, the available Zr–Hf separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

  1. Titanium(IV), zirconium, hafnium and thorium

    International Nuclear Information System (INIS)

    Brown, Paul L.; Ekberg, Christian

    2016-01-01

    Titanium can exist in solution in a number of oxidation states. The titanium(IV) exists in acidic solutions as the oxo-cation, TiO 2+ , rather than Ti 4+ . Zirconium is used in the ceramics industry and in nuclear industry as a cladding material in reactors where its reactivity towards hydrolysis reactions and precipitation of oxides may result in degradation of the cladding. In nature, hafnium is found together with zirconium and as a consequence of the contraction in ionic radii that occurs due to the 4f -electron shell, the ionic radius of hafnium is almost identical to that of zirconium. All isotopes of thorium are radioactive and, as a consequence of it being fertile, thorium is important in the nuclear fuel cycle. The polymeric hydrolysis species that have been reported for thorium are somewhat different to those identified for zirconium and hafnium, although thorium does form the Th 4 (OH) 8 8+ species.

  2. Translucency and Strength of High-Translucency Monolithic Zirconium-Oxide Materials

    Science.gov (United States)

    2016-05-12

    Capt Todd D. Church APPROVED: Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide Materials C~t) Kraig/[ Vandewalle Date...copyrighted material in the thesis/dissertation manuscript entitled: "Translucency arid Strength of High-Translucency Monolithic Zirconium -Oxide...Translucency Monolithic Zirconium -Oxide Materials Abstract Dental materials manufacturers have developed more translucent monolithic zirconium oxide

  3. Tests for depositing thin films of metallic zirconium; Essais de depot de zirconium metallique en couches minces

    Energy Technology Data Exchange (ETDEWEB)

    Bentolila, J.; Pattoret, A.; Platzer, R.

    1957-01-15

    The authors report a study which aimed at obtaining a thin, adhesive and non porous coating of metallic zirconium on a uranium substrate by means of chemical process. The main required condition was not to go beyond the uranium phase change temperature (650 C). Two kinds of tests have been performed: on the one hand, tests of reduction of zirconium tetrachloride in non aqueous solvent medium, and on the other hand, tests of vacuum decomposition of zirconium hydride. As far as the first tests are concerned, the authors studied organic solvent media (reduction by aluminium and lithium hydride, action of organic-magnesium compounds), and liquid ammoniac. For the second test type, they describe the apparatus, the preparation of the zirconium hydride, preparation of the substrate surfaces, coating preparation, and decomposition process. Results are discussed in terms of temperature, of presence of copper powder in the coating, of early surface hydriding of uranium, surface polishing.

  4. Analysis of hafnium in zirconium alloys

    International Nuclear Information System (INIS)

    Kondo, Isao; Sakai, Fumiaki; Ohuchi, Yoshifusa; Nakamura, Hisashi

    1977-01-01

    It is required to analyse alloying components and impurity elements in the acceptance analysis of zirconium alloys as the material for fuel cladding tubes and pressure tubes for advanced thermal reactors. Because of extreme similarity in chemical properties between zirconium and hafnium, about 100 ppm of hafnium is usually contained in zirconium alloys. Zircaloy-2 alloy and 2.5% Nb-zirconium with the addition of hafnium had been prepared as in-house standard samples for rapid analysis. Study was made on fluorescent X-ray analysis and emission spectral analysis to establish the analytical method. By using these in-house standard samples, acceptance analysis was successfully carried out for the fuel cladding tubes for advanced thermal reactors. Sulfuric acid solution was prepared from JAERI-Z 1, 2 and 3, the standard sample for zircaloy-2 prepared by the Analytical Committee on Nuclear Fuel and Reactor Materials, JAERI, and zirconium oxide (Hf 1 ppm/Zr). Standard Hf solution was added to the sulfuric acid solution step by step, to make up a series of the standard oxide samples by the precipitation process. By the use of these standard samples, the development of the analytical method and joint analysis were made by the three-member analytical technique research group including PNC. The analytical precision for the fluorescent X-ray analysis was improved by attaching a metallic yttrium filter to the window of an X-ray tube so as to suppress the effect due to zirconium matrix. The variation factor of the joint analysis was about 10% to show good agreement, and the indication value was determined. (Kobatake, H.)

  5. Study of the microstructural and mechanical properties of titanium-niobium-zirconium based alloys processed with hydrogen and powder metallurgy for use in dental implants; Estudo das propriedades mecanicas e microestruturais de ligas a base de titanio-niobiozirconio processados com hidrogenio e metalurgia do po para utilizacao em implantes dentarios

    Energy Technology Data Exchange (ETDEWEB)

    Duvaizem, Jose Helio

    2009-07-01

    Hydrogen has been used as pulverization agent in alloys based on rare earth and transition metals due to its extremely high diffusion rate even on low temperatures. Such materials are used on hydrogen storage dispositives, generation of electricity or magnetic fields, and are produced by a process which the first step is the transformation of the alloy in fine powder by miling. Besides those, hydrogenium is also being used to obtain alloys based on titanium - niobium - zirconium in the pulverization. Powder metallurgy is utilized on the production of these alloys, making it possible to obtain structures with porous surface as result, requirement for its application as biomaterials. Other advantages of powder metallurgy usage include better surface finish and better microstructural homogeneity. In this work samples were prepared in the Ti-13Nb-13Zr composition. The hydrogenation was performed at 700 degree C, 600 degree C, and 500 degree C for titanium, niobium and zirconium respectively. After hydrogenation, the milling stage was carried out on high energy planetary ball milling with 200rpm during 90 minutes, and also in conventional ball milling for 30 hours. Samples were pressed in uniaxial press, followed by isostatic cold press, and then sintered at 1150 degree C for 7-13 hours. Microstructural properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and x-ray diffraction. Mechanical and structural properties determined were density, microhardness and moduli of elasticity. The sample sintered at 1150 degree C for 7h, hydrogenated using 10.000 mbar and produced by milling on high energy planetary ball milling presented the best mechanical properties and microstructural homogeneity. (author)

  6. High purity zirconium obtainment through the iodine compounds transport method

    International Nuclear Information System (INIS)

    Bolcich, J.C.; Zuzek, E.; Dutrus, S.M.; Corso, H.L.

    1987-01-01

    This paper describes the experimental method and the equipment designed, constructed and actually applied for the high purity zirconium obtainment from a zirconium sponge of the nuclear type. The mechanism of purification is based on the impure metal attack with gaseous iodine (at 200 deg C) to obtain zirconium tetra iodine as main product which is then transformed into a pure zirconium base (at 1000-1300 deg C), precipitating the metallic zirconium and releasing the gaseous iodine. From the first experiences carried out, pure zirconium has been obtained from an initial filament of 0.5 mm of diameter as well as wires up to 2.5 mm of diameter. This work presents the results from the studies and analysis made to characterize the material obtained. Finally, the refining methods to which the zirconium produced may be submitted so as to optimize the final purity are discussed. (Author)

  7. Quercetin as colorimetric reagent for determination of zirconium

    Science.gov (United States)

    Grimaldi, F.S.; White, C.E.

    1953-01-01

    Methods described in the literature for the determination of zirconium are generally designed for relatively large amounts of this element. A good procedure using colorimetric reagent for the determination of trace amounts is desirable. Quercetin has been found to yield a sensitive color reaction with zirconium suitable for the determination of from 0.1 to 50?? of zirconium dioxide. The procedure developed involves the separation of zirconium from interfering elements by precipitation with p-dimethylaminoazophenylarsonic acid prior to its estimation with quercetin. The quercetin reaction is carried out in 0.5N hydrochloric acid solution. Under the operating conditions it is indicated that quercetin forms a 2 to 1 complex with zirconium; however, a 2 to 1 and a 1 to 1 complex can coexist under special conditions. Approximate values for the equilibrium constants of the complexes are K1 = 0.33 ?? 10-5 and K2 = 1.3 ?? 10-9. Seven Bureau of Standards samples of glass sands and refractories were analyzed with excellent results. The method described should find considerable application in the analysis of minerals and other materials for macro as well as micro amounts of zirconium.

  8. Antimony removal from aqueous solutions using Zirconium hydroxide

    International Nuclear Information System (INIS)

    Petrescu, D.; Velciu, L.; Bucur, C.

    2016-01-01

    In this paper it is presented an experimental test for non-radioactive antimony removal from aqueous solutions using zirconium hydroxide powder. Also, it was studied how the temperature and pH influences antimony adsorption onto zirconium hydroxide surface. After the adsorption, solutions were filtered on Cellulose Mixed Ester Membrane with 0.2 μm pore size to remove the zirconium powder and then the aqueous solutions were sent to Inductively Coupled Plasma Optic Emission Spectrometry (ICP-OES) for quantitative analysis of Sb. Zirconium hydroxide powders were examined by optical microscopy. For the solutions that were tested at pH 4.5 and 10.2 the antimony concentration dropped below the detection limit of ICP-OES device, proof of antimony adsorption on zirconium hydroxide. Also, for the other tested solutions which had pH=12 the antimony concentration reduced with 77% and 80%. The temperature had no influence upon adsorption mechanism. (authors)

  9. Molten salt extractive distillation process for zirconium-hafnium separation

    International Nuclear Information System (INIS)

    McLaughlin, D.F.; Stoltz, R.A.

    1989-01-01

    This patent describes an improvement in a process for zirconium-hafnium separation. It utilizes an extractive distillation column with a mixture of zirconium and hafnium tetrachlorides introduced into a distillation column having a top and bottom with hafnium enriched overheads taken from the top of the column and a molten salt solvent circulated through the column to provide a liquid phase, and with molten salt solvent containing zirconium chloride being taken from the bottom of the distillation column. The improvements comprising: utilizing a molten salt solvent consisting principally of lithium chloride and at least one of sodium, potassium, magnesium and calcium chlorides; stripping of the zirconium chloride taken from the bottom of the distillation column by electrochemically reducing zirconium from the molten salt solvent; and utilizing a pressurized reflux condenser on the top of the column to add the hafnium chloride enriched overheads to the molten salt solvent previously stripped of zirconium chloride

  10. Iron titanium manganase alloy hydrogen storage

    Science.gov (United States)

    Reilly, James J.; Wiswall, Jr., Richard H.

    1979-01-01

    A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe.sub.1-x Mn.sub.x where x is in the range of about 0.02 to 0.5 and the method of storing hydrogen using said alloy.

  11. Evaluation of the DSC technique in the determination of the terminal temperature solubility of hydrogen in Zircaloy 4

    International Nuclear Information System (INIS)

    Vizcaino, Pablo; Banchik, Abraham D.

    1999-01-01

    The determination of the terminal temperature solubility of hydrogen in the zirconium alloys is a matter of our interest, since the hydride precipitation in these materials make them susceptible to the delay hydrogen cracking (DHC). Nowadays efforts are directed to the determination of this parameter on irradiated materials. In this frame we have begun a program to determine these curves on irradiated zirconium alloys like Zircaloys, Zr 2.5% Nb, Zr 1% Nb, zirconium sponge and high oxygen zirconium with different microstructures using the differential scanning calorimeter technique. The earlier task that we have imposed to us is the evaluation the reproducibility of this technique and the influence of the heating and cooling rates on the results. With these objectives we have initiated this work measuring the terminal temperature solubility (TTS) in unirradiated recrystallized and cold worked Zircaloy-4. We have found that the reproducibility of the technique is good; the average values (TSSD) and (TSSP) agree within the experimental error and the dispersions are low. Variance analysis indicates that the values of TSSD and TSSP do not depend on the heating and cooling rates. Within the rank analyzed the differences in the measurements are only possible to be attributed to statistical and/or experimental errors. The obtained curves of solubility show to a good agreement with the values obtained by others authors until 200 ppm (weight) of hydrogen. Similar comparisons between precipitation curves have not been made in regard to which these values depend on the maximum temperature reached in the experience. (author)

  12. Techniques for chemical characterization of zirconium and its alloys

    International Nuclear Information System (INIS)

    Iyer, K.V.; Bassan, M.K.T.; Sudersanan, M.

    2002-01-01

    Chemical characterization of zirconium and its alloys such as zircaloy, Zr-Nb, etc for minor and trace constituents like Nb, Ti, Fe, Cr, Ni, Sn, Al etc has been carried out. Zirconium, being a major constituent, has been determined by gravimetry as zirconium oxide while other constituents like Nb, Ti, Fe have been determined by spectrophotometric methods. Other metals of importance at trace level have been estimated by AAS or ICPAES. The judicious use of both conventional and modern instrumental methods of analysis helps in the characterization of zirconium and its alloys for various major and minor constituents. The role of matrix effect in the determination was also investigated and methods have been worked out based on a preliminary separation of zirconium by a hydroxide precipitation. (author)

  13. Conductivity variations in composites of. alpha. -zirconium phosphate and alumina

    Energy Technology Data Exchange (ETDEWEB)

    Slade, R.C.T.; Knowles, J.A. (Dept. of Chemistry, Exeter Univ. (UK))

    Composite proton-conducting solid electrolytes have been formed from {alpha}-zirconium hydrogen phosphate ({alpha}-Zr(HPO{sub 4}){sub 2}.H{sub 2}O, {alpha}-ZrP) and aluminas (Al{sub 2}O{sub 3}) in varying mole ratios. Conductivity variations as a function of temperature have been characterised and compared to that for a delaminated {alpha}-ZrP (no alumina). There are no appreciable conductivity enhancements on composite formation, but conductivity for materials ca. 50 mole% in alumina can be comparable to the delaminated materials. Differential scanning calorimetry shows the composites to have different thermal properties to simple admixtures. High resolution {sup 31}P NMR studies show reaction to form aluminium phosphate at the interface between components. (orig.).

  14. Intercalation chemistry of zirconium 4-sulfophenylphosphonate

    International Nuclear Information System (INIS)

    Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

    2013-01-01

    Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4′-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules. - Graphical abstract: Nitrogen-containing organic compounds can be intercalated into the interlayer space of zirconium 4-sulfophenylphosphonate. - Highlights: • Zirconium 4-sulfophenylphosphonate was examined as a host material in intercalation chemistry. • A wide range of nitrogen-containing organic compounds were intercalated. • Possible arrangement of the intercalated species is described

  15. Chemistry of titanium, zirconium and thorium picramates

    International Nuclear Information System (INIS)

    Srivastava, R.S.; Agrawal, S.P.; Bhargava, H.N.

    1976-01-01

    Picramates of titanium, zirconium and thorium are prepared by treating the aqueous sulphate, chloride and nitrate solutions with sodium picramate. Micro-analysis, colorimetry and spectrophotometry are used to establish the compositions (metal : ligand ratio) of these picramates as 1 : 2 (for titanium and zirconium) and 1 : 4 (for thorium). IR studies indicate H 2 N → Me coordination (where Me denotes the metal). A number of explosive properties of these picramates point to the fact that the zirconium picramate is thermally more stable than the picramates of titanium and thorium. (orig.) [de

  16. Study of the behaviour of some heavy elements in solvents containing hydrogen fluoride; Etude du comportement de quelques elements lourds dans des solvants a base d'acide fluorhydrique

    Energy Technology Data Exchange (ETDEWEB)

    Tarnero, M [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1967-01-01

    The anhydrous liquid mixtures: dinitrogen tetroxide-hydrogen fluoride and antimony pentafluoride-hydrogen fluoride were studied as solvents for heavy elements interesting nuclear energy: uranium, thorium, zirconium and for some of their compounds. For N{sub 2}O{sub 4}-HF mixtures, electric conductivity measurements and liquid phase infrared spectra were also obtained. Uranium and zirconium tetrafluoride are much more soluble in N{sub 2}O{sub 4}-HF mixtures than in pure hydrogen fluoride. Uranium dissolved in these mixtures is pentavalent. In SbF{sub 5}-HF mixtures, uranium dissolves with hydrogen evolution and becomes trivalent. The solid compound resulting from the dissolution is a fluoro-antimonate: U(SbF{sub 6}){sub 3}. (author) [French] On a etudie les melanges liquides anhydres: peroxyde d'azote-acide fluorhydrique et pentafluorure d'antimoine-acide fluorhydrique comme solvants d'elements lourds interessant l'energie nucleaire: uranium, thorium, zirconium et de quelques uns de leurs composes. Pour les melanges N{sub 2}O{sub 4}-HF on a egalement effectue des mesures de conductivite electrique, ainsi que des spectres d'absorption infrarouge en phase liquide. Le tetrafluorure d'uranium et le tetrafluorure de zirconium sont beaucoup plus solubles dans les melanges N{sub 2}O{sub 4}-HF que dans l'acide fluorhydrique. L'uranium dissous dans ces melanges est a l'etat pentavalent. Dans les melanges SbF{sub 5}-HF l'uranium se dissout avec degagement d'hydrogene et passe a l'etat trivalent. Le compose solide resultant de la dissolution est un fluoantimoniate: U(SbF{sub 6}){sub 3}. (auteur)

  17. 21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

    Science.gov (United States)

    2010-04-01

    ... zirconium. 700.16 Section 700.16 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an ingredient... indicates that certain zirconium compounds have caused human skin granulomas and toxic effects in the lungs...

  18. Investigations of titamium and zirconium hydrides to determine suitability of recoverable tritium immobilization for the Pickering tritium removal system

    International Nuclear Information System (INIS)

    Noga, J.O.

    1981-11-01

    A tritium removal system will be constructed at Pickering Nuclear Generating station to reduce the adverse effects of this radioactive hydrogen isotope. This report summarizes various properties of titanium and zirconium sponge hydrides which have been selected as suitable candidates for tritium product immobilization. Equilibrium pressure-composition-temperature data indicates that both materials behave suitably to provide a safe, solid form of tritium storage. Titanium tritide is recommended as the best choice due to higher dissociation pressures which can be achieved at equivalent temperatures when compared to zirconium tritide. Higher dissociation pressures would result in faster and more efficient recovery of tritium gas from the immobilized state. It is evident from the stability of these compounds that their utilization as tritides will greatly enhance the integrity of tritium storage

  19. Internal hydrogen embrittlement of gamma-stabilized uranium alloys

    International Nuclear Information System (INIS)

    Powell, G.L.; Koger, J.W.; Bennett, R.K.; Williamson, A.L.; Hemperly, V.C.

    1976-01-01

    Relationships between the tensile ductility and fracture characteristics of as-quenched, gamma-stabilized uranium alloys (uranium--10 wt percent molybdenum, uranium--8.5 wt percent niobium, uranium--10 wt percent niobium, and uranium--7.5 wt percent niobium--2.5 wt percent zirconium), the hydrogen content of the tensile specimens, and the hydrogen gas pressure during the annealing at 850 0 C of the tensile test blanks prior to quenching were established. For these alloys, the tensile ductility decreases only slightly with increasing hydrogen content up to a critical hydrogen concentration above which the tensile ductility drops to nearly zero. The only alloy not displaying this sharp drop in tensile ductility was U--7.5 Nb--2.5 Zr, probably because sufficiently high hydrogen contents could not be achieved under our experimental arrangements. The critical hydrogen content for ductility loss increased with increasing hydrogen solubility in the alloy. Fracture surfaces produced by internal hydrogen embrittlement do not resemble those produced by stress corrosion cracking (SCC) in aqueous environments containing chloride ions. 8 figs

  20. Processing fissile material mixtures containing zirconium and/or carbon

    Science.gov (United States)

    Johnson, Michael Ernest; Maloney, Martin David

    2013-07-02

    A method of processing spent TRIZO-coated nuclear fuel may include adding fluoride to complex zirconium present in a dissolved TRIZO-coated fuel. Complexing the zirconium with fluoride may reduce or eliminate the potential for zirconium to interfere with the extraction of uranium and/or transuranics from fission materials in the spent nuclear fuel.

  1. Hot zirconium cathode sputtered layers for useful surface modification

    International Nuclear Information System (INIS)

    Duckworth, R.G.

    1986-01-01

    It has been found that multilayer zirconium based sputtered coatings can greatly improve the wear properties of a wide variety of mechanical components, machine tools, and metal surfaces. Although a hot (approximately 1000 0 C) cathode is employed, temperature sensitive components can be beneficially treated, and for precision parts a total coating thickness of only 0.5μm is often perfectly effective. Even at the highest coating rates substrate temperatures are below 300 0 C. For the corrosion protection of less well finished surfaces thicker layers are usually required and it is important that relatively stress free layers are produced. The authors employed a variety of tailored zirconium/zirconium nitride/zirconium oxide mixed layers to solve a number of tribological problems for some 5 or 6 years. However, it is only recently that they designed, built, and commissioned rapid cycle, multiple cathode, load-lock plant for economic production of such coatings. This paper provides an introduction to this method of depositing pure zirconium and pure synthetic zirconium nitride films

  2. IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

    Science.gov (United States)

    Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

    2013-01-01

    Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

  3. Mathematical model of the reformer sponge iron cycle

    Energy Technology Data Exchange (ETDEWEB)

    Fraser, S.; Hacker, V.; Evers, B.; Hierzer, J.; Besenhard, J.O. [Graz University of Technology, Graz (Austria). Inst. for Chemical Technology of Inorganic Materials Christian Doppler Pilot-Lab. for Fuel Cell Systems

    2003-07-01

    An innovative hydrogen production process called the Reformer Sponge Iron Cycle (RESC), based on redox reactions of iron ore pellets, was mathematically modeled. The hydrogen is produced by blowing steam over hot iron pellets in the oxidation stage, resulting in the oxidation of the iron. Synthesis gas coming from a reformer mixed with a fraction of recycled off-gas was used to reduce the iron oxide pellets (wuestite and-or magnetite) in the reduction stage, leading once more to iron . Once the mathematical model was developed, it was verified utilizing experimental data. Based on calculations of the equilibrium gas concentrations for reformer and sponge iron reactor (SIR), the model computes mass fluxes, molar fluxes, partial pressures, and variations of them throughout the complete cycle. The recycle rate, which determines the fraction of SIR off-gas recycled and added to the input gas stream, was optimized to maximize the amount of iron oxide reduced for a certain input gas flow. 5 refs., 4 figs.

  4. Determination of microquantities of zirconium and thorium in uranium dioxide

    International Nuclear Information System (INIS)

    Weber de D'Alessio, Ana; Zucal, Raquel.

    1975-07-01

    A method for the determination of 10 to 50 ppm of zirconium and thorium in uranium IV oxide of nuclear purity is established. Zirconium and thorium are retained in a strong cation-exchange resin Dowex 50 WX8 in 1 M HCl. Zirconium is eluted with 0,5% oxalic acid solution and thorium with 4% ammonium oxalate. The colorimetric determination of zirconium with xilenol orange is done in perchloric acid after destructtion of oxalic acid and thorium is determined with arsenazo III in 5 M HCl. 10 μg of each element were determined with a standard deviation of 2,1% for thorium and 3,4% for zirconium. (author) [es

  5. Separation process of zirconium and hafnium; Procede de separation du zirconium et du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Hure, J; Saint-James, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1955-07-01

    About the separation different processes of zirconium-hafnium, the extraction by solvent in cross-current is the most easily the process usable on an industrial scale. It uses tributyl phosphate as solvent, diluted with white spirit to facilitate the decanting. Some exploratory tests showed that nitric environment seemed the most favorable for extraction; but a lot of other factors intervene in the separation process. We studied the influence of the acidity successively, the NO{sub 3}{sup -} ions concentration, the role of the cation coming with NO{sub 3}{sup -}, as well as the influence of the concentration of zirconium in the solution on the separation coefficient {beta} = {alpha}{sub Zr} / {alpha}{sub Hf}. (M.B.) [French] Des differents procedes de separation zirconium-hafnium, l'extraction par solvant en contre-courant est le procede le plus facilement utilisable a l'echelle industrielle. On utilise comme solvant le phosphate de tributyle, dilue avec du white spirit pour faciliter les decantations. Des essais preliminaires ont montre que le milieu nitrique semblait le plus favorable a l'extraction; mais beaucoup d'autres facteurs interviennent dans le processus de separation. Nous avons etudie successivement l'influence de l'acidite, celle de la concentration en ions NO{sub 3}{sup -}, le role du cation accompagnant NO{sub 3}{sup -}, ainsi que l'influence de la concentration en zirconium de la solution sur le coefficient de separation {beta} = {alpha}{sub Zr} / {alpha}{sub Hf}. (MB)

  6. Contribution to the study of the physico-chemical mechanisms of metallic cation extraction by alkylphosphoric acids. Extraction of zirconium (IV) by di-2-ethylhexyl phosphoric acid (DEHPA)

    International Nuclear Information System (INIS)

    Carbonnier, J.-L.

    1979-02-01

    Extraction of zirconium, especially at high concentration (0.1M), by dodecane diluted DEHPA (HA) from hydrochloric or nitric aqueous phases of 0.1 to 10 M acidity was studied. The composition, structure and polymerisation of the complexes extracted were determined by chemical analysis, viscosimetry, infrared spectrometry and light scattering. A Zr(OH) 2 A 2 .2HNO 3 , type structure is proposed for these complexes instead of the generally accepted form: Zr(OH) 2 (NO 3 ) 2 .2HA. Similarly in hydrochloric solution: Zr(OH) 2 A 2 .2HCl. Polymerisation in the organic phase results from the juxtaposition of two factors; firstly zirconium saturation (formation of bridges by DEHPA between zirconium atoms) and secondly the nature the equeous phase. In slightly acid hydrochloric solution (pH = 1.3) the aqueous plymers of zirconium are extracted in the organic phase as polynuclear complexes; in nitric solution no polynuclear complexes are observed but the nitric acid molecules extracted set up hydrogen bonds which explain the increased viscosity and gelification of the organic phases [fr

  7. Device of measuring hydrogen in U-H-Zr fuel pellet

    International Nuclear Information System (INIS)

    Li Ming; Guo Qiaoru; Xu Xiuqing

    1992-01-01

    A device used for the determination of hydrogen content in U-H-Zr fuel pellet and its precision determination are introduced. The influence of different flow of carry gas, extracting temperature and collecting time on the determination of hydrogen content is researched separately. While the flow of carry gas is 85-100 mL/min and extracting temperature increasing to 1550 deg C, the best collecting time may be reduced to 18 min from 30 min, the determination of zirconium hydrogenate reference standard sample shows that the precision of six time determination is smaller than ±2%, determination error is 2%. The rate of recovery of hydrogen is 99.3%. The test shows that the device and its determination method are stable and operation is simple

  8. The determination, by flow-injection analysis, of iron, sulphate, silver and cadmium

    International Nuclear Information System (INIS)

    Jones, E.A.

    1983-01-01

    This report describes the spectrophotometric determination by flow-injection analysis including, where necessary, liquid-liquid extraction of iron with 1,10-phenanthroline; of sulphate by its catalytic effect on the methylthymol blue-zirconium reaction; of silver with bromopyrogallol red and 1,10-phenanthroline; and of cadmium with dithizone. Optimum conditions for each system are established, and sensitivities and ranges of determination are given

  9. A study of the fixing of phosphoric ions by zirconium-montmorillonite; Etude de la fixation d'ions phosphoriques par la montmorillonite-zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Bittel, R; Boursat, C; Platzer, R [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    In connection with the research carried out on the purification of nuclear reactor water, we have undertaken a study of the ion-exchange properties of acid montmorillonite. In a previous paper, we described the preparation of zirconium-montmorillonite small plate. The present article aims to study some of the properties of the clay obtained. We have observed that zirconium-montmorillonite fixes very strongly the phosphorus from solutions of phosphoric acid or of phosphates: on 1 g of clay it is possible to fix 1,2 milli-atoms-gram of zirconium and the zirconium montmorillonite itself fixes 2,1 milli-atoms-gram of phosphorus. An explanation of these experimental results, which is as much chemical as mineralogical, is the hypothesis that the fixing of phosphoric ions modifies the distribution of the ions between the platelets and precipitates a very slightly soluble product of the type diphospho-zirconic acid. (author) [French] En rapport avec des recherches sur I'epuration de l'eau des reacteurs nucleaires nous avons entrepris une etude sur les proprietes d'echangeur d'ions de la montmorillonite-acide. Dans une precedente publication, nous avons decrit la preparation des plaquettes de montmorillonite-zirconium. La presente communication a pour but d'etudier quelques proprietes de l'argile obtenue. Nous avons constate que la montmorilionite-zirconium fixe le phosphore de solutions d'acide phosphorique ou de phosphate avec une grande intensite: sur 1 g d'argile, on peut fixer 1,2 atomes-gramme de zirconium, et la montmorillonite-zirconium fixe a son tour 2,1 milli-atomesgramme de phosphore. Une explication des resultats experimentaux, tant d'ordre chimique que d'ordre mineralogique, consiste en l'hypothese suivant laquelle la fixation d'ions phosphoriques modifierait la repartition des ions entre les feuillets avec precipitation du compose tres peu soluble (type: acide diphosphozirconique). (auteur)

  10. A computation model for the corrosion resistance of nanocrystalline zirconium metal

    International Nuclear Information System (INIS)

    Zhang Xiyan; Shi Minghua; Liu Nianfu; Wei Yiming; Li Cong; Qiu Shaoyu; Zhang Qiang; Zhang Pengcheng

    2007-01-01

    In this paper a computation model of corrosion rate-grain size of nanocrystalline and ultra-fine zirconium has been presented. The model is based on the Wagner's theory and the electron theory of solids. The conductivity, electronic mean free path and grain size of metal were considered. By this model, the corrosion rate of zirconium metal under different temperature was computed. The results show that the corrosion weight gain and rate constant of nanocrystalline zirconium is lower than that of zirconium with coarse grain size. And the corrosion rate constant and weight gain of nanocrystalline zirconium metal decrease with the decrease of grain size. So the refinement of grain size can remarkably improve the corrosion resistance of zirconium metal. (authors)

  11. Characterisation of hydrides in a zirconium alloy, by EBSD

    International Nuclear Information System (INIS)

    Ubhi, H.S.; Larsen, K.

    2012-01-01

    Zirconium alloys are used in nuclear reactors owing to their low capture cross-section for thermal neutrons and good mechanical and corrosion properties. However, they do suffer from delayed hydrogen cracking (DHC) due to formation of hydride particles. This study shows how the electron back-scatter diffraction (EBSD) technique can be used to characterise hydrides and their orientation relationship with the matrix. Hydrided EB weld specimens were prepared by electro-polishing, characterised using Oxford instruments AZtecHKL EBSD apparatus and software attached to a FEG SEM. Hydrides were found to exist as fine intra granular plates and having the Blackburn orientation relationship, i.e. (0002)Zr//(111)hydride and (1120)Zr//(1-10)hydride. The hydrides were also found to contain sigma 3 boundaries as well as local misorientations. (author)

  12. Electrochemical stripping determination of traces of copper, lead, cadmium and zinc in zirconium metal and zirconium dioxide

    International Nuclear Information System (INIS)

    Stulik, K.; Beran, P.; Dolezal, J.; Opekar, F.

    1978-01-01

    Procedures have been developed for the determination of copper, lead, cadmium and zinc in zirconium metal and zirconium dioxide, at concentrations of 1ppm or less. Zirconium metal was dissolved in sulphuric acid, and zirconium dioxide decomposed under pressure with hydrofluoric acid. Sample solutions were prepared in dilute sulphuric acid. For the stripping determination, the sample solution was either mixed with a complexing tartrate base electrolyte or the pre-electrolysis was carried out in acid solution, with the acid solution being exchanged for a pure base electrolyte (e.g. an acetate buffer) for the stripping step. The stripping step was monitored by d.c., differential pulse and Kalousek commutator voltammetry and the three methods were compared. A stationary mercury-drop electrode can generally be used for all the methods, whereas a mercury-film electrode is suitable only for the d.c. voltammetric determination of copper, lead and cadmium, as pulse measurements with films are poorly reproducible and the electrodes are easily damaged. The relative standard deviation does not exceed 20%. Some samples contained relatively large amounts of copper, which is best separated by electrodeposition on a platinum electrode. (author)

  13. 40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under this...

  14. Investigation of anodic oxide coatings on zirconium after heat treatment

    International Nuclear Information System (INIS)

    Sowa, Maciej; Dercz, Grzegorz; Suchanek, Katarzyna; Simka, Wojciech

    2015-01-01

    Highlights: • Oxide layers prepared via PEO of zirconium were subjected to heat treatment. • Surface characteristics were determined for the obtained oxide coatings. • Heat treatment led to the partial destruction of the anodic oxide layer. • Pitting corrosion resistance of zirconium was improved after the modification. - Abstract: Herein, results of heat treatment of zirconium anodised under plasma electrolytic oxidation (PEO) conditions at 500–800 °C are presented. The obtained oxide films were investigated by means of SEM, XRD and Raman spectroscopy. The corrosion resistance of the zirconium specimens was evaluated in Ringer's solution. A bilayer oxide coatings generated in the course of PEO of zirconium were not observed after the heat treatment. The resulting oxide layers contained a new sublayer located at the metal/oxide interface is suggested to originate from the thermal oxidation of zirconium. The corrosion resistance of the anodised metal was improved after the heat treatment

  15. Tube in zirconium base alloy for nuclear fuel assembly and manufacturing process of such a tube

    International Nuclear Information System (INIS)

    Mardon, J.P.; Senevat, J.; Charquet, D.

    1996-01-01

    This patent concerns the description and manufacturing guidelines of a zirconium alloy tube for fuel cladding or fuel assembly guiding. The alloy contains (in weight) 0.4 to 0.6% of tin, 0.5 to 0.8% of iron, 0.35 to 0.50% of vanadium and 0.1 to 0.18% of oxygen. The carbon and silicon tenors range from 100 to 180 ppm and from 80 to 120 ppm, respectively. The alloy contains only zirconium, plus inevitable impurities, and is completely recrystallized. Corrosion resistance tests were performed on tubes made of this alloy and compared to corrosion tests performed on zircaloy 4 tubes. These tests show a better corrosion resistance and a lower corrosion kinetics for the new alloy, even in presence of lithium and iodine, and a lower hydridation rate. The mechanical resistance of this alloy is slightly lower than the one of zircaloy 4 but becomes equivalent or slightly better after two irradiation cycles. The ductility remains always equal or better than for zircaloy 4. (J.S.)

  16. Electrochemical heterogeneity and corrosion resistance of a welded titanium-zirconium joint

    International Nuclear Information System (INIS)

    Polyakov, S.G.; Goncharov, A.B.; Onoprienko, L.M.; Smiyan, O.D.

    1992-01-01

    The electrochemical behavior and corrosion resistance of various welded joints of zirconium alloy N-2.5 with commercial titanium VT1 made by the argon-arc method are studied. Electrochemical heterogeneity is studied by measuring the distribution of potentials over the surface, galvanic currents, and recording of polarization curves for different zones of a welded joint in 5% sulfuric acid solution at 340 K. It is established that electrochemical heterogeneity of the zones of an N-2.5 + VT1 welded joint leads to acceleration of the cathodic process in a welded joint and the anodic process along the fusion line from the titanium direction where the greatest hydrogenation of the metal and corrosion damage is correspondingly observed

  17. The terminal solid solubility of hydrogen and deuterium in Zr-2.5Nb alloys

    Energy Technology Data Exchange (ETDEWEB)

    Ritchie, I G; Pan, Z L; Puls, M P [Atomic Energy of Canada Ltd., Pinawa, MB (Canada). Whiteshell Labs.

    1997-02-01

    The presence of hydrides in zirconium based alloys is an important factor in assessing the potential for delayed hydride cracking in pressure tubes and the embrittlement of other in-core components fabricated from these alloys. Consequently, the terminal solid solubility (TSS) of hydrogen in the zirconium alloys used in the Nuclear Industry is an important parameter. However, at the low hydrogen concentrations found in practice, the TSS is difficult to measure accurately and even the measurements of hydrogen concentrations by standard techniques are notoriously difficult to make reproducibly at the nominal levels found in pressure tube materials. The presence of hydrides, their dissolution and nucleation gives rise to a number of internal friction phenomena and changes in Young`s modulus that can be useful from the practical point of view. These phenomena can be used to establish expressions for the TSS as a function of temperature, the hysteresis between dissolution and nucleation and hydrogen supercharging from the gas phase. In particular, such studies show that the hysteresis between the TSS measured during heating and cooling is particularly sensitive to the thermal history of the sample. This paper reviews the phenomena involved and presents some recent results on Zr-2.5Nb pressure tube material. (author). 28 refs, 17 figs, 6 tabs.

  18. Embrittlement of the alloy U 7.5 Nb 2.5 Zr by gaseous oxygen and hydrogen

    International Nuclear Information System (INIS)

    Lepoutre, D.; Nomine, A.M.; Miannay, D.

    1981-04-01

    Embrittlement of the alloy uranium 7.5 niobium 2.5 zirconium in gaseous oxygen and hydrogen versus stress intensity, temperature and pressure is studied using rupture mechanics. Cracking speed is determined. In oxygen, only cracks are produced and embrittlement is due to oxidation. In hydrogen at high pressure an hydride is formed and at low pressure cracks are produced but the mechanism is not identified [fr

  19. Hydrogen calibration of GD-spectrometer using Zr-1Nb alloy

    Science.gov (United States)

    Mikhaylov, Andrey A.; Priamushko, Tatiana S.; Babikhina, Maria N.; Kudiiarov, Victor N.; Heller, Rene; Laptev, Roman S.; Lider, Andrey M.

    2018-02-01

    To study the hydrogen distribution in Zr-1Nb alloy (Э110 alloy) GD-OES was applied in this work. Qualitative analysis needs the standard samples with hydrogen. However, the standard samples with high concentrations of hydrogen in the zirconium alloy which would meet the requirements of the shape, size are absent. In this work method of Zr + H calibration samples production was performed at the first time. Automated Complex Gas Reaction Controller was used for samples hydrogenation. To calculate the parameters of post-hydrogenation incubation of the samples in an inert gas atmosphere the diffusion equations were used. Absolute hydrogen concentrations in the samples were determined by melting in the inert gas atmosphere using RHEN602 analyzer (LECO Company). Hydrogen distribution was studied using nuclear reaction analysis (HZDR, Dresden, Germany). RF GD-OES was used for calibration. The depth of the craters was measured with the help of a Hommel-Etamic profilometer by Jenoptik, Germany.

  20. Beryllium and zirconium

    International Nuclear Information System (INIS)

    Salesse, Marc

    1959-01-01

    Pure beryllium and zirconium, both isolated at about the same date but more than a century ago remained practically unused for eighty years. Fifteen years ago they were released from this state of inactivity by atomic energy, which made them into current metal a with an annual production which runs into tens of tons for the one and thousands for the other. The reasons for this promotion promise well for the future of the two metals, which moreover will probably find additional uses in other branches of industry. The attraction of beryllium and zirconium for atomic energy is easily explained. The curve of figure 1 gives the price per gram of uranium-235 as a function of enrichment: this price increases by about a factor of 3 on passing from natural uranium (0, 7 percent 235 U) to almost pure uranium-235. Because of their tow capture cross-section beryllium and zirconium make it possible, or at least easier, to use natural uranium and they thus enjoy an advantage the extent of which must be calculated for each reactor or fuel element project, but which is generally considerable. It will be seen later that this advantage should be based on figures which are even more favourable that would appear from the simple ratio 3 of the price of pure uranium- 235 contained in natural uranium. Reprint of a paper published in 'Industries Atomiques' - n. 1-2, 1959

  1. Catalyst support effects on hydrogen spillover

    Science.gov (United States)

    Karim, Waiz; Spreafico, Clelia; Kleibert, Armin; Gobrecht, Jens; Vandevondele, Joost; Ekinci, Yasin; van Bokhoven, Jeroen A.

    2017-01-01

    Hydrogen spillover is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support. The phenomenon has been much studied and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide. Here we use the enhanced precision of top-down nanofabrication to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations, reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage and catalytic reactions involving hydrogen, and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.

  2. Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

    Science.gov (United States)

    Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

    2017-12-01

    We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

  3. CATALYTICALLY ENHANCED SYSTEMS FOR HYDROGEN STORAGE. Final report

    International Nuclear Information System (INIS)

    Craig M. Jensen

    2007-01-01

    Previous U.S. DOE sponsored research at the University of Hawaii resulted in the development of methods of doping of sodium aluminum hydride, NaAlH4 with titanium, zirconium and other catalysts such that: dehydriding occurs at temperatures as low as 100 C; rehydriding requires less than 1 h; and >4 weight percent hydrogen can be repeatedly cycled through dehydriding/rehydriding. These materials appeared to be on the threshold of practical viability as hydrogen carriers for onboard fuel cells. However, it was apparent that further kinetic enhancement was required to achieve commercial viability. Thus, one of the primary goals of this project was to develop the requisite improved catalysts. Over the course of this project, a variety of titanium and zirconium dopant precursors were investigated. Moreover, the approach was to conduct guided search for improved catalysts by obtaining a fundamental understanding of the chemical nature of the titanium dopants and their mechanism of action. Therefore, the projected also aimed to determined the chemical nature of the titanium species that are formed upon mechanical milling of NaAlH4 with the dopant precursors through synchrotron X-ray and neutron diffraction as well as transmission electron microscopy, scanning electron microscopy, and electron paramagnetic resonance (EPR) spectroscopy. In addition to kinetic studies, insight into the mechanism of action of the dopants was gained through studies of the destabilization of hydrogen in NaAlH4 by the dopants through infrared, NMR, and anelastic spectroscopy

  4. Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

    Directory of Open Access Journals (Sweden)

    Michael M. Bobek

    2012-10-01

    Full Text Available A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM and electron dispersive X-ray spectroscopy (EDS, the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

  5. PROCESS OF DISSOLVING ZIRCONIUM ALLOYS

    Science.gov (United States)

    Shor, R.S.; Vogler, S.

    1958-01-21

    A process is described for dissolving binary zirconium-uranium alloys where the uranium content is about 2%. In prior dissolution procedures for these alloys, an oxidizing agent was added to prevent the precipitation of uranium tetrafluoride. In the present method complete dissolution is accomplished without the use of the oxidizing agent by using only the stoichiometric amount or slight excess of HF required by the zirconium. The concentration of the acid may range from 2M to 10M and the dissolution is advatageously carried out at a temperature of 80 deg C.

  6. Mathematical model of the reformer sponge iron cycle

    International Nuclear Information System (INIS)

    Fraser, S.; Hacker, V.; Evers, B.; Hierzer, J.; Besenhard, J.O.

    2003-01-01

    A mathematical model of the Reformer Sponge Iron Cycle (RESC), an innovative hydrogen production process based on redox reactions of iron ore pellets is presented. In the oxidation stage of the RESC, hydrogen is produced by blowing steam over hot iron pellets, hence oxidizing the iron. In the reduction stage, synthesis gas coming from a reformer mixed with a fraction of recycled off-gas is used to reduce the iron oxide pellets (wuestite and/or magnetite) back into iron again. A mathematical model of the complete RESC was developed and verified with experimental data. The model is based on calculations of the equilibrium gas concentrations for reformer and Sponge Iron Reactor (SIR). The current model computes mass fluxes, molar fluxes, partial pressures and variations of the respective throughout the complete cycle. The recycle rate, determining the fraction of SIR off-gas recycled and added to the input gas stream was subsequently optimized in order to maximize the amount of iron oxide reduced for a certain input gas flow. (author)

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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

  8. Laser-Based Additive Manufacturing of Zirconium

    Directory of Open Access Journals (Sweden)

    Himanshu Sahasrabudhe

    2018-03-01

    Full Text Available Additive manufacturing of zirconium is attempted using commercial Laser Engineered Net Shaping (LENSTM technique. A LENSTM-based approach towards processing coatings and bulk parts of zirconium, a reactive metal, aims to minimize the inconvenience of traditional metallurgical practices of handling and processing zirconium-based parts that are particularly suited to small volumes and one-of-a-kind parts. This is a single-step manufacturing approach for obtaining near net shape fabrication of components. In the current research, Zr metal powder was processed in the form of coating on Ti6Al4V alloy substrate. Scanning electron microscopy (SEM and energy dispersive spectroscopy (EDS as well as phase analysis via X-ray diffraction (XRD were studied on these coatings. In addition to coatings, bulk parts were also fabricated using LENS™ from Zr metal powders, and measured part accuracy.

  9. Coprecipitation of neptunium and plutonium with iron and zirconium dibutyl phosphates

    International Nuclear Information System (INIS)

    Sokhina, L.P.; Rovnyj, S.I.; Goncharuk, L.V.

    1988-01-01

    Neptunium and plutonium coprecipitation with precipitates of dibutyl phosphates of some elements significant for radiochemical technology is studied. By the ability to coprecipitation of actinides with precipitates of dibutyl phosphates the cations may be arranged in the series Fe > Al > La > ≥ Zr ≥ Th. The composition of neptunium and plutonium mixed precipitates on the basis of iron dibutyl phosphates corresponding to the formula (Me(NO 3 ) 2 Al 2 ) n x · FeA 3 , where Me-neptunium or plutonium, A-anion of dibutyl phosphoric acid, n=1-4, is determined. Solubility of mixed precipitations in nitric acid and carbonate solutions is studied. Mixed precipitations on the basis of iron dibutyl phosphates are found to have the least solubility, their solubility being lower than that of individual compounds of dibutyl phoshates. The mechanism of formation of mixed precipitates is suggested and discussed

  10. Titanium zirconium and hafnium coordination compounds with vanillin thiosemicarbazone

    International Nuclear Information System (INIS)

    Konunova, Ts.B.; Kudritskaya, S.A.

    1987-01-01

    Coordination compounds of titanium zirconium and hafnium tetrachlorides with vanillin thiosemicarbazone of MCl 4 x nLig composition, where n=1.5, 4 for titanium and 1, 2, 4 for zirconium and hafnium, are synthesized. Molar conductivity of ethanol solutions is measured; IR spectroscopic and thermochemical investigation are carried out. The supposition about ligand coordination via sulfur and azomethine nitrogen atoms is made. In all cases hafnium forms stable compounds than zirconium

  11. Zero-valent iron nanoparticles preparation

    International Nuclear Information System (INIS)

    Oropeza, S.; Corea, M.; Gómez-Yáñez, C.; Cruz-Rivera, J.J.; Navarro-Clemente, M.E.

    2012-01-01

    Graphical abstract: Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH 3 ) 3 ) 2 ] 2 ] at room temperature and a pressure of 3 atm. The synthesized nanoparticles were spherical and had diameters less than 5 nm. Highlights: ► Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH 3 ) 3 ) 2 ] 2 ]. ► The conditions of reaction were at room temperature and a pressure of 3 atm. ► The synthesized nanoparticles were spherical and had diameters less than 5 nm. -- Abstract: Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH 3 ) 3 ) 2 ] 2 ] at room temperature and a pressure of 3 atm. To monitor the reaction, a stainless steel pressure reactor lined with PTFE and mechanically stirred was designed. This design allowed the extraction of samples at different times, minimizing the perturbation in the system. In this way, the shape and the diameter of the nanoparticles produced during the reaction were also monitored. The results showed the production of zero-valent iron nanoparticles that were approximately 5 nm in diameter arranged in agglomerates. The agglomerates grew to 900 nm when the reaction time increased up to 12 h; however, the diameter of the individual nanoparticles remained almost the same. During the reaction, some byproducts constituted by amino species acted as surfactants; therefore, no other surfactants were necessary.

  12. The chemical vapor deposition of zirconium carbide onto ceramic substrates

    International Nuclear Information System (INIS)

    Glass A, John Jr.; Palmisiano, Nick Jr.; Welsh R, Edward

    1999-01-01

    Zirconium carbide is an attractive ceramic material due to its unique properties such as high melting point, good thermal conductivity, and chemical resistance. The controlled preparation of zirconium carbide films of superstoichiometric, stoichiometric, and substoichiometric compositions has been achieved utilizing zirconium tetrachloride and methane precursor gases in an atmospheric pressure high temperature chemical vapor deposition system

  13. Modelling of Zirconium and Hafnium separation using continuous annular chromatography

    International Nuclear Information System (INIS)

    Moch-Setyadji; Endang Susiantini

    2014-01-01

    Nuclear degrees of zirconium in the form of a metal alloy is the main material for fuel cladding of NPP. Zirconium is also used as sheathing UO 2 kernel in the form of ZrC as a substitute of SiC in the fuel elements of High Temperature Reactor (HTR). Difficulty separating hafnium from zirconium because it has a lot of similarities in the chemical properties of Zr and Hf. Annular chromatography is a device that can be used for separating of zirconium and hafnium to obtain zirconium nuclear grade. Therefore, it is necessary to construct the mathematical modelling that can describe the separation of zirconium and hafnium in the annular chromatography containing anion resin dowex-1X8. The aim of research is to perform separation simulation by using the equilibrium model and mass transfer coefficient resulted from research. Zr and Hf feed used in this research were 26 and 1 g/l, respectively. Height of resin (L), angular velocity (ω) and the superficial flow rate (uz) was varied to determine the effect of each parameter on the separation of Zr and Hf. By using Kd and Dv values resulted previous research. Simulation results showed that zirconium and hafnium can be separated using a continuous annular chromatography with high resin (long bed) 50 cm, superficial flow rate of 0.001 cm/s, the rotation speed of 0.006 rad/min and 20 cm diameter annular. In these conditions the results obtained zirconium concentration of 10,303.226 g/m 3 and hafnium concentration of 12.324 g/m 3 (ppm). (author)

  14. Hydrogen production in a PWR during LOCA

    International Nuclear Information System (INIS)

    Cassette, P.

    1984-01-01

    Hydrogen generation during a PWR LOCA has been estimated for design basis accident and for two more severe hypothetical accidents. Hydrogen production during design basis accident is a rather slow mechanism, allowing in the worst case, 15 days to connect a hydrogen recombining unit to the containment atmosphere monitoring system. Hydrogen generated by steam oxidation during more severe hypothetical accidents was found limited by steam availability and fuel melting phenomena. Uncertainty is, however, still remaining on corium-zirconium-steam interaction. In the worst case, calculations lead to the production of 500 kg of hydrogen, thus leading to a volume concentration of 15% in containment atmosphere, assuming homogeneous hydrogen distribution within the reactor building. This concentration is within flammability limits but not within detonation limits. However, hydrogen detonation due to local hydrogen accumulation cannot be discarded. A major uncertainty subsisting on hydrogen hazard is hydrogen distribution during the first hours of the accident. This point determines the effects and consequences of local detonation or deflagration which could possibly be harmful to safeguard systems, or induce missile generation in the reactor building. As electrical supply failures are identified as an important contributor to severe accident risk, corrective actions have been taken in France to improve their reliability, including the installation of a gas turbine on each site to supplement the existing sources. These actions are thus contributing to hydrogen hazard reduction

  15. Young's modulus of crystal bar zirconium and zirconium alloys (zircaloy-2, zircaloy-4, zirconium-2.5wt% niobium) to 1000 K

    International Nuclear Information System (INIS)

    Rosinger, H.E.; Ritchie, I.G.; Shillinglaw, A.J.

    1975-09-01

    This report contains experimentally determined data on the dynamic elastic moduli of zircaloy-2, zircaloy-4, zirconium-2.5wt% niobium and Marz grade crystal bar zirconium. Data on both the dynamic Young's moduli and shear moduli of the alloys have been measured at room temperature and Young's modulus as a function of temperature has been determined over the temperature range 300 K to 1000 K. In every case, Young's modulus decreases linearly with increasing temperature and is expressed by an empirical equation fitted to the data. Differences in Young's modulus values determined from specimens with longitudinal axes parallel and perpendicular to the rolling direction are small, as are the differences between Young's moduli determined from strip, bar stock and fuel sheathing. (author)

  16. In vitro assessment of artifacts induced by titanium, titanium-zirconium and zirconium dioxide implants in cone-beam computed tomography.

    Science.gov (United States)

    Sancho-Puchades, Manuel; Hämmerle, Christoph H F; Benic, Goran I

    2015-10-01

    The aim of this study was to test whether or not the intensity of artifacts around implants in cone-beam computed tomography (CBCT) differs between titanium, titanium-zirconium and zirconium dioxide implants. Twenty models of a human mandible, each containing one implant in the single-tooth gap position 45, were cast in dental stone. Five test models were produced for each of the following implant types: titanium 4.1 mm diameter (Ti4.1 ), titanium 3.3 mm diameter (Ti3.3 ), titanium-zirconium 3.3 mm diameter (TiZr3.3 ) and zirconium dioxide 3.5-4.5 mm diameter (ZrO3.5-4.5 ) implants. For control purposes, three models without implants were produced. Each model was scanned using a CBCT device. Gray values (GV) were recorded at eight circumferential positions around the implants at 0.5 mm, 1 mm and 2 mm from the implant surface (GVT est ). GV were assessed in the corresponding volumes of interest (VOI) in the control models without implants (GVC ontrol ). Differences of gray values (ΔGV) between GVT est and GVC ontrol were calculated as percentages. One-way ANOVA and post hoc tests were applied to detect differences between implant types. Mean ΔGV for ZrO3.5-4.5 presented the highest absolute values, generally followed by TiZr3.3 , Ti4.1 and Ti3.3 implants. The differences of ΔGV between ZrO3.5-4.5 and the remaining groups were statistically significant in the majority of the VOI (P ≤ 0.0167). ΔGV for TiZr3.3 , Ti4.1 and Ti3.3 implants did not differ significantly in the most VOI. For all implant types, ΔGV showed positive values buccally, mesio-buccally, lingually and disto-lingually, whereas negative values were detected mesially and distally. Zirconium dioxide implants generate significantly more artifacts as compared to titanium and titanium-zirconium implants. The intensity of artifacts around zirconium dioxide implants exhibited in average the threefold in comparison with titanium implants. © 2014 John Wiley & Sons A/S. Published by John Wiley

  17. Spectrophotometric titration of sulfates in the presence of zirconium

    International Nuclear Information System (INIS)

    Kuznetsov, V.V.; Kotova, S.S.; Molokanova, L.G.; Chekmarev, A.M.; Yagodin, G.A.

    1978-01-01

    The procedure has been proposed for express determination of sulphate ions in the presence of zirconium by spectrophotometric titration with the use of barium chloride and nitrochromazo as an indicator. The procedure is based on bonding zirconium into a more stable complex with EDTA (ethylenediaminotetraacetic acid). The presence of excess of EDTA and zirconium (4) complexonate in the solution being titrated does not affect the titration curve shape and the character of break on the curve in the equivalence point. A complete demasking of SO 4 2- is observed in the case of 1O-fold excess of EDTA with respect to zirconium (4). Statistic evaluation of the method has shown that the results of titration can be distorted by chance errors only

  18. CH3SH adsorption properties and mechanism of deodorant filter made of iron hydroxide on porous iron frame; Tetsu takotaisei dasshu filter no methyl mercaptan jokyo seino to jokyo kiko

    Energy Technology Data Exchange (ETDEWEB)

    Noda, T. [Nippon Steel Corp., Tokyo (Japan)

    1998-05-10

    It is suggested that methyl mercaptan is decomposed to methyl sulfide and hydrogen by reaction with the a-iron hydroxide, and then the methyl sulfide combines with sulfur crystal and the hydrogen changes into water by the chemical reaction with the {alpha}-iron hydroxide. A deodorant filter was made by treating porous metallic iron with an aqueous solution of L-ascorbic acid, iron (II) sulfate and calcium hydroxide aqueous solution to deposit the iron ascorbate and the {alpha}-iron hydroxide on it. Then the deodorant filter was exposed to the hydrogen sulfide to yield the sulfur crystals on the surface of the deodorant filter. The methyl mercaptan removal capacity of the deodorant filter was studied with repetition of removal tests. Results show that the methyl mercaptan removal capacity of the deodorant filter is a little smaller than that of conventional granular activated carbon. 6 refs., 6 figs., 3 tabs.

  19. Waterside corrosion of zirconium alloys in nuclear power plants

    International Nuclear Information System (INIS)

    Jeong, Yong Hwan; Baek, B. J.; Park, S. Y. and others

    1999-08-01

    The overview of corrosion and hydriding behaviors of Zr-based alloy under the conditions of the in-reactor service and in the absence of irradiation is introduced in this report. The metallurgical characteristics of Zr-based alloys and the thermo-mechanical treatments on the microstructures and the textures in the manufacturing process for fuel cladding are also introduced. The factors affecting the corrosion of Zr alloy in reactor are summarized. And the corrosion mechanism and hydrogen up-take are discussed based on the laboratory and in-reactor results. The phenomenological observations of zirconium alloy corrosion in reactors are summarized and the models of in-reactor corrosion are exclusively discussed. Finally, the effects of irradiation on the corrosion process in Zr alloy were investigated mainly based on the literature data. (author). 538 refs., 26 tabs., 105 figs

  20. Study of the uranium-zirconium diffusion; Etude de la diffusion uranium-zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Adda, Y; Mairy, C; Bouchet, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    The intermetallic diffusion of uranium fuel and zirconium used as cladding is studied. Intermetallic diffusion can occur during the cladding of uranium rods and uranium can penetrate the zirconium cladding. Different parameters are involved in this mechanism as structure and mechanical properties of the diffusion area as well as presence of impurities in the metal. The uses of different analysis techniques (micrography, Castaing electronic microprobe, microhardness and autoradiography) have permitted to determine with great accuracy the diffusion coefficient in gamma phase (body centered cubic system) and the results have given important information on the intermetallic diffusion mechanisms. The existence of the Kirkendall effect in the U-Zr diffusion is also an argument in favor of the generality of the diffusion mechanism by vacancies in body centered cubic system. (M.P.)

  1. Electrochemistry study of the influence of local hydrogen generation in carbon steel bio-corrosion mechanisms in presence of iron reducing bacteria (Shewanella oneidensis)

    International Nuclear Information System (INIS)

    Moreira, R.; Libert, M.; Tribollet, B.; Vivier, V.

    2012-01-01

    Document available in extended abstract form only. The safe disposal of nuclear waste is a major concern for the nuclear energy industry. The high-level long-lived waste (HLNW) should be maintained for millions of years in clay formations at 500 metres depth in order to prevent the migration of radionuclides. Thence, different kinds of materials such as, carbon steel, stainless steel, concrete, clay, etc., are chosen aiming to last as long as possible and to preserve the radioactivity properties. In contrast, the anoxic corrosion of the different metallic envelopes is an expected phenomenon due to the changes on the environmental conditions (such as re-saturation) within HLNW repositories. In this context, corrosion products like iron oxides (i.e. magnetite, Fe 3 O 4 ), and hydrogen will be also expected. On the one hand, hydrogen poses a significant threat to the nuclear waste repository when it is accumulated for a long time in the surrounding clay - such hydrogen production may damage the barrier properties of the geological formation, affecting the safety of the repository. On the other hand, hydrogen production represents a new energy source for bacterial growth, especially in such environments with low content of biodegradable organic matter. Moreover, some hydrogeno-trophic bacteria can also use Fe 3+ as an electron acceptor for their development. Therefore, the biological activity and biofilm formation could interfere in the metal corrosion behaviour. This phenomenon is widely known by MIC (Microbiologically Influenced Corrosion), which can represent a huge problem when promoting local corrosion. The objective of this study is to better understand the influence of local hydrogen formation in the carbon steel bio-corrosion process in the presence of Shewanella oneidensis MR-1, a model of Iron Reducing Bacteria (IRB), in order to evaluate the impact of the bacterial activity in terms of long term behaviour of geological disposal materials. In this study

  2. CFD simulations for premixed hydrogen-air deflagration from a vented chamber

    International Nuclear Information System (INIS)

    Gera, B.; Ganju, S.

    2015-01-01

    In water cooled power reactors, significant quantities of hydrogen could be produced by a steam-zirconium (fuel clad) reaction following a postulated loss-of-coolant accident (LOCA) along with non-availability of Emergency Core Cooling System (ECCS). Hydrogen in air has the potential for uncontrolled combustion, which has given rise to public concern over the years. The generated hydrogen gets distributed in the different compartment of nuclear reactor containment and may form combustible mixture. Hence, various experimental activities have been performed around the world to investigate severe accident phenomena related to hydrogen combustion. Recently, with the rising concerns for local hydrogen control, numerical calculations for space resolved hydrogen distribution and combustion in the compartment have become an important requirement. Considering all these issues computations have been performed using commercial CFD code CFDACE+ for deflagration of lean dry hydrogen air mixture for a reported experiment. The paper describes the modelling details and main results of the investigation and comparison with experiments

  3. Delayed hydride cracking in zirconium alloys in pressure tube nuclear reactors. Final report of a coordinated research project 1998-2002

    International Nuclear Information System (INIS)

    2004-10-01

    This report describes all of the research work undertaken as part of the IAEA coordinated research project on hydrogen and hydride induced degradation of the mechanical and physical properties of zirconium based alloys, and includes a review of the state of the art in understanding crack propagation by Delayed Hydride Cracking (DHC), and details of the experimental procedures that have produced the most consistent set of DHC rates reported in an international round-robin exercise to this date. It was concluded that 1) the techniques for performing measurements of the rate of delayed hydride cracking in zirconium alloys have been transferred from the host laboratory to other countries; 2) by following a strict procedure, a very consistent set of values of crack velocity were obtained by both individual laboratories and between the different laboratories; 3) the results over a wide range of test temperatures from materials with various microstructures fitted into the current theoretical framework for delayed hydride cracking; 4) an inter-laboratory comparison of hydrogen analysis revealed the importance of calibration and led to improvements in measurement in the participating laboratories and 5) the success of the CRP in achieving its goals has led to the initiation of some national programmes

  4. Iron sponge installation clicks at Retlaw plant

    Energy Technology Data Exchange (ETDEWEB)

    1965-06-21

    Iron sponge desulfurization, often ignored by plant designers in favor of the monoethanolamine process, may offer economic advantages in sweetening of small gas volumes with low hydrogen sulfide and carbon dioxide content. The process removes hydrogen sulfide and mercaptans by passing sour gas through vessels loosely packed with wood shavings impregnated by a hydrated form of iron oxide, which reacts with the hydrogen sulfide to form ferric sulfide. The disadvantages are that carbon dioxide is not removed, hydrate formation is a danger in cold weather, and gas sales may be lost when towers are down for servicing. Periodic regeneration of beds takes about a day, and sponges must be replaced occasionally. Despite these shortcomings, the process may prove economical, since a typical plant costs $110,000 as compared to $270,000 for an amine unit. The expense of operating the plant is $23,000 compared with $28,000 for the amine unit. Thus, economics clearly favor the iron sponge process.

  5. Development of a hydrogen permeation sensor for future tritium applications

    Energy Technology Data Exchange (ETDEWEB)

    Llivina, L.; Colominas, S.; Abellà, J., E-mail: sergi.colominas@iqs.es

    2014-10-15

    Highlights: • Designing and testing of a hydrogen permeation sensor. • Palladium and α-iron have been used as a hydrogen permeation materials in the sensor. • The experiments performed using both membranes showed that the operation of the sensors in the equilibrium mode required at least several hours to reach the hydrogen equilibrium pressure. - Abstract: Tritium monitoring in lithium–lead eutectic is of great importance for the performance of liquid blankets in fusion reactors. In addition, tritium measurements will be required in order to proof tritium self-sufficiency in liquid metal breeding systems. On-line hydrogen (isotopes) sensors must be design and tested in order to accomplish these goals. In this work, an experimental set up was designed in order to test the permeation hydrogen sensors at 500 °C. This experimental set-up allowed working with controlled environments (different hydrogen partial pressures) and the temperature was measured using a thermocouple connected to a temperature controller that regulated an electrical heater. In a first set of experiments, a hydrogen sensor was constructed using an α-iron capsule as an active hydrogen area. The sensor was mounted and tested in the experimental set up. In a second set of experiments the α-iron capsule was replaced by a welded thin palladium disk in order to minimize the death volume. The experiments performed using both membranes (α-iron and palladium) showed that the operation of the sensors in the equilibrium mode required at least several hours to reach the hydrogen equilibrium pressure.

  6. Uranium (Vi) sorption onto zirconium diphosphate chemically modified

    International Nuclear Information System (INIS)

    Garcia G, N.; Ordonez R, E.

    2010-10-01

    This work deals with the uranium (Vi) speciation after sorption onto zirconium diphosphate (ZrP 2 O 7 ) surface, hydrated and in a surface modified with organic acids. Oxalic and citric acids were chosen to modify the ZrP 2 O 7 surface because they have poly carboxylic groups and they mimic the organic matter in nature. Thus the interest of this work is to evaluate the uranium (Vi) sorption edge at different s ph values in natural and modified surfaces. The luminescence technique (fluorescence and phosphorescence, respectively) was used for the quantification and speciation of uranyl sorbed at the zirconium diphosphate interface. The fluorescence experiment, showed that adsorption of uranyl on surface of zirconium diphosphate tends to 100%. The speciation shows that there are different complexes in surface which were formed between zirconium diphosphate and uranyl, since it is produced a displacement of wavelength in fluorescence spectra of each system. (Author)

  7. A study of a production process for hafnium-free zirconium from zircon

    International Nuclear Information System (INIS)

    Ratanalert, N.

    1985-01-01

    The purpose of this experiment was to extract and purify the zirconium from zircon. The effects of time of extraction and stripping of zirconium, concentration of feed solution, concentration of hydrochloric acid in stripping process, equilibrium curve of extraction of zirconium and hafnium and equilibrium curve of stripping zirconium or scrubbing hafnium were studied from standard zirconium and hafnium. The results, subsequently were applied to the extraction procedures for zirconium from zircon. Minus 100 mesh zircon was fused with sodium hydroxide in the ratio of 1 : 6 at 700 degree C for l hour. After fusion the zirconate was leached with water and dissolved in hot concentrated hydrochloric acid. Zirconyl chloride octahydrate crystallized out when the solution was cooled. An agueons solution of zirconyl chloride was used as the feed to the hexone - thiocyanate solvent extraction process. This was prepared by dissolving zirconyl chloride octahydrate crystal in waster. This zirconium feed solution in 1 M HCl and 1 M N H 4 CNS was extracted with 2.7 m N H 4 CNS in hexone and then stripped with 3.6 M HCl the aqueous phase was got rid of thiocyanate ion by extracting with pure hexone, then the zirconium in aqueous phase was precipitated with sulfuric acid and ammonium hydroxide at pH 1.8 - 2.0 and zirconium oxide was obtained by ignition at 700 degree C. The process could be modified to improve the purity of zirconium by using cation exchange resin to get rid of thiocyanate ion after solvent extraction process

  8. Minimalistic Liquid-Assisted Route to Highly Crystalline α-Zirconium Phosphate.

    Science.gov (United States)

    Cheng, Yu; Wang, Xiaodong Tony; Jaenicke, Stephan; Chuah, Gaik-Khuan

    2017-08-24

    Zirconium phosphates have potential applications in areas of ion exchange, catalysis, photochemistry, and biotechnology. However, synthesis methodologies to form crystalline α-zirconium phosphate (Zr(HPO 4 ) 2 ⋅H 2 O) typically involve the use of excess phosphoric acid, addition of HF or oxalic acid and long reflux times or hydrothermal conditions. A minimalistic sustainable route to its synthesis has been developed by using only zirconium oxychloride and concentrated phosphoric acid to form highly crystalline α-zirconium phosphate within hours. The morphology can be changed from platelets to rod-shaped particles by fluoride addition. By varying the temperature and time, α-zirconium phosphate with particle sizes from nanometers to microns can be obtained. Key features of this minimal solvent synthesis are the excellent yields obtained with high atom economy under mild conditions and ease of scalability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electrochemical impedance spectroscopic study of passive zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Ai Jiahe; Chen Yingzi [Center for Electrochemical Science and Technology, Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Urquidi-Macdonald, Mirna [Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, PA 16802 (United States); Macdonald, Digby D. [Center for Electrochemical Science and Technology, Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States)], E-mail: ddm2@psu.edu

    2008-09-30

    Spent, unreproccessed nuclear fuel is generally contained within the operational fuel sheathing fabricated from a zirconium alloy (Zircaloy 2, Zircaloy 4, or Zirlo) and is then stored in a swimming pool and/or dry storage facilities until permanent disposal in a licensed repository. During this period, which begins with irradiation of the fuel in the reactor during operation, the fuel sheathing is exposed to various, aggressive environments. The objective of the present study was to characterize the nature of the passive film that forms on pure zirconium in contact with an aqueous phase [0.1 M B(OH){sub 3} + 0.001 M LiOH, pH 6.94] at elevated temperatures (in this case, 250 deg. C), prior to storage, using electrochemical impedance spectroscopy (EIS) with the data being interpreted in terms of the point defect model (PDM). The results show that the corrosion resistance of zirconium in high temperature, de-aerated aqueous solutions is dominated by the outer layer. The extracted model parameter values can be used in deterministic models for predicting the accumulation of general corrosion damage to zirconium under a wide range of conditions that might exist in some repositories.

  10. Some recent trends in the use of zirconium alloys for nuclear service

    International Nuclear Information System (INIS)

    Balaramamoorthy, K.

    1992-01-01

    Without any exception nuclear power reactors particularly the water cooled ones, operating in the World use natural or slightly enriched uranium oxide fuel pellets with zirconium alloy cladding. While the zirconium alloys have proven to be successful in their designed usage, a desire for longer lifetimes of core components and increased duty cycle puts more demand on materials performance. This demand has led to more in depth studies of phenomena associated with zirconium alloy corrosion mechanism, fine tuning of the zirconium alloy composition, development of fabrication techniques and to the evaluation of newer zirconium alloys for critical applications. (author). 5 refs., 32 figs

  11. Translucency and Strength of High Translucency Monolithic Zirconium Oxide Materials

    Science.gov (United States)

    2016-05-17

    Zirconium -Oxide Materials presented at/published to the Journal of General Dentistry with MDWI 41-108, and has been assigned local file #16208. 2...Zirconia-Oxide Materials 6. TITLE OF MATERIAL TO BE PUBLISHED OR PRESENTED: Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide...OBSOLETE 48. DATE Page 3 of 3 Pages Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide Materials Abstract Dental materials

  12. DISSOLUTION OF ZIRCONIUM AND ALLOYS THEREFOR

    Science.gov (United States)

    Swanson, J.L.

    1961-07-11

    The dissolution of zirconium cladding in a water solution of ammonium fluoride and ammonium nitrate is described. The method finds particular utility in processing spent fuel elements for nuclear reactors. The zirconium cladding is first dissolved in a water solution of ammonium fluoride and ammonium nitrate; insoluble uranium and plutonium fiuorides formed by attack of the solvent on the fuel materiai of the fuel element are then separated from the solution, and the fuel materiai is dissolved in another solution.

  13. Physics of coal methane: decisive role of iron compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gavriljuk, V. G., E-mail: gavr@imp.kiev.ua; Skoblik, A. P. [G.V. Kurdyumov Institute for Metal Physics (Ukraine); Shanina, B. D.; Konchits, A. A. [V. Ye. Lashkarev Institute for Semiconductor Physics (Ukraine)

    2016-12-15

    The role of iron in formation of the coal methane is clarified based on the studies performed on the coal samples taken from different mines in Donetsk coal basin. Using Mössbauer spectroscopy, a correlation is found between the iron content and methane capacity of coal seams. By means of electron paramagnetic resonance, it is found that iron increases the concentration of non-compensated electron spins, i.e. dangled bonds at the carbon atoms. These bonds can be occupied by hydrogen atoms as a prerequisite of methane formation. The two-valence iron is shown to be the most effective in the increase of spin concentration. By using the ion mass spectrometry, the modelling of methane formation is carried out on the mechanical mixture of the iron-free reactor graphite, iron compounds and diluted sulphuric acid as a source of hydrogen atoms. The proposed mechanism is also confirmed by methane formation in the mixture of iron compounds and the coal from the mine where the iron and methane are practically absent.

  14. Quantitative hydrogen analysis in fusion-relevant materials by SIMS

    International Nuclear Information System (INIS)

    Jaeger, W.

    1991-04-01

    In fusion reactors graphite brazed on metallic substrates is commonly used for plasma-exposed components of the First Wall. Exposed to high heat-, hydrogen- and deuterium-fluxes, the stability of the braze under such conditions is essential. A sample of graphite brazed with zirconium on a molybdenum high temperature alloy was cut and exposed to a deuterium plasma (dose 10 22 cm -2 ). Secondary Ion Mass Spectroscopy (SIMS) has proven to combine high sensitivity to hydrogen and deuterium with the ability to perform depth profiling. Thus SIMS investigations should determine the extent of deuterium diffusion into the braze and the substrate. SIMS measurement conditions were optimized with special regard to energy filtering and to computer controlled magnetic field adjustment. Step scan measurements to obtain information on the surface concentration of deuterium and depth profiling to determine the distribution of the bulk concentration were performed. In the braze, directly exposed to the plasma, the deuterium content was up to a few atomic percent. The shielding of a thin graphite layer (0.5 mm) reduced the deuterium content to approximately 300 ppm at., but diffusion was still present. For deuterium quantification a homogenous graphite standard and molybdenum- and zirconium-implantation standards were used. With respect to the diffusivity of deuterium, MoD/Mo and ZrD/Zr ratios were measured. Different energy filtering was used to distinguish trapped and free deuterium. The comparison of experimental depth profiles with theoretical Monte Carlo simulations showed the effects of implantation damage in the bulk and of trapping. The relative sensitivity factors for deuterium in graphite, molybdenum and zirconium were calculated. (author)

  15. International strategic minerals inventory summary report; zirconium

    Science.gov (United States)

    Towner, R.R.

    1992-01-01

    Zircon, a zirconium silicate, is currently the most important commercial zirconium-bearing mineral. Baddeleyite, a natural form of zirconia, is less important but has some specific end uses. Both zircon and baddeleyite occur in hard-rock and placer deposits, but at present all zircon production is from placer deposits. Most baddeleyite production is from hard-rock deposits, principally as a byproduct of copper and phosphate-rock mining. World zirconium resources in identified, economically exploitable deposits are about 46 times current production rates. Of these resources, some 71 percent are in South Africa, Australia, and the United States. The principal end uses of zirconium minerals are in ceramic applications and as refractories, abrasives, and mold linings in foundries. A minor amount, mainly of zircon, is used for the production of hafnium-free zirconium metal, which is used principally for sheathing fuel elements in nuclear reactors and in the chemical-processing industry, aerospace engineering, and electronics. Australia and South Africa are the largest zircon producers and account for more than 70 percent of world output; the United States and the Soviet Union account for another 20 percent. South Africa accounts for almost all the world's production of baddeleyite, which is about 2 percent of world production of contained zirconia. Australia and South Africa are the largest exporters of zircon. Unless major new deposits are developed in countries that have not traditionally produced zircon, the pattern of world production is unlikely to change by 2020. The proportions, however, of production that come from existing producing countries may change somewhat.

  16. Zirconium coatings doped with nanoparticles for the protection of stainless steel

    International Nuclear Information System (INIS)

    Pineda, F; Vargas, E; Martinez, C; Sancy, M; Rabagliati, F.M; Pavez, J; Paez, M.A

    2008-01-01

    The anticorrosive protection of metal alloys, like stainless steel, is usually carried out with chrome-based coatings, but the toxic wastes associated with the process minimizes its applicability. The above has motivated the search for alternative protection methodologies, among which are the inorganic polymers prepared by the sol-gel method, which are a viable protection alternative because of their outstanding chemical and physical properties in aggressive environments. Despite the method's benefits, the application of sol-gel coatings to metals exposed to highly corrosive materials is restricted due to the substantial porosity of the films. Recent studies report that this limiting factor can be diminished by adding inorganic nanoparticles to the polymeric matrices, significantly improving the anticorrosive properties of the coatings. Considering the above, this work evaluated the inclusion of iron oxide nanoparticles (III) in zirconium polymeric matrices for the protection of 316 and 316L stainless steel. Electrochemical techniques, such as polarization curves and electrochemical impedance spectroscopy and morphological analysis with atomic force microscopy were used for this purpose. The responses obtained showed improvements in the anticorrosive properties of the zirconium films when doped with nanoparticles, and the best protective response was obtained with the minimum amount of the nanomaterial, aided by a significant increase in the metallic material's passivity. A critical content of nanoparticles was also identified in the polymeric matrix, above which the coating suffers serious deterioration, caused by the apparent formation of percolation channels leading to the oversaturation of the polymeric matrix

  17. Influence of electrolyte nature on steel membrane hydrogen permeability

    International Nuclear Information System (INIS)

    Lisovskij, A.P.; Nazarov, A.P.; Mikhajlovskij, Yu.N.

    1993-01-01

    Effect of electrolyte nature on hydrogen absorption of carbonic steel membrane at its cathode polarization is studied. Electrolyte buffering by anions of subdissociated acids is shown to increase hydrogen flow though the membrane in acid electrolytes. Mechanisms covering dissociation of proton-bearing anion in the electrolyte near-the-electron layer or dissociative adsorption on steel surface are suggested. Effect of proton-bearing bases forming stable complex compounds with iron, is studied. Activation of anode process of iron solution is shown to increase the rate of hydrogen penetration

  18. Capture of Tritium Released from Cladding in the Zirconium Recycle Process

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, Barry B [ORNL; Bruffey, Stephanie H [ORNL; DelCul, Guillermo Daniel [ORNL; Walker, Trenton Baird [ORNL

    2016-08-31

    Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-based cladding and could be released from the cladding when the solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using nonradioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.

  19. Capture of Tritium Released from Cladding in the Zirconium Recycle Process

    Energy Technology Data Exchange (ETDEWEB)

    Bruffey, Stephanie H [ORNL; Spencer, Barry B [ORNL; DelCul, Guillermo Daniel [ORNL

    2016-08-31

    This report is issued as the first revision to FCRD-MRWFD-2016-000297. Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-based cladding and could be released from the cladding when the solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using non-radioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.

  20. Corrosion resistant zirconium alloys prepared by powder metallurgy

    International Nuclear Information System (INIS)

    Wojeik, C.C.

    1984-01-01

    Pure zirconium and zirconium 2.5% niobium were prepared by powder metallurgy. The powders were prepared directly from sponge and consolidated by cold isostatic pressing and sintering. Hot isostatic pressing was also used to obtain full density after sintering. For pure zirconium the effects of particle size, compaction pressure, sintering temperature and purity were investigated. Fully densified zirconium and Zr-2.5%Nb exhibited tensile properties comparable to cast material at room temperature and 300 0 F (149 0 C). Pressed and sintered material having density of 94-99% had slightly lower tensile properties. Corrosion tests were performed in boiling 65% H/sub 2/SO/sub 4/, 70% HNO/sub 3/, 20% HCl and 20% HCl + 500 ppm FeCl/sub 3/ (a known pitting solution). For fully dense material the observed corrosion behavior was nearly equivalent to cast material. A slightly higher rate of attack was observed for samples which were only 94-99% dense. Welding tests were also performed on zirconium and Zr-2.5%Nb alloy. Unlike P/M titanium alloys, these materials had good weldability due to the lower content of volatile impurities in the powder. A slight amount of weld porosity was observed but joint efficiencies were always not 100%, even for 94-99% density samples. Several practical applications of the P/M processed material will be briefly described

  1. Zero-valent iron nanoparticles preparation

    Energy Technology Data Exchange (ETDEWEB)

    Oropeza, S. [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico); Corea, M., E-mail: mcoreat@yahoo.com.mx [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico); Gómez-Yáñez, C. [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico); Cruz-Rivera, J.J. [Universidad Autónoma de San Luis Potosí, Instituto de Metalurgia, Sierra Leona 550, San Luis Potosí, C.P. 78210 (Mexico); Navarro-Clemente, M.E., E-mail: mnavarroc@ipn.mx [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico)

    2012-06-15

    Graphical abstract: Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 2}] at room temperature and a pressure of 3 atm. The synthesized nanoparticles were spherical and had diameters less than 5 nm. Highlights: ► Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 2}]. ► The conditions of reaction were at room temperature and a pressure of 3 atm. ► The synthesized nanoparticles were spherical and had diameters less than 5 nm. -- Abstract: Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 2}] at room temperature and a pressure of 3 atm. To monitor the reaction, a stainless steel pressure reactor lined with PTFE and mechanically stirred was designed. This design allowed the extraction of samples at different times, minimizing the perturbation in the system. In this way, the shape and the diameter of the nanoparticles produced during the reaction were also monitored. The results showed the production of zero-valent iron nanoparticles that were approximately 5 nm in diameter arranged in agglomerates. The agglomerates grew to 900 nm when the reaction time increased up to 12 h; however, the diameter of the individual nanoparticles remained almost the same. During the reaction, some byproducts constituted by amino species acted as surfactants; therefore, no other surfactants were necessary.

  2. Investigation on the corrosion resistance of zirconium in nitric acid

    International Nuclear Information System (INIS)

    Fauvet, P.; Mur, P.

    1990-01-01

    Zirconium in nitric solutions exhibits an excellent corrosion resistance in the passive state, and a mediocre corrosion resistance in the unpassive state with risk of stress corrosion cracking. Results of the influence of some parameters (medium, potential, temperature, stress, friction, metallurgical structure and surface state) on zirconium passivation are presented. Zirconium remains passive in a large range of HNO 3 concentration (at least up to 14.4N), in the presence of oxidizing ions (Cr 4 , Ce 4 ), in a spent fuel dissolution solution. Zirconium is depassived by friction at high speed and pressure, by platinum coupling in boiling 14.4N HNO 3 with or without stress, or by imposed deformation speed under high potential. (A.B.)

  3. Thermotransport of nitrogen and oxygen in β-zirconium

    NARCIS (Netherlands)

    Vogel, D.L.; Rieck, G.D.

    1971-01-01

    An investigation of thermotransport of nitrogen in ß-zirconium is reported. Using a method previously described, the heat of transport turned out to be 25.1 kcal/mole with a standard deviation of 2.5 kcal/mole. The formerly published value of the heat of transport of oxygen in ß-zirconium, viz. 20

  4. First-principles study of the stability and diffusion properties of hydrogen in zirconium carbide

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiao-Yong [Institute of Applied Physics and Computational Mathematics, Beijing 100088 (China); Lu, Yong [Institute of Applied Physics and Computational Mathematics, Beijing 100088 (China); Beijing Computational Science Research Center, Beijing 100084 (China); Zhang, Ping, E-mail: zhang_ping@iapcm.ac.cn [Institute of Applied Physics and Computational Mathematics, Beijing 100088 (China)

    2016-10-15

    The stability and diffusion properties of interstitial hydrogen atom in bulk ZrC have been investigated by first-principles calculations. In energy, hydrogen atoms prefer to occupy the carbon substitutional site (C-SS) with a negative formation energy, consistent with the experimental observations. In the C-SS, the hydrogen atom obtains 0.702 electrons from its 1 NN Zr atoms, tending to achieve the most stable 1s{sup 2} electronic state. Two hydrogen atoms in the same tetrahedral interstitial site are able to form a pairing cluster along the 〈110〉 direction with the H−H pair equilibrium distance of 1.30 Å, nearly twice the length of H{sub 2} bond, suggesting a relatively weak interaction between the H−H pair. The diffusion energy barriers of hydrogen in pure and vacancy pre-existing ZrC matrix are calculated. It is found that the presence of native vacancies will capture the hydrogen atoms due to the large energy barrier to jump out the vacancy. Furthermore, the temperature-dependent diffusion coefficients of interstitial hydrogen, deuterium, and tritium in ZrC are predicted using the transition state theory.

  5. Process for scavenging hydrogen sulfide from hydrocarbon gases

    International Nuclear Information System (INIS)

    Fox, I.

    1981-01-01

    A process for scavenging hydrogen sulfide from hydrocarbon gases utilizes iron oxide particles of unique chemical and physical properties. These particles have large surface area, and are comprised substantially of amorphous Fe 2 O 3 containing a crystalline phase of Fe 2 O 3 , Fe 3 O 4 and combinations thereof. In scavenging hydrogen sulfide, the iron oxide particles are suspended in a liquid which enters into intimate mixing contact with hydrocarbon gases; the hydrogen sulfide is reacted at an exceptional rate and only acid-stable reaction products are formed. Thereafter, the sweetened hydrocarbon gases are collected

  6. Dielectric properties of zirconium dioxide-based ceramics

    International Nuclear Information System (INIS)

    Vladimirova, O.S.; Gruzdev, A.I.; Koposova, Z.L.; Lyutsareva, L.A.

    1985-01-01

    This paper studies the dielectric properties of materials based on stabilized zirconium dioxide with Co 3 O 4 additions possessing a high temperature-coefficient of resistance. These materials are promising for manufacturing resistance temperature gages that work under an oxidizing atmosphere at 370-1270 degrees K. The obtained results indicate the possibility of developing temperature gases possessing highsensitivity from stabilized zirconium dioxide with Co 3 O 4 additions

  7. METHOD OF IMPROVING CORROSION RESISTANCE OF ZIRCONIUM

    Science.gov (United States)

    Shannon, D.W.

    1961-03-28

    An improved intermediate rinse for zirconium counteracts an anomalous deposit that often results in crevices and outof-the-way places when ordinary water is used to rinse away a strong fluoride etching solution designed to promote passivation of the metal. The intermediate rinse, which is used after the etching solution and before the water, is characterized by a complexing agent for fluoride ions such as aluminum or zirconium nitrates or chlorides.

  8. Chemistry and the iron - only hydrogenase

    International Nuclear Information System (INIS)

    Tard, C.; Razavet, M.; Liu, X.; Ibrahim, S.; Pickett, Ch.

    2005-01-01

    Complete text of publication follows: Chemistry related to the hydrogenases is developing very rapidly and providing some informative insights into how the biological systems might function. Although still very much at a blue skies stage, there is some prospect for the design of artificial assemblies, materials and devices with technological application for hydrogen production/uptake provided robust system can be designed with low over potentials for hydrogen/proton interconversion (1). The iron-only hydrogenase possesses a peculiar di-iron unit coordinated by CO and CN, ligands which are normally associated with poisoning biological function. This sub-site unit is attached to a [4Fe4S] cubane center to form the catalytic site of the hydrogenase which is known as the 'H-cluster'. The synthesis of artificial sub-sites will first be described together with how their structures, spectroscopy and reactivity provides some key insights into the natural system viz. unprecedented bridging carbonyl and Fe(I) motifs in biology (2-4). How we have approached putting together the entire iron-sulfur framework of the H-cluster will then be described together with its electron-transfer and electrocatalytic properties (4). Finally, I will describe some early work on how we are beginning to incorporate structural motifs of the active-site into conducting polymer matrices, how they function as (albeit poor) electrocatalysts for hydrogen evolution, and where we see the way ahead. (1)The Chemistry and the Hydrogenases. D.J. Evans and C.J. Pickett, Chem. Soc. Rev., 32, 268-275, 2003; (2)Electron-Transfer at a Di-thiolate-Bridged Di-Iron Assembly; Electrocatalytic Hydrogen Evolution. S.J. Borg, T. Behrsing and S.P. Best, M. Ravazet, X. Liu and C.J. Pickett, J Amer. Chem. Soc., 2004, 126, 509-533; (3) Dissecting the intimate mechanism of cyanation of [Fe2S3] complexes related to the active site of all-iron hydrogenases by DFT analysis of energetics, transition states, intermediates and

  9. The behaviour of hydrogen in Excel alloy

    Energy Technology Data Exchange (ETDEWEB)

    Ells, C.E. [Atomic Energy of Canada Ltd., Chalk River, ON (Canada). Chalk River Nuclear Labs.; Coleman, C.E. [Atomic Energy of Canada Ltd., Chalk River, ON (Canada). Chalk River Nuclear Labs.; Cheadle, B.A. [Atomic Energy of Canada Ltd., Chalk River, ON (Canada). Chalk River Nuclear Labs.; Sagat, S. [Atomic Energy of Canada Ltd., Chalk River, ON (Canada). Chalk River Nuclear Labs.; Rodgers, D.K. [Atomic Energy of Canada Ltd., Chalk River, ON (Canada). Chalk River Nuclear Labs.

    1995-12-15

    To enable mitigation of deleterious effects from hydride on the mechanical behaviour of Excel alloy, Zr-3.5 wt.% Sn-0.8 wt.% Mo-0.8 wt.% Nb, the behaviours of hydrogen and hydride in the alloy have been studied. Properties of interest are the terminal solid solubility, diffusivity, heat of transport, stress reorientation, and the initiation and crack growth of delayed hydride cracking. The results obtained are compared with those of other zirconium-rich alloys, notably Zr-2.5 wt.% Nb. (orig.)

  10. Pharmacological ascorbate and ionizing radiation (IR increase labile iron in pancreatic cancer

    Directory of Open Access Journals (Sweden)

    Justin C. Moser

    2014-01-01

    Full Text Available Labile iron, i.e. iron that is weakly bound and is relatively unrestricted in its redox activity, has been implicated in both the pathogenesis as well as treatment of cancer. Two cancer treatments where labile iron may contribute to their mechanism of action are pharmacological ascorbate and ionizing radiation (IR. Pharmacological ascorbate has been shown to have tumor-specific toxic effects due to the formation of hydrogen peroxide. By catalyzing the oxidation of ascorbate, labile iron can enhance the rate of formation of hydrogen peroxide; labile iron can also react with hydrogen peroxide. Here we have investigated the magnitude of the labile iron pool in tumor and normal tissue. We also examined the ability of pharmacological ascorbate and IR to change the size of the labile iron pool. Although a significant amount of labile iron was seen in tumors (MIA PaCa-2 cells in athymic nude mice, higher levels were seen in murine tissues that were not susceptible to pharmacological ascorbate. Pharmacological ascorbate and irradiation were shown to increase the labile iron in tumor homogenates from this murine model of pancreatic cancer. As both IR and pharmacological ascorbate may rely on labile iron for their effects on tumor tissues, our data suggest that pharmacological ascorbate could be used as a radio-sensitizing agent for some radio-resistant tumors.

  11. Primary Stability of Zirconium vs Titanium Implants: An In Vitro Comparison

    Science.gov (United States)

    2015-06-05

    of any copyrighted material in the thesis manuscript entitled: Primary Stability of Zirconium vs Titanium Implants: An In Vitro Comparison Is...Uniformed Services University Date: 02/20/2015 Primary Stability of Zirconium vs Titanium Implants: An In Vitro Comparison By...the thesis manuscript entitled: Primary Stability of Zirconium vs Titanium Implants: An In Vitro Comparison Is appropriately acknowledged

  12. Separation of zirconium from hafnium by ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Felipe, Elaine C.B.; Palhares, Hugo G.; Ladeira, Ana Claudia Q., E-mail: elainecfelipe@yahoo.com.br, E-mail: hugopalhares@gmail.com, E-mail: ana.ladeira@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2013-07-01

    Zirconium and hafnium are two of the most important metals for the nuclear industry. Hafnium occurs in all zirconium ores usually in the range 2 - 3%. However, for the most nuclear industry applications, it is necessary to use a zirconium of extremely pure level. The current work consists in the separation of zirconium and hafnium by the ion exchange method in order to obtain a zirconium concentrate of high purity. The zirconium and hafnium liquors were produced from the leaching of the Zr(OH){sub 4} and Hf(OH){sub 4} with nitric acid for 24 hours. From these two liquors it was prepared one solution containing 7.5 x 10{sup -2} mol L{sup -1} of Zr and 5.8 x 10{sup -3} mol L{sup -1} of Hf with acidity of 1 M. Ion exchange experiments were carried out in batch with the resins Dowex 50WX4, Dowex 50WX8 100, Dowex 50WX8 50, Amberlite IR-120 and Marathon C at constant temperature 28 deg C. Other variables such as, acidity and agitation were kept constant. The data were adjusted to Langmuir equation in order to calculate the maximum loading capacity (q{sub max}) of the resins, the distribution coefficient (K{sub d}) for Zr and Hf and the separation factor (α{sub Hf}{sup Zr} ). The results of maximum loading capacity (q{sub max}) for Zr and Hf, in mmol g{sup -}1, showed that the most suitable resins for columns experiments are: Dowex 50WX4 50 (q{sub max} Z{sub r} = 2.21, Hf = 0.18), Dowex 50WX8 50 (q{sub max} Zr = 1.89, Hf = 0.13) and Amberlite (q{sub max} Zr = 1.64, Hf = 0.12). However, separations factors, α{sub Hf}{sup Zr}, showed that the resins are not selective. (author)

  13. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Science.gov (United States)

    2010-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of the...

  14. Development of Self-Healing Zirconium-Silicide Coatings for Improved Performance Zirconium-Alloy Fuel Cladding

    Energy Technology Data Exchange (ETDEWEB)

    Sridharan, Kumar [University of Wisconsin-Madison; Mariani, Robert [Idaho National Lab. (INL), Idaho Falls, ID (United States); Bai, Xianming [Idaho National Lab. (INL), Idaho Falls, ID (United States); Xu, Peng [Westinghouse Electric Company; Lahoda, Ed [Westinghouse Electric Company

    2018-03-31

    Given the long-term goal of developing such coatings for use with nuclear reactor fuel cladding, this work describes results of oxidation and corrosion behavior of bulk zirconium-silicide and fabrication of zirconium-silicide coatings on zirconium-alloy test flats, tube configurations, and SiC test flats. In addition, boiling heat transfer of these modified surfaces (including ZrSi2 coating) during clad quenching experiments is discussed in detail. Oxidation of bulk ZrSi2 was found to be negligible compared to Zircaloy-4 (a common Zr-alloy cladding material) and mechanical integrity of ZrSi2 was superior to that of bulk Zr2Si at high temperatures in ambient air. Very interesting and unique multi-nanolayered composite of ZrO2 and SiO2 were observed. Physical model for the oxidation has been proposed wherein Zr–Si–O mixture undergoes a spinodal phase decomposition into ZrO2 and SiO2, which is manifested as a nanoscale assembly of alternating layer of the two oxides. Steam corrosion at high pressure (10.3 MPa) led to weight loss of ZrSi2 and produced oxide scale with depletion of silicon, possibly attributed to volatile silicon hydroxide, gaseous silicon monoxide, and a solubility of silicon dioxide in water. Only Zircon phase (ZrSiO4) formed during oxidation of ZrSi2 at 1400°C in air, and allowed for immobilization silicon species in oxide scale in the aqueous environments. Zirconium-silicide coatings (on zirconium-alloy substrates) investigated in this study were deposited primarily using magnetron sputter deposition method and slurry method, although powder spray deposition processes cold spray and thermal spray methods were also investigated. The optimized ZrSi2 sputtered coating exhibited a highly protective nature at elevated temperatures in ambient air by mitigating oxygen permeation to the underlying zirconium alloy substrate. The high oxidation resistance of the coating has been shown to be due to nanocrystalline SiO2 and ZrSiO4 phases in the amorphous

  15. Influence of zirconium ions on the sorption of carrier-free radiophosphate (32P)

    International Nuclear Information System (INIS)

    Friedmann, Ch.; Schoenfeld, T.

    1975-01-01

    In acid solutions the addition of zirconium ions largely affects the sorption of carrier-free radiophosphate on various materials. With some sorbents, such as diatomeceous earth, clay minerals or activated charcoal, the addition of small quantities of zirconium leads to a substantial increase of 32 P adsorption. On the other hand, important quantities of zirconium cause decrease of sorption. With alumina as an adsorbent, any addition of zirconium leads to reduced adsorption of radiophosphate. These phenomena are due to the formation of soluble zirconium-phosphate complex ions. (author)

  16. Characterization of hydrogen levels by ultrasonic techniques in zirconium alloys of nuclear interest

    International Nuclear Information System (INIS)

    Gomez, Martin P.

    2003-01-01

    In this work, a Master Thesis, it was examined the ratio between hydrogen quantity forming hydrides, and ultrasonic waves parameters such as propagation velocity and attenuation, for Zry-4 samples. It was to find some typical behavior for the studied parameters changing hydrogen quantity added as hydrides, for a future use as an on field NDT. With that purpose were constructed fourteen samples, eleven with added hydrogen. Three samples were left without charge as standard samples for charge and annealing processes. The quantity of hydrogen added as hydrides was varied between 0 and 516.7 ppm. Ultrasound measurements were made with compressive waves at frequencies of 10 and 30 MHz. Attenuation has been measured at both frequencies and velocity at 30 MHz. Propagation velocity showed a raising rate for test samples. For samples with hydridation conditions used in this work, this parameter would allow to measure hydrogen quantity forming hydrides with an error in the two digits of the ppm range. Attenuation measurements showed a raising tendency too, but in this case are unable for hydrides quantification, caused by a high error in attenuation measurements for both frequencies and for a fluctuating behavior at 30 MHz. (author) [es

  17. Influence of hydrogen on the oxygen solubility in Zircaloy-4

    Energy Technology Data Exchange (ETDEWEB)

    Guilbert-Banti, Séverine, E-mail: severine.guilbert@irsn.fr [Institut de Radioprotection et de Sûreté Nucléaire, SEREX/LE2M, Bâtiment 327, BP3, 13115 Saint Paul lez Durance (France); Lacote, Pauline; Taraud, Gaëlle [Institut de Radioprotection et de Sûreté Nucléaire, SEREX/LE2M, Bâtiment 327, BP3, 13115 Saint Paul lez Durance (France); Berger, Pascal [NIMBE, CEA, CNRS, Université Paris-Saclay, 91191 Gif-sur-Yvette (France); Desquines, Jean; Duriez, Christian [Institut de Radioprotection et de Sûreté Nucléaire, SEREX/LE2M, Bâtiment 327, BP3, 13115 Saint Paul lez Durance (France)

    2016-02-15

    Despite the influence of hydrogen on the behavior of zirconium fuel cladding in many nuclear safety issues, the pseudo-binary Zircaloy-4 – oxygen phase diagram still lacks of data, especially above 1000 °C. The aim of this study was to provide experimental data to better assess the influence of hydrogen on the oxygen solubility in Zircaloy-4. Homogenized two-phase Zircaloy-4 samples were elaborated from 300 to 1000 wppm pre-hydrided samples. Local distributions were characterized thoroughly using Electron Probe Micro-Analysis (EPMA) for oxygen and Elastic Recoil Detection Analysis (ERDA) for hydrogen. The data obtained in this work were included in the pseudo-binary Zircaloy-4 – oxygen phase diagram and have shown that hydrogen has limited influence on the α + β → β transus. Regarding the α → α + β transus, no influence of hydrogen concentration in the α phase below 400 wppm was evidenced.

  18. Adsorption and diffusion of hydrogen in Zircaloy-4

    International Nuclear Information System (INIS)

    Torres, E.; Desquines, J.; Baietto, M.C.; Coret, M.; Wehling, F.; Blat-Yrieix, M.; Ambard, A.

    2015-01-01

    Hydrogen in zirconium alloys is considered in many nuclear safety issues. Below 500 Celsius degrees, rather limited knowledge is available on the combined hydrogen adsorption at the sample surface and diffusion in the metal. A modeling of hydrogen gaseous charging has been established starting with a set of relevant laws and parameters derived from open literature. Simulating the hydrogen charging process requires simultaneous analysis of gaseous surface adsorption, hydrogen solid-solution diffusion and precipitation, when exceeding the material solubility limit. The modeling has been extended to reproduce the solid-gas exchange. Gaseous charging experiments have been performed at 420 C. degrees on Stress Relieved Annealed (SRA) Zircaloy-4 cladding samples to validate the model. The sample hydrogen content has been systematically measured after charging and compared to the calculated value thus providing a validation of the adsorption modeling. Complementary tests have been carried out on Recrystallized Annealed (RXA) Zircaloy-4 rods to characterize the combined diffusion and adsorption process. The hydrogen concentration distribution has been characterized using an inverse technique based on destructive analyses of the samples. This additional set of data was relevant for the validation of the hydrogen combined adsorption/diffusion modeling up to 420 C. degrees. (authors)

  19. Photometric determination of zirconium in phosphorites by reaction with arsenazo III

    Energy Technology Data Exchange (ETDEWEB)

    Nikol' skaya, I V; Maksimov, A V

    1976-05-01

    The reaction between zirconium and arsenazo III has been studied over a wide range of hydrochloric acid concentration and under different conditions. 6 and 9 M HCl solutions are optimal for determining zirconium; the least effect of phosphate ions and color stability in time are observed in this case. The determination of zirconium should be carried out using 10-fold reagent excess and in 15-20 min after adding the reagent. The interference of phosphate ions has been estimated. A procedure has been developed for photometric determination of zirconium in phosphorites with prior acid separation of soluble impurities.

  20. Selective liquid phase hydrogenation of furfural to furfuryl alcohol by Ru/Zr-MOFs

    NARCIS (Netherlands)

    Yuan, Q.; Zhang, D.; Haandel, van L.; Ye, F.; Xue, T.; Hensen, E.J.M.; Guan, Y.

    2015-01-01

    Selective hydrogenation of furfural to furfuryl alcohol under mild conditions was evaluated over Ru nanoparticles supported on a series of zirconium based metal organic frameworks (UiO-66, UiO-67, Zr6-NDC, MIL-140A, MIL-140B, and MIL-140C). The particle size and oxidation state of Ru in the

  1. Research and development of zirconium industry in China

    International Nuclear Information System (INIS)

    Liu Jianzhang; Tian Zhenye

    2001-01-01

    The development of uranium material for nuclear power and silicon material for information industry represents two revolutionary changes in the material field in 20-th century. The development of these kinds of materials not only brings about great revolution of technology in the material field, but also promotes the great advancement of the world economy. Zirconium or its alloy, as one of the most important material in atomic age, just as the same as foreign countries has been developed under promotion of nuclear submarine project in China, and building of civil nuclear power reactor then has been laid a solid foundation for zirconium industry and provide a broad market for zirconium material

  2. Zirconium distribution in the system HNO3-H2O-TBP-diluent

    International Nuclear Information System (INIS)

    Shu, J.; Araujo, B.F. de.

    1984-01-01

    The extraction behaviour of zirconium in TBP/diluent-HNO 3 -H 2 O systems is studied in order to increase the uranium decontamination factor by adjusting the extraction conditions so that zirconium extraction is kept at a minimum. Equilibrium diagram, TBP concentration, aqueous: organic phases ratio, salting-out effects and uranium loading in the organic phase were the main factors studied. All the experiments have been carried out with zirconium in the 10 -2 - 10 -3 M concentration range. The extractant degradation products influence upon zirconium behaviour was also verified. With the data obtained it was possible to introduce some modifications in the standard Purex flowsheet with the increase of the decontamination of uranium product from zirconium. (Author) [pt

  3. Manufacturing process to reduce large grain growth in zirconium alloys

    International Nuclear Information System (INIS)

    Rosecrans, P.M.

    1987-01-01

    A method is described of treating cold worked zirconium alloys to reduce large grain growth during thermal treatment above its recrystallization temperature. The method comprises heating the zirconium alloy at a temperature of about 1300 0 F. to 1350 0 F. for about 1 to 3 hours subsequent to cold working the zirconium alloy and prior to the thermal treatment at a temperature of between 1450 0 -1550 0 F., the thermal treatment temperature being above the recrystallization temperature

  4. Simulation of hydrogen migration and blisters formation in zirconium alloys

    International Nuclear Information System (INIS)

    Saliba, R.O.

    1991-06-01

    The phenomenon of hydrogen migration and hydride blister growth after pressure tube/calandria tube contact in CANDU reactors is addressed. This phenomenon is by now regarded as an important factor limiting reactors lifetime, since it originated Pickering incident in 1983. Numerical results of thermally-assisted diffusion in excellent agreement with quasi-analytical solutions of the mathematical model were obtained. A sensitivity analysis was performed to assess the accuracy of these results. Some two-dimensional calculations are also included to demonstrate the capabilities of the numerical methods. The main outcomes of the work are the following: a through understanding of the mathematics and physics involved in hydrogen migration under thermal gradients. The validation of a numerical procedure based on a regularization of the constitutive equations. Blister growth rates in slab geometries for initial concentrations that span the full range of technological interest. Some preliminary two-dimensional results allow the design of future developments. (Author) [es

  5. Process principles for minimisation of hydrogen sulphate concentration in digester gas by means of iron salts. Verfahrensgrundsaetze zur Minimierung der Schwefelwasserstoffkonzentration im Faulgas mit Eisensalzen

    Energy Technology Data Exchange (ETDEWEB)

    Stachowske, M.

    1991-01-01

    The paper presents the results of studies in which different iron salts were employed for the specific purpose of minimising hydrogen sulphide as a component of digester gas. The studies on H[sub 2]S minimisation in digester gas by means of iron salt were performed on untreated sludge from municipal wastewater purification and on wastewater with a heavy organic load from a slaughterhouse. The results are complemented by fundamental studies for clarifying the formation of the digester gas components CH[sub 4] and H[sub 2]S. (orig./EF)

  6. Method of purifying zirconium tetrachloride and hafnium tetrachloride in a vapor stream

    International Nuclear Information System (INIS)

    Snyder, T.S.; Stolz, R.A.

    1992-01-01

    This patent describes a method of purifying zirconium tetrachloride and hafnium tetrachloride in a vapor stream from a sand chlorinator in which the silicon and metals present in sand fed to the chlorinator are converted to chlorides at temperatures over about 800 degrees C. It comprises cooling a vapor stream from a sand chlorinator, the vapor stream containing principally silicon tetrachloride, zirconium tetrachloride, and hafnium tetrachloride contaminated with ferric chloride, to a temperature of from about 335 degrees C to about 600 degrees C; flowing the vapor stream through a gaseous diffusion separative barrier to produce a silicon tetrachloride-containing vapor stream concentrated in zirconium tetrachloride and hafnium tetrachloride and a silicon tetrachloride-containing vapor stream depleted in zirconium tetrachloride and hafnium tetrachloride; adsorbing the ferric chloride in the separative barrier; and recovering the silicon tetrachloride stream concentrated in zirconium tetrachloride and hafnium tetrachloride separately from the silicon tetrachloride stream depleted in zirconium tetrachloride and hafnium tetrachloride

  7. Stabilization of hydrogen peroxide using tartaric acids in Fenton and fenton-like oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Hyung Suk; Kim, Jeong-Jin; Kim, Young-Hun [Andong National University, Andong (Korea, Republic of)

    2016-03-15

    The stabilization of hydrogen peroxide is a key factor in the efficiency of a Fenton reaction. The stability of hydrogen peroxide was evaluated in a Fenton reaction and Fenton-like reactions in the presence of tartaric acid as a stabilizer. The interactions between ferrous or ferric iron and tartaric acid were observed through spectroscopic monitoring at variable pH around pKa{sub 1} and pKa{sub 2} of the stabilizer. Ferric iron had a strong interaction with the stabilizer, and the strong interaction was dominant above pKa{sub 2}. At a low pH, below pKa{sub 1}, the stabilizing effect was at its maximum and the prolonged life-time of hydrogen peroxide gave a higher efficiency to the oxidative degradation of nitrobenzene. In Fenton-like reactions with hematite, the acidic conditions caused dissolution of iron from an iron oxide, and an increase in iron species was the result. Tartaric acid showed a stabilizing effect on hydrogen peroxide in the Fentonlike system. The stabilization by tartaric acid might be due to an inhibition of catalytic activity of dissolved iron, and the stabilization strongly depends on the ionization state of the stabilizer.

  8. Stabilization of hydrogen peroxide using tartaric acids in Fenton and fenton-like oxidation

    International Nuclear Information System (INIS)

    Oh, Hyung Suk; Kim, Jeong-Jin; Kim, Young-Hun

    2016-01-01

    The stabilization of hydrogen peroxide is a key factor in the efficiency of a Fenton reaction. The stability of hydrogen peroxide was evaluated in a Fenton reaction and Fenton-like reactions in the presence of tartaric acid as a stabilizer. The interactions between ferrous or ferric iron and tartaric acid were observed through spectroscopic monitoring at variable pH around pKa 1 and pKa 2 of the stabilizer. Ferric iron had a strong interaction with the stabilizer, and the strong interaction was dominant above pKa 2 . At a low pH, below pKa 1 , the stabilizing effect was at its maximum and the prolonged life-time of hydrogen peroxide gave a higher efficiency to the oxidative degradation of nitrobenzene. In Fenton-like reactions with hematite, the acidic conditions caused dissolution of iron from an iron oxide, and an increase in iron species was the result. Tartaric acid showed a stabilizing effect on hydrogen peroxide in the Fentonlike system. The stabilization by tartaric acid might be due to an inhibition of catalytic activity of dissolved iron, and the stabilization strongly depends on the ionization state of the stabilizer.

  9. Determination of impurities in zirconium by emission spectrograph method

    International Nuclear Information System (INIS)

    Simbolon, S.; Masduki, B.; Aryadi

    2000-01-01

    Analysis of B, Cd, Si and Cr elements in zirconium oxide was carried out. Zirconium oxide was made by precipitating zirconium solution with oxalic acid and calcination was at temperature 900 oC for four hours. Silver chloride compound as much as 10% was used as a distillation carrier and 7 step filtration was used to reduce the impurities element spectra having high density. It was found that B concentration is between 3.80 and 7.44 ppm, Cd less then 0.5 ppm, Si between 74.38-150.33 ppm and Cr between 19.90-45.76 ppm. (author)

  10. Low stress creep behaviour of zirconium

    International Nuclear Information System (INIS)

    Prasad, N.

    1989-01-01

    Creep behaviour of alpha zirconium of grain size varying between 16 and 55 μm has been investigated in the temperature range 813 to 1003K at stresses upto 5.5 MNm -2 using high sensitive spring specimen geometry. Creep experiments on specimens of 50 μm grain size revealed a transition from lattice diffusion controlled viscous creep at temperatures greater than 940K to grain boundary diffusion controlled viscous creep at lower temperatures. Tests conducted on either side of the transition suggest the dominance of Nabarro-Herring and Coble creep processes respectively. Evidence for power-law creep has been observed in practically all the creep tests. Based on the experimental data obtained in the present study and those recently reported by Novotny et al (1985), Langdon creep mechanism maps have bee n constructed at 873 and 973K. With the help of these maps for zirconium and those published for titanium the low stress creep behaviour of zirconium and titanium are compared. (author). 22 refs., 11 figs., 3 tabs

  11. An internal friction peak caused by hydrogen in maraging steel

    International Nuclear Information System (INIS)

    Usui, Makoto; Asano, Shigeru

    1996-01-01

    Internal friction in hydrogen-charged iron and steel has so far been studied by a large number of investigators. For pure iron, a well-defined peak of internal friction has been observed under the cold-worked and hydrogen-charged conditions. This is called the hydrogen cold-work peak, or the Snoek-Koester relaxation, which originates from the hydrogen-dislocation interaction. In the present study, a high-strength maraging steel (Fe-18Ni-9Co-5Mo) was chosen as another high-alloy steel which is known to be very susceptible to hydrogen embrittlement. The purpose of this paper is to show a new internal friction peak caused by hydrogen in the maraging steel and to compare it with those found in stainless steels which have so far been studied as typical engineering high-alloy materials

  12. In situ iron-57 Moessbauer spectroscopic investigations of the effect of titania surface area on the reducibility of titania-supported iron oxide

    International Nuclear Information System (INIS)

    Berry, F.J.; Du Hongzhang

    1990-01-01

    Iron-57 Moessbauer spectroscopy has been used to monitor the reducibility in hydrogen of iron oxides supported on titania of differing surface areas. The results show that although Fe 3+ in the iron oxide supported on low surface area titania (11 m 2 g -1 ) is not amenable to facile reduction at low temperatures, complete reduction to metallic iron is achieved by treatment at 600deg C. The data also show that the extent of reduction at elevated temperatures exceeds that which is obtained on similar silica- and alumina-supported systems. Fe 3+ in iron oxide supported on higher surface area titania (50 m 2 g -1 and 240 m 2 g -1 ) is partially reduced in hydrogen at 235deg C to Fe 2+ but fails to attain complete reduction to the metallic state following treatment at 600deg C. The results are related to the different dispersions of iron oxide which can be attained on titania of differing surface area and the consequent interactions between the support and the supported phases. (orig.)

  13. Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

    NARCIS (Netherlands)

    Filiz, B.C.; Gnanakumar, E.S.; Martinez-Arias, A.; Gengler, R.; Rudolf, P.; Rothenberg, G.; Shiju, N.R.

    We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrOx(OH)4−2x and ZrO2). Although the final compositions of the catalysts are the

  14. Highly Selective Hydrogenation of Levulinic Acid to gamma-Valerolactone Over Ru/ZrO2 Catalysts

    NARCIS (Netherlands)

    Filiz, Bilge Coskuner; Gnanakumar, Edwin S.; Martinez-Arias, Arturo; Gengler, Regis; Rudolf, Petra; Rothenberg, Gadi; Shiju, N. Raveendran

    We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrOx(OH)(4-2x) and ZrO2). Although the final compositions of the catalysts are the

  15. Thin polycrystalline diamond films protecting zirconium alloys surfaces: From technology to layer analysis and application in nuclear facilities

    Energy Technology Data Exchange (ETDEWEB)

    Ashcheulov, P. [Institute of Physics, Academy of Sciences Czech Republic v.v.i, Na Slovance 2, CZ-182 21, Prague 8 (Czech Republic); Škoda, R.; Škarohlíd, J. [Czech Technical University in Prague, Faculty of Mechanical Engineering, Technická 4, Prague 6, CZ-160 07 (Czech Republic); Taylor, A.; Fekete, L.; Fendrych, F. [Institute of Physics, Academy of Sciences Czech Republic v.v.i, Na Slovance 2, CZ-182 21, Prague 8 (Czech Republic); Vega, R.; Shao, L. [Texas A& M University, Department of Nuclear Engineering TAMU-3133, College Station, TX TX 77843 (United States); Kalvoda, L.; Vratislav, S. [Faculty of Nuclear Science and Physical Engineering, Czech Technical University in Prague, Brehova 7, CZ-115 19, Prague 1 (Czech Republic); Cháb, V.; Horáková, K.; Kůsová, K.; Klimša, L.; Kopeček, J. [Institute of Physics, Academy of Sciences Czech Republic v.v.i, Na Slovance 2, CZ-182 21, Prague 8 (Czech Republic); Sajdl, P.; Macák, J. [University of Chemistry and Technology, Power Engineering Department, Technická 3, Prague 6, CZ-166 28 (Czech Republic); Johnson, S. [Nuclear Fuel Division, Westinghouse Electric Company, 5801 Bluff Road, Hopkins, SC 29209 (United States); Kratochvílová, I., E-mail: krat@fzu.cz [Institute of Physics, Academy of Sciences Czech Republic v.v.i, Na Slovance 2, CZ-182 21, Prague 8 (Czech Republic); Faculty of Nuclear Science and Physical Engineering, Czech Technical University in Prague, Brehova 7, CZ-115 19, Prague 1 (Czech Republic)

    2015-12-30

    Graphical abstract: - Highlights: • In this work we showed that films prepared by MW-LA-PECVD technology can be used as anticorrosion protective layer for Zircaloy2 nuclear fuel claddings at elevated temperatures (950 °C) when α phase of zirconium changes to β phase (more opened for oxygen/hydrogen diffusion). Quality of PCD films was examined by Raman spectroscopy, XPS, SEM, AFM and SIMS analysis. • The polycrystalline diamond films were of high quality - without defects and contaminations. After hot steam oxidation (950 °C) a high level of structural integrity of PCD layer was observed. Both sp{sup 2} and sp{sup 3} C phases were present in the protective PCD layer. Higher resistance and a lower degree of impedance dispersion was found in the hot steam oxidized PCD coated Zircaloy2 samples, which may suggest better protection of the Zircaloy2 surface. The PCD layer blocks the hydrogen diffusion into the Zircaloy2 surface thus protecting the material from degradation. • Hot steam oxidation tests confirmed that PCD coated Zircaloy2 surfaces were effectively protected against corrosion. Presented results demonstrate that the PCD anticorrosion protection can significantly prolong service life of Zircaloy2 nuclear fuel claddings in nuclear reactors even at elevated temperatures. - Abstract: Zirconium alloys can be effectively protected against corrosion by polycrystalline diamond (PCD) layers grown in microwave plasma enhanced linear antenna chemical vapor deposition apparatus. Standard and hot steam oxidized PCD layers grown on Zircaloy2 surfaces were examined and the specific impact of polycrystalline Zr substrate surface on PCD layer properties was investigated. It was found that the presence of the PCD coating blocks hydrogen diffusion into the Zircaloy2 surface and protects Zircaloy2 material from degradation. PCD anticorrosion protection of Zircaloy2 can significantly prolong life of Zircaloy2 material in nuclear reactors even at temperatures above Zr

  16. Spectrofluorimetric determination of hafnium and zirconium with 3,7-dihydroxyflavone

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Takushi; Suzuki, Osamu; Seuzuki, Tetsuo; Murata, Akira

    1986-04-01

    The absorptive and fluorescent characteristics of the hafnium and zirconium complexes of 3-hydroxyflavone and its 12 hydroxy and methoxy derivatives have been studied. The fluorescence of the 1:1 hafnium - 3,7-dihydroxyflavone complex (lambdasub(ex.)397 nm,lambdasub(em.) 465 nm) in 3 M hydrochloric acid has been used to determine 2-40 ng ml/sup -1/ of hafnium. The fluorescence of the 1:1 zirconium - 3,7-dihydroxyflavone complex (lambdasub(ex.) 395 nm, lambda sub(em.) 465 nm) at pH 2.0 in 0.02 M sulphate solution has been used to determine 2-40 ng ml/sup -1/ of zirconium. These methods are very sensitive and can be used for the simultaneous determination of hafnium and zirconium with an error of about 5%.

  17. Geologic structure of Gofitsky deposit of titanium and zirconium and perspectives of the reserve base of titanium and zirconium in Russia

    Science.gov (United States)

    Kukhmazov, Iskander

    2016-04-01

    With the fall of the Soviet Union, all the mining deposits of titanium and zirconium appeared outside of Russian Federation. Therefore the studying of deposits of titanium and zirconium in Russia is very important nowadays. There is a paradoxical situation in the country: in spite of possible existence of national mineral resource base of Ti-Zr material, which can cover needs of the country, Russia is the one of the largest buyers of imported Ti-Zr material in the world. Many deposits are not mined, and those which are in the process of mining have poor reserves. Demand for this raw material is very great not only for Russia, but also for the world in general. Today there is a scarcity of zircon around the world and it will only increase through time. Therefore prices of products of titanium and zirconium also increase. Consequently Russian deposits of titanium and zirconium with higher content than foreign may become competitive. Russia is forced to buy raw materials (zirconium and titanium production) from former Soviet Union countries at prices higher than the world's and thus incur huge losses, including customs charges. Russia should create its own mineral resource base of Ti-Zr. Studied titanium-zirconium deposits of Stavropol region may become the basis for the south part of Russia. At first, Beshpagirsky deposit should be pointed out. It has large reserves of ore sands with high content of Ti-Zr. A combination of favorable geographical position of the area with developed industrial infrastructure makes it very beneficial as an object for high priority development. Gofitsky deposit should be pointed out as well. Its sands have a wide areal distribution and a high content of titanium and zirconium. Chokrak, Karagan-Konksk and Sarmatian sediments of the Miocene of Gofitsky deposit are productive for titanium and zirconium placers within Stavropol region of Russia. Gofitsky deposit was evaluated from financial and economic point of view and the following data

  18. Collaborative study of the colorimetric determination of zirconium in antiperspirant aerosols

    International Nuclear Information System (INIS)

    Beavin, P. Jr.

    1977-01-01

    A previously published method for determining zirconium in antiperspirant aerosols was collaboratively studied by 7 laboratories. The method consists of 2 procedures: a rapid dilution procedure for soluble zirconium compounds or a lengthier fusion procedure for total zirconium followed by colorimetric determination. The collaborators were asked to perform the following: Spiking materials representing 4 levels of soluble zirconium were added to weighed portions of a zirconium-free cream base concentrate and the portions were assayed by the dilution procedure. Spiking materials representing 4 levels of zirconium in either the soluble or the insoluble form (or as a mixture) were also added to portions of the same concentrate and these portions were assayed by the fusion procedure. They were also asked to concentrate and assay, by both procedures, 2 cans each of 2 commercial aerosol antiperspirants containing zirconyl hydroxychloride. The average percent recoveries and standard deviations for spiked samples were 99.8-100.2 and 1.69-2.71, respectively, for soluble compounds determined by the dilution procedure, and 93.8-97.4 and 3.09-4.78, respectively, for soluble and/or insoluble compounds determined by the fusion procedure. The average perent zirconium found by the dilution procedure in the 2 commercial aerosol products was 0.751 and 0.792. Insufficient collaborative results were received for the fusion procedure for statistical evaluation. The dilution procedure has been adopted as official first action

  19. Electron microscopy of nuclear zirconium alloys

    International Nuclear Information System (INIS)

    Versaci, R.A.; Ipohorski, Miguel

    1986-01-01

    Transmission electron microscopy observations of the microstructure of zirconium alloys used in fuel sheaths of nuclear power reactors are reported. Specimens were observed after different thermal and mechanical treatment, similar to those actually used during fabrication of the sheaths. Electron micrographs and electron diffraction patterns of second phase particles present in zircaloy-2 and zircaloy-4 were also obtained, as well as some characteristic parameters. Images of oxides and hydrides most commonly present in zirconium alloys are also shown. Finally, the structure of a Zr-2,5Nb alloy used in CANDU reactors pressure tubes, is observed by electron microscopy. (Author) [es

  20. Texture-geometric deformational effects in some metal-hydrogen systems

    International Nuclear Information System (INIS)

    Spivak, L.V.; Kats, M.Ya.

    1992-01-01

    Possible deformation effects were studied in vanadium, tantalum, niobium, palladium and iron which occurred during electrolytic hydrogenation of specimens preliminarily deformed by torsion and then annealed. Noticeable texture-geometric effects were observed and related to the system tendency to enhance the degree of specimen form symmetry during hydrogenation. The latter was an off-beat realization of Le-Chatelier principle. It was assumed that the nature of deformation effects was connected with one of minimization channels for overall elastic stress fields in metals being hydrogenated. Some distinction was revealed in behaviour of 5a group metal, palladium and iron

  1. Process for hydrogenating coal and coal solvents

    Science.gov (United States)

    Tarrer, Arthur R.; Shridharani, Ketan G.

    1983-01-01

    A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260.degree. C. to 315.degree. C. in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275.degree. C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350.degree. C.

  2. A review of the inorganic and organometallic chemistry of zirconium

    International Nuclear Information System (INIS)

    Kalvins, A.K.

    1985-01-01

    The results of a literature review of the inorganic and organometallic chemistry of zirconium are presented. Compounds with physical and chemical properties compatible with the requirements of an ir laser zirconium isotope separation process have been identified

  3. Evaluation of the intrinsic and extrinsic fracture behavior of iron aluminides

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, B.R.; Kang, B.S. [West Virginia Univ., Morgantown, WV (United States)

    1998-07-27

    Iron aluminides have excellent corrosion resistance in high-temperature oxidizing-sulfidizing environments; however, there are problems at room and medium temperatures with hydrogen embrittlement as related to exposure to moisture. In this research, a coordinated computational modeling/experimental study of mechanisms related to environmental-assisted fracture behavior of selected iron aluminides has been undertaken. The modeling and the experimental work connect at the level of coordinated understanding of the mechanisms for hydrogen penetration and for loss of strength and susceptibility to fracture. The focus of the modeling component has been on the challenging question of accurately predicting the iron vacancy formation energy in Fe{sub 3}Al and the subsequent tendency, if present, for vacancy clustering. The authors have successfully performed, on an ab initio basis, the first calculation of the vacancy formation energy in Fe{sub 3}Al. These calculations include lattice relaxation effects which are quite large for one of the two types of iron sites. This has significant implications for vacancy clustering effects with consequences for hydrogen diffusion. Indeed, the ab-initio-based estimate of the divacancy binding energy indicates a likely tendency toward such clustering for iron vacancies on the sites with large lattice relaxation. The experimental work has focused on the relationship of the choice and concentration of additives to the improvement of resistance to hydrogen embrittlement and hence to the fracture behavior.

  4. Formation of poorly crystalline iron monosulfides: Surface redox reactions on high purity iron, spectroelectrochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Hansson, E.B. [Geological Institute, University of Copenhagen, Oster Voldgade 10, Copenhagen K, DK-1350 (Denmark); Odziemkowski, M.S. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)]. E-mail: marek@sciborg.uwaterloo.ca; Gillham, R.W. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)

    2006-11-15

    In the use of iron for reductive dehalogenation of chlorinated solvents in ground water, due to presence of sulfate-reducing bacteria the formation of hydrogen sulfide is expected. To simulate those processes the interface between 99.99% pure iron and 0.1 M NaHCO{sub 3} deoxygenated solution with 3.1 x 10{sup -5}-7.8 x 10{sup -3} M Na{sub 2}S . 9H{sub 2}O added was studied. The surface processes were characterised by the in situ normal Raman spectroscopy (NRS) and ex situ techniques; X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX). The open circuit potential (OCP) was monitored during in situ NRS measurements, and potentiodynamic anodic polarization measurements were carried out to reveal electrochemical behaviour of iron electrode. Open circuit potential-time transients indicated that the native oxide is unstable in deaerated bicarbonate solution and undergoes reductive dissolution (i.e. autoreduction) leaving the metallic Fe covered by Fe(OH){sub 2}, adsorbed OH{sup -}, and patches of 'magnetite-like' oxide. Immediately upon injection of the Na{sub 2}S-solution the iron interface undergoes complex redox surface processes and a poorly crystalline FeS film forms. Potentiodynamic anodic polarization measurements indicated a mechanical breakdown of the FeS film. The origin and initiation of this breakdown process is not clear but is probably a result of internal stress developed during film growth. Based on surface studies supported by electrochemical measurements, a conceptual model for the complex redox processes occurring at the iron interface is proposed. This model describes the structural development of a poorly crystalline FeS, which breaks down, allowing further dissolution of the Fe and formation of FeOOH at the interface. Simultaneously and despite the existence of thick layer of FeS the entrance of hydrogen was evident as the typical hydrogen cracks in bulk of the

  5. Mechanical resistance of zirconium implant abutments: A review of the literature

    Science.gov (United States)

    Vaquero-Aguilar, Cristina; Torres-Lagares, Daniel; Jiménez-Melendo, Manuel; Gutiérrez-Pérez, José L.

    2012-01-01

    The increase of aesthetic demands, together with the successful outcome of current implants, has renewed interest in the search for new materials with enough mechanical properties and better aesthetic qualities than the materials customarily used in implanto-prosthetic rehabilitation. Among these materials, zirconium has been used in different types of implants, including prosthetic abutments. The aim of the present review is to analyse current scientific evidence supporting the use of this material for the above mentioned purposes. We carried out the review of the literature published in the last ten years (2000 through 2010) of in vitro trials of dynamic and static loading of zirconium abutments found in the databases of Medline and Cochrane using the key words zirconium abutment, fracture resistance, fracture strength, cyclic loading. Although we have found a wide variability of values among the different studies, abutments show favourable clinical behaviour for the rehabilitation of single implants in the anterior area. Such variability may be explained by the difficulty to simulate daily mastication under in vitro conditions. The clinical evidence, as found in our study, does not recommend the use of implanto-prosthetic zirconium abutments in the molar area. Key words: Zirconium abutment, zirconium implant abutment, zirconia abutment, fracture resistance, fracture strength, cyclic loading. PMID:22143702

  6. Synthesis, Characterization and Antimicrobial Activity of Zirconium (IV) Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Shobhana; Jain, Asha; Saxena, Sanjiv [Univ. of Rajasthan, Jaipur (India)

    2012-08-15

    Heteroleptic complexes of zirconium (IV) derived from bulky Schiff base ligands containing a sulphur atom and oximes of heterocyclic β-diketones of the general formula ZrLL' (where L'H{sub 2}=RCNH(C{sub 6}H{sub 4})SC : C(OH)N(C{sub 6}H{sub 5})N : CCH{sub 3}, R=-C{sub 6}H{sub 5}, -C{sub 6}H{sub 4}Cl(p) and L'H{sub 2}=R'C : (NOH)C : C(OH)N(C{sub 6}H{sub 5})N : CCH{sub 3}, R' = -CH{sub 2}CH{sub 3}, -C{sub 6}H{sub 5}, -C{sub 6}H{sub 4}Cl (p) were prepared by the reactions of zirconium tetrachloride with disodium salts of Schiff bases (L Na{sub 2}) and oximes of heterocyclic β-diketones (L' Na{sub 2}) in 1:1:1 molar ratio in dry refluxing THF. The structures of these monomeric zirconium (IV) complexes were elucidated with the help of elemental analysis, molecular weight measurements, spectroscopic (IR, NMR and mass) studies. A distorted trigonal bipyramidal geometry may be suggested for these heteroleptic zirconium (IV) complexes. The ligands (bulky Schiff base ligands containing a sulphur atom and oximes of heterocyclic β-diketones) and their heteroleptic complexes of zirconium (IV) were screened against A. flavus, P. aeruginesa and E. coli.

  7. Lunar-derived titanium alloys for hydrogen storage

    Science.gov (United States)

    Love, S.; Hertzberg, A.; Woodcock, G.

    1992-01-01

    Hydrogen gas, which plays an important role in many projected lunar power systems and industrial processes, can be stored in metallic titanium and in certain titanium alloys as an interstitial hydride compound. Storing and retrieving hydrogen with titanium-iron alloy requires substantially less energy investment than storage by liquefaction. Metal hydride storage systems can be designed to operate at a wide range of temperatures and pressures. A few such systems have been developed for terrestrial applications. A drawback of metal hydride storage for lunar applications is the system's large mass per mole of hydrogen stored, which rules out transporting it from earth. The transportation problem can be solved by using native lunar materials, which are rich in titanium and iron.

  8. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Science.gov (United States)

    2010-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges resulting...

  9. Hydrogen peroxide stabilization in one-dimensional flow columns

    Science.gov (United States)

    Schmidt, Jeremy T.; Ahmad, Mushtaque; Teel, Amy L.; Watts, Richard J.

    2011-09-01

    Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H 2O 2 propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO.

  10. Internal friction and Young's modulus measurements in Zr-2.5Nb alloy doped with hydrogen

    International Nuclear Information System (INIS)

    Ritchie, I.G.; Pan, Z.-L.

    1992-01-01

    The presence of hydrides is an important factor in assessing the potential for delayed hydride cracking in Zr-2.5Nb alloys, and consequently, the terminal solid solubility (TSS) of hydrogen in the material is an important parameter. In pure zirconium doped with hydrogen, the TSS is marked by a dissolution peak of internal friction on heating and a truncated precipitation peak associated with hydride nucleation on cooling. These phenomena occur only at low frequencies and are accompanied in torsion pendulum studies by autotwisting of the sample (or zero-point drift) that stops abruptly at the TSS. Neither the dissolution/precipitation peaks nor the autotwisting phenomena are observed in Zr-2.5Nb. However, the TSS is also marked by an abrupt change in the slope of Young's modulus as a function of temperature. This phenomenon is observed regardless of the frequency (in the range 1 Hz to 120 kHz) and in both pure zirconium and Zr-2.5Nb alloys. The reasons for the absence of the dissolution/precipitation peak in Zr-2.5Nb alloys are discussed and the use of Young's modulus changes to investigate the TSS of hydrogen and the hysteresis between heat-up and cool-down TSS curves is demonstrated. (author)

  11. Laves intermetallics in stainless steel-zirconium alloys

    International Nuclear Information System (INIS)

    Abraham, D.P.; McDeavitt, S.M.; Richardson, J.W. Jr.

    1997-01-01

    Laves intermetallics have a significant effect on properties of metal waste forms being developed at Argonne National Laboratory. These waste forms are stainless steel-zirconium alloys that will contain radioactive metal isotopes isolated from spent nuclear fuel by electrometallurgical treatment. The baseline waste form composition for stainless steel-clad fuels is stainless steel-15 wt.% zirconium (SS-15Zr). This article presents results of neutron diffraction measurements, heat-treatment studies and mechanical testing on SS-15Zr alloys. The Laves intermetallics in these alloys, labeled Zr(Fe,Cr,Ni) 2+x , have both C36 and C15 crystal structures. A fraction of these intermetallics transform into (Fe,Cr,Ni) 23 Zr 6 during high-temperature annealing; the authors have proposed a mechanism for this transformation. The SS-15Zr alloys show virtually no elongation in uniaxial tension, but exhibit good strength and ductility in compression tests. This article also presents neutron diffraction and microstructural data for a stainless steel-42 wt.% zirconium (SS-42Zr) alloy

  12. Transfer Hydrogenation: Employing a Simple, In Situ Prepared Catalytic System

    KAUST Repository

    Ang, Eleanor Pei Ling

    2017-04-01

    Transfer hydrogenation has been recognized to be an important synthetic method in both academic and industrial research to obtain valuable products including alcohols. Transition metal catalysts based on precious metals, such as Ru, Rh and Ir, are typically employed for this process. In recent years, iron-based catalysts have attracted considerable attention as a greener and more sustainable alternative since iron is earth abundant, inexpensive and non-toxic. In this work, a combination of iron disulfide with chelating bipyridine ligand was found to be effective for the transfer hydrogenation of a variety of ketones to the corresponding alcohols in the presence of a simple base. It provided a convenient and economical way to conduct transfer hydrogenation. A plausible role of sulfide next to the metal center in facilitating the catalytic reaction is demonstrated.

  13. Evaluation of Conditions for Hydrogen Induced Degradation of Zirconium Alloys during Fuel Operation and Storage. Final Report of a Coordinated Research Project 2011-2015

    International Nuclear Information System (INIS)

    2015-12-01

    This publication reports on the work carried out in 2011–2015 in the coordinated research project (CRP) on the evaluation of conditions for hydrogen induced degradation of zirconium alloys during fuel operation and storage. The CRP was carried out to evaluate the threshold condition for delayed hydride cracking (KIH) in pressurized water reactors and zircaloy-4 and E635M fuel claddings, with application to in-pile operation and spent fuel storage. The project consisted of adding hydrogen to samples of cladding and measuring K IH by one of four methods. The CRP was the third in the series, of which the results of the first two were published in IAEA-TECDOC-1410 and IAEA-TECDOC-1649, in 2004 and 2010, respectively. This publication includes all of the research work performed in the framework of the CRP, including details of the experimental procedures that led to a set of data for tested materials. The research was conducted by representatives from 13 laboratories from all over the world. In addition to the basic goal to transfer the technology of the testing techniques from experienced laboratories to those unfamiliar with the methods, the CRP was set up to develop experimental procedures to produce consistent sets of data, both within a single laboratory and among different laboratories. The material condition and temperature history were prescribed, and laboratories chose one or two of four methods of loading that were recommended in an attempt to develop standard sets of experimental protocols so that consistent results could be obtained. Experimental discrepancies were minimized through careful attention to details of microstructure, temperature history and stress state in the samples, with the main variation being the mode of loading

  14. Methods for the preparation of ultra-pure anhydrous zirconium tetrafluoride from zirconium tetraborohydride, researches in connection with halide glasses

    International Nuclear Information System (INIS)

    Tortevois, R.

    1990-01-01

    The synthesis of ultrapure zirconium tetrafluoride, the main component of fluorozirconate based optical fibers, was successfully attempted from zirconium tetraborohydride. Of the fluorinating agents used, nitrogen trifluoride doesn't react with zirconium tetraborohydride while xenon difluoride reacts too violently and leads to phases which contain boron. The fluorination in a compatible solvent enabled us to minimize the degradation. The best results were obtained with the fluorination of Zr(BH 4 ) 4 dissolved in CFCl 3 at -40 deg C by anhydrous HF. Using several analytical methods such as graphite furnace atomic absorption and proton activation, we analyzed the purity. The degree of transition element impurities is less than the ppm level for ZrF 4 . The dehydration of ZrF 4 ,H 2 O and ZrF 4 ,3H 2 O at room temperature by CIF 3 in gaseous and liquid state was also investigated. At exceptionally low temperature, this process allows oxide and oxyfluoride components to be reduced

  15. Identification and characterization of a new Zirconium hydride

    International Nuclear Information System (INIS)

    Zhao, Z.

    2007-01-01

    In order to control the integrity of the fuel clad, alloy of zirconium, it is necessary to predict the behavior of zirconium hydrides in the environment (temperature, stress...), at a microscopic scale. A characterization study by TEM of hydrides has been realized. It shows little hydrides about 500 nm, in hydride Zircaloy 4. Then a more detailed study identified a new hydride phase presented in this paper. (A.L.B.)

  16. Sorption of cesium on titanium and zirconium phosphates

    International Nuclear Information System (INIS)

    Lebedev, V.N.; Mel'nik, N.A.; Rudenko, A.V.

    2003-01-01

    Titanium and zirconium phosphates were prepared from mineral raw materials of the Kola Peninsula. Their capability to recover cesium cations from the model solutions and liquid radioactive waste (LRW) was studied. Titanium phosphate prepared from solutions formed by titanite breakdown demonstrates greater distribution coefficients of cesium as compared to zirconium phosphate. Titanium phosphate as a cheaper agent featuring greater sorption capacity was recommended for treatment of LRW to remove cesium [ru

  17. [The clinical application of zirconium-dioxide-ceramics. Case report].

    Science.gov (United States)

    Somfai, Dóra; Zsigmond, Ágnes; Károlyházy, Katalin; Kispély, Barbara; Hermann, Péter

    2015-12-01

    Due to its outstanding physical, mechanical and esthetic properties, zirconium-dioxide is one of the most popular non-metal denture, capable of surpassing PFM in most cases. The recent advances of CAD/CAM technology makes it a good alternitve. Here we show the usefulness of zirconium-dioxide in everyday dental practice through three case reports.

  18. Distribution of zirconium in the nitric acid-water-TPB-diluent system

    International Nuclear Information System (INIS)

    Shu, J.; Floh de Araujo, B.

    1984-10-01

    This paper deals with the extraction behaviour of zirconium in TBP/diluent-HNO 3 -H 2 O systems. The main purpose is to increase the uranium decontamination factor by adjusting the extraction conditions so that zirconium extraction is kept at a mininum. Equilibrium diagram, TBP concentration, aqueous: organic phases ratio, salting-out effects and uranium loading in the organic phase were the main factors studied. All the experiments have been carried out with zirconium in the 10 -2 - 10 -3 M concentration range. The extractant degradation products influence upon ziconium behaviour was also verified. With the data obtained it was possible to introduce some modification in the standard Purex flow-sheet with the increase of the decontamination of uranium from zirconium. 5 refs., 9 figs

  19. Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

    Science.gov (United States)

    Forato, Florian; Liu, Hao; Benoit, Roland; Fayon, Franck; Charlier, Cathy; Fateh, Amina; Defontaine, Alain; Tellier, Charles; Talham, Daniel R; Queffélec, Clémence; Bujoli, Bruno

    2016-06-07

    Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.

  20. Separation process of zirconium and hafnium

    International Nuclear Information System (INIS)

    Hure, J.; Saint-James, R.

    1955-01-01

    About the separation different processes of zirconium-hafnium, the extraction by solvent in cross-current is the most easily the process usable on an industrial scale. It uses tributyl phosphate as solvent, diluted with white spirit to facilitate the decanting. Some exploratory tests showed that nitric environment seemed the most favorable for extraction; but a lot of other factors intervene in the separation process. We studied the influence of the acidity successively, the NO 3 - ions concentration, the role of the cation coming with NO 3 - , as well as the influence of the concentration of zirconium in the solution on the separation coefficient β = α Zr / α Hf . (M.B.) [fr

  1. Zirconium diselenite microstructures, formation and mechanism

    Science.gov (United States)

    Naik, Chandan C.; Salker, A. V.

    2018-04-01

    In this work, a series of microstructures of zirconium diselenite (Zr(SeO3)2) has been prepared via a simple precipitation method at room temperature without adding any organic surfactants. Phase purity of the sample has been checked by X-ray Diffraction. From the SEM, FESEM, and TEM images spheroid nanoparticles to the starfish-like structure of zirconium diselenite are detected. The morphological evolution processes were investigated carefully following time-dependent experiments and a growth mechanism has been proposed. Two different crystal growth processes, the oriented attachment process accompanying the Ostwald ripening process were held responsible for the formation of a structure resembling starfish having four arms.

  2. Process for hydrogenating coal and coal solvents

    Energy Technology Data Exchange (ETDEWEB)

    Shridharani, K.G.; Tarrer, A.R.

    1983-02-15

    A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260/sup 0/ C to 315/sup 0/ C in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275/sup 0/ C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350/sup 0/ C.

  3. Zirconium-made equipment for the new La Hague reprocessing plants

    International Nuclear Information System (INIS)

    Decours, J.; Demay, R.; Bernard, C.; Mouroux, J.P.; Simonnet, J.

    1991-01-01

    The use of zirconium was developed to solve some problems of severe corrosion in boiling nitric medium, and to guarantee the service life of the equipment concerned. The paper presents the experience gained since the early 1970s, when the first units made of zirconium were used in French reprocessing plants. For the new La Hague UP3 and UP2 800 plants, it was decided to extend the use of zirconium to make large-scale equipment and, to do so, a major R and D program was implemented, of which the main results are presented

  4. In-situ stabilization of radioactive zirconium swarf

    Science.gov (United States)

    Hess, Clay C.

    1999-01-01

    The method for treating ignitable cutting swarf in accordance with the present invention involves collecting cutting swarf in a casting mold underwater and injecting a binder mixture comprising vinyl ester styrene into the vessel to fill void volume; and form a mixture comprising swarf and vinyl ester styrene; and curing the mixture. The method is especially useful for stabilizing the ignitable characteristics of radioactive zirconium cutting swarf, and can be used to solidify zirconium swarf, or other ignitable finely divided material, underwater. The process could also be performed out of water with other particulate wastes.

  5. Preparation of high-purity zirconium dioxide from baddeleyite

    International Nuclear Information System (INIS)

    Voskobojnikov, N.B.; Skiba, G.S.

    1996-01-01

    Interaction of baddeleyite concentrate with calcium oxide and calcium chloride in the process of caking is studied. The influence of grain size on calcium zirconate formation is tested. Conditions for cake leaching by hydrochloric acid and zirconium(4) oxychloride purification from calcium and silicon compounds by recrystallization are reported. Zirconium dioxide corresponding to specifications (6-2 special purity) is obtained with a high (more than 90%) chemical yield. 9 refs., 1 tab

  6. Study of some properties of zirconium phosphate; Etude de quelques proprietes du phosphate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Prospert, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-05-01

    Zirconium phosphate has been studied with a view to using it as an ion exchanger: the first objective was to develop a method of preparation easy to apply and also reproducible. To this end, several tests were carried out varying the molar ratios of phosphorus and of zirconium. Some physical properties such as the diffraction of X-rays were examined. The work then involved certain chemical properties, particularly the percentages of free water and structural water given by the loss on calcination, the Karl-Fisher method and the weight losses by thermogravimetry. Finally an attempts was made to apply the exchanger to the separation of alkaline ions. The static tests showed that the order of fixation of these ions was Cs{sup +} > Rb{sup +} >> K{sup +} > Na{sup +}. Tests with columns showed that Na{sup +} and K{sup +} were easily separable, as was the Rb{sup +}-Cs{sup +} mixture, this last pair being fairly difficult to dissociate. (author) [French] Le phosphate de zirconium a ete etudie en vue de son utilisation comme echangeur d'ions: le premier but a atteindre a ete de mettre au point une preparation pouvant se reveler facilement utilisable ainsi qu'aisement reproductible. A cet effet, plusieurs essais ont ete effectues en faisant varier les rapports molaires du phosphore et du zirconium. Quelques proprietes physiques, telle la diffraction des rayons X, ont ete abordees. Ensuite, l'etude a porte sur certaines proprietes chimiques, particulierement les pourcentages d'eau libre et d'eau de structure par des pertes au feu, utilisation de la methode de Karl-Fisher, ainsi que des pertes de poids a la thenmobalance. Enfin, on a tente d'utiliser l'echangeur a la separation des ions alcalins. Les etudes statiques ont permis de constater que l'ordre de fixation de ces ions etait Cs{sup +} > Rb{sup +} >> K{sup +} > Na{sup +}. Les essais effectues en colonne ont montre que Na{sup +} et K{sup +} etaient aisement separables entre eux, ainsi que du couple Rb{sup +}-Cs{sup +}, ce

  7. Downhole Upgrading of Orinoco Basin Extra-Heavy Crude Oil Using Hydrogen Donors under Steam Injection Conditions. Effect of the Presence of Iron Nanocatalysts

    Directory of Open Access Journals (Sweden)

    Cesar Ovalles

    2015-03-01

    Full Text Available An extra-heavy crude oil underground upgrading concept and laboratory experiments are presented which involve the addition of a hydrogen donor (tetralin to an Orinoco Basin extra-heavy crude oil under steam injection conditions (280–315 °C and residence times of at least 24-h. Three iron-containing nanocatalysts (20 nm, 60 nm and 90 nm were used and the results showed increases of up to 8° in API gravity, 26% desulfurization and 27% reduction in the asphaltene content of the upgraded product in comparison to the control reaction using inert sand. The iron nanocatalysts were characterized by SEM, XPS, EDAX, and Mössbauer spectroscopy before and after the upgrading reactions. The results indicated the presence of hematite (Fe2O3 as the predominant iron phase. The data showed that the catalysts were deactivating by particle sintering (~20% increase in particle size and also by carbon deposition. Probable mechanisms of reactions are proposed.

  8. Concept Feasibility Report for Electroplating Zirconium onto Uranium Foil - Year 2

    Energy Technology Data Exchange (ETDEWEB)

    Coffey, Greg W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meinhardt, Kerry D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Joshi, Vineet V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pederson, Larry R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lavender, Curt A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Burkes, Douglas [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-03-01

    The Fuel Fabrication Capability within the U.S. High Performance Research Reactor Conversion Program is funded through the National Nuclear Security Administration (NNSA) NA-26 (Office of Material Management and Minimization). An investigation was commissioned to determine the feasibility of using electroplating techniques to apply a coating of zirconium onto depleted uranium/molybdenum alloy (U-10Mo). Electroplating would provide an alternative method to the existing process of hot roll-bonding zirconium foil onto the U-10Mo fuel foil during the fabrication of fuel elements for high-performance research reactors. The objective of this research was to develop a reproducible and scalable plating process that will produce a uniform, 25 μm thick zirconium metal coating on U-10Mo foil. In previous work, Pacific Northwest National Laboratory (PNNL) established a molten salt electroplating apparatus and protocol to plate zirconium metal onto molybdenum foil (Coffey 2015). During this second year of the research, PNNL furthered this work by moving to the U-10Mo alloy system (90 percent uranium:10 percent molybdenum). The original plating apparatus was disassembled and re-assembled in a laboratory capable of handling low-level radioactive materials. Initially, the work followed the previous year’s approach, and the salt bath composition was targeted at the eutectic composition (LiF:NaF:ZrF4 = 26:37:37 mol%). Early results indicated that the formation of uranium fluoride compounds would be problematic. Other salt bath compositions were investigated in order to eliminate the uranium fluoride production (LiF:NaF = 61:39 mol% and LiF:NaF:KF = 46.5:11.5:42 mol% ). Zirconium metal was used as the crucible for the molten salt. Three plating methods were used—isopotential, galvano static, and pulsed plating. The molten salt method for zirconium metal application provided high-quality plating on molybdenum in PNNL’s previous work. A key advantage of this approach is that

  9. Zirconium elasticity modules

    International Nuclear Information System (INIS)

    Vavra, G.

    1978-01-01

    Considered are the limit and the intermediate values of the Young modulus E, modulus of shear G and of linear modulus of compression K obtainable at various temperatures (4.2 to 1133 K) for single crystals of α-zirconium. Determined and presented are the corrected isotropic elasticity characteristics of E, G, K over the above range of temperatures of textured and non-textured α-Zr

  10. Method of fabricating zirconium metal for use in composite type fuel cans

    International Nuclear Information System (INIS)

    Imahashi, Hiromichi; Inagaki, Masatoshi; Akabori, Kimihiko; Tada, Naofumi; Yasuda, Tetsuro.

    1985-01-01

    Purpose: To mass produce zirconium metal for fuel cans with less radiation hardening. Method: Zirconium sponges as raw material are inserted in a hearth mold and a procedure of melting the zirconium sponges portionwise by using a melting furnace having electron beams as a heat source while moving the hearth is repeated at least for once. Then, the rod-like ingot after melting is melted again in a vacuum or inert gas atmosphere into an ingot of a low oxygen density capable of fabrication. A composite fuel can billet is formed by using the thus obtained zirconium ingot and a zircalloy, and a predetermined composite type fuel can is manufactured by way of hot extrusion and pipe drawing fabrication. The raw material usable herein is zirconium sponge with an oxygen density of 400 ppm or higher and the content of impurity other than oxygen is between 1000 - 5000 ppm in total, or the molten material thereof. (Kamimura, M.)

  11. History of the development of zirconium alloys for use in nuclear reactors

    International Nuclear Information System (INIS)

    Rickover, H.G.; Geiger, L.D.; Lustman, B.

    1975-01-01

    The technical problems and the major decisions made during the early development of zirconium alloys for use in naval reactors are outlined. A summary is given of the development of commercial sources of supply for zirconium and hafnium metal over the period 1950 to 1965, and the problems encountered in obtaining zirconium needed for early naval prototype and shipboard reactors are identified. Steps taken in the Government procurement process are described and statistics on production amounts, prices, and inventory are included. Also included are the technical aspects associated with the development of zirconium for water-cooled nuclear reactors, beginning in early 1949 when the Bettis Atomic Power Laboratory was established as a part of the Naval Reactors Program. While in the course of the next 25 years, small-scale investigations were performed on other potential core structural materials such as stainless steel, niobium, aluminum, and beryllium, the pressure for continual development, improvement, and application of zirconium was predominant and unrelenting. (U.S.)

  12. Study of the production of zirconium tetrachloride by chlorination of its oxide

    International Nuclear Information System (INIS)

    Seo, E.S.M.

    1983-01-01

    The studies carried out on the production of zirconium tetrachloride by chlorination of pure zirconium oxide with carbon tetrachloride and chlorine in the presence of carbon. In the process of chlorination with carbon tetrachloride, the chlorination efficiency increases with the rise in temperature at intervals between 450 and 750 0 C. The flow of the carbon tetrachloride vapour was 1.50l/min. Higher temperatures of 700 to 850 0 C were used for the zirconium oxide chlorination in the presence of carbon, and the flowrate of the chlorine gas used in the process was 0.50 l/min. Pure zirconium oxide chlorination as well as zirconium oxide - carbon misture chlorination have been studied in connection with the time of reaction at different temperatures and the apparent rate constant, the activation energies, the order of reaction in relation to the concentration of the gases (CCl 4 and Cl 2 ) and the content of carbon in the pellet have all been determined. (Author) [pt

  13. Hydrogen-induced delayed cracking: 1. Strain energy effects on hydrogen solubility

    International Nuclear Information System (INIS)

    Puls, M.P.

    1978-08-01

    Based on Li, Oriani and Darken's derivation of the chemical potential of a solute in a stressed solid and Eshelby's method for obtaining the strain energy of solids containing coherent inhomogeneous inclusions, we have carried out a detailed theoretical analysis of the factors governing hydrogen solubility in stressed and unstressed zirconium and its alloys. Specifically, the analysis demonstrates the strong influence hydride self-stresses may have on the terminal solid solubility of hydrogen in zirconium. The self-energy arises due to the misfit strains between matrix and precipitate. We have calculated the total molal self-strain energy of some commonly observed δ and γ-hydride shapes and orientations. The magnitude of this energy is substantial. Thus for γ-hydride plates lying on basal planes, it is 4912 J/mol, while for γ-hydride needles with the needle axis parallel to the directions of the α-zirconium matrix, it is 2662 J/mol. This self-strain energy causes a shift in the terminal solid solubility. For example, at 77 o C, assuming fully constrained basal plane δ-hydride plates, the terminal solid solubility is increased 5.4 times over the stress-free case. We have also calculated the effect of external stress on the terminal solid solubility. This is governed by the interaction energy arising from the interaction of the applied stresses with the precipitate's misfit strain components. The interaction energy has been calculated for δ and γ-hydride plates and needles, taking full account of the anisotropy of the misfit. The interaction energy is negative for tensile applied stresses and, as a result of the anisotropic misfit, is texture-dependent. Its magnitude is small for most applied stresses but can achieve values of the order of the self-strain energy in the plastic zone of a plane-strain crack. We have also carried out a careful analysis of the solubility data of Kearns and Erickson and Hardie. This analysis is based partly on the theoretical

  14. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Burtron H. Davis

    1999-01-01

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe(sub 3)O(sub 4). Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to(epsilon)(prime)-Fe(sub 2.2)C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to(chi)-Fe(sub 5)C(sub 2) and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe(sub 3)O(sub 4); however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94%(chi)-Fe(sub 5)C(sub 2), deactivated rapidly as the carbide was oxidized to Fe(sub 3)O(sub 4). No difference in activity, stability or deactivation rate was found for(chi)-Fe(sub 5)C(sub 2) and(epsilon)(prime)-Fe(sub 2.2)C

  15. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Burtron H. Davis

    1999-04-30

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe{sub 3}O{sub 4}. Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to {epsilon}{prime}-Fe{sub 2.2}C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to {chi}-Fe{sub 5}C{sub 2} and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe{sub 3}O{sub 4}; however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94% {chi}-Fe{sub 5}C{sub 2}, deactivated rapidly as the carbide was oxidized to Fe{sub 3}O{sub 4}. No difference in activity, stability or deactivation rate was found for {chi}-Fe{sub 5}C{sub 2} and {epsilon}{prime}-Fe{sub 2.2}C.

  16. τ - hydrogen phosphate of zirconia in sodium salt form and some of its properties

    International Nuclear Information System (INIS)

    Fernandez V, S.M.; Ordonez R, E.

    2004-01-01

    It is reported the obtaining and characterization in the sodium salt form of the τ-hydrogen phosphate of zirconium in sodium form, this compound it was synthesized, for a new technique developed in the laboratory of Dept. of Chemistry of the ININ. The characterization was carried out for XRD, IR, Sem and EDS the thermal gravimetric analysis is also reported. (Author)

  17. Bioactivity and biocompatibility of hydroxyapatite-based bioceramic coatings on zirconium by plasma electrolytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Aktuğ, Salim Levent, E-mail: saktug@gtu.edu.tr [The Department of Materials Science and Engineering, Gebze Technical University, Gebze, Kocaeli 41400 (Turkey); Durdu, Salih, E-mail: durdusalih@gmail.com [The Department of Industrial Engineering, Giresun University, Merkez, Giresun 28200 (Turkey); Yalçın, Emine, E-mail: emine.yalcin@giresun.edu.tr [The Department of Biology, Giresun University, Merkez, Giresun 28200 (Turkey); Çavuşoğlu, Kültigin, E-mail: kultigin.cavusoglu@giresun.edu.tr [The Department of Biology, Giresun University, Merkez, Giresun 28200 (Turkey); Usta, Metin, E-mail: ustam@gtu.edu.tr [The Department of Materials Science and Engineering, Gebze Technical University, Gebze, Kocaeli 41400 (Turkey); Materials Institute, Marmara Research Center, TUBITAK, Gebze, Kocaeli 41470 (Turkey)

    2017-02-01

    In the present work, hydroxyapatite (HAP)-based plasma electrolytic oxide (PEO) coatings were produced on zirconium at different current densities in a solution containing calcium acetate and β-calcium glycerophosphate by a single step. The phase structure, surface morphology, functional groups, thickness and roughness of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), eddy current method and surface profilometer, respectively. The phases of cubic-zirconia, calcium zirconate and HAP were detected by XRD. The amount of HAP and calcium zirconate increased with increasing current density. The surface of the coatings was very porous and rough. Moreover, bioactivity and biocompatibility of the coatings were analyzed in vitro immersion simulated body fluid (SBF) and MTT (3-(4,5-dimethyl thiazol-2yl)-2,5-diphenyl tetrazolium bromide) assay, hemolysis assay and bacterial formation. The apatite-forming ability of the coatings was evaluated after immersion in SBF up to 28 days. After immersion, the bioactivity of HAP-based coatings on zirconium was greater than the ones of uncoated zirconium and zirconium oxide-based surface. The bioactivity of PEO surface on zirconium was significantly improved under SBF conditions. The bacterial adhesion of the coatings decreased with increasing current density. The bacterial adhesion of the coating produced at 0.370 A/cm{sup 2} was minimum compared to uncoated zirconium coated at 0.260 and 0.292 A/cm{sup 2}. The hemocompatibility of HAP-based surfaces was improved by PEO. The cell attachment and proliferation of the PEO coatings were better than the one of uncoated zirconium according to MTT assay results. - Highlights: • Hydroxyapatite was formed on zirconium at different current densities by single-step plasma electrolytic oxidation. • The amount of hydroxyapatite and calcium-based phases increased with

  18. French hydrogen markets in 2008-Overview and future prospects

    International Nuclear Information System (INIS)

    Le Duigou, A.; Amalric, Y.; Miguet, M.

    2011-01-01

    This study analyses the current industrial hydrogen markets in France on both a European and international scale, while endeavouring to assess future prospects by 2030. Hydrogen is produced either on purpose or unintentionally as a co-product. Intentional production of hydrogen, generally from natural gas, is classified as captive or merchant hydrogen. France produces about 920,000 metric tons of hydrogen annually. The producer and consumer industries are, in decreasing order of importance are: oil for refinery and petrochemicals, ammonia, iron and steel (co-production), chemicals, and chlorine (co-production). The intentional production of hydrogen from natural gas amounts to less than that co-produced: 40% compared with 60%. The amount of burned hydrogen is about 25% of the total. Production-related carbon dioxide emissions range between 1% and 2% of the total emissions in France. There is an increasing trend in the industrial hydrogen production, essentially due to the oil industry whereas a decline in production is expected in the ammonia industry. The annual production around 2030 should therefore be greater than 1 million metric tons (MMT) per year. If the iron and steel industry were to use hydrogen in every possible situation, it would double the total quantity of hydrogen produced and consumed in France. (authors)

  19. An analysis on local hydrogen concentration in the large dry PWR containment of Ulchin 3,4 in Korea

    International Nuclear Information System (INIS)

    Hong, S.W.; Kim, H.D.; Chung, S.H.

    1994-01-01

    The local hydrogen concentration was analyzed during two different severe accident scenarios (TMLB' and medium size LOCA) using CONTAIN code for the Ulchin 3,4 PWR containment type which is under construction in Korea. Sensitivity studies on the equivalent fraction of zirconium oxidation in the reactor vessel and the flow loss coefficient in the flow path between compartments were also carried out in order to investigate the effect of the these parameters on the local hydrogen concentration. Finally, the effect of temperature and turbulence intensity on the flame velocity was evaluated, and a sample calculation was performed by updating the model of the CONTAIN code. The calculated results show that the maximum local hydrogen concentration appears in the cavity compartment. lie hydrogen burn, however, is not likely to occur in this compartment for both scenarios due to low oxygen concentrations. Hydrogen burns are more likely to occur at the stern generator compartments for TMLB' accident and at the reactor vessel annulus compartment during medium size LOCA When the equivalent fraction of in-vessel zirconium oxidation is assumed to be 75 %, the possibility of detonation is much more increased. The change of flow loss coefficients between flow paths about 2 times affects on the magnitude of the maximum local hydrogen concentration but nearly no influence on the timing and the location of the compartment attaining the maximum local hydrogen concentration. The local hydrogen concentration in the compartments seems to be stratified after vessel failure but to be stabilized afterwards. When temperature and turbulence intensity are considered in the flame velocity model, the flame speed is much greater than the previous results, but the containment load is not increased very much. (author)

  20. Development of zirconium alloy tube manufacturing technology

    International Nuclear Information System (INIS)

    Kim, In Kyu; Park, Chan Hyun; Lee, Seung Hwan; Chung, Sun Kyo

    2009-01-01

    In late 2004, Korea Nuclear Fuel Company (KNF) launched a government funded joint development program with Westinghouse Electric Co. (WEC) to establish zirconium alloy tube manufacturing technology in Korea. Through this program, KNF and WEC have developed a state of the art facility to manufacture high quality nuclear tubes. KNF performed equipment qualification tests for each manufacturing machine with the support of WEC, and independently carried out product qualification tests for each tube product to be commercially produced. Apart from those tests, characterization test program consisting of specification test and characterization test was developed by KNF and WEC to demonstrate to customers of KNF the quality equivalency of products manufactured by KNF and WEC plants respectively. As part of establishment of performance evaluation technology for zirconium alloy tube in Korea, KNF carried out analyses of materials produced for the characterization test program using the most advanced techniques. Thanks to the accomplishment of the development of zirconium alloy tube manufacturing technology, KNF is expected to acquire positive spin off benefits in terms of technology and economy in the near future

  1. Lithium aluminate/zirconium material useful in the production of tritium

    Science.gov (United States)

    Cawley, W.E.; Trapp, T.J.

    A composition is described useful in the production of tritium in a nuclear reactor. Lithium aluminate particles are dispersed in a matrix of zirconium. Tritium produced by the reactor of neutrons with the lithium are absorbed by the zirconium, thereby decreasing gas pressure within capsules carrying the material.

  2. Anticorrosive Behavior and Porosity of Tricationic Phosphate and Zirconium Conversion Coating on Galvanized Steel

    Science.gov (United States)

    Velasquez, Camilo S.; Pimenta, Egnalda P. S.; Lins, Vanessa F. C.

    2018-05-01

    This work evaluates the corrosion resistance of galvanized steel treated with tricationic phosphate and zirconium conversion coating after painting, by using electrochemical techniques, accelerated and field corrosion tests. A non-uniform and heterogeneous distribution of zirconium on the steel surface was observed due to preferential nucleation of the zirconium on the aluminum-rich sites on the surface of galvanized steel. The long-term anti-corrosion performance in a saline solution was better for the phosphate coating up to 120 days. The coating capacitance registered a higher increase for the zirconium coatings than the phosphate coatings up to 120 days of immersion. This result agrees with the higher porosity of zirconium coating in relation to the phosphate coating. After 3840 h of accelerated corrosion test, and after 1 year of accelerated field test, zirconium-treated samples showed an average scribe delamination length higher than the phosphate-treated samples.

  3. Pulse radiolysis studies of iron(I) in aqueous solutions

    International Nuclear Information System (INIS)

    Nenadovic, M.T.; Micic, O.I.; Muk, A.A.

    1980-01-01

    The absorption spectrum and decay kinetics of the products of the reactions of iron(II) ions with hydrated electrons and hydrogen atoms have been studied in aqueous solution using pulse-radiolysis techniques. Iron(I) is formed by reaction with hydrated electrons and its absorption spectrum is reported and discussed. The formation of molecular hydrogen by reaction of Fe + with water is suppressed by other solutes present in the solutions. In acidic solutions containing [SO 4 ] 2- , the intermediates formed in the reaction with H atoms decay by a first-order process and produce molecular hydrogen, but the rate of their decay does not depend only on the oxonium ion concentration but also on intermolecular rearrangement in the [FeSO 4 -H] complex. (author)

  4. Thermodynamic Database for Zirconium Alloys

    International Nuclear Information System (INIS)

    Jerlerud Perez, Rosa

    2003-05-01

    For many decades zirconium alloys have been commonly used in the nuclear power industry as fuel cladding material. Besides their good corrosion resistance and acceptable mechanical properties the main reason of using these alloys is the low neutron absorption. Zirconium alloys are exposed to a very severe environment during the nuclear fission process and there is a demand for better design of this material. To meet this requirement a thermodynamic database is developed to support material designers. In this thesis some aspects about the development of a thermodynamic database for zirconium alloys are presented. A thermodynamic database represents an important facility in applying thermodynamic equilibrium calculations for a given material providing: 1) relevant information about the thermodynamic properties of the alloys e.g. enthalpies, activities, heat capacity, and 2) significant information for the manufacturing process e.g. heat treatment temperature. The basic information in the database is first the unary data, i.e. pure elements; those are taken from the compilation of the Scientific Group Thermodata Europe (SGTE) and then the binary and ternary systems. All phases present in those binary and ternary systems are described by means of the Gibbs energy dependence on composition and temperature. Many of those binary systems have been taken from published or unpublished works and others have been assessed in the present work. All the calculations have been made using Thermo C alc software and the representation of the Gibbs energy obtained by applying Calphad technique

  5. HYDROGEN IN THE EARTH’S OUTER CORE, AND ITS ROLE IN THE DEEP EARTH GEODYNAMICS

    Directory of Open Access Journals (Sweden)

    V. N. Rumyantsev

    2016-01-01

    Full Text Available The content of hydrogen in the outer core of the Earth is roughly quantified from the dependence of the density of iron (viewed as the main component of the core on the amount of hydrogen dissolved in the core, with account of the most likely presence of iron hydrogen in the outer core, and the matter’s density jumps at the boundaries between the outer liquid core and the internal solid core (that is devoid of hydrogen and the mantle. Estimations for the outer liquid core show that the hydrogen content varies from 0.67 wt. % at the boundary with the solid inner core to 3.04 wt. % at the boundary with the mantle.Iron occlusion is viewed as the most likely mechanism for the iron–nickel core to capture such a significant amount of hydrogen. Iron occlusion took place at the stage of the young sun when the metallic core emerged in the cooling protoplanetary cloud containing hydrogen in high amounts, and non-volatile hydrogen was accumulated. Absorption (occlusion of molecular hydrogen was preceded by dissociation of molecules into atoms and ionization of the atoms, as proved by results of studies focused on Fe–H2 system, and hydrogen dissipation was thus prevented. The core matter was subject to gravitational compression at high pressures that contributed to the forced rapprochement of protons and electrons which interaction resulted by the formation of hydrogen atoms. Highly active hydrogen atoms reacted with metals and produced hydrides of iron and nickel, FeH and NiH. While the metallic core and then the silicate mantle were growing and consolidating, the stability of FeH and NiH was maintained due to pressures that were steadily increasing. Later on, due to the impacts of external forces on the Earth, marginal layers at the mantle–core boundary were detached and displaced, pressures decreased in the system, and iron and nickel hydrides were decomposed to produce molecular hydrogen. Consequences of the hydrides transformation into

  6. Materials and fabrication processes for operation in hot hydrogen

    International Nuclear Information System (INIS)

    Tuffias, R.H.; Duffy, A.J.; Arrieta, V.M.; Abrams, W.M.; Benander, R.E.

    1997-01-01

    Operation in hot (2500 endash 3000 K) hydrogen severely limits the choice of structural materials. Rhenium is nonreactive with and has low permeability to hydrogen, and has sufficient strength up to 2800 K. Carbon, in the form of graphite or carbon composites, has excellent high temperature strength but reacts with hydrogen to form methane at a rapid rate above 2000 K. The carbides of zirconium, niobium, hafnium, and tantalum are nonreactive with and have low permeability to hydrogen, but they can be reliably fabricated only in the form of coatings. In order to demonstrate the Integrated Solar Upper Stage (ISUS) solar-thermal propulsion concept, rhenium and rhenium-coated graphite were chosen as the structural materials for the receiver-absorber-converter (RAC) component of the ISUS system. Several methods were investigated for fabricating the rhenium parts and coatings, with chemical vapor deposition (CVD) and Ultramet chosen as the most likely process and company for success. The CVD or rhenium and other refractory materials were thus applied to the ISUS program for fabrication of the RAC subsystem. copyright 1997 American Institute of Physics

  7. low dose irradiation growth in zirconium

    International Nuclear Information System (INIS)

    Fortis, A.M.

    1987-01-01

    Low dose neutron irradiation growth in textured and recrystallized zirconium, is studied, at the Candu Reactors Calandria temperature (340 K) and at 77 K. It was necessary to design and build 1: A facility to irradiate at high temperatures, which was installed in the Argentine Atomic Energy Commission's RA1 Reactor; 2: Devices to carry out thermal recoveries, and 3: Devices for 'in situ' measurements of dimensional changes. The first growth kinetics curves were obtained at 365 K and at 77 K in a cryostat under neutron fluxes of similar spectra. Irradiation growth experiments were made in zirconium doped with fissionable material (0,1 at % 235 U). In this way an equivalent dose two orders of magnitude greater than the reactor's fast neutrons dose was obtained, significantly reducing the irradiation time. The specimens used were bimetallic couples, thus obtaining a great accuracy in the measurements. The results allow to determine that the dislocation loops are the main cause of irradiation growth in recrystallized zirconium. Furthermore, it is shown the importance of 'in situ' measurements as a way to avoid the effect that temperature changes have in the final growth measurement; since they can modify the residual stresses and the overconcentrations of defects. (M.E.L.) [es

  8. Study of zirconium-addition binary systems

    International Nuclear Information System (INIS)

    Wozniakova, B.; Kuchar, L.

    1975-01-01

    The curves are given of the solid and the liquid of binary zirconium-addition systems. Most additions reduce the melting temperature of zirconium. The only known additions to increase the melting temperature are nitrogen, oxygen and hafnium. Also given are the transformation curves of the systems and the elements are given which reduce or raise the temperature of α-β transformation. From the Mendeleev table into which are plotted the curves of the solid and the liquid of binary systems it is possible to predict the properties of unknown binary systems. For the calculations of the curves of the solid and the liquid, 1860 degC was taken as the temperature of zirconium melting. For the calculations of transformation curves, 865 degC was taken as the temperature of α-β transformation. The equations are given of the curves of the solid and the liquid and of the transformation curves of some Zr-addition systems. Also given are the calculated equilibrium distribution coefficients and the equilibrium distribution coefficients of the transformation of additions in Zr and their limit values for temperatures approximating the melting point or the temperature of the transformation of pure Zr, and the values pertaining to eutectic and peritectic or eutectoid and peritectoid temperatures. (J.B.)

  9. Bioremediation of zirconium from aqueous solution by coriolus versicolor: process optimization

    International Nuclear Information System (INIS)

    Amin, M.; Bhatti, H. N.; Sadaf, S.

    2013-01-01

    In the present study the potential of live mycelia of Coriolus versicolor was explored for the removal of zirconium from simulated aqueous solution. Optimum experimental parameters for the bioremediation of zirconium using C. versicolor biomass have been investigated by studying the effect of mycelia dose, concentration of zirconium, contact time and temperature. The isothermal studies indicated that the ongoing bioremediation process was exothermic in nature and obeyed Langmuir adsorption isotherm model. The Gibbs free energy (ΔG), entropy (ΔS) and enthalpy (ΔH) of bioremediation were also determined. The result showed that bioremediation of zirconium by live C. versicolor was feasible and spontaneous at room temperature. The equilibrium data verified the involvement of chemisorption during the bioremediation. The kinetic data indicated the operation of pseudo-second order process during the biosorption of zirconium from aqueous solution. Maximum bioremediation capacity (110.75 mg/g) of C. versicolor was observed under optimum operational conditions: pH 4.5, biomass dose 0.05 mg/100 mL, contact time 6 h and temperature 30 degree C. The results showed that C. versicolor could be used for bioremediation of heavy metal ions from aqueous systems. (author)

  10. Evaluation of a Zirconium Recycle Scrubber System

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, Barry B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bruffey, Stephanie H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-04-01

    A hot-cell demonstration of the zirconium recycle process is planned as part of the Materials Recovery and Waste Forms Development (MRWFD) campaign. The process treats Zircaloy® cladding recovered from used nuclear fuel with chlorine gas to recover the zirconium as volatile ZrCl4. This releases radioactive tritium trapped in the alloy, converting it to volatile tritium chloride (TCl). To meet regulatory requirements governing radioactive emissions from nuclear fuel treatment operations, the capture and retention of a portion of this TCl may be required prior to discharge of the off-gas stream to the environment. In addition to demonstrating tritium removal from a synthetic zirconium recycle off-gas stream, the recovery and quantification of tritium may refine estimates of the amount of tritium present in the Zircaloy cladding of used nuclear fuel. To support these objectives, a bubbler-type scrubber was fabricated to remove the TCl from the zirconium recycle off-gas stream. The scrubber was fabricated from glass and polymer components that are resistant to chlorine and hydrochloric acid solutions. Because of concerns that the scrubber efficiency is not quantitative, tests were performed using DCl as a stand-in to experimentally measure the scrubbing efficiency of this unit. Scrubbing efficiency was ~108% ± 3% with water as the scrubber solution. Variations were noted when 1 M NaOH scrub solution was used, values ranged from 64% to 130%. The reason for the variations is not known. It is recommended that the equipment be operated with water as the scrubbing solution. Scrubbing efficiency is estimated at 100%.

  11. Evaluation of selectivity and thermodynamic characteristics of doubly charged cations on zirconium titanate from aqueous and alcoholic solutions

    International Nuclear Information System (INIS)

    Zakaria, E.S.; Ali, I.M.; El-Naggar, I.M.

    2005-01-01

    The ion exchange of Ni 2+ /H + and Co 2+ /H + have been determined using solution of 0.1 ionic strength for both forward and backward reactions at 25 degree C by batch technique. The thermodynamic equilibrium constants for the exchange process have been calculated using Gains Thomas equation. The preference series Ni 2+ >Co 2+ was determined. The ion exchange selectivity for exchange of Ni 2 + and Co 2+ ions with hydrogen ions on zirconium titanate have been investigated for aqueous and 25% of methanol and ethanol solutions. The values of thermodynamic functions for the studied systems have been calculated

  12. Preparation and Characterization of Hydrous Zirconium Oxide Formed by Homogeneous Precipitation

    Directory of Open Access Journals (Sweden)

    Silva G.L.J.P. da

    2002-01-01

    Full Text Available This paper reports on the preparation, characterization and study of the ion exchange behavior of hydrous zirconium oxides formed by homogeneous precipitation from zirconium oxychloride. The precipitants used were obtained by thermal decomposition of urea, sodium nitrite or ammonium carbonate. Seven compounds were prepared and characterized by thermal analysis, X-ray diffractometry and by surface area measurements. Amorphous forms were obtained in each case, a result that agrees with those obtained by conventional gel precipitation methodology. All these materials present surface area values of >148 m².g-1, determined after heat treatment at 50 °C. The ion exchange behavior of each hydrous zirconium oxide prepared was studied using K+ as the exchanged species and the results compared with those obtained for hydrous zirconium oxide originally precipitated by the sol gel method.

  13. Assessment of hydrogen levels in Zircaloy-2 by non-destructive testing

    International Nuclear Information System (INIS)

    De, P.K.; John, J.T.; Banerjee, S.; Jayakumar, T.; Thavasimuthu, M.; Raj, B.

    1998-01-01

    A non-destructive assessment of Zircaloy-2 samples charged with hydrogen in the range of 50 to 1150 mg/kg has been made using ultrasonic and eddy current testing. It has been found that the ratio of the longitudinal to the shear wave velocity is a parameter which can be directly correlated with the hydrogen content up to a level of 100 to 200 mg/kg. This parameter together with the values of longitudinal and shear wave velocities can be utilized in a multi-parametric correlation approach for estimation of higher levels of the hydrogen content (up to 1150 mg/kg). The sensitivity at different ranges has been found to be acceptable. Ultrasonic attenuation measurements at higher frequencies and eddy current test parameter are also effective for estimation of hydrogen levels above 250 mg/kg in zirconium alloys. Microstructural characterization including TEM studies have been carried out for studying the influence of the type and the morphology of hydride precipitates on ultrasonic parameters. (orig.)

  14. Determination of the ruthenium, cerium and zirconium radio-activity of sea-water by carrying-over and adsorption using manganese dioxide

    International Nuclear Information System (INIS)

    Guegueniat, P.

    1967-01-01

    Principle: Manganese dioxide is precipitated in the medium to be analyzed by the action of hydrogen peroxide on potassium permanganate. Large volumes of sea-water are treated by successive adsorptions of 80 litre fractions using always the same precipitate obtained from 30 g of potassium permanganate. Some examples are given concerning the analysis of 80, 160, 1000 and 2000 litres of water. Advantages of the technique: The existence of low activities due to ruthenium, zirconium and cerium can be demonstrated if sufficiently large volumes of water are treated. (author) [fr

  15. Superficial effects during the activation of zirconium AB2 alloys

    International Nuclear Information System (INIS)

    Zerbino, J; Visitin, A; Triaca, W

    2005-01-01

    The activation of zirconium nickel alloys with and without the addition of chromium and titanium is investigated through electrochemical and optical techniques.These alloys show high hydrogen absorption capacity and are extensively used in metal hydride batteries.Recent investigations in aqueous 1 M KOH indicate oxide layer growth and occlusion of hydrogen species in the alloys during the application of different cathodic potential programmes currently used in the activation process.In this research several techniques such as voltammetry, ellipsometry, energy dispersive analysis of X-rays EDAX, and scanning electron microscopy SEM are applied on the polished massive alloy Zr 1 -xTi x , x=0.36 y 0.43, and Zr 1 -xTi x CrNi, x=0.1,0.2 y 0.4.Data analysis shows that the stability, compactness and structure of the passive layers are strongly dependent on the applied potential programme.The alloy activation depends on the formation of deepen crevices that remain after a new polishing. Microscopic observation shows increase in the crevices thickness after the cathodic sweep potential cycling, which produces fragmentation of the grains and oxide growth during the activation process.This indicates metal breaking and intergranular dissolution that take place together with oxide and hydride formation.In some cases the resultant crevice thickness is one or two orders higher than that of the superficial oxide growth indicating intergranular localised corrosion

  16. Development of new zirconium alloys for PWR fuel rod claddings

    International Nuclear Information System (INIS)

    Zhao Wenjin; Zhou Bangxin; Miao Zhi; Li Cong; Jiang Hongman; Yu Xiaowei; Jiang Yourong; Huang Qiang; Gou Yuan; Huang Decheng

    2001-01-01

    An advanced zirconium alloys containing Sn, Nb, Fe and Cr have been developed. The relationships between manufacturing, microstructure and corrosion performance for the new alloys have been studied. The effects of both heat treatment and chemistry on corrosion behavior were assessed by autoclave tests in lithia water at 633 K and high-temperature steam at 773 K. Analytical electron microscopy demonstrated that the best out-of-pile corrosion performance was obtained for microstructure containing a fine and uniform distribution of β-Nb and Zr(Fe, Nb) 2 particles. Autoclave testing in LiOH solution indicated that two kinds of alloys (N18, N36) showed the lower corrosion rate than the reference Zr-4 tested, and especially, the corrosion resistance in superheated steam at 773 K was much better. Moreover, the mechanical properties were superior to Zr-4. And the hydrogen absorption data for all of alloys from corrosion reactions under various corrosion conditions showed a linear increase with the oxide thickness

  17. Synthesis, characterization and optical properties of novel N donor ligands-chelated zirconium(IV) complexes

    Science.gov (United States)

    Shahroosvand, Hashem; Nasouti, Fahimeh; Mohajerani, Ezeddin; Khabbazi, Amir

    2012-11-01

    Novel zirconium complexes have been synthesized by using a mixture of zirconium nitrate, 1,2,4,5-benzen tetracarboxylic acid (H4btec), 1,10-phenanthroline(phen) and potassium thiocyanate. Monodentate coordination mode of btec acid for all complexes was investigated by FT-IR spectroscopy. The complexes were also characterized by UV-Vis, 1H NMR, CHN, ICP-AES. The reaction details and features were described and discussed. The photoluminescence emission of seven zirconium complexes was shown two series peaks: first, sharp and intense bands from 300 to 500 nm and broadened with less intensity from 650 to 750 nm for the second bands. Each of the zirconium compounds were doped in PVK:PBD blend as host. The ratio of zirconium complexes for each type were modified 8 wt.% in PVK:PBD(100:40). The electroluminescence spectra of zirconium complexes were indicated a red shift rather than PVK:PBD blend. We suggest that the electroplex occurring at PVK-Zr complex interface.

  18. An evaluated neutronic data file for elemental zirconium

    International Nuclear Information System (INIS)

    Smith, A.B.; Chiba, S.

    1994-09-01

    A comprehensive evaluated neutronic data file for elemental zirconium is derived and presented in the ENDF/B-VI formats. The derivation is based upon measured microscopic nuclear data, augmented by model calculations as necessary. The primary objective is a quality contemporary file suitable for fission-reactor development extending from conventional thermal to fast and innovative systems. This new file is a significant improvement over previously available evaluated zirconium files, in part, as a consequence of extensive new experimental measurements reported elsewhere

  19. Surface analytical investigations of the interaction between the getter material ZrCo and hydrogen and the influence of different contamination gases on the hydrogen storage capacity

    International Nuclear Information System (INIS)

    Glasbrenner, H.

    1991-11-01

    In this work the results of surface analytical investigations of the alloy ZrCo used for hydrogen storage as well as of the interaction of the alloy with hydrogen and various contamination gases present in a nuclear fusion reactor will be presented and discussed with respect to the application of ZrCo as getter material for tritium. The characterization of the ZrCo alloy showed that on the surface a stable ZrO 2 -layer is formed, which is, however, inhomogeneous. On the phase boundary solid / gas of samples exposed to hydrogen up to the stoichiometrical composition ZrCoH 2.8 a Co enrichment was observed. If the alloy ZrCo is activated before hydrogen take-up in the same way as other getter materials by heating under vacuum, the hydrogenation occurs faster and nearly complete. Zirconium is the alloy component responsible for the hydrogen storage. If a gas reacts nearly exclusively with the alloy component Co, a smaller decrease in the hydrogen storage capacity will be noticed. By exposition to CO and CO 2 mainly compounds with cobalt are formed. However, if the gas produces compounds with Zr like carbide, nitride, or oxide, the result is a strong decrease of the hydrogen storage capacity of the getter. (orig./MM) [de

  20. Effect of zirconium addition on the recrystallization behaviour of a ...

    Indian Academy of Sciences (India)

    In the present work, zirconium was added to a commercial Al–Cu–Mg alloy and by heat treatment Al3Zr particles were precipitated and after forging, the grain size was an order of magnitude lower than the alloy without zirconium. Transmission electron microscopy was employed to characterize the second phase particles, ...