Rare Earths in fluorite deposits of Elika Formation (East of Mazandaran Province

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Zahra Mehraban

2016-07-01

Full Text Available Introduction The Central Alborz in eastern Mazandaran province is host to the most important carbonate-hosted fluorite deposits in Iran, such as Pachi-Miana, Sheshroodbar, Era and Kamarposht. In these deposits, mineralization occurs in the upper parts of the middle Triassic Elika formation (Vahabzadeh et al., 2009 and references therein. These deposits have long been studied, and various models are presented for ore genesis. Nevertheless, ore genesis in these deposits is still unclear. The present study of the geochemistry of the REEs of these deposits is intended to improve genetic models. Materials and methods Three hundred samples were taken from above mentioned deposits. Samples were categorized into 5 groups: (1 fluorite ore types, (2 ore-stage calcite, (3 carbonate host rocks, (4 basaltic rock around the deposits, and (5 shale of the Shemshak formation. Fourteen pure fluorite samples, 4 samples of pure calcite, 4 samples of carbonate host rock, 1 sample of basalt and 1 sample of shale were analyzed for REEs by ICP-MS at West Lab in Australia. Results Analytical data on fluorite from the Elika deposits show very low REE concentrations (0.5-18ppm, in calcite(0.5-3ppm in carbonate host rocks – limestone (1.8-7ppm, and in dolomitic limestone 6.5ppm, compared with upper Triassic basalt (43ppm and shale (261ppm. REE in fluorite of these deposits are strongly enriched (10 3 to 10 6 times relative to normal sea water, ore stage calcite and carbonate host rocks, especially for mid-REEs (Eu, Gd and heavy REEs (Lu, Yb, La/Yb=~0.05. Also, LREEs depletion (La/Sm= 2-10 and HREEs (La/Yb=0.01-0.08 relatively enrichment of fluorites compared with limestone (La/Sm=2.5-4, La/Yb=0.1-1.5 and dolomitic limestone (La/Sm=4.28, La/Yb=0.07-0.4 host rocks as well as positive Eu anomaly are the most important REEs signatures in fluorites. Fluorite elsewhere in the world with low total REE conten thas been interpreted to have a sedimentary origin (Ronchi et al

Evaluation of Sulfonate-Based Collectors with Different Hydrophobic Tails for Flotation of Fluorite

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Renji Zheng

2018-02-01

Full Text Available This investigation aims to demonstrate the effects of hydrophobic tails on the affinity and relevant flotation response of sulfonate-based collectors for fluorite. For this purpose, a series of alkyl sulfonates with different hydrophobic tails, namely sodium decanesulfonate (C10, sodium dodecylsulfate (C12, sodium hexadecanesulfonate (C16, and sodium dodecylbenzenesulfonate (C12B were applied. The flotation tests showed that C12 and C12B had a better collecting performance than C10 and C16 at pH < 10, and the flotation recovery of fluorite was higher when adopting C12B as a collector compared with C12 with a strong base. The adsorption behaviors of collectors on the fluorite surface were studied through zeta potential, Fourier transform infrared (FTIR, and X-ray photoelectron spectroscopy (XPS analyses. It was found that the affinity of alkyl sulfonates for fluorite was enhanced with the increase of the alkyl chain length from C10 to C16. The existence of phenyl in the hydrophobic tail of sulfonates could improve its activity for fluorite by reducing its surface tension. The abnormal phenomenon C16 with a high affinity for fluorite had a low collecting performance for fluorite mainly due to its overlong alkyl chain, resulting in low solubility in pulp, which restrained its interaction with fluorite. We concluded that C12B was the most applicable collector for fluorite among these reagents due to its high activity, high solubility, and low cost, which was further substantiated by calculating their molecular frontier orbital energy.

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

OpenAIRE

Jonathan M. Solomon; Jacob Shamblin; Maik Lang; Alexandra Navrotsky; Mark Asta

2016-01-01

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated e...

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

Science.gov (United States)

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-12-01

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

Trace-element and Sr-Nd isotopic evidence for the origin of the Sardinian fluorite mineralization (Italy)

International Nuclear Information System (INIS)

Castorina, F.; Masi, U.; Padalino, G.; Palomba, M.

2008-01-01

The fluorite-bearing hydrothermal mineralization in Sardinia mainly occurs within Paleozoic volcanic and metasedimentary rocks. Only 3 occurrences are located in volcanic and siliciclastic Cenozoic rocks. Most Sardinian fluorites exhibit relatively high rare earth and Y (REY) contents, strong positive Y anomalies, slightly negative Ce and generally positive Eu anomalies. These features indicate that the REY were mobilized mainly from non-carbonate rocks. Neither Sr nor Nd isotopes can be used to date radiometrically the Sardinian fluorites. However, the measured Sr-isotope ratios of the fluorites hosted by Paleozoic rocks fit mixing lines in the 1000/Sr versus 87 Sr/ 86 Sr plot once recalculated at 280 Ma, suggesting that the age inferred for the correction probably represents that of the formation of the fluorite mineralization. Mixing likely occurred between diluted surficial waters and brines circulating mainly through the Lower Paleozoic metasedimentary basement. The Cenozoic fluorites exhibit chemical and isotopic features similar to those of the Paleozoic fluorites, except the Nuraghe Onigu fluorite displaying a possible contribution of Sr from Cenozoic magmatic rocks. The initial ε Nd values of the Paleozoic fluorites fit the age proposed for the formation of the deposits. Moreover, the values suggest that radiogenic Nd was provided to the fluids from the Ordovician siliciclastic basement, except for 3 deposits where the potential source rocks of Nd were mainly Ordovician acidic magmatic rocks. The initial ε Nd values of the Cenozoic fluorites suggest a provenance of Nd essentially from the leaching of Variscan granitoids

U-Th/He ages of fluorite mineralizations of the Tangua alkaline intrusion; Idades U-Th/He das mineralizacoes de fluorita da intrusao alcalina de Tangua

Energy Technology Data Exchange (ETDEWEB)

Geraldes, M.C.; Vargas, T., E-mail: geraldes@uerj.br, E-mail: vargas@uerj.br [Universidade do Estado do Rio de Janeiro (UERJ), RJ (Brazil). Faculdade de Geologia; Evans, N., E-mail: Noreen.Evans@csiro.au [CSIRO and Curtin University for Technology, Western Australia (Australia); Nummer, A.R., E-mail: nummer@ufrrj.br [Universidade Federal Rural do Rio de Janeiro (DEGEOC/IA/UFRRJ), RJ (Brazil)

2015-07-01

The Tangua massif is part of a group of alkaline complexes that occurs in an extensive zone of faults and E-W lineaments and includes the Brazilian Southeastern Rift. This work presents U-He ages of the fluorite mineralization. The Tangua alkaline massif is emplaced in coarse-grained biotite gneiss (Oriental Domain, central portion of the Ribeira belt). Cataclastic gneiss with intense weathering are restricted to the intrusion contacts. The alkaline body is comprised of pulaskites and umptekites, nephelinesyenites, foiaites, and pseudoleucite foiaites and is cut by phonolite dykes, trachytes and alkaline lamprophyres. In the locality of Barbosao, veins of fluorite occur, accompanied by silica and pyrite within trachyte dykes. These veins are parallel to the gneiss foliation (N 50 - 70 E) with an average thickness of 30 cm and the fluorite contains limonite and manganese oxides inclusions. The U-He ages range from <2Ma to 73Ma. The older age is coherent with 80-65 ma range of K-Ar ages reported in the literature. The veins of fluorite crosscut the lithologies associated with shear zones, and are important to economic exploration in the region. The petrographic and U-Th/He sating studies indicate the fluorite formation coeval to alkaline intrusion and meteoric water fluid circulation recently. (author)

The fluorite-pyrochlore transformation of Ho2-yNdyZr2O7

International Nuclear Information System (INIS)

Clements, Richard; Hester, James R.; Kennedy, Brendan J.; Ling, Chris D.; Stampfl, Anton P.J.

2011-01-01

Twelve members of the Ho 2-y Nd y Zr 2 O 7 series, prepared using conventional solid state methods, have been characterised by neutron powder diffraction. Ho 2 Zr 2 O 7 has a defect fluorite structure whereas Nd 2 Zr 2 O 7 is found to adopt the ordered pyrochlore structure with the composition induced fluorite-pyrochlore transformation occurring near y=1. Rietveld analysis on the neutron data for all the compositions reveals an increase in lattice parameter as a function of y across the entire series, with a small discontinuity associated with the transformation. The neutron profile results suggest that domains of pyrochlore-type initially begin to form before crystallising into a separate phase, and therefore that anion and cation ordering processes are distinct. There is a strong correlation between the extent of disorder in the anion sublattice and the x-parameter of 48f oxygen. These results point the way to a better understanding of the stability observed in pyrochlore structures. - Graphical abstract: Neutron diffraction profiles for Nd 2-y Ho y Zr 2 O 7 type oxides reveal details of the transformation from the ordered pyrochlore structure (y=0) to the disordered fluorite structure (y=2). Highlights: → Structures of twelve members of the Ho 2-y Nd y Zr 2 O 7 series studied using neutron powder diffraction. → Domains of pyrochlore-type materials form at low doping levels. → Higher doping stabilises the pyrochlore. → Anion and cation ordering processes are distinct.

Thermoluminescence in fluorite: sensitization mechanism

International Nuclear Information System (INIS)

Cruz, M.T. da; Watanabe, S.; Mayhugh, M.R.

1974-01-01

The sensitization of the major glow peaks (approximately to 100 and 200 0 C) in fluorite correlates with population of traps causing higher temperature glow peaks. When considered with supralinearity results, it is concluded that either the sensitization results from an increase in trap-filling efficiencies, or the deeper traps are not filled during irradiation

Factors influencing the determination of fluorite by means of neutron activation analysis

International Nuclear Information System (INIS)

Lutze, H.

1975-01-01

Proceeding from the necessity of a rapid analysis of fluorite by neutron activation of an unprepared drill core the influence of interfering elements, of inhomogeneous fluorite distribution, of the sample volume and of moisture are examined. Recommendations are given to overcome these interferences. (author)

Thermoluminescence in fluorite: sensitization mechanism

Energy Technology Data Exchange (ETDEWEB)

Cruz, M.T. da; Watanabe, S; Mayhugh, M R

1974-11-01

The sensitization of the major glow peaks (approximately to 100 and 200/sup 0/ C) in fluorite correlates with population of traps causing higher temperature glow peaks. When considered with supralinearity results, it is concluded that either the sensitization results from an increase in trap-filling efficiencies, or the deeper traps are not filled during irradiation.

Application of X-ray technique to characterization of fluorite sample

International Nuclear Information System (INIS)

Cancado, R.Z.L.; Luz Ferreira, O. da.

1986-01-01

This investigation had the purpose of characterizing fluorite veins of ''Mineracao Sartor'', in Itaborai region/RJ, which is an excelent geographic position in relation to the consuming market. These studies have in view to give subsidy to future works to the best fluorite utilization. They realized tests with X-rays diffractometer and spectrometer, polarizing microscope and with a mounting of electric circuit to measure the type of semiconductivity. (C.M.C.T.R.) [pt

Coagulation of fines in fluorite froth flotation; Coagulacion de finos en la flotacion de la fluorita

Energy Technology Data Exchange (ETDEWEB)

Sarquis, P. E.; Gonzalez, M.; Moyano, A.; Bazan, V.

2011-07-01

Fluorite, a valuable mineral in the metallurgical industry, can be found together with silicates, carbonates and oxides in ore deposits. Commercial concentrates with more than 95 % of CaF{sub 2} are obtained processing the mineral in flotation plants and using oleic acid as fluorite collector. Depressor reagents such as sodium silicate, tannin and sodium carbonate are commonly employed to allow the oleic acid selective performance. These reagents cause a dispersant effect separating the solid-liquid solution on tailing plants. Fine particles in the recovered water enter the circuit and affect the flotation efficiency. The effect of coagulant ions was studied as a method to clarify the returned water. The problem of the presence of these ions is related to its reactions with the collector by the formation of compounds and possibly on the selectivity. Variable quantities of Al{sup 3}+, Fe{sup 3}+ and Ca{sup 2}+ ions were added to the flotation to evaluate its effect on the fluorite recovery, in the selectivity and in solids content in recirculation water. Results show that some ions fail to improve water quality and are detrimental to flotation. On the contrary, some ions contribute to reduce fine content in suspension. Therefore, although there is a recovery reduction, such effect can be counteracted increasing the collector consumption a little. (Author) 21 refs.

Thermodynamic determination of fluorite phases of the ULnO4 type

International Nuclear Information System (INIS)

Paula, H.C.B.

1981-12-01

A method for the determination of structure and thermodynamical stability of fluorite phases of the ULnO 4 type is presented. Through the use of a solid body galvanic chain with CaO-doped ZrO 2 working as an oxygen ion conductor solid electrolyte, phase transformation temperatures are determined, as well as solubility enthalpies and entropies for ULnO 4 systems (Ln= Sm, Tb, Er, Ho, Tm, YB). X-ray analyses confirmed the electrochemical measurements. The emf measurement system is checked by using binary oxides with known composition and oxygen partial pressure. A comparison between stabilities of analysed compounds is also presented. (Author) [pt

Ab-initio calculation for cation vacancy formation energy in anti-fluorite structure

Science.gov (United States)

Saleel, V. P. Saleel Ahammad; Chitra, D.; Veluraja, K.; Eithiraj, R. D.

2018-04-01

Lithium oxide (Li2O) has been suggested as a suitable breeder blanket material for fusion reactors. Li+ vacancies are created by neutron irradiation, forming bulk defect complex whose extra character is experimentally unclear. We present a theoretical study of Li2O using density functional theory (DFT) with a plane-wave basis set. The generalized gradient approximation (GGA) and local-density approximation (LDA) were used for exchange and correlation. Here we address the total energy for defect free, cation defect, cation vacancy and vacancy formation energy in Li2O crystal in anti-fluorite structure.

Conclusion - Admixture elements as indicators of fluorite genesis

International Nuclear Information System (INIS)

Fayziev, A.R.

2002-01-01

The information obtained during scientific researches was generalized and analyzed. It was defined that studying of qualitative composition and quantitative content revealed the geochemical features of fluorite.

Study of thermophysical and anharmonic properties of fluorite compounds

International Nuclear Information System (INIS)

Singh, R.K.; Pandey, N.K.

1983-01-01

An extensive study is made of thermophysical and anharmonic properties of fluorite compounds using an interionic potential, which consists of a long-range Coulomb and three-body interactions and the short-range overlap repulsion and van der Waals attraction. The agreement achieved between experimental and theoretical results on third-order elastic constants and pressure derivatives of second order elastic constants are generally better than those obtained by others. This potential succeeds in predicting various thermophysical properties, like compressibility and its pressure and temperature derivatives, thermal expansion and Grueneisen parameters of seven crystals of fluorite structure. (author)

High-throughput continuous hydrothermal flow synthesis of Zn-Ce oxides: unprecedented solubility of Zn in the nanoparticle fluorite lattice.

Science.gov (United States)

Kellici, Suela; Gong, Kenan; Lin, Tian; Brown, Sonal; Clark, Robin J H; Vickers, Martin; Cockcroft, Jeremy K; Middelkoop, Vesna; Barnes, Paul; Perkins, James M; Tighe, Christopher J; Darr, Jawwad A

2010-09-28

High-throughput continuous hydrothermal flow synthesis has been used as a rapid and efficient synthetic route to produce a range of crystalline nanopowders in the Ce-Zn oxide binary system. High-resolution powder X-ray diffraction data were obtained for both as-prepared and heat-treated (850 degrees C for 10 h in air) samples using the new robotic beamline I11, located at Diamond Light Source. The influence of the sample composition on the crystal structure and on the optical and physical properties was studied. All the nanomaterials were characterized using Raman spectroscopy, UV-visible spectrophotometry, Brunauer-Emmett-Teller surface area and elemental analysis (via energy-dispersive X-ray spectroscopy). Initially, for 'as-prepared' Ce(1-x)Zn(x)O(y), a phase-pure cerium oxide (fluorite) structure was obtained for nominal values of x=0.1 and 0.2. Biphasic mixtures were obtained for nominal values of x in the range of 0.3-0.9 (inclusive). High-resolution transmission electron microscopy images revealed that the phase-pure nano-CeO(2) (x=0) consisted of ca 3.7 nm well-defined nanoparticles. The nanomaterials produced herein generally had high surface areas (greater than 150 m(2) g(-1)) and possessed combinations of particle properties (e.g. bandgap, crystallinity, size, etc.) that were unobtainable or difficult to achieve by other more conventional synthetic methods.

[Assessment of Soil Fluorine Pollution in Jinhua Fluorite Ore Areas].

Science.gov (United States)

Ye, Qun-feng; Zhou, Xiao-ling

2015-07-01

The contents of. soil total fluorine (TF) and water-soluble fluorine (WF) were measured in fluorite ore areas located in Jinhua City. The single factor index, geoaccumulation index and health risk assessment were used to evaluate fluorine pollution in soil in four fluorite ore areas and one non-ore area, respectively. The results showed that the TF contents in soils were 28. 36-56 052. 39 mg.kg-1 with an arithmetic mean value of 8 325.90 mg.kg-1, a geometric mean of 1 555. 94 mg.kg-1, and a median of 812. 98 mg.kg-1. The variation coefficient of TF was 172. 07% . The soil WF contents ranged from 0. 83 to 74. 63 mg.kg-1 with an arithmetic mean value of 16. 94 mg.kg-1, a geometric mean of 10. 59 mg.kg-1, and a median of 10. 17 mg.kg-1. The variation coefficient of WF was 100. 10%. The soil TF and WF contents were far higher than the national average level of the local fluorine epidemic occurrence area. The fluoride pollution in soil was significantly affected by human factors. Soil fluorine pollution in Yangjia, Lengshuikeng and Huajie fluorite ore areas was the most serious, followed by Daren fluorite ore area, and in non-ore area there was almost no fluorine pollution. Oral ingestion of soils was the main exposure route. Sensitivity analysis of model parameters showed that children's weight exerted the largest influence over hazard quotient. Furthermore, a significant positive correlation was found among the three kinds of evaluation methods.

Optical storage media based on fluorite activated crystals

International Nuclear Information System (INIS)

Mokienko, I.Yu.; Poletimov, A.E.; Shcheulin, A.S.

1991-01-01

Earlier studied mechanisms of photo- and thermotransformations of defects in pure and activated additively coloured crystals with fluorite structure are considered to suggest several methods of reversible optical recording of images, characterized by high resistance to high-power laser radiation and mechanical deformation

Stability of fluorite-type La{sub 2}Ce{sub 2}O{sub 7} under extreme conditions

Energy Technology Data Exchange (ETDEWEB)

Zhang, F.X., E-mail: zhangfx@umich.edu [Department of Earth and Environmental Sciences, The University of Michigan, Ann Arbor, MI 48109 (United States); State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao, Hebei 066004 (China); Tracy, C.L. [Department of Materials Science and Engineering, The University of Michigan, Ann Arbor, MI 48109 (United States); Lang, M. [Department of Nuclear Engineering, University of Tennessee, Knoxville, TN 37966 (United States); Ewing, R.C. [Department of Geological Sciences, Stanford University, Stanford, CA 94305 (United States)

2016-07-25

The structural stability of fluorite-type La{sub 2}Ce{sub 2}O{sub 7} was studied at pressure up to ∼40 GPa and under hydrothermal conditions of ∼1 GPa and up to 350 °C, respectively, using synchrotron X-ray diffraction (XRD) and Raman scattering measurements. XRD measurements indicated that the fluorite-type La{sub 2}Ce{sub 2}O{sub 7} is not stable at pressures greater than 22.6 GPa and gradually transformed to a high-pressure phase. The high-pressure phase is not stable and changed back to the fluorite-type structure when pressure is released. The La{sub 2}Ce{sub 2}O{sub 7} fluorite is also not stable under hydrothermal conditions and began to react with water at 200–250 °C. Both Raman and XRD results suggest that lanthanum hydroxide La(OH){sub 3} and La{sup 3+}-doped CeO{sub 2} fluorite are the dominant products after hydrothermal treatment. - Graphical abstract: The fluorite-type La{sub 2}Ce{sub 2}O{sub 7} reacted with water at hydrothermal condition (1 GPa, and above 200 °C), and formed rare earth hydroxides. - Highlights: • La{sub 2}Ce{sub 2}O{sub 7} transforms to a metastable phase at pressure higher than 21 GPa. • La{sub 2}Ce{sub 2}O{sub 7} reacts with water at ∼1 GPa and above 200 °C. • The pressure-induced phase transition is reversible.

Surface modelling on heavy atom crystalline compounds: HfO2 and UO2 fluorite structures

International Nuclear Information System (INIS)

Evarestov, Robert; Bandura, Andrei; Blokhin, Eugeny

2009-01-01

The study of the bulk and surface properties of cubic (fluorite structure) HfO 2 and UO 2 was performed using the hybrid Hartree-Fock density functional theory linear combination of atomic orbitals simulations via the CRYSTAL06 computer code. The Stuttgart small-core pseudopotentials and corresponding basis sets were used for the core-valence interactions. The influence of relativistic effects on the structure and properties of the systems was studied. It was found that surface properties of Mott-Hubbard dielectric UO 2 differ from those found for other metal oxides with the closed-shell configuration of d-electrons

Disorder–order phase transformation in a fluorite-related oxide thin film: In-situ X-ray diffraction and modelling of the residual stress effects

International Nuclear Information System (INIS)

Gaboriaud, R.J.; Paumier, F.; Lacroix, B.

2016-01-01

This work is focused on the transformation of the disordered fluorite cubic-F phase to the ordered cubic-C bixbyite phase, induced by isothermal annealing as a function of the residual stresses resulting from different concentrations of microstructural defects in the yttrium oxide, Y_2O_3. This transformation was studied using in-situ X-ray diffraction and was modelled using Kolmogorov–Johnson–Mehl–Avrami (KJMA) analysis. The degree of the disorder of the oxygen network was associated with the residual stress, which was a key parameter for the stability and the kinetics of the transition of the different phases that were present in the thin oxide film. When the degree of disorder/residual stress level is high, this transition, which occurs at a rather low temperature (300 °C), is interpreted as a transformation of phases that occurs by a complete recrystallization via the nucleation and growth of a new cubic-C structure. Using the KJMA model, we determined the activation energy of the transformation process, which indicates that this transition occurs via a one-dimensional diffusion process. Thus, we present the analysis and modelling of the stress state. When the disorder/residual stress level was low, a transition to the quasi-perfect ordered cubic-C structure of the yttrium oxide appeared at a rather high temperature (800 °C), which is interpreted as a classic recovery mechanism of the cubic-C structure. - Highlights: • Rare earth oxide thin films • XRD analysis • Phase transformation modelling • Residual stress effects • Crystallographic phase stability

Disorder–order phase transformation in a fluorite-related oxide thin film: In-situ X-ray diffraction and modelling of the residual stress effects

Energy Technology Data Exchange (ETDEWEB)

Gaboriaud, R.J.; Paumier, F. [Institut Pprime, Department of Material Sciences, CNRS-University of Poitiers SP2MI-BP 30179, 86962 Futuroscope-Chasseneuil cedex (France); Lacroix, B. [CSIC, Institut de Ciencia de Materiales, University of Sevilla, Avenida Américo Vespucio, 49, 41092 Sevilla (Spain)

2016-02-29

This work is focused on the transformation of the disordered fluorite cubic-F phase to the ordered cubic-C bixbyite phase, induced by isothermal annealing as a function of the residual stresses resulting from different concentrations of microstructural defects in the yttrium oxide, Y{sub 2}O{sub 3}. This transformation was studied using in-situ X-ray diffraction and was modelled using Kolmogorov–Johnson–Mehl–Avrami (KJMA) analysis. The degree of the disorder of the oxygen network was associated with the residual stress, which was a key parameter for the stability and the kinetics of the transition of the different phases that were present in the thin oxide film. When the degree of disorder/residual stress level is high, this transition, which occurs at a rather low temperature (300 °C), is interpreted as a transformation of phases that occurs by a complete recrystallization via the nucleation and growth of a new cubic-C structure. Using the KJMA model, we determined the activation energy of the transformation process, which indicates that this transition occurs via a one-dimensional diffusion process. Thus, we present the analysis and modelling of the stress state. When the disorder/residual stress level was low, a transition to the quasi-perfect ordered cubic-C structure of the yttrium oxide appeared at a rather high temperature (800 °C), which is interpreted as a classic recovery mechanism of the cubic-C structure. - Highlights: • Rare earth oxide thin films • XRD analysis • Phase transformation modelling • Residual stress effects • Crystallographic phase stability.

High-pressure phase transformations of fluorite-type dioxides

International Nuclear Information System (INIS)

Lin-Gun Liu

1980-01-01

Phase transformations in six fluorite-type dioxides ('TbO 2 ', PbO 2 , 'PrO 2 ', CeO 2 , UO 2 and ThO 2 in the order of increasing cation size, where the quotation marks indicate non-stoichiometric materials) have been investigated in the diamond-anvil press coupled with laser heating. Together with earlier work, the results show that the post-fluorite phase transformations of these dioxides fall into two groups. The smaller cation group (HfO 2 , ZrO 2 and 'TbO 2 ') transforms to a cotunnite or a distorted cotunnite-type structure at pressures in the vicinity of 100 kbar and at about 1000 0 C. The larger cation group (from PbO 2 to ThO 2 ) is believed to transform to a different type of orthorhombic modification at high pressures. It is plausible that this high-pressure phase may possess a Ni 2 Si-related structure, as was observed in ThO 2 and 'PrO 2 ' at pressures greater than 150 and 200 kbar, respectively. (orig./ME)

Direct reading spectrochemical determination of aluminium, iron and silicon in fluorite

International Nuclear Information System (INIS)

Roca, M.

1966-01-01

A quantitative spectrochemical method for the determination of Al, Fe and Si in fluorite has been worked out. The sample was supported in a graphite electrode with crater of 5 mm. in diameter, 2,5 mm deep, and burned by a d.c. are in a direct reading spectrometer. The excitation of samples has been studied without dilution as well as using graphite powder as diluent in the ratios 1:1, 1:4, and 1:9; the latter factor was chosen. Ag, Ca, Co, Cr, Mo and Sn were tested as internal standards. It has not been found any significant inter element effect. It is necessary to use natural fluorite as base material for the standards. (Author) 5 refs

Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

Science.gov (United States)

Sotnikova, Irina; Vladykin, Nikolai

2015-04-01

Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and

Solid State Structure-Reactivity Studies on Bixbyites, Fluorites and Perovskites Belonging to the Vanadate, Titanate and Cerate Families

Science.gov (United States)

Shafi, Shahid P.

This thesis primarily focuses on the systematic understanding of structure-reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in-situ techniques including powder x-ray diffraction and thermogravimetric-differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure-reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite-type oxide ion conductor Ce1-xInxO2-delta (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO 3-delta perovskites and the subsequent CO2-capture reaction

Damage evolution of ion irradiated defected-fluorite La 2 Zr 2 O 7 epitaxial thin films

Energy Technology Data Exchange (ETDEWEB)

Kaspar, Tiffany C.; Gigax, Jonathan G.; Shao, Lin; Bowden, Mark E.; Varga, Tamas; Shutthanandan, Vaithiyalingam; Spurgeon, Steven R.; Yan, Pengfei; Wang, Chongmin; Ramuhalli, Pradeep; Henager, Charles H.

2017-05-01

Pyrochlore-structure oxides, A2B2O7, may exhibit remarkable radiation tolerance due to the ease with which they can accommodate disorder by transitioning to a defected fluorite structure. The mechanism of defect formation was explored by evaluating the radiation damage behavior of high quality epitaxial La2Zr2O7 thin films with the defected fluorite structure, irradiated with 1 MeV Zr+ at doses up to 10 displacements per atom (dpa). The level of film damage was evaluated as a function of dose by Rutherford backscattering spectrometry in the channeling geometry (RBS/c) and scanning transmission electron microscopy (STEM). At lower doses, the surface of the La2Zr2O7 film amorphized, and the amorphous fraction as a function of dose fit well to a stimulated amorphization model. As the dose increased, the surface amorphization slowed, and amorphization appeared at the interface. Even at a dose of 10 dpa, the core of the film remained crystalline, despite the prediction of amorphization from the model. To inform future ab initio simulations of La2Zr2O7, the bandgap of a thick La2Zr2O7 film was measured to be indirect at 4.96 eV, with a direct transition at 5.60 eV.

Chemical ordering in substituted fluorite oxides: A computational investigation of Ho2 Zr2 O7 and RE2 Th2 O7 (RE=Ho, Y, Gd, Nd, La)

OpenAIRE

Solomon, JM; Shamblin, J; Lang, M; Navrotsky, A; Asta, M

2016-01-01

© 2016 The Author(s). Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ord...

Surface modelling on heavy atom crystalline compounds: HfO{sub 2} and UO{sub 2} fluorite structures

Energy Technology Data Exchange (ETDEWEB)

Evarestov, Robert [Department of Quantum Chemistry, St. Petersburg State University, 26 Universitetsky Prospect, Peterhof, St. Petersburg 198504 (Russian Federation)], E-mail: re1973@re1973.spb.edu; Bandura, Andrei; Blokhin, Eugeny [Department of Quantum Chemistry, St. Petersburg State University, 26 Universitetsky Prospect, Peterhof, St. Petersburg 198504 (Russian Federation)

2009-01-15

The study of the bulk and surface properties of cubic (fluorite structure) HfO{sub 2} and UO{sub 2} was performed using the hybrid Hartree-Fock density functional theory linear combination of atomic orbitals simulations via the CRYSTAL06 computer code. The Stuttgart small-core pseudopotentials and corresponding basis sets were used for the core-valence interactions. The influence of relativistic effects on the structure and properties of the systems was studied. It was found that surface properties of Mott-Hubbard dielectric UO{sub 2} differ from those found for other metal oxides with the closed-shell configuration of d-electrons.

A kinetic study of the replacement of calcite marble by fluorite

Science.gov (United States)

Trindade Pedrosa, Elisabete; Boeck, Lena; Putnis, Christine V.; Putnis, Andrew

2016-04-01

Replacement reactions are relevant in any situation that involves the reequilibration between a solid and an aqueous fluid phase and are commonly controlled by an interface-coupled dissolution-precipitation mechanism (Putnis and Putnis, 2007). These reactions control many large-scale Earth processes whenever aqueous fluids are available, such as during metamorphism, metasomatism, and weathering. An important consequence of coupled dissolution-precipitation is the generation of porosity in the product phase that then allows the infiltration of the fluid within the mineral being replaced. Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in earth sciences and engineering. Fluorite (CaF2) occurs in all kinds of rocks (igneous, sedimentary, and metamorphic) and its origin is commonly associated with hydrothermal fluids. Moreover, calcium carbonate has been suggested as a successful seed material for the sequestration of fluoride from contaminated waters (Waghmare and Arfin, 2015). The aim of the present work is to investigate aspects of the replacement of calcium carbonate by fluorite to better understand the mechanism and kinetics of this reaction. Small cubes (˜ 3 × 3 × 3 mm) of Carrara marble (CaCO3 > 99 %) were cut and reacted with a 4 M ammonium fluoride (NH4F) solution for different times (1 to 48 hours) and temperatures (60, 80, 100, and 140 ° C). The microstructure of the product phases was analysed using SEM. The kinetics of replacement was monitored from the Rietveld analysis of X-ray powder diffraction patterns of the products as a function of temperature and reaction time. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement) and the product phase (fluorite) was highly porous. The activation energy Ea (kJ/mol) of the replacement reaction was empirically determined by both model-fitting and model-free methods. The isoconversional method yielded an

(100) faceted anion voids in electron irradiated fluorite

International Nuclear Information System (INIS)

Johnson, E.

1979-01-01

High fluence electron irradiation of fluorite crystals in the temperature range 150 to 320 K results in formation of a simple cubic anion void superlattice. Above 320 K the damage structure changes to a random distribution of large [001] faceted anion voids. This voidage behaviour, similar to that observed in a range of irradiated metals, is discussed in terms points defect rather than conventional colour centre terminology. (Auth.)

Conductivity and hydration trends in disordered fluorite and pyrochlore oxides: A study on lanthanum cerate–zirconate based compounds

DEFF Research Database (Denmark)

Besikiotis, Vasileios; Ricote, Sandrine; Jensen, Molly Hjorth

2012-01-01

In the present contribution we discuss the influence of order/disorder on the concentration and mobility of ionic charge carriers in undoped and acceptor (calcium) doped fluorite and pyrochlore structured lanthanum cerate–zirconate solid solutions: (La1−yCay)2(Ce1−xZrx)2O7−δ (y=0, 0.02, 0.10; x=0...... enthalpy becomes more exothermic with higher cerium content, i.e. with more disordered materials. The proton conductivity decreases upon acceptor substitution of La3+ with Ca2+ which is attributed to trapping of the charge carriers by the effectively negative acceptor....

The Improvement Effect of Dispersant in Fluorite Flotation: Determination by the Analysis of XRD and FESEM-EDX

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Y. J. Li

2015-01-01

Full Text Available Different dispersants were added in the dispersion process to improve the efficiency of fluorite flotation. The types and dosage of dispersant on the improvement of fluorite flotation were investigated; when the sodium polyacrylate (SPA was used as the dispersant and its addition is 0.5%, the concentrate grade of CaF2 increased from 90% to 98% and the fluorite recovery increased from 81% to 85%. Methods of X-ray powder diffraction (XRD, field emission scanning electron microscopy (FESEM, and Energy dispersive X-ray spectrometer (EDX were used to characterize the sample. According to the analysis of results, the optimal sample consisted of CaF2 and very little CaCO3 in the size range of 0–5 μm. It could be concluded that the mechanism of improvement for the concentrate grade and recovery of CaF2 was attributed to the change of potential energy barrier which caused the separation of particles with different charge. All results indicate that SPA has a great potential to be an efficient and cost-effective dispersant for the improvement of fluorite flotation.

The orthorhombic fluorite related compounds Ln/sub 3/RuO/sub 7/, Ln=Nd, Sm and Eu

International Nuclear Information System (INIS)

Van Berkel, F.P.F.; Ijdo, D.J.W.

1986-01-01

Fluorite-related Ru(V) compound with composition Ln/sub 3/RuO/sub 7/ have been found. These compounds with space group Cmcm adopt a superstructure of the cubic fluorite structure with a/sub orth/=2a/sub c/, b/sub orth/=c/sub orth/=a/sub c/√2. These compounds have the same structure as La/sub 3/NbO/sub 7/

Spectroscopic and computer modelling studies of mixed-cation superionic fluorites

CSIR Research Space (South Africa)

Netshisaulu, TT

2005-10-19

Full Text Available into the local environments of the Cd and Pb cations (as a function of composition and temperature) in CdF2 (xPbF(2)) mixed-cation superionic fluorites. A high degree of disorder is shown around both cations. However, the extent of disorder is even larger around...

Solid thermoluminescent dosemeter of sodium tetraborate and brazilian fluorite sensible to thermal neutrons

International Nuclear Information System (INIS)

Fratin, L.; Cruz, M.T. da

1987-01-01

A solid termoluminescent dosemeter of sodium tetraborate and brazilian fluorite sensible to thermal neutrons is described. The nuclears reactions 1) 10 B + n → 7 Li + He + Q1 (6,1%) where: Q1=2,79 MeV and Eα1 = 1,758 MeV and 2) 10 B + n → 7 Li* + 4 He + Q2 (93,9%) where: Q2 = 2,316 MeV and E2α 2 = 1,474 MeV are responsible by the thermoluminescent response of the thermal neutrons dosemeters. The stages in the fabrication process of this dosemeter of which are:1) sodium tetraborate vitrification, 2) mixture and pressing 3) sintering are cited. The obtainment of a natural fluorite dosemeter with sodium chloride is also shown. (C.G.C.) [pt

Measurements of CaF2 concentration in fluorite ore using thermoluminescence techniques

International Nuclear Information System (INIS)

Lembo, L.; Maestri, G.; Pimpinella, M.; Benzi, V.; Muntoni, C.

1990-01-01

Fluorite powder is produced by means of a flotation process on crude ore extracted by the mines. A full automation of the flotation plant would reduce the operating cost and improve the quality and recovery of fluorite production. However, taking into account that the efficiency of a flotation cycle is directly dependent on the CaF 2 content in the concentrate and tail products, this automation requires a quasi-real-time quantitative analysis of CaF 2 concentration in the floated pulp. The feasibility was studied of using a thermoluminescence technique as an on-line analysis method to measure the CaF 2 concentration during the flotation cycle. A first set of experimental conditions to determine CaF 2 content in acid-grade fluorspar has been already developed and the preliminary results so far obtained are presented. (author)

Fluid evolution and mineralogy of Mn-Fe-barite-fluorite mineralizations at the contact of the Thuringian Basin, Thüringer Wald and Thüringer Schiefergebirge in Germany

Directory of Open Access Journals (Sweden)

Majzlan Juraj

2016-02-01

Full Text Available Numerous small deposits and occurrences of Mn-Fe-fluorite-barite mineralization have developed at the contact of the Thuringian Basin, Thüringer Wald and Thüringer Schiefergebirge in central Germany. The studied mineralizations comprise the assemblages siderite+ankerite-calcite-fluorite-barite and hematite-Mn oxides-calcite-barite, with the precipitation sequence in that order within each assemblage. A structural geological analysis places the origin of the barite veins between the Middle Jurassic and Early Cretaceous. Primary fluid inclusions contain water vapour and an aqueous phase with NaCl and CaCl2 as the main solutes, with salinities mostly between 24–27 mass. % CaCl2 eq. Th measurements range between 85 °C and 160 °C in barite, between 139 °C and 163 °C in siderite, and between 80 °C and 130 °C in fluorite and calcite. Stable isotopes (S, O point to the evaporitic source of sulphur in the observed mineralizations. The S,C,O isotopic compositions suggest that barite and calcite could not have precipitated from the same fluid. The isotopic composition of the fluid that precipitated barite is close to the sea water in the entire Permo–Mesozoic time span whereas calcite is isotopically distinctly heavier, as if the fluids were affected by evaporation. The fluid evolution in the siliciclastic/volcanic Rotliegend sediments (as determined by a number of earlier petrological and geochemical studies can be correlated with the deposition sequence of the ore minerals. In particular, the bleaching of the sediments by reduced Rotliegend fluids (basinal brines could be the event that mobilized Fe and Mn. These elements were deposited as siderite+ankerite within the Zechstein carbonate rocks and as hematite+Mn oxides within the oxidizing environment of the Permian volcanic and volcanoclastic rocks. A Middle-Jurassic illitization event delivered Ca, Na, Ba, and Pb from the feldspars into the basinal brines. Of these elements, Ba was

Importance of surface structure on dissolution of fluorite

DEFF Research Database (Denmark)

Godinho, Jose; Piazolo, Sandra; Balic Zunic, Tonci

2014-01-01

forming the initial surface and its inclination to the closest stable planes, which are specific for each surface orientation. During an initial dissolution regime dissolution rates decrease significantly, even though the total surface area increases. During a second dissolution regime, some surfaces...... by the relative stability of the planes and type of edges that constitute a surface needs to be considered. Significant differences between dissolution rates calculated based on surface area alone, and based on surface reactivity are expected for materials with the fluorite structure....

Diagenetic and post-diagenetic fabrics in the Kamarposht fluorite mine (east of Mazandaran province: Explainaton and genetic interpretation

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Faezeh Nabiloo

2017-11-01

Full Text Available Introduction Upper part of Elika Formation (middle Triassic in the central Alborz as one of the most important fluorite districts in Iran is the host of some carbonate rock-hosted fluorite deposits such as Kamarposht, Pachi-Miana, Shashroodbar, Era (Alirezaee, 1989; Gorjizad, 1996; Rastad and Shariatmadar, 2001; Rajabi et al., 2013; Vahabzadeh et al., 2013; Zabihitabar and Shafiei, 2015. One of the main active fluorite mines in the central Alborz is Kamarposht which is located at the southeast of DoAb in the Mazandaran province. The Kamarposht mine has 75000 tons of ores and mining there has begun in 2005. The effects and evidences of underground mining in the northern and southern parts of this mine indicate high-grade and coarse-grained ore zones which have fluorite, galena and barite. Until now, basic economic geology studies in the Kamarposht mine including mineralogy, fabric and texture of mineralization for introducing a new fluorite mine in Iran have not been carried out. The present study is based on field observations and macroscopic as well as microscopic studies aimed at identification of morphology and mode of occurrence of the ore body, mineralogy and fabric of mineralization and discussion of as well as presentation of a new genetic model for the Kamarposht mine. Materials and methods For the present research study, field geology and sampling were carried out to collect 100 samples from various fluorite ore-types and carbonate host rocks. The samples prepared for thin section (n=55 and polished-thin sections (n=22. Results Field observations indicate that economic mineable ore zones of the Kamarposht mine are mainly hosted by dolomitic limestone and silicified carbonate horizons of the Elika Formation. The ore zones have fluorite, barite and galena which are mainly located in fractured and faulted zones as well as karstic cavities in the host horizons. Coarse grain and euhedral fluorites with various colors, significant presence of

Selective Separation of Fluorite, Barite and Calcite with Valonea Extract and Sodium Fluosilicate as Depressants

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Zijie Ren

2017-02-01

Full Text Available Fluorite, barite and calcite are important industry minerals. However, they often co-exist, presenting difficulty in selectively separating them due to their similar surface properties. In this study, valonea extract and sodium fluosilicate were used as depressants to selectively separate them by flotation, with sodium oleate as the collector. The single mineral flotation results showed that valonea extract displayed the strongest depression on calcite, while sodium fluosilicate displayed the strongest depression on barite. These two depressants allowed selective separation of the three minerals through sequential flotation. The flotation of mixed minerals showed that 94% of the calcite was successfully depressed by the valonea extract, and 95% recovery of the fluorite was achieved in the subsequent flotation with sodium fluosilicate depressing barite. The different depressant–mineral interactions were investigated via electro-kinetic studies and molecular dynamics (MD simulations using the Materials Studio 6.0 program. The valonea extract exhibited the strongest adsorption on the calcite surface, and sodium fluosilicate exhibited the strongest adsorption on the barite surface, which prevented oleate species from reacting with Ca2+ or Ba2+ surface sites. This study provides useful guidance for how to process fluorite, barite and calcite resources.

Geochemical characterization of rare earth elements from fluorite deposits of Tangua district - RJ

International Nuclear Information System (INIS)

Coelho, C.E.S.; Dardenne, M.A.

1987-01-01

The Tangua fluorite vein-type deposits are related to an alkaline complex of the same name, and situated in the District of Itaborai, in the State of Rio de Janeiro. The plutonic body of nepheline syenites (Tangua Massif) intrudes basement gneisses, with dykes and sills of trachitic and phonolitic nature of hundreds of meters in length and centimeters to tens of meters in thickness. The fluorite veins are emplaced both in gneisses and alkaline rocks (plutonic body and dykes) in NE-ENE structures created or reactivated during the opening of the South Atlantic Ocean. The geochemical study of rare earth elements reveals that these mineralizations show very low contents in these elements, and a relatively high fractionation spectres. In the deposit environment, four mineralization phases were differenciated, with the first one being considered as the initial solution; the second one characterized by a new europium rich-solution; the third one, representing the evolution of this new solution, but in a reducing environment, with precipitation of pyrite; and the last one, representing a new batch of the initial solution. As a consequence of the REE's and fluid inclusions studies, we are able to suggest an origen by weathering of the country rocks due to superficial meteorics solutions along faults and fractures, that when heated in deep environments, promote lixiviation of silica and fluorine and precipitate the fluorites when their ascending movement comes to an end. (author) [pt

Investigation of thermally induced anion disorder in fluorites using neutron scattering techniques

DEFF Research Database (Denmark)

Hutchings, M T; Clausen, Kurt Nørgaard; Dickens, M H

1984-01-01

Some materials with the fluorite structures show a pronounced specific heat anomaly well below their melting temperature. This anomaly is a consequence of lattice disorder and is associated with the onset of fast-ion conduction. This paper presents the results of a series of experiments in which...

INAA in the determination of the elemental constituents of a natural fluorite

International Nuclear Information System (INIS)

Balogun, F.A.; Tubosun, I.A.; Adesanmi, C.A.; Ajao, J.A.; Akanle, A.O.; Spyrou, N.M.; Ojo, J.O.

1997-01-01

A complementary use of the comparative and the semi-absolute variations of instrumental neutron activation analysis (INAA) has enabled us to determine 22 different elements in a sample of natural fluorite originating from the younger granite province of Nigeria. The mineral has a brownish purple appearance with some veinlets having a deep purple coloration. Of all the 22 elements measured, Fe (851.36 ppm), Sb (7.69 ppm), Ag (87.4 ppm), Hg (2.71 ppm) and Se (1.97 ppm) are found to be exclusive to the veinlets while Au (109.15 ppm), Co (2.15 ppm) and W (173.20 ppm) are concentrated in the main matrix of the fluorite. With the aid of the semi-absolute method, it was possible to measure the Au concentration in the IAEA Soil-7 reference material to be 56.83±5.87% ppm. A qualitative electron microprobe analysis (EMA) showed that the bulk of the matrix is composed mainly of Ca and F, as expected. (author)

The structural priciples that underlie the higher oxides of the rare earths

International Nuclear Information System (INIS)

Kang, Z.C.; Zhang, J.; Eyring, L.

1996-01-01

The structural principle that accounts for the anion-deficient, fluorite-related homologous series of higher rare earth oxides has awaited the determination of a sufficient number of their structures to test hypotheses. Recent structure refinement of five additional members has permitted extraction of a number of generalizations concerning their crystallization behavior. These general principles are outlined. Furthermore, based on the fluorite structure itself, a phenomenological structural principle is outlined that (1) unifies all known and possible phases in these fluorite-related systems under one generic formula, (2) models all known structures correctly and (3) enables modeling of any unknown structure or polymorph in the series. All that is required are electron diffraction patterns adequate to determine the supercell and a knowledge of its composition. (orig.)

Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

Energy Technology Data Exchange (ETDEWEB)

Karthik, Chinnathambi, E-mail: Karthikchinnathambi@boisestate.edu [Department of Materials Science and Engineering, Boise State University, 1910 University drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415 (United States); Anderson, Thomas J. [Department of Materials Science and Engineering, Boise State University, 1910 University drive, Boise, ID 83725 (United States); Gout, Delphine [Oak Ridge National Lab, Neutron Scattering Science Division, Oak Ridge, TN (United States); Ubic, Rick [Department of Materials Science and Engineering, Boise State University, 1910 University drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415 (United States)

2012-10-15

A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which became weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.

Oxygen potentials of transuranium oxides

International Nuclear Information System (INIS)

Haruyoshi Otobe; Mituso Akabori; Arai Yasuo; Kazuo Minato

2008-01-01

The oxygen potentials of pyrochlore-type Pu 2 Zr 2 O 7+y , fluorite-type (Pu 0.5 Zr 0.5 )O 2-x and AmO 2-x have been measured by the electromotive force (EMF) method with a zirconia solid-electrolyte. The oxygen potentials of these oxides were reviewed. The phase relations, microstructure, equilibrium state of these oxides were discussed, referring to the isothermal curve of the oxygen potentials. (authors)

Laser site selective spectroscopy of rare-earth defects in fluorites

International Nuclear Information System (INIS)

Murdoch, K.M.

1998-01-01

Full text: Rare-earth (R 3+ ) doped fluorites (CaF 2 , SrF 2 , and BaF 2 ) have long been a model system for investigating the defect chemistry of crystalline solids. The trivalent R 3+ ions substitute for the divalent cations of the host and are charge compensated by the inclusion of additional interstitial fluoride ions (F - j ). A variety of R 3+ centres arise, including cubic symmetry R 3+ sites remote from any F - j , single R 3+ ions associated with one neighbouring F - j , and clusters of R 3+ associated with multiple F - j . Additional R 3+ centres are produced by chemical modifications involving the substitution of host anions or cations. Numerous experimental studies have shown that the relative populations of these centres are determined by the size of the R 3+ ions, the R 3+ concentration in the crystal, the crystals thermal history, and any pressure treatments. A considerable volume of theoretical work has also been presented to interpret these results. Laser site selective spectroscopy has proved a powerful technique for probing the defect chemistry of R 3+ doped fluorites. Some of the important results and conclusions of these experiments will be reviewed. A detailed account, with references to the original studies, has also been published recently

Geo economical studies of Mina Florencia (Fluorite)

International Nuclear Information System (INIS)

Gomez Rifas, C.; Mari, C.; Theune, C.; Bosse, R.

1982-01-01

This report describes the works of Prospecting of Fluorite in Mina Florencia, in Maldonado Province. The project began in January of 1981, with the elaboration of a regional geologic cartography scale 1/20.000 of an area of 90,85 kilometers and cartography detailed scale 1/5.000 of the immediate area to Mina Florencia (6 kilometer that demonstrated the existence other veins of similar characteristic of the mine in exploration. Later on they were carried out geophysical studies (resistividad and electromagnetism, under the direction of the geophysical Fritz R. Haut of the BGR). The main geophysical anomalies inside the mining concession was studied by mechanical well, which results were showed in this report.

Continental basinal origin of ore fluids from southwestern Massif central fluorite veins (Albigeois, France): evidence from fluid inclusion and stable isotope analyses

International Nuclear Information System (INIS)

Munoz, M.; Boyce, A.J.; Courjault-Rade, P.; Fallick, A.E.; Tollon, F.

1999-01-01

The most important fluorspar mining district in France is located in the Palaeozoic basement of the Albigeois in southwestern French Massif Central. The massive fluorite is hosted within large E-W striking fractures, crosscutting Cambro-Ordovician clastics, associated with large zones of hypersilicified tectonic breccia which form the wall of the mined deposits. Fluid inclusion data for pre-fluorite and fluorite stage fluids have salinities between 20-26 wt% NaCl equiv., with homogenisation temperatures between 85-170C. Furthermore, low first ice melting temperatures (around -50C) indicates the presence of significant CaCl 2 and possibly MgCl 2 together with NaCl. Calculated fluid δ 18 O for pre-fluorite quartz ranges from -9.1per thousand to -5.2per thousand, with δD between -55per thousand to -64per thousand, placing the data directly on the present day meteoric water line. Fluorite stage fluids have δ 18 O between +0.1per thousand to +3.2per thousand, and δD ranging from -53per thousand to -75per thousand, indicating an interacted meteoric fluid origin. Combining the fluid inclusion and stable isotope data illustrates that the main fluorite depositing fluid has characteristics typical of a basinal brine. The authors have no evidence that a magmatic system was involved in the deposit genesis. The proposed model highlights that mineralisation was related to major Mesozoic extensional events coinciding with the gradual opening of the Atlantic and Tethys oceans. In order to account for the chemistry of the fluids, and the siting of the deposits, the authors postulate a genetic relationship with local, continental, evaporite-bearing basins coincident with, and controlled by the E-W fractures. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

Kinetic characterization of the first peak of natural fluorite from low ...

African Journals Online (AJOL)

Fluorite samples were irradiated with a low dose-rate (40 μGys-1 ) β- irradiation source to a test dose of 1.2 mGy and the heating rates of β = 1,3 and 5o Cs were considered, in order to minimize the effect of temperature lag. The role of thermal quenching (W) was investigated by evaluating the activation energy using the ...

Electrical impedance studies of uranium oxide

International Nuclear Information System (INIS)

Hampton, R.N.

1986-11-01

The thesis presents data on the electrical properties of uranium oxide at temperatures from 1700K to 4.2K, and pressures between 25 K bar and 70 K bar. The impedance data were analysed using the technique of complex plane representation to establish the conductivity and dielectric constant of uranium dioxide. The thermophysical data were compared with previously reported experimental and theoretical work on uranium dioxide and other fluorite structured oxides. (U.K.)

Application of mathematical statistics methods to study fluorite deposits

International Nuclear Information System (INIS)

Chermeninov, V.B.

1980-01-01

Considered are the applicability of mathematical-statistical methods for the increase of reliability of sampling and geological tasks (study of regularities of ore formation). Compared is the reliability of core sampling (regarding the selective abrasion of fluorite) and neutron activation logging for fluorine. The core sampling data are characterized by higher dispersion than neutron activation logging results (mean value of variation coefficients are 75% and 56% respectively). However the hypothesis of the equality of average two sampling is confirmed; this fact testifies to the absence of considerable variability of ore bodies

A new anion-deficient fluorite-related superstructure of Bi{sub 28}V{sub 8}O{sub 62}

Energy Technology Data Exchange (ETDEWEB)

Đorđević, T., E-mail: tamara.djordjevic@univie.ac.at [Institut für Mineralogie und Kristallographie-Geozentrum, Universität Wien, Althansstr. 14, A-1090 Wien (Austria); Karanović, Lj., E-mail: ljika2002@yahoo.com [Laboratory for Crystallography, Faculty of Mining and Geology, University of Belgrade, Đušina 7, 11000 Belgrade (Serbia)

2014-12-15

New hydrothermally synthesized Bi{sub 28}V{sub 8}O{sub 62} was structurally characterized using single-crystal X-ray diffraction data. Bi{sub 28}V{sub 8}O{sub 62} crystallizes in the novel type of defect fluorite structure related to the face-centered cubic δ-Bi{sub 2}O{sub 3}. It is monoclinic, s. g. P2{sub 1}/c, and the relation to the fluorite subcell is given as a∼(3/2)a{sub F}+(3/2)c{sub F}; b∼ −b{sub F}; c∼2a{sub F} −4c{sub F} (F in subscript indicate the unit cell parameter of fluorite). Its structure is characterized by slabs of edge sharing OBi{sub 4} tetrahedra surrounded by the OBi{sub 3} triangles. As a part of these OBi{sub 3} triangles, two positionally disordered Bi{sup 3+} cations were observed in the marginal part of the slabs. The slabs are extending along b axis and are linked by inter-slab portion of the structure composed of VO{sub 4} tetrahedra and BiO{sub 6−x} coordination polyhedra, where x is a number of vacant oxygen sites. Raman spectra verified the coordination environment of vanadium atoms in the structure. - Graphical abstract: The [4{sup ¯}01] projection of two slabs and inter-slab part of the structure in one layer parallel to the (3{sup ¯}08)=(002{sup ¯}){sub F} plane (F in subscript indicate a fluorite type structure). The large green circles are Bi atoms. Small blue circles represent partly and fully occupied O sites, respectively. Pink (hatched black) are V1O{sub 4} and blue (hatched white) are V2O{sub 4} coordination tetrahedra. - Highlights: • Single crystals of Bi{sub 28}V{sub 8}O{sub 62} were grown using hydrothermal technique. • The crystal structure of Bi{sub 28}V{sub 8}O{sub 62} was solved using single-crystal XRD method. • Bi{sub 28}V{sub 8}O{sub 62} has an anion-deficient fluorite-related superstructure. • Raman spectrum confirmed the coordination environment of vanadium atoms. • Relation to the structurally related compound was discussed.

Effect of natural irradiation in fluorites: possible implications for nuclear waste management?

Czech Academy of Sciences Publication Activity Database

Vlček, V.; Skála, Roman; Goliáš, V.; Drahokoupil, Jan; Čížek, J.; Strnad, L.; Ederová, J.

2012-01-01

Roč. 57, č. 1 (2012), s. 45-52 ISSN 1802-6222 R&D Projects: GA ČR GA106/07/0805; GA AV ČR KAN300100801 Institutional research plan: CEZ:AV0Z30130516 Keywords : fluorite * irradiation * X-ray diffraction * differential scanning calorimetry * defects * real structure Subject RIV: DB - Geology ; Mineralogy Impact factor: 0.804, year: 2012

Thin film ionic conductors based on cerium oxide

International Nuclear Information System (INIS)

Haridoss, P.; Hellstrom, E.; Garzon, F.H.; Brown, D.R.; Hawley, M.

1994-01-01

Fluorite and perovskite structure cerium oxide based ceramics are a class of materials that may exhibit good oxygen ion and/or protonic conductivity. The authors have successfully deposited thin films of these materials on a variety of substrates. Interesting orientation relationships were noticed between cerium oxide films and strontium titanate bi-crystal substrates. Near lattice site coincidence theory has been used to study these relationships

TEM and HRTEM study of oxide particles in an Al-alloyed high-Cr oxide dispersion strengthened ferritic steel with Hf addition

International Nuclear Information System (INIS)

Dou, Peng; Kimura, Akihiko; Kasada, Ryuta; Okuda, Takanari; Inoue, Masaki; Ukai, Shigeharu; Ohnuki, Somei; Fujisawa, Toshiharu; Abe, Fujio; Jiang, Shan; Yang, Zhigang

2017-01-01

The nanoparticles in an Al-alloyed high-Cr oxide dispersion strengthened (ODS) ferritic steel with Hf addition, i.e., SOC-16 (Fe-15Cr-2W-0.1Ti-4Al-0.62Hf-0.35Y 2 O 3 ), have been examined by transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Relative to an Al-alloyed high-Cr ODS ferritic steel without Hf addition, i.e., SOC-9 (Fe-15.5Cr-2W-0.1Ti-4Al-0.35Y 2 O 3 ), the dispersion morphology and coherency of the oxide nanoparticles in SOC-16 were significantly improved. Almost all the small nanoparticles (diameter <10 nm) in SOC-16 were found to be consistent with cubic Y 2 Hf 2 O 7 oxides with the anion-deficient fluorite structure and coherent with the bcc steel matrix. The larger particles (diameter >10 nm) were also mainly identified as cubic Y 2 Hf 2 O 7 oxides with the anion-deficient fluorite structure. The results presented here are compared with those of SOC-9 with a brief discussion of the underlying mechanisms of the unusual thermal and irradiation stabilities of the oxides as well as the superior strength, excellent irradiation tolerance and extraordinary corrosion resistance of SOC-16.

The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

Energy Technology Data Exchange (ETDEWEB)

Miao, Yinbin, E-mail: miao2@illinois.edu [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Mo, Kun [Nuclear Engineering Division, Argonne National Laboratory, Lemont, IL 60493 (United States); Cui, Bai [Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, Lincoln, NE 68588 (United States); Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Chen, Wei-Ying [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Miller, Michael K.; Powers, Kathy A. [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37830 (United States); McCreary, Virginia; Gross, David [Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Almer, Jonathan [X-ray Science Division, Argonne National Laboratory, Lemont, IL 60493 (United States); Robertson, Ian M. [Department of Material Science and Engineering, University of Wisconsin-Madison, Madison, WA 53706 (United States); Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Stubbins, James F. [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)

2015-03-15

This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between the oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.

The reasons for the color green fluorite Mehmandooye cover using UV spectroscopy and XRF results

Science.gov (United States)

Pirzadeh, Sara; Zahiri, Reza

2016-04-01

Fluorite mineral or fluorine with chemical formula CaF2 is most important mineralfluor in nature. This mineral crystallization to colors yellow, green, pink, blue, purple, colorless and sometimes black andin cubic system crystallized.assemi transparent and glass with polished.fluoritethe purity include 48/9% fluoreand 51/9% calcium. How the creation colors in minerals different greatly indebted to Kurt Nassau research from Bell Labs, Murray Hill, New Jersey.almostall the mechanisms that cause color in minerals, are the result of the interaction of light waves with the electrons The main factors affecting the color generation include the following: 1)the presence of a constructive element inherent (essential ingredient mineral composition) 2)The presence of a minor impurities (such a element as involved in latticesolid solution) 3) appearancedefects in the crystal structure 4) There are some physical boundaries with distances very small and delicate, like blades out of the solution (which may be the play of colors or Chatvyansy) 5) Mixing mechanical impurities dispersed in a host mineral Based on the results of the analysis, XRF and UV spectrum and also based on the results of ICP, because the color green fluorite examined, the focus color (F_center) and also the presence of some elementsintermediate (such as Y (yttrium). [1] Bill, H., Calas, G. Color centres associated rare earth ions and the origin of coloration in natural fluorites// PhysChem Min, (1978), v 3, pp. 117-131.

TEM and HRTEM study of oxide particles in an Al-alloyed high-Cr oxide dispersion strengthened ferritic steel with Hf addition

Energy Technology Data Exchange (ETDEWEB)

Dou, Peng, E-mail: doup@tsinghua.edu.cn [School of Materials Science and Engineering, Chongqing University, Chongqing 400044 (China); Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan); Kimura, Akihiko, E-mail: kimura@iae.kyoto-u.ac.jp [Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan); Kasada, Ryuta, E-mail: r-kasada@iae.kyoto-u.ac.jp [Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan); Okuda, Takanari, E-mail: okuda.takanari@kki.kobelco.com [Kobelco Research Institute, 1-5-5 Takatsukadai, Nishi-ku, Kobe, Hyogo 651-2271 (Japan); Inoue, Masaki, E-mail: inoue.masaki@jaea.go.jp [Advanced Nuclear System R& D Directorate, Japan Atomic Energy Agency, 4002 Narita, O-arai, Ibaraki 311-1393 (Japan); Ukai, Shigeharu, E-mail: s-ukai@eng.hokudai.ac.jp [Graduate School of Engineering, Hokkaido University, N13, W8, Kita-ku, Sapporo 060-8628 (Japan); Ohnuki, Somei, E-mail: ohnuki@eng.hokudai.ac.jp [Graduate School of Engineering, Hokkaido University, N13, W8, Kita-ku, Sapporo 060-8628 (Japan); Fujisawa, Toshiharu, E-mail: fujisawa@esi.nagoya-u.ac.jp [EcoTopia Science Institute, Nagoya University, Furo, Chikusa-ku, Nagoya 464-8603 (Japan); Abe, Fujio, E-mail: ABE.Fujio@nims.go.jp [Structural Metals Center, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Jiang, Shan, E-mail: js93518@gmail.com [School of Materials Science and Engineering, Chongqing University, Chongqing 400044 (China); Yang, Zhigang, E-mail: zgyang@tsinghua.edu.cn [Key Laboratory of Advanced Materials (MOE), School of Materials Sciences and Engineering, Tsinghua University, Beijing 100084 (China)

2017-03-15

The nanoparticles in an Al-alloyed high-Cr oxide dispersion strengthened (ODS) ferritic steel with Hf addition, i.e., SOC-16 (Fe-15Cr-2W-0.1Ti-4Al-0.62Hf-0.35Y{sub 2}O{sub 3}), have been examined by transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Relative to an Al-alloyed high-Cr ODS ferritic steel without Hf addition, i.e., SOC-9 (Fe-15.5Cr-2W-0.1Ti-4Al-0.35Y{sub 2}O{sub 3}), the dispersion morphology and coherency of the oxide nanoparticles in SOC-16 were significantly improved. Almost all the small nanoparticles (diameter <10 nm) in SOC-16 were found to be consistent with cubic Y{sub 2}Hf{sub 2}O{sub 7} oxides with the anion-deficient fluorite structure and coherent with the bcc steel matrix. The larger particles (diameter >10 nm) were also mainly identified as cubic Y{sub 2}Hf{sub 2}O{sub 7} oxides with the anion-deficient fluorite structure. The results presented here are compared with those of SOC-9 with a brief discussion of the underlying mechanisms of the unusual thermal and irradiation stabilities of the oxides as well as the superior strength, excellent irradiation tolerance and extraordinary corrosion resistance of SOC-16.

Relationship between uranium-molybdenum, fluorite and gold deposits within provinces of continental volcanicity

International Nuclear Information System (INIS)

Modnikov, I.S.; Skvortsova, K.V.; Chesnokov, L.V.

1974-01-01

The article gives a comparative description of and the age relationships between uranium-molybdenum, gold and fluorite mineralizations in the areas of development of adhesite-diorite and liparite-granite vulcanoplutonic formations, which are most fully and intensively manifest in the intra-anticlinal and median blocks of folded regions in the final stages of geosynclinal development or during the final stages of tectono-magmatic activation. These formations usually fill vulcano-tectonic depression structures - overlaid troughs and inherited delections. The geological and geochemical data are evidence of the close temporal link between the hydrothermal process of ore formation and the type and scale of manifestations of the vulcano-plutonic magmatism that is responsible for the general geochemical features of the ores of deposits of various types. The formation of gold, fluorite and uranium-molybdenum deposits occurred immediately after the completion of effusive and intrusive magmatism during a single metallogenic cycle. The spatial distribution of the ore fields and deposits depends chiefly on the peculiarities of the tectonic make-up of the depression structures, and also on the type and scale of the manifestations of vulcano-plutonic magmatism. (B.Ya.)

Naturally irradiated fluorite as a historic violet pigment: Raman spectroscopic and X-ray diffraction study

Czech Academy of Sciences Publication Activity Database

Čermáková, Zdeňka; Bezdička, Petr; Němec, I.; Hradilová, J.; Šrein, V.; Blažek, Jan; Hradil, David

2015-01-01

Roč. 46, č. 2 (2015), s. 236-243 ISSN 0377-0486 R&D Projects: GA ČR GAP103/12/2211 Institutional support: RVO:61388980 ; RVO:67985556 Keywords : fluorite * pigment * fluorescence bands * diffraction lines broadening * irradiation Subject RIV: CA - Inorganic Chemistry Impact factor: 2.395, year: 2015

Topotactic oxidation pathway of ScTiO3 and high-temperature structure evolution of ScTiO3.5 and Sc4Ti3O12-type phases.

Science.gov (United States)

Shafi, Shahid P; Hernden, Bradley C; Cranswick, Lachlan M D; Hansen, Thomas C; Bieringer, Mario

2012-02-06

The novel oxide defect fluorite phase ScTiO(3.5) is formed during the topotactic oxidation of ScTiO(3) bixbyite. We report the oxidation pathway of ScTiO(3) and structure evolution of ScTiO(3.5), Sc(4)Ti(3)O(12), and related scandium-deficient phases as well as high-temperature phase transitions between room temperature and 1300 °Cusing in-situ X-ray diffraction. We provide the first detailed powder neutron diffraction study for ScTiO(3). ScTiO(3) crystallizes in the cubic bixbyite structure in space group Ia3 (206) with a = 9.7099(4) Å. The topotactic oxidation product ScTiO(3.5) crystallizes in an oxide defect fluorite structure in space group Fm3m (225) with a = 4.89199(5) Å. Thermogravimetric and differential thermal analysis experiments combined with in-situ X-ray powder diffraction studies illustrate a complex sequence of a topotactic oxidation pathway, phase segregation, and ion ordering at high temperatures. The optimized bulk synthesis for phase pure ScTiO(3.5) is presented. In contrast to the vanadium-based defect fluorite phases AVO(3.5+x) (A = Sc, In) the novel titanium analogue ScTiO(3.5) is stable over a wide temperature range. Above 950 °C ScTiO(3.5) undergoes decomposition with the final products being Sc(4)Ti(3)O(12) and TiO(2). Simultaneous Rietveld refinements against powder X-ray and neutron diffraction data showed that Sc(4)Ti(3)O(12) also exists in the defect fluorite structure in space group Fm3m (225) with a = 4.90077(4) Å. Sc(4)Ti(3)O(12) undergoes partial reduction in CO/Ar atmosphere to form Sc(4)Ti(3)O(11.69(2)).

A molecular dynamics study on the oxygen diffusion in doped fluorites: the effect of the dopant distribution

Energy Technology Data Exchange (ETDEWEB)

Tarancon, A. [M2E/XaRMAE/IREC, Department of Advanced Materials for Energy Applications, Catalonia Institute for Energy Research (IREC), Josep Pla 2, Torre 2, B2, 08019 Barcelona (Spain); Morata, A.; Peiro, F. [MIND/XaRMAE/IN2UB, Department of Electronics, University of Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Dezanneau, G. [Laboratoire Structures, Proprietes et Modelisation des Solides, Grande Voie des Vignes, Ecole Centrale Paris, F-92295 Chatenay-Malabry Cedex (France)

2011-02-15

The effect of the dopant distribution on the oxygen diffusion in doped fluorites typically used for solid oxide fuel cells electrolyte applications has been analysed by using molecular dynamics simulations. The oxygen mass transport in both yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria has been studied and compared in the range of temperatures between 1,159 and 1,959 K. A new methodology based on the analysis of local environments is used to describe the diffusion process at an atomic scale. Preferred vacancy migration pathways, most suitable conduction models, energy landscapes and jump efficiency have been detailed for each material. Finally, a particular case of non-random distribution of dopants in YSZ is presented in order to quantitatively evaluate the effect of the dopant pattern on the mass transport properties and the potential of the methodology developed here for understanding and foreseeing real configurations at the nanoscale. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Low temperature synthesis of fluorite-type Ce-based oxides of ...

Indian Academy of Sciences (India)

M MALATHI

F-type oxides can be considered as multi-functional materials due to the ... The photoluminescence property of the rare earth ions was also studied, and the color coordinates were calculated using CIE ... active photocatalysts with a view to utilize solar light. Hence ... It consists of a cylindrical quartz double walled tube with.

Investigation of lanthanide ions and other paramagnetic impurities in natural fluorite by electron paramagnetic resonance: examples of application to mining exploration and geochemistry

International Nuclear Information System (INIS)

Chatagnon, B.

1981-01-01

This research thesis reports the application to geology, and more particularly to geochemistry and mining exploration, of a physical method: the electron paramagnetic resonance (EPR). After a report of a bibliographical investigation on mineralogy and geochemistry of fluorite and lanthanides, as well as on paramagnetic centres observed by physicists in synthetic fluorite, the author reports an experimental work, and describes two examples of application of EPR: firstly, the exploration of radioactive ores, and secondly, with the joint use of neutron activation analysis, the characterization of the redox status of the hydrothermal solution which is at the origin of fluorinated mineralisation

Properties of complex tungstates, niobates, translated with fluorite-like structure

International Nuclear Information System (INIS)

Vetkina, S.N.; Zolin, V.F.; Sirotinkin, V.P.; Smirnov, S.A.

1989-01-01

Spectra of ternary tungstates, niobates and tantalates (MeLa 2 WO 7 , La 3 TO 7 ; Me=Ba, Sr; T=Ta, Nb) related to the layered fluorite group are analyzed. The laser pumping and time resolved luminescence are used for selecting spectra of unequivalent centers. The symmetry of the first center is near to the distorted cubic one. The vibrational spectra of europium in Eu 3 NbO 7 and SrLa 2 WO 7 are due to the chain-like structure of niobates and to the net-like structure of tantalates. The stimulated emission of Nd 3+ in powders of BaLa 2 WO 7 and La 3 NbO 7 is observed at wavelengths of 1.07 and 1.063 μm, respectively

Synthesis of Fluorite (CaF2 Crystal from Gypsum Waste of Phosphoric Acid Factory in Silica Gel

Directory of Open Access Journals (Sweden)

Mohammad Misbah Khunur

2012-06-01

Full Text Available This paper report the synthesis and characterization of fluorite single crystal prepared from gypsum waste of phosphoric acid production in silica gel. Instead of its high calcium, gypsum was used to recycle the waste which was massively produces in the phosphoric acid production. The gypsum waste, the raw material of CaCl2 supernatant, was dissolved in concentrated HCl and then precipitated as calcium oxalate (CaC2O4 by addition of ammonium oxalate. The CaCl2 was obtained by dissolving the CaC2O4 with HCl 3M. The crystals were grown at room temperature in silica gel and characterized by AAS, FTIR and powder XRD. The optimum crystal growth condition, which is pH of gel, CaCl2 concentration and growth time, were investigated. The result shows that at optimum condition of pH 5.80, CaCl2 concentrations of 1.2 M, and growth time of 144 hours, colorless crystals with the longest size of 3 mm, were obtained (72.57%. Characterization of the synthesized crystal by AAS indicates that the obtained crystal has high purity. Meanwhile, analysis by FTIR spectra shows a Ca–F peak at 775 cm-1, and powder-XRD analysis confirms that the obtained crystal was fluorite (CaF2. © 2012 BCREC UNDIP. All rights reservedReceived: 11st April 2012; Revised: 4th June 2012; Accepted: 13rd June 2012[How to Cite: M.M. Khunur, A. Risdianto, S. Mutrofin, Y.P. Prananto. (2012. Synthesis of Fluorite (CaF2 Crystal from Gypsum Waste of Phosphoric Acid Factory in Silica Gel. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 71-77.  doi:10.9767/bcrec.7.1.3171.71-77 ][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.3171.71-77 ] | View in 

Phase Behavior and Equations of State of the Actinide Oxides

Science.gov (United States)

Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

2017-12-01

The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

Direct reading spectrochemical determination of aluminium, iron and silicon in fluorite; Determinacion espectroquimica de lectura directa de aluminio, hierro y silicio en fluorita

Energy Technology Data Exchange (ETDEWEB)

Roca, M

1966-07-01

A quantitative spectrochemical method for the determination of Al, Fe and Si in fluorite has been worked out. The sample was supported in a graphite electrode with crater of 5 mm. in diameter, 2,5 mm deep, and burned by a d.c. are in a direct reading spectrometer. The excitation of samples has been studied without dilution as well as using graphite powder as diluent in the ratios 1:1, 1:4, and 1:9; the latter factor was chosen. Ag, Ca, Co, Cr, Mo and Sn were tested as internal standards. It has not been found any significant inter element effect. It is necessary to use natural fluorite as base material for the standards. (Author) 5 refs.

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

International Nuclear Information System (INIS)

Hinatsu, Yukio; Doi, Yoshihiro

2013-01-01

Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr 3 OsO 7 exhibits magnetic transitions at 8 and 73 K, and Tb 3 OsO 7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln 3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr 3 OsO 7 exhibits magnetic transitions at 8 and 73 K, and Tb 3 OsO 7 magnetically orders at 8 and 60 K. Highlights: ► Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. ► Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). ► These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

Thermal expansion studies on uranium-neodymium mixed oxide solid solutions

International Nuclear Information System (INIS)

Panneerselvam, G.; Venkata Krishnan, R.; Antony, M.P.; Nagarajan, K.

2012-01-01

Uranium-Neodymium mixed oxides solid solutions (U 1-y Nd y ) O 2 (y=0.2-0.95) were prepared by combustion synthesis using citric acid as fuel. Structural characterization and computation of lattice parameter was carried out from room temperature X-ray diffraction measurements. Single-phase fluorite structure was observed up to y=0.80. For solid solutions with y>0.80 additional Nd 2 O 3 lines were visible

Electron paramagnetic resonance and neutron activation study of lanthanide ions behaviour in fluorite. Application to the geochemical study of Montroc and Burc veins (Tarn)

International Nuclear Information System (INIS)

Meary, Alain

1983-01-01

In order to obtain a better understanding of fluorite deposits, rare earth impurities have been analyzed for a large number of samples taken from cross-sections of several low temperature hydrothermal veins; two types of measurements have been used: Electron Paramagnetic Resonance (EPR) and Neutron Activation Analysis (NAA). This enabled us to measure a 'deficit of spins' relative to the total lanthanide concentration, this deficit reveals that the paramagnetic center observed by EPR is not the only mode of incorporation. For Gd no marked deficit is observed; that is the ratio of spin concentrations to total concentration [Gd 3+ ]/[Gd total ] is close to 1 in all the samples; on the other hand, the ratios [Eu 2+ ]/[Eu total ], [Ce 3- F i - ]/[Ce total ], and [Yb 3+ ]/ [Yb total ] exhibit large variations. The first result suggests that the major part of the lanthanides in the samples is incorporated in the crystal lattice and that clustering of lanthanides ions is not important. Deficit of spins observed for Ce and Nd are probably due to the dissociation of paramagnetic complexes Ce 3+ -F i - and Nd 3+ -F i - ; for Eu, it may be attributed to the oxidized state Eu 3+ . Moreover, the sign and the amplitude of the anomaly exhibited by Eu in the normalized lanthanides spectra may be correlated with the majority valence state of Eu in the crystal: a marked positive anomaly belongs to a deficit of paramagnetic divalent Eu and, inversely, if divalent Eu is the majority valence state, the Eu anomaly appears to be negative. The results obtained for the Montroc vein are consistent with a model involving discontinuous injections of hydrothermal solutions. They may be connected to variations of oxygen fugacity arising from cooling of these solutions and from precipitation of sulfides during fluorite precipitation. (author) [fr

Effect of electronegativity on the mechanical properties of metal hydrides with a fluorite structure

International Nuclear Information System (INIS)

Ito, Masato; Setoyama, Daigo; Matsunaga, Junji; Muta, Hiroaki; Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

2006-01-01

Bulk titanium, yttrium, and zirconium hydrides, which have the same structure as that of fluorite-type fcc C 1, were produced and their mechanical properties were investigated. With an increase in the hydrogen content, the lattice parameters of titanium and zirconium hydrides increased, whereas those of yttrium hydride decreased. The elastic moduli of titanium and zirconium hydrides decreased by hydrogen addition, whereas those of yttrium hydride increased. There are linear relations between the electronegativities and hydrogen content dependence of the properties. Therefore, the mechanical properties of the metal hydrides are considered to be determined by a common rule based on the electronegativity

Study of genesis in Qahr-Abad fluorite deposit using fluid inclusion, southeast of Saqqez, the Kurdistan province

Directory of Open Access Journals (Sweden)

Mehrdad Barati

2017-07-01

Full Text Available Introduction The Qahr-abad fluorite deposit is located in the area of 36°10′ 3′′ N and 46°34′ 21′′E within the Sanandaj-Sirjan district east of the Kurdistan province , Iran and it is located ~57 km southeast of the city of Saqqez (Kholghi Khasraghi, 1999. This deposit is developed as scatter lenses, veins, and veinlets (stockwork structure within carbonate rocks of Elika formation and controlled by the regional NW–SE trending Zagross thrust nappe system. Fault trends in this area are perpendicular to fault trends in the Zagros zone. The fault dips are nearly vertical and mineralization has occurred in the brecciation fault zone (Talaii, 2010. The rough geological instruction of the deposit has indicated that it is similar to worldwide Epithermal deposits. The mineralization occurs as replacement (type I/ open-space (type II vein fillings and bodies within Mesozoic lime stones (mostly Upper Triassic and Lower Jurassic members of the Elika Formation, where they crop out to form horst structures. The mineralization is typically associated with post Pliocene disjunctive faults, which in part appear to have served as channel ways for the fluorite forming fluids that are representative of the geological setting of the mineralized area. Fluorite occurs in several color variations such as green, violet, blue, white or colorless, and is accompanied by quartz, barite and calcite (Moslehi, 2013. Materials and methods The minerals sampled for the fluid inclusion study include fluorite from mineralization stages. Samples covered all ore types. Micro thermometry analyses for 23 samples were performed after careful microscopic observation of 35 sections and 30 doubly polished sections. Micro thermometry was undertaken using a Linkam THS600 heating-freezing stage, with a measurable temperature range of between −196 and +600 °C (precision of freezing data and homogenization temperature of ±0.2 °C. Micro thermometry was undertaken in the

The ionic conductivity and defect structure of fluorite-type solid solutions Basub(1-x)Usub(x)Fsub(2+2x)

International Nuclear Information System (INIS)

Ouwerkerk, M.

1986-01-01

The crystal growth and the characterization of the solid solutions Msub(1-x)Usub(x)Fsub(2+2x) (M = Ca, Sr, Ba and Pb) are described. X-ray diffraction and X-ray fluorescence methods have been utilized to determine the U 4+ content of the solid solutions. The incorporation of UF 4 in PbF 2 is found to have a stabilizing effect on the β-PbF 2 (fluorite) structure. A study of the conductivity properties of Basub(1-x)Usub(x)Fsub(2+2x) and of Pbsub(1-x)Usub(x)Fsub(2+2x) is presented. The effect of an anion excess on the diffuse phase transition and the specific heat anomaly of single crystals Msub(1-x)Usub(x)Fsub(2+2x) was studied with impedance spectroscopy and calorimetric measurements. Finally, a study of the fluorite-type solid solutions Basub(1-x)Lasub(x)Fsub(2+x) and Basub(1-x)Usub(x)Fsub(2+2x) using the Thermally Stimulated Depolarization Current (TSDC) technique is presented. (Auth.)

Dislocation motion and high temperature plasticity of binary and ternary oxides

International Nuclear Information System (INIS)

Bretheau, T.; Castaing, J.; Rabier, J.; Veyssiere, P.

1979-01-01

Literature dealing with the plasticity of single crystal oxides deformed at elevated temperatures and the associated mobility of dislocations is reviewed. The experimental approach to the subject is examined critically by selecting oxides and deforming samples and by studying their specific mechanical behaviour, characterizing the deformation substructures and modelling the rate controlling processes. Since oxides with the simple rocksalt structure (Mg0, Ni0, Co0, Fe0,...) are not representative of all oxides, examples of other structures are also examined in detail, including Ti0 2 and Cu 2 0 oxides with fluorite (Zr0 2 , U0 2 ), with corundum (A1 2 0 3 ) and with spinel (MgA1 2 0 4 ternary) structures. Occasionally work on more exotic compounds like Y 2 0 3 or some with the garnet structure is included. (UK)

Electronic structures of (Pb sub 2 Cu)Sr sub 2 Eu sub x Ce sub n sub - sub x Cu sub 2 O sub 2 sub n sub + sub 6 (n=2, 3): Effect of fluorite blocks between adjacent CuO sub 2 layers

CERN Document Server

Arai, M

2003-01-01

The electronic structures of (Pb sub 2 Cu)Sr sub 2 Eu sub x Ce sub n sub - sub x Cu sub 2 O sub 2 sub n sub + sub 6 (n = 2, 3) compounds which have fluorite blocks between two adjacent CuO sub 2 layers have been studied by using ab-initio method. It is found that the anisotropy is enhanced by inserting the fluorite blocks. The Fermi velocity perpendicular to the CuO sub 2 layers decreases as the thickness of fluorite blocks increases. The Eu substitution is found to affect both the atomic positions and electronic structures. The distance between apical oxygen and copper becomes shorter by the Eu substitution. The energy bands derived from oxygens in the fluorite blocks approach Fermi energy as the content of Eu substitution increases. (author)

Determination of enrichment processes and radon concentration in underground mines of fluorite and coal in Santa Catarina state: criteria for radiation risk assessment

International Nuclear Information System (INIS)

Santos, Carlos Eduardo Lima dos

2008-01-01

The inhalation of radon present in underground mines can imply in the deposition of its descendants in the lungs, which may cause harm to the lungs tissues and induce cancer. Concentration of radon not greater than 500 Bq/m 3 in the environment of underground mines is considered to be acceptable internationally and concentrations above 1500 Bq/m 3 require protective measures for the miners. The objectives of this research work are to determine the enrichment processes and the concentrations of radon in air, as well as the resulting doses due to the presence of this radionuclide in three underground mines of fluorite and three underground mines of coal in the State of Santa Catarina. The concentration of radon was measured employing two types of detectors of nuclear tracks (SSNTD), the LEXAN and the CR-39. This detection method consists in counting, with the help of a microscope, tracks resulting from the interaction of alpha particles with the film, due to the penetration of Rn-222 in the interior of the detector chamber and its decaying process. Contents of radium in collected samples of rocks, minerals and underground water were determined and compared with the corresponding radon concentration found in the underground air. It was observed that the coal mines showed low concentrations of radon, which can be explained by the low concentration of radium in rocks (sandstones and siltites in the foot wall and hang wall) and in the coal that composes the mining environment or, yet still, due to the good ventilation system. The average dose to the workers of the coal mines was estimated as 0.7 mSv/a, value inferior to the limit of 1 mSv/a established by the Brazilian Nuclear Energy Commission (CNEN) for members of the public, and corresponding to a risk of fatal cancer after 50 years of work under this condition of 0.2%. On the other hand, the fluorite mines showed much higher concentrations of radon and superior to 1000 Bq/m 3 . The inefficiency of the ventilation

Thermal and chemical variations of the Nigerian Benue trough lead-zinc-barite-fluorite deposits

Science.gov (United States)

Ogundipe, Ibukun Emmanuel

2017-08-01

The Benue trough is an intra-continental rift initiated in the Cretaceous during the opening of the South Atlantic Ocean. Lead-zinc-barite-fluorite mineralization occurs along the 600 km axis of the trough in three discrete sub-basins which coincide with the lower, middle and upper mineral districts of the Benue Valley. Lithologically these sub-basins are dominated by black carbonaceous shale in the Lower Benue, platform carbonates in the Middle Benue and sandstones in the Upper Benue. Micro-thermometric analysis of fluid inclusions in sphalerite, fluorite, barite and quartz have shown that each mineral district has its own unique thermal and chemical imprint. For example, the temperature can be bracketed between 109 °C and 160 °C for lower Benue, 89 °C-144 °C for the Middle Benue and 176 °C-254 °C for the Upper Benue. Chemical differentiation also exists between each mineral district with the Lower Benue having 22 wt % equivalent NaCl while the Middle and Upper Benue have 18 and 16 wt % equivalent NaCl respectively. This study shows that inter-district thermal and chemical variations exist between the ore-stage sulfide and post-sulfide gangue minerals of the entire Benue Valley. Similarly, intra-district thermal and chemical variations have also been observed among all the paragenetic minerals of each district. The thermal variations may be as a result of variations in the geothermal gradient accompanying continental rifting from one district to the other. The variations in the chemistry between the Lower Benue and the Upper Benue paragenic minerals may be as a result of the distinct lithological differences across the Benue Trough.

Amphoteric oxide semiconductors for energy conversion devices: a tutorial review.

Science.gov (United States)

Singh, Kalpana; Nowotny, Janusz; Thangadurai, Venkataraman

2013-03-07

In this tutorial review, we discuss the defect chemistry of selected amphoteric oxide semiconductors in conjunction with their significant impact on the development of renewable and sustainable solid state energy conversion devices. The effect of electronic defect disorders in semiconductors appears to control the overall performance of several solid-state ionic devices that include oxide ion conducting solid oxide fuel cells (O-SOFCs), proton conducting solid oxide fuel cells (H-SOFCs), batteries, solar cells, and chemical (gas) sensors. Thus, the present study aims to assess the advances made in typical n- and p-type metal oxide semiconductors with respect to their use in ionic devices. The present paper briefly outlines the key challenges in the development of n- and p-type materials for various applications and also tries to present the state-of-the-art of defect disorders in technologically related semiconductors such as TiO(2), and perovskite-like and fluorite-type structure metal oxides.

Phase transition of the orthorhombic fluorite-related compounds Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, Eu)

Energy Technology Data Exchange (ETDEWEB)

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.j [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doi, Yoshihiro; Nishimine, Hiroaki; Wakeshima, Makoto [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Sato, Mineo [Department of Chemistry and Chemical Engineering, Faculty of Engineering, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181 (Japan)

2009-12-04

Rare earth iridium oxides Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, and Eu) were prepared and their structures were determined by X-ray diffraction measurements. At room temperature, Pr{sub 3}IrO{sub 7} crystallized in an orthorhombic superstructure of cubic fluorite with space group Cmcm. The differential thermal analysis (DTA) and specific heat measurements for Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, and Eu) showed a phase transition at 262, 342, 420, and 485 K, respectively. At low temperatures, Ln{sub 3}IrO{sub 7} crystallized in a monoclinic structure with the space group P2{sub 1}/n. The transition temperatures increased with decreasing the ionic radius of rare earths, which indicates that the transition is stress-induced and occurs with the lattice contraction on cooling. These results for Ln{sub 3}IrO{sub 7} were compared with the phase transitions observed for Ln{sub 3}MoO{sub 7}, Ln{sub 3}RuO{sub 7}, Ln{sub 3}ReO{sub 7}, and Ln{sub 3}OsO{sub 7}.

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb)

Energy Technology Data Exchange (ETDEWEB)

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doi, Yoshihiro [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan)

2013-02-15

Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln{sup 3+} sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. Highlights: Black-Right-Pointing-Pointer Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. Black-Right-Pointing-Pointer Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). Black-Right-Pointing-Pointer These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

Deposition and characterisation of epitaxial oxide thin films for SOFCs

KAUST Repository

Santiso, José

2010-10-24

This paper reviews the recent advances in the use of thin films, mostly epitaxial, for fundamental studies of materials for solid oxide fuel cell (SOFC) applications. These studies include the influence of film microstructure, crystal orientation and strain in oxide ionic conducting materials used as electrolytes, such as fluorites, and in mixed ionic and electronic conducting materials used as electrodes, typically oxides with perovskite or perovskite-related layered structures. The recent effort towards the enhancement of the electrochemical performance of SOFC materials through the deposition of artificial film heterostructures is also presented. These thin films have been engineered at a nanoscale level, such as the case of epitaxial multilayers or nanocomposite cermet materials. The recent progress in the implementation of thin films in SOFC devices is also reported. © 2010 Springer-Verlag.

Key insights on the structural characterization of textured Er2O3–ZrO2 nano-oxides prepared by a surfactant-free solvothermal route

International Nuclear Information System (INIS)

Julián-López, Beatriz; Luz, Verónica de la; Gonell, Francisco; Cordoncillo, Eloisa; López-Haro, Miguel; Calvino, Jose J.; Escribano, Purificación

2012-01-01

Highlights: ► Structural resolution of fluorite vs. pyrochlore in small nanocrystals. ► Simple template-free solvothermal synthesis of Er 2 O 3 –ZrO 2 nanooxides. ► Good control over size, morphology and surface properties (280 m 2 g −1 ). - Abstract: Zirconia-mixed oxides can exhibit cubic fluorite and pyrochlore structure. Their discrimination is not easy in nanooxides with a crystal size close to that of a few unit cells. In this work, high resolution transmission electron microscopy (HRTEM) has been employed to provide key insights on the structural characterization of a nanometric and porous mixed Er 2 O 3 –ZrO 2 oxide. The material was prepared by a simple template-free solvothermal route that provided nanocrystalline powders at low temperature (170 °C) with spherical morphology, and high surface area (∼280 m 2 g −1 ). The porosity was mainly originated from the assembling of organic complexing agents used in the synthesis to limit the crystal growth and to control hydrolysis and condensation reaction rates. The samples were characterized by thermal analysis, X-ray diffraction, scanning electron microscopy and N 2 adsorption measurements. A detailed study by HRTEM was conducted on microtomed samples. It was observed that the material was made of nanocrystals packed into spherical agglomerates. HRTEM simulations indicated that it is not possible to identify the pyrochlore phase in nanoparticles with diameter below 2 nm. In our samples, the analysis of the HRTEM lattice images by means of fast Fourier transform (FFT) techniques revealed well defined spots that can be assigned to different planes of a cubic fluorite-type phase, even in the raw material. Raman spectroscopy was also a powerful technique to elucidate the crystalline phase of the materials with the smallest nanoparticles. HREM and Raman results evidenced that the material is constituted, irrespective of the temperature of the final calcination step, by an ensemble of randomly

Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Véronique Pitchon

2012-02-01

Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

Key insights on the structural characterization of textured Er{sub 2}O{sub 3}-ZrO{sub 2} nano-oxides prepared by a surfactant-free solvothermal route

Energy Technology Data Exchange (ETDEWEB)

Julian-Lopez, Beatriz, E-mail: julian@qio.uji.es [Departamento de Quimica Inorganica y Organica, Universitat Jaume I, Avda. Vicente Sos Baynat s/n, 12071 Castellon (Spain); Luz, Veronica de la; Gonell, Francisco; Cordoncillo, Eloisa [Departamento de Quimica Inorganica y Organica, Universitat Jaume I, Avda. Vicente Sos Baynat s/n, 12071 Castellon (Spain); Lopez-Haro, Miguel; Calvino, Jose J. [Departamento de Ciencia de los Materiales e Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Campus Rio San Pedro, Puerto Real, 11510 Cadiz (Spain); Escribano, Purificacion [Departamento de Quimica Inorganica y Organica, Universitat Jaume I, Avda. Vicente Sos Baynat s/n, 12071 Castellon (Spain)

2012-04-05

Highlights: Black-Right-Pointing-Pointer Structural resolution of fluorite vs. pyrochlore in small nanocrystals. Black-Right-Pointing-Pointer Simple template-free solvothermal synthesis of Er{sub 2}O{sub 3}-ZrO{sub 2} nanooxides. Black-Right-Pointing-Pointer Good control over size, morphology and surface properties (280 m{sup 2} g{sup -1}). - Abstract: Zirconia-mixed oxides can exhibit cubic fluorite and pyrochlore structure. Their discrimination is not easy in nanooxides with a crystal size close to that of a few unit cells. In this work, high resolution transmission electron microscopy (HRTEM) has been employed to provide key insights on the structural characterization of a nanometric and porous mixed Er{sub 2}O{sub 3}-ZrO{sub 2} oxide. The material was prepared by a simple template-free solvothermal route that provided nanocrystalline powders at low temperature (170 Degree-Sign C) with spherical morphology, and high surface area ({approx}280 m{sup 2} g{sup -1}). The porosity was mainly originated from the assembling of organic complexing agents used in the synthesis to limit the crystal growth and to control hydrolysis and condensation reaction rates. The samples were characterized by thermal analysis, X-ray diffraction, scanning electron microscopy and N{sub 2} adsorption measurements. A detailed study by HRTEM was conducted on microtomed samples. It was observed that the material was made of nanocrystals packed into spherical agglomerates. HRTEM simulations indicated that it is not possible to identify the pyrochlore phase in nanoparticles with diameter below 2 nm. In our samples, the analysis of the HRTEM lattice images by means of fast Fourier transform (FFT) techniques revealed well defined spots that can be assigned to different planes of a cubic fluorite-type phase, even in the raw material. Raman spectroscopy was also a powerful technique to elucidate the crystalline phase of the materials with the smallest nanoparticles. HREM and Raman results evidenced

Determination of enrichment processes and the concentrations of radon in underground mines of fluorite and coal in Santa Catarina state: criteria for evaluation of radiological risks

International Nuclear Information System (INIS)

Santos, Carlos Eduardo Lima dos

2008-01-01

The inhalation of radon present in underground mines can imply in the deposition of its descendent in the lungs, which may cause harm to the lungs tissues and induce cancer. Concentration of radon not greater than 500 Bq/m3 in the environment of underground mines is considered to be acceptable internationally and concentrations above 1500 Bq/m3 require protective measures for the miners. The objectives of this research work are to determine the enrichment processes and the concentrations of radon in air, as well as the resulting doses due to the presence of this radionuclide in three underground mines of fluorite and three underground mines of coal in the State of Santa Catarina. The concentration of radon was measured employing two types of detectors of nuclear tracks (SSNTD), the LEXAN and the CR-39. This detection method consists in counting, with the help of a microscope, tracks resulting from the interaction of alpha particles with the film, due to the penetration of Rn-222 in the interior of the detector chamber and its decaying process. Contents of radium in collected samples of rocks, minerals and underground water were determined and compared with the corresponding radon concentration found in the underground air. It was observed that the coal mines showed low concentrations of radon, which can be explained by the low concentration of radium in rocks (sandstones and siltites in the footwall and hang wall) and in the coal that composes the mining environment or, yet still, due to the good ventilation system. The average dose to the workers of the coal mines was estimated as 0.7 mSv/a, value inferior to the limit of 1 mSv/a established by the Brazilian Nuclear Energy Commission (CNEN) for members of the public, and corresponding to a risk of fatal cancer after 50 years of work under this condition of 0.2%. On the other hand, the fluorite mines showed much higher concentrations of radon and superior to 1000 Bq/m3. The inefficiency of the ventilation system

Energetics and Defect Interactions of Complex Oxides for Energy Applications

Science.gov (United States)

Solomon, Jonathan Michael

The goal of this dissertation is to employ computational methods to gain greater insights into the energetics and defect interactions of complex oxides that are relevant for today's energy challenges. To achieve this goal, the development of novel computational methodologies are required to handle complex systems, including systems containing nearly 650 ions and systems with tens of thousands of possible atomic configurations. The systems that are investigated in this dissertation are aliovalently doped lanthanum orthophosphate (LaPO4) due to its potential application as a proton conducting electrolyte for intermediate temperature fuel cells, and aliovalently doped uranium dioxide (UO2) due to its importance in nuclear fuel performance and disposal. First we undertake density-functional-theory (DFT) calculations on the relative energetics of pyrophosphate defects and protons in LaPO4, including their binding with divalent dopant cations. In particular, for supercell calculations with 1.85 mol% Sr doping, we investigate the dopant-binding energies for pyrophosphate defects to be 0.37 eV, which is comparable to the value of 0.34 eV calculated for proton-dopant binding energies in the same system. These results establish that dopant-defect interactions further stabilize proton incorporation, with the hydration enthalpies when the dopants are nearest and furthest from the protons and pyrophosphate defects being -1.66 eV and -1.37 eV, respectively. Even though our calculations show that dopant binding enhances the enthalpic favorability of proton incorporation, they also suggest that such binding is likely to substantially lower the kinetic rate of hydrolysis of pyrophosphate defects. We then shift our focus to solid solutions of fluorite-structured UO 2 with trivalent rare earth fission product cations (M3+=Y, La) using a combination of ionic pair potential and DFT based methods. Calculated enthalpies of formation with respect to constituent oxides show higher

Structure and activity of tellurium-cerium oxide acrylonitrile catalysts

International Nuclear Information System (INIS)

Bart, J.C.J.; Giordano, N.

1982-01-01

Ammoxidation of propylene to acrylonitrile (ACN) was investigated over various silica-supported (Te,Ce)O catalysts at 360 and 440 0 C. The binary oxide system used consists of a single nonstoichiometric fluorite-type phase α-(Ce,Te)O 2 up to about 80 mole% TeO 2 and a tellurium-saturated solid solution β-(Ce,Te)O 2 at higher tellurium concentrations. The ACN yield varies almost linearly with the tellurium content of (Ce,Te)O 2 . The β-(Ce,Te)O 2 phase is the most active component of the system (propylene conversion and ACN selectivity at 440 C of 76.7 and 74%, respectively) and is slightly more selective to ACN than α-Te0 2 . Tellurium reduces the overoxidation properties of cerium and selective oxidation occurs through Te(IV)-bonded oxygen

Synthesis and characterization of new oxides and oxynitrides of niobium; Synthese und Charakterisierung neuer Oxide und Oxidnitride des Niobs

Energy Technology Data Exchange (ETDEWEB)

Orthmann, Steven

2017-11-02

By different synthesis routes the first oxide nitrides in the series scandium-niobium-oxygen-nitrogen could be synthesized and characterized. ScNb{sub 4}O{sub 7}N{sub 3}, which crystallizes in the rutile-type structure, exhibit a band gap of 2.62 eV after a short oxidation. Furthermore anion-deficit NbSc{sub 2}(O,N,□){sub 6} with fluorite-type structure could be synthesized. UV-Vis measurements point to a band gap of 3.36 eV after a short oxidation of the product. In the series zirconium-niobium-oxygen-nitrogen new oxides and oxide nitrides could be synthesized. By replacing zirconium with hafnium isotopical compounds with comparable composition could be obtained. The crystal structure of these new compounds is discussed respecting magnetism and the results of electron microscopy and neutron diffraction. By partially substitution of niobium with magnesium or zinc three additional oxide nitrides with the compositions Mg{sub 2}Nb{sub 4}O{sub 2}N{sub 5}, Zn{sub 2}NbO{sub 0,3}N{sub 2,8}, and ZnNb{sub 3}O{sub 0,1}N{sub 4,5}, showing a tetragonal Nb{sub 4}N{sub 5}-type structure, could be synthesized.

Solid state chemistry of rare earth oxides. Final report, September 1, 1950--July 31, 1977

International Nuclear Information System (INIS)

Eyring, L.

1977-07-01

Work under Contract E(11-1)-1109 and its antecedents has been primarily for the purpose of obtaining detailed thermodynamic, kinetic and structural information on the complex rare earth oxides of praseodymium and terbium. These systems exhibit homologous series of ordered phases, order-disorder transformations, wide-range nonstoichiometric phases, chemical hysteresis in two-phase regions and many other solid state reaction phenomena. Fluorite-related materials of importance to ERDA occur as nuclear fuels, radiation power sources, insulators and solid electrolytes. The rare earth oxides serve directly as model systems for such similar materials and, in a more general sense, they serve as models of solids in general since they exhibit nearly the full range of solid state properties

Topotactic oxidative and reductive control of the structures and properties of layered manganese oxychalcogenides.

Science.gov (United States)

Hyett, Geoffrey; Barrier, Nicolas; Clarke, Simon J; Hadermann, Joke

2007-09-12

Topotactic modification, by both oxidation and reduction, of the composition, structures, and magnetic properties of the layered oxychalcogenides Sr4Mn3O7.5Cu2Ch2 (Ch=S, Se) is described. These Mn3+ compounds are composed of alternating perovskite-type strontium manganese oxide slabs separated by anti-fluorite-type copper chalcogenide layers and are intrinsically oxide deficient in the central layer of the perovskite slabs. The systems are unusual examples of perovskite-related compounds that may topotactically be both oxidized by fluorination and reduced by deintercalation of oxygen from the oxide-deficient part of the structure. The compounds exhibit antiferromagnetic ordering of the manganese magnetic moments in the outer layers of the perovskite slabs, while the other moments, in the central layers, exhibit spin-glass-like behavior. Fluorination has the effect of increasing the antiferromagnetic ordering temperature and the size of the ordered moment, whereas reduction destroys magnetic long-range order by introducing chemical disorder which leads to both further disorder and frustration of the magnetic interactions in the manganese oxide slab.

Oxide-ion and proton conducting electrolyte materials for clean energy applications: structural and mechanistic features.

Science.gov (United States)

Malavasi, Lorenzo; Fisher, Craig A J; Islam, M Saiful

2010-11-01

This critical review presents an overview of the various classes of oxide materials exhibiting fast oxide-ion or proton conductivity for use as solid electrolytes in clean energy applications such as solid oxide fuel cells. Emphasis is placed on the relationship between structural and mechanistic features of the crystalline materials and their ion conduction properties. After describing well-established classes such as fluorite- and perovskite-based oxides, new materials and structure-types are presented. These include a variety of molybdate, gallate, apatite silicate/germanate and niobate systems, many of which contain flexible structural networks, and exhibit different defect properties and transport mechanisms to the conventional materials. It is concluded that the rich chemistry of these important systems provides diverse possibilities for developing superior ionic conductors for use as solid electrolytes in fuel cells and related applications. In most cases, a greater atomic-level understanding of the structures, defects and conduction mechanisms is achieved through a combination of experimental and computational techniques (217 references).

Nuclear magnetic resonance in superionic conductors with fluorite-type structure; Ressonancia magnetica nuclear em condutores superionicos de estrutura fluorita

Energy Technology Data Exchange (ETDEWEB)

Souto, Sergio Paulo Amaral

1991-12-31

The {sup 19} F NMR relaxation times T{sub 1} and T{sub 2} were measured in ternary and nonstoichiometric compounds with the fluorite-type structure. We have studied the Na{sub 0-4} Y{sub 0-6} F{sub 2-2} crystal in the temperature range 600 K to 900 K, where the crystal has not the fluorite structure. The T{sub 1} values were measured in 2 Larmor frequencies: 20.42 MHz and 34.24 MHz. The results for T{sub 1} were seem to be qualitatively similar to those measured in the system with two inequivalent sublattices. The T{sub 2} measurements, in the Pb{sub O84} Bi{sub 0-16} F{sub 2-16} crystal, were made during temperature cycles in the range of 300 K to 830 K. The difference in activation energy between cooling and heating half cycles, found to be approximately 0.08 eV, appear to be associated with the change in the clusters structure and not to the energy of defect formation. Finally, similar T{sub 2} measurements during temperature cycling was made in K{sub 0-4} Bi{sub 0-6} F{sub 2-2} : 2% Pb F{sub 2} crystal, in the temperature range 300 K to 800 K, but in this case no difference in the cooling and heating results was observed. We also measured, in the same temperature range, the T{sub 1} relaxation time in 3 Larmor frequencies: 11.71 MHz, 20.42 MHz and 34.24 Mhz. This results appear to indicate the existence of two hopping mechanism. (author). 132 refs., 68 figs.

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

Science.gov (United States)

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

2013-12-16

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

Characterization of composite metal-ceramic of nickel-oxide cerium doped gadolinium

International Nuclear Information System (INIS)

Silva, M.L.A. da; Varela, M.C.R.S.

2016-01-01

Composite nickel doped cerium oxide are used in SOFC anode materials. In this study we evaluated the effect of the presence of gadolinium on the properties of composite nickel and ceria and. The supports were synthesized by sol-gel method. The impregnation with nickel nitrate was taken sequentially, followed by calcination. The materials were characterized by X-ray diffraction, measurement of specific surface area, temperature programmed reduction, Raman spectroscopy. The presence of gadolinium retained the fluorite structure of ceria by forming a solid solution, also not influencing significantly on the specific surface area of the support. On the other hand, there was a decrease in the area catalysts, which can be attributed to sintering of nickel. Furthermore, addition of gadolinium favored the formation of intrinsic and extrinsic vacancies in cerium oxide, which leads to an increase in the ionic conductivity of the solid, desirable property for an SOFC anode catalyst. (author)

A study of a ceria-zirconia-supported manganese oxide catalyst for combustion of Diesel soot particles

Energy Technology Data Exchange (ETDEWEB)

Sanchez Escribano, V.; Fernandez Lopez, E.; del Hoyo Martinez, C. [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Pa. de la Merced s/n, E-37008 Salamanca (Spain); Gallardo-Amores, J.M. [Lab. Complutense de Altas Presiones, Departamento de Quimica Inorganica I, Universidad Complutense, Ciudad Universitaria, E-28040 Madrid (Spain); Pistarino, C.; Panizza, M.; Resini, C.; Busca, G. [Dipartimento di Ingegneria Chimica e di Processo, Universita di Genova, P.le J.F. Kennedy, Pad. D, I-16129 Genoa (Italy)

2008-04-15

A study has been conducted on the structural and morphological characterization of a Ce-Zr mixed oxide-supported Mn oxide as well as on its catalytic activity in the oxidation of particulate matter arising from Diesel engines. X-ray powder diffraction analysis (XRD) and FT-IR and FT-Raman spectroscopy evidence that the support is a fluorite-like ceria-zirconia solid solution, whereas the supported phase corresponds to the manganese oxide denoted as bixbyite ({alpha}-Mn{sub 2}O{sub 3}). Thermal analyses and FT-IR spectra in air at varying temperatures of soot mechanically mixed with the catalyst evidence that the combustion takes place to a total extent in the range 420-720 K, carboxylic species being detected as intermediate compounds. Moreover, the soot oxidation was studied in a flow reactor and was found to be selective to CO{sub 2}, with CO as by-product in the range 420-620 K. The amount of the generated CO decreases significantly with increasing O{sub 2} concentration in the feed. (author)

General description of new equipment 'Fluorite-III' for Bor-Oendoer fluorate factory

International Nuclear Information System (INIS)

Bayar, V.; Basankhueue, O.; Ganzorig, J.; Dushan, P.; Lodoisamba, S.; Otgooloi, B.; Tsehlmehg, A.; Shagjjamba, D.

1992-01-01

A new equipment 'Fluorite-III' is described which is used to register and analyze three kinds of following informations: 1. Pulse count for determination of ore's concentration which is transferring by the factory conveyor. 2. Pulse count for determination of ore's thickness which is transferring also by the factory conveyor. 3. Information about that: Is the conveyor moving or not during our measurements. First and second kinds of information are registered by two detectors which is established on the different places from the factory conveyor. Constraction of these detectors are the same. Every one of them consists of a ''photo multiplier tube'' and a scintillator of ''sodium-iodine''. The third information is corresponding to the ''transistor and transistical logic'' level. Every counters data and the information about the conveyor should be transferred every time to the computer which is compatible with the IBM/PC for further treatment through the following devices: 1. Three State Buffer which is made from ''Generic Array Logic'' device. 2. Universal Asynchronous Receiver and Transmitter (UART) which is of type (AY 3-1015). 3. 20 milli-ampere current interface with optical isolators. Also in this way but in reverse order by these devices we can control all processes of the measurements from the computer. 1 fig

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

Science.gov (United States)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

Science.gov (United States)

Hinatsu, Yukio; Doi, Yoshihiro

2013-02-01

Ternary rare-earth osmates Ln3OsO7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr3OsO7 exhibits magnetic transitions at 8 and 73 K, and Tb3OsO7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice.

Lanthanum gallate and ceria composite as electrolyte for solid oxide fuel cells

International Nuclear Information System (INIS)

Li Shuai; Li Zhicheng; Bergman, Bill

2010-01-01

The composite of doped lanthanum gallate (La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 , LSGM) and doped ceria (Ce 0.8 Sm 0.2 O 1.9 , CSO) was investigated as an electrolyte for solid oxide fuel cell (SOFC). The LSGM-CSO composite was examined by X-ray diffraction (XRD) and impedance spectroscopy. It was found that the sintered LSGM-CSO composite contains mainly fluorite CeO 2 phase and a minority impurity phase, Sm 3 Ga 5 O 12 . The LSGM-CSO composite electrolyte shows a small grain boundary response in the impedance spectroscopy as compared to LSGM and CSO pellets. The composite electrolyte exhibits the highest conductivity in the temperature range of 250-600 o C, compared to LSGM and CSO. The LSGM-CSO composite can be expected to be an attractive intermediate temperature electrolyte material for solid oxide fuel cells.

Accelerator-based analytical technique in the evaluation of some Nigeria's natural minerals: Fluorite, tourmaline and topaz

Energy Technology Data Exchange (ETDEWEB)

Olabanji, S.O. [Istituto Nazionale di Fisica Nucleare (INFN), Laboratori Nazionali di Legnaro (LNL), viale dell' Universita 2, 35020 Legnaro, Padova (Italy)]. E-mail: skayode2002@yahoo.co.uk; Ige, O.A. [Natural History Museum, Obafemi Awolowo University, Ile-Ife (Nigeria); Mazzoli, C. [Dipartimento di Mineralogia e Petrologia, Universita di Padova, 35100 Padova (Italy); Ceccato, D. [Istituto Nazionale di Fisica Nucleare (INFN), Laboratori Nazionali di Legnaro (LNL), viale dell' Universita 2, 35020 Legnaro, Padova (Italy); Dipartimento di Fisica, Universita di Padova, via Marzolo 8, 35100 Padova (Italy); Akintunde, J.A. [CERD, Obafemi Awolowo University, Ile-Ife (Nigeria); De Poli, M. [Istituto Nazionale di Fisica Nucleare (INFN), Laboratori Nazionali di Legnaro (LNL), viale dell' Universita 2, 35020 Legnaro, Padova (Italy); Moschini, G. [Istituto Nazionale di Fisica Nucleare (INFN), Laboratori Nazionali di Legnaro (LNL), viale dell' Universita 2, 35020 Legnaro, Padova (Italy); Dipartimento di Fisica, Universita di Padova, via Marzolo 8, 35100 Padova (Italy)

2005-10-15

For the first time, the complementary accelerator-based analytical technique of PIXE and electron microprobe analysis (EMPA) were employed for the characterization of some Nigeria's natural minerals namely fluorite, tourmaline and topaz. These minerals occur in different areas in Nigeria. The minerals are mainly used as gemstones and for other scientific and technological applications and therefore are very important. There is need to characterize them to know the quality of these gemstones and update the geochemical data on them geared towards useful applications. PIXE analysis was carried out using the 1.8 MeV collimated proton beam from the 2.5 MV AN 2000 Van de Graaff accelerator at INFN, LNL, Legnaro, Padova, Italy. The novel results which show many elements at different concentrations in these minerals are presented and discussed.

Chemical solution route to self-assembled epitaxial oxide nanostructures.

Science.gov (United States)

Obradors, X; Puig, T; Gibert, M; Queraltó, A; Zabaleta, J; Mestres, N

2014-04-07

Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials.

Lanthanum gallate and ceria composite as electrolyte for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Li Shuai, E-mail: shuail@kth.s [Department of Materials Science and Engineering, School of Industrial Engineering and Management, Royal Institute of Technology, SE 10044 Stockholm (Sweden); Li Zhicheng [School of Materials Science and Engineering, Central South University, 410083 Changsha, Hunan (China); Bergman, Bill [Department of Materials Science and Engineering, School of Industrial Engineering and Management, Royal Institute of Technology, SE 10044 Stockholm (Sweden)

2010-03-04

The composite of doped lanthanum gallate (La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 2.85}, LSGM) and doped ceria (Ce{sub 0.8}Sm{sub 0.2}O{sub 1.9}, CSO) was investigated as an electrolyte for solid oxide fuel cell (SOFC). The LSGM-CSO composite was examined by X-ray diffraction (XRD) and impedance spectroscopy. It was found that the sintered LSGM-CSO composite contains mainly fluorite CeO{sub 2} phase and a minority impurity phase, Sm{sub 3}Ga{sub 5}O{sub 12}. The LSGM-CSO composite electrolyte shows a small grain boundary response in the impedance spectroscopy as compared to LSGM and CSO pellets. The composite electrolyte exhibits the highest conductivity in the temperature range of 250-600 {sup o}C, compared to LSGM and CSO. The LSGM-CSO composite can be expected to be an attractive intermediate temperature electrolyte material for solid oxide fuel cells.

Interacting Frenkel defects at high concentration and the superionic transition in fluorite crystals

International Nuclear Information System (INIS)

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

1980-11-01

A spherical cell model is proposed to account for the explicit concentration dependence of Frenkel defects in an ionic system. In the model, the linearized Debye-Hueckel equation is soluble exactly, subject to the boundary condition that the electric field is zero at the cell boundary R, related to the concentration α of defects by R proportional to csup(-1/3). This screened field is used to calculate the chemical potential, which in turn leads to a condition for the instability of the interacting defect assembly. This condition allows one to calculate the enhancement of the concentration of defects above its Arrhenius value at the point of instability in terms of (a) the critical concentration csub(c), (b) a/R, where a is the radius of defect and (c) the Debye-Hueckel screening length kappasub(c). It is clear from the cell model that this enhancement factor is reduced somewhat in the relevant range of parameters in some of the fluorites from its value in extended Debye-Hueckel theory. It is anticipated that the instability discussed here should afford an upper bound to csub(c) at the superionic transition, within the range of validity of the model. The excess he at capacity csub(p) is also discussed briefly. (author)

Preparation of catalysts based on Ce-Mn mixed oxide by coprecipitation for combustion of n-hexane

International Nuclear Information System (INIS)

Picasso, Gino; Zavala, Cesar; Cruz, Romulo; Sun Kou, Rosario; Lopez, Alcides

2013-01-01

Catalysts based on Ce-Mn mixed with different Ce/Mn molar ratios ranging from 0,5 to 2 have been prepared by coprecipitation at pH constant with ageing times of 4, 18 and 24 h for combustion of n-hexane. XRD patterns of the mixed oxides showed the majority presence of fluorite phase. Specific BET surface areas of mixed oxides were always higher than their single counterparts and their adsorption isotherm depicted a mesoporous surface of Type IV. TPR thermograms confirmed the presence of mixed oxide phase, whose profile shifted to smaller temperatures with increasing content of ceria. Catalytic tests were performed with 2000 ppm of n-hexane and WHSV of 80 h -1 in a fixed-bed reactor. For all samples, only CO 2 and water were observed at total conversion and no partial combustion products were obtained. Ce-Mn mixed oxides were more active than simple oxide samples no matter the aging time. Mixed samples presented thermal stability in contrast with simple ones. Mixed sample with Ce/Mn molar ratio of 2 depicted the highest activity probably due to higher surface area and better reducibility ability of mixed phase. (author)

Study On Beneficiation Technology Of Dong Pao Rare-Earth-Barite-Fluorite With Two Product Plans About Content And Recovery Of Rare-Earth Fine Ores

International Nuclear Information System (INIS)

Duong Van Su; Truong Thi Ai; Bui Ba Duy; Bui Thi Bay; Nguyen Hong Ha; Le Thi Hong Ha; Doan Thi Mo; Doan Dac Ban; Nguyen Hoang Son

2014-01-01

The ore sample used in the research was taken from the F3 ore bodies and the sample of the F7, F9 and F16 ore bodies which contain the average of 5.98% TR 2 O 3 ; they are multi-metals ore which is difficult to enrich, highly weather with very complex ingredients. The process of the experiment is the ore is crushed, ground, screened and classified reasonably to -0.1 mm and divided into 3 particle size with the following technique: (1) -0.020 mm is primary sludge and the rare-earth fine ore; (2) 0.075-1 mm is gotten through the sludge concentrating table with the output is the 2 parts: the heavy part which is dried magnetic separator with high magnetism to get the rare-earth fine ore and the light one; (3) Light minerals, non-magnetic and ferromagnetic minerals group are ground together to 85% of them get size within -0.075 mm then mix it with 0.020-0.075 mm group. Using flotation separator, get barite-rare earth mixture and fluorite. After that, we separate this mixture by secondary flotation and get refined rare earth, barite and fluorite mineral. The result of the theme: (1) product plan A-rare-earth fine ore has TR 2 O 3 content archive 42.07% with recovery is 69.70%; (2) product plan B-rare-earth fine ore has TR 2 O 3 content archive 29.64% with recovery is 80.01%. (author)

Synthesis, characterization and antibacterial activity of hybrid chitosan-cerium oxide nanoparticles: As a bionanomaterials.

Science.gov (United States)

Senthilkumar, R P; Bhuvaneshwari, V; Ranjithkumar, R; Sathiyavimal, S; Malayaman, V; Chandarshekar, B

2017-11-01

The hybrid chitosan cerium oxide nanoparticles were prepared for the first time by green chemistry approach using plant leaf extract. The intense peak observed around 292nm in the UV-vis spectrum indicate the formation of cerium oxide nanoparticles. The XRD pattern revealed that the hybrid chitosan-cerium oxide nanoparticles have a polycrystalline structure with cubic fluorite phase. The FTIR spectrum of prepared samples showed the formation of Ce-O bonds and chitosan main chains COC and CO. The FESEM image of hybrid chitosan cerium oxide nanoparticles revealed that the particles are spherical in shape with grains size varying from 23.12nm to 89.91nm. EDAX analysis confirmed the presence of Ce, O, C and N elements in the prepared sample. TEM images showed that the prepared hybrid chitosan-cerium oxide nanoparticles are predominantly uniform in size and most of the particles are spherical in shape with less agglomeration and the particles size varies from 3.61nm to 24.40nm. The prepared chitosan cerium oxide nanoparticles of 50μL concentration showed good antibacterial properties against test pathogens, which was confirmed by the FESEM analysis. The prepared small particle size facilitate that these hybrid ChiCO 2 NPs could effectively be used in biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Properties of complex tungstates, niobates, translated with fluorite-like structure. Svojstva slozhnykh vol'framatov, niobatov, tantalatov s flyuoritopodobnoj strukturoj

Energy Technology Data Exchange (ETDEWEB)

Vetkina, S N; Zolin, V F; Sirotinkin, V P; Smirnov, S A

1989-04-01

Spectra of ternary tungstates, niobates and tantalates (MeLa{sub 2}WO{sub 7}, La{sub 3}TO{sub 7}; Me=Ba, Sr; T=Ta, Nb) related to the layered fluorite group are analyzed. The laser pumping and time resolved luminescence are used for selecting spectra of unequivalent centers. The symmetry of the first center is near to the distorted cubic one. The vibrational spectra of europium in Eu{sub 3}NbO{sub 7} and SrLa{sub 2}WO{sub 7} are due to the chain-like structure of niobates and to the net-like structure of tantalates. The stimulated emission of Nd{sup 3+} in powders of BaLa{sub 2}WO{sub 7} and La{sub 3}NbO{sub 7} is observed at wavelengths of 1.07 and 1.063 {mu}m, respectively.

Grain-boundary oxidation of used CANDU fuel exposed to dry air at 150 degrees C for a prolonged period

International Nuclear Information System (INIS)

Hocking, W.H.; Behnke, R.; Duclos, A.M.

1995-01-01

The grain-boundary chemistry of used CANDU fuel exposed to dry air at 150 degrees C for a prolonged period has been investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). High degrees of surface oxidation have been determined using the chemical-shift effects for the uranium photoelectron emission, but these must be largely restricted to thin films. The observed distribution of segregated fission products implies an absence of major fuel restructuring and SEM examinations revealed mainly subtle changes in the UO 2 grain structure. These findings are consistent with metallographic evidence of pervasive grain-boundary attack, despite only slight bulk alteration of the fluorite-lattice structure. (author)

First-Principles Modeling of ThO2 Solid Solutions with Oxides of Trivalent Cations

Science.gov (United States)

Alexandrov, Vitaly; Asta, Mark; Gronbech-Jensen, Niels

2010-03-01

Solid solutions formed by doping ThO2 with oxides of trivalent cations, such as Y2O3 and La2O3, are suitable for solid electrolyte applications, similar to doped zirconia and ceria. ThO2 has also been gaining much attention as an alternative to UO2 in nuclear energy applications, the aforementioned trivalent cations being important fission products. In both cases the mixing energetics and short-range ordering/clustering are key to understanding structural and transport properties. Using first-principles atomistic calculations, we address intra- and intersublattice interactions for both cation and anion sublattices in ThO2-based fluorite-type solid solutions and compare the results with similar modeling studies for related trivalent-doped zirconia systems.

Formation of defect-fluorite structured NdNiOxHy epitaxial thin films via a soft chemical route from NdNiO3 precursors.

Science.gov (United States)

Onozuka, T; Chikamatsu, A; Katayama, T; Fukumura, T; Hasegawa, T

2016-07-26

A new phase of oxyhydride NdNiOxHy with a defect-fluorite structure was obtained by a soft chemical reaction of NdNiO3 epitaxial thin films on a substrate of SrTiO3 (100) with CaH2. The epitaxial relationship of this phase relative to SrTiO3 could be controlled by changing the reaction temperature. At 240 °C, NdNiOxHy grew with a [001] orientation, forming a thin layer of infinite-layer NdNiO2 at the interface between the NdNiOxHy and the substrate. Meanwhile, a high-temperature reaction at 400 °C formed [110]-oriented NdNiOxHy without NdNiO2.

Ceria-Based Anodes for Next Generation Solid Oxide Fuel Cells

Science.gov (United States)

Mirfakhraei, Behzad

Mixed ionic and electronic conducting materials (MIECs) have been suggested to represent the next generation of solid oxide fuel cell (SOFC) anodes, primarily due to their significantly enhanced active surface area and their tolerance to fuel components. In this thesis, the main focus has been on determining and tuning the physicochemical and electrochemical properties of ceria-based MIECs in the versatile perovskite or fluorite crystal structures. In one direction, BaZr0.1Ce0.7Y0.1 M0.1O3-delta (M = Fe, Ni, Co and Yb) (BZCY-M) perovskites were synthesized using solid-state or wet citric acid combustion methods and the effect of various transition metal dopants on the sintering behavior, crystal structure, chemical stability under CO2 and H 2S, and electrical conductivity, was investigated. BZCY-Ni, synthesized using the wet combustion method, was the best performing anode, giving a polarization resistance (RP) of 0.4 O.cm2 at 800 °C. Scanning electron microscopy and X-ray diffraction analysis showed that this was due to the exsolution of catalytic Ni nanoparticles onto the oxide surface. Evolving from this promising result, the effect of Mo-doped CeO 2 (nCMO) or Ni nanoparticle infiltration into a porous Gd-doped CeO 2 (GDC) anode (in the fluorite structure) was studied. While 3 wt. % Ni infiltration lowered RP by up to 90 %, giving 0.09 O.cm2 at 800 °C and exhibiting a ca. 5 times higher tolerance towards 10 ppm H2, nCMO infiltration enhanced the H2 stability by ca. 3 times, but had no influence on RP. In parallel work, a first-time study of the Ce3+ and Ce 4+ redox process (pseudocapacitance) within GDC anode materials was carried out using cyclic voltammetry (CV) in wet H2 at high temperatures. It was concluded that, at 500-600 °C, the Ce3+/Ce 4+ reaction is diffusion controlled, probably due to O2- transport limitations in the outer 5-10 layers of the GDC particles, giving a very high capacitance of ca. 70 F/g. Increasing the temperature ultimately

Mechanism of mechanochemical synthesis of complex oxides and the peculiarities of their nano-structurization determining sintering

Directory of Open Access Journals (Sweden)

Zyryanov V.V.

2005-01-01

Full Text Available A mechanism of superfast mechanosynthesis reaction for oxide systems is proposed on the base of a dynamics study. The threshold effect and linear dependence of the chemical response on the effective temperature of the reaction zone are established. Major factors are determined: molecular mass of reagents, enthalpy and difference of reagents in Mohs’s hardness, which also influence the composition of the primary product. Primary acts are characterized by a superfast roller mechanism of mass transfer with the formation of a transient dynamic state (D*. Secondary acts slowly approximate the composition of the product to the composition of the starting mixture by diffusion mass transfer in a deformation mixing regime with a contribution of a rotation (roller mechanism. The list of structure types for complex oxides derived by mechanosynthesis includes perovskites, fluorites, pyrochlors, sheelites, and some other ones. Powders of crystal products display multilevel structurization. In all studied complex oxides strong disordering of the “anti-glass” type was observed. The mechanism of sintering was studied in BaTiO3 powders of different origin and in metastable complex oxides derived by mechanosynthesis. The major contribution in shrinkage belongs to rearrangements of crystalline particles as a whole. Structure transformations accompany, as a rule, sintering of inhomogeneous powders derived by mechanosynthesis.

Magnetic interactions in praseodymium ruthenate Pr{sub 3}RuO{sub 7} with fluorite-related structure

Energy Technology Data Exchange (ETDEWEB)

Inabayashi, Masaki; Doi, Yoshihiro; Wakeshima, Makoto; Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp

2017-06-15

Solid solutions Pr{sub 3}(Ru{sub 1-x}Ta{sub x})O{sub 7} (0≤x≤1.0) and (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7} (0≤x≤0.7) were obtained as a single phase compound. They crystallize in an orthorhombic superstructure derived from that of the cubic fluorite with space group Cmcm. The results of the Rietveld analysis for X-ray diffraction profiles of Pr{sub 3}(Ru{sub 1-x}Ta{sub x})O{sub 7} showed that Ru and Ta atoms are randomly situated at the six-coordinate 4b site. For (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7}, with increasing the concentration of Y ions (x value), the smaller Y ions occupy selectively the seven-coordinate 8g site rather than the eight-coordinate 4a site. Through magnetic susceptibility measurements for Pr{sub 3}(Ru{sub 1-x}Ta{sub x})O{sub 7}, the antiferromagnetic transition temperatures decrease linearly with increasing x value, and at x=0.75 no magnetic ordering was found down to 1.8 K, indicating the magnetic interaction is not one-dimensional, but three-dimensional. On the other hand, the antiferromagnetic transition temperature for (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7} decreases with increasing x value, but above x≥0.50 it becomes constant (~12 K). This result indicates that Pr{sup 3+} ions at the seven-coordinate site greatly contribute to the antiferromagnetic interactions observed in (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7}. Density functional calculations of Pr{sub 3}RuO{sub 7} demonstrate that the electronic structure gives insulating character and that oxygen 2p orbitals hybridize strongly with Ru 4d orbitals in the valence band (VB). Near the top of VB, the Pr 4 f orbitals at the seven-coordinated site also show a weak hybridization with the O(1) 2p orbitals. The Ru-O(1)-Pr superexchange pathway take part in three-dimensional magnetic interaction and play an important role in an enhancement of long-range magnetic ordering. - Graphical abstract: The spin densities and the spin polarization of Pr{sub 3}RuO{sub 7} are shown

Study of the R-(Zr,W)-(O,N) (R = Y, Nd, Sm, Gd, Yb) oxynitride system

Energy Technology Data Exchange (ETDEWEB)

Tessier, Franck, E-mail: Franck.Tessier@univ-rennes1.fr [UMR CNRS 6226 ' Sciences Chimiques de Rennes' , equipe ' Verres et Ceramiques' , Universite de Rennes 1, 35042 Rennes cedex (France); Maillard, Pascal [UMR CNRS 6226 ' Sciences Chimiques de Rennes' , equipe ' Verres et Ceramiques' , Universite de Rennes 1, 35042 Rennes cedex (France); Orhan, Emmanuelle [Laboratoire Science des Procedes Ceramiques et Traitements de Surface, UMR CNRS 6638, Universite de Limoges, 123 Avenue Albert Thomas, 87060 Limoges cedex (France); Chevire, Francois [UMR CNRS 6226 ' Sciences Chimiques de Rennes' , equipe ' Verres et Ceramiques' , Universite de Rennes 1, 35042 Rennes cedex (France)

2010-02-15

The replacement of tantalum by the couple Zr/W within the RTa-O-N systems (R = Y, Nd, Sm, Gd, Yb), enables the preparation of novel oxide and oxynitride phases in the R-Zr-W-O-N system. R{sub 2}Zr{sub 2-x}W{sub x}O{sub 7+x} oxides exhibit the fluorite-type (x < 0.9) and scheelite (x {approx} 1) structures. Corresponding oxynitride compositions are of the fluorite-type and show different colors, for example in the case of ytterbium: pale yellow (x = 0.2 or 0.25), green (x = 0.5-0.8) and brown for the tungsten-rich samples (x = 0.9, 1). Photocatalytic activity measurements have been performed to investigate the overall water splitting behavior of these colored phases.

Opto-electronic properties of bismuth oxide films presenting different crystallographic phases

Energy Technology Data Exchange (ETDEWEB)

Gomez, Celia L. [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Posgrado en Ciencia e Ingeniería de Materiales, UNAM, Unidad de Posgrado, Edificio C, Piso 1, Zona Cultural de CU, México, D.F. 04510 (Mexico); Depablos-Rivera, Osmary, E-mail: osmarydep@yahoo.com [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Posgrado en Ciencia e Ingeniería de Materiales, UNAM, Unidad de Posgrado, Edificio C, Piso 1, Zona Cultural de CU, México, D.F. 04510 (Mexico); Silva-Bermudez, Phaedra [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Instituto Nacional de Rehabilitación, Calz. México Xochimilco No. 289 Col. Arenal de Guadalupe, C.P.14389, Ciudad de México, D.F. (Mexico); Muhl, Stephen [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico); Zeinert, Andreas; Lejeune, Michael; Charvet, Stephane; Barroy, Pierre [Laboratoire de Physique de la Matière Condensée, Université de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens Cedex 1 (France); Camps, Enrique [Instituto Nacional de Investigaciones Nucleares, Carretera México-Toluca S/N, kilómetro 36.5. La Marquesa, Municipio de Ocoyoacac, CP 52750, Estado de México (Mexico); Rodil, Sandra E. [Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior s/n CU, México D.F. 04510 (Mexico)

2015-03-02

The optical, electrical and structural properties of bismuth oxide thin films deposited by radio frequency reactive magnetron sputtering were studied. The Bi{sub 2}O{sub 3} thin films were grown on Si and glass substrates under different power and substrate temperatures in an oxygen-enriched plasma leading to films with different crystalline phase as evidenced by X-ray diffraction and Raman spectroscopy. The optical properties of the films were measured using ellipsometric spectroscopy and optical transmission spectra. In order to parameterize the optical dispersion functions (n, k) of the films, the Tauc–Lorentz dispersion model was used. The optical bandgap was then assessed by different methods and the results are compared to the thermal variations of the electrical resistivity of the films. It was found that the refractive index, extinction coefficient and optical gap strongly depend on the deposition conditions and the crystalline phase; the fluorite defect cubic δ-Bi{sub 2}O{sub 3} phase showed the lowest optical gap and lower resistivity. - Highlights: • Different bismuth oxide phases were obtained by sputtering. • The power and substrate temperature were the two key parameters. • Room temperature delta-Bi{sub 2}O{sub 3} thin films were obtained. • The optical bandgap was around 1.5 and 2.2 eV, depending on the phase. • The bismuth oxide films presented activation energies around 1 eV.

Opto-electronic properties of bismuth oxide films presenting different crystallographic phases

International Nuclear Information System (INIS)

Gomez, Celia L.; Depablos-Rivera, Osmary; Silva-Bermudez, Phaedra; Muhl, Stephen; Zeinert, Andreas; Lejeune, Michael; Charvet, Stephane; Barroy, Pierre; Camps, Enrique; Rodil, Sandra E.

2015-01-01

The optical, electrical and structural properties of bismuth oxide thin films deposited by radio frequency reactive magnetron sputtering were studied. The Bi 2 O 3 thin films were grown on Si and glass substrates under different power and substrate temperatures in an oxygen-enriched plasma leading to films with different crystalline phase as evidenced by X-ray diffraction and Raman spectroscopy. The optical properties of the films were measured using ellipsometric spectroscopy and optical transmission spectra. In order to parameterize the optical dispersion functions (n, k) of the films, the Tauc–Lorentz dispersion model was used. The optical bandgap was then assessed by different methods and the results are compared to the thermal variations of the electrical resistivity of the films. It was found that the refractive index, extinction coefficient and optical gap strongly depend on the deposition conditions and the crystalline phase; the fluorite defect cubic δ-Bi 2 O 3 phase showed the lowest optical gap and lower resistivity. - Highlights: • Different bismuth oxide phases were obtained by sputtering. • The power and substrate temperature were the two key parameters. • Room temperature delta-Bi 2 O 3 thin films were obtained. • The optical bandgap was around 1.5 and 2.2 eV, depending on the phase. • The bismuth oxide films presented activation energies around 1 eV

Determination of thermodynamic properties and stability limit from fluorite phase of uranium and lanthanide mixed oxides, using galvanic cells with solid electrolytes

International Nuclear Information System (INIS)

Santiago, T.N.

1980-10-01

A method for thermodynamic properties determination for oxygen solubility in oxide systems at temperature interval 973 ≤ T [K] ≤ 1773 is described. A galvanic cell using as solid electrolytes zircon dioxide doped with 15% of calcium oxide is presented. This method was used for determining the phase change, temperature dependent, of uranium-lanthanides-oxygen Ln U O 4 stoichiometric system. (C.G.C.)

Lattice dynamics of ThO2

International Nuclear Information System (INIS)

Gupta, M.K.; Goel, Prabhatasree; Mittal, R.; Choudhury, N.; Chaplot, S.L.

2012-01-01

Thorium oxide finds application in nuclear industry. It is also used as a solid state electrolyte and an optical component material. ThO 2 is found in fluorite Fm3m structure. Actinide oxides are found to undergo superionic transition at elevated temperatures, when oxygen atoms start showing liquid like diffusion behaviour

Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

Science.gov (United States)

Pemartin-Biernath, Kelly; Vela-González, Andrea V.; Moreno-Trejo, Maira B.; Leyva-Porras, César; Castañeda-Reyna, Iván E.; Juárez-Ramírez, Isaías; Solans, Conxita; Sánchez-Domínguez, Margarita

2016-01-01

Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W) microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD), below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM). Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg) was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications. PMID:28773602

Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

Directory of Open Access Journals (Sweden)

Kelly Pemartin-Biernath

2016-06-01

Full Text Available Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD, below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM. Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications.

Bi1−xNbxO1.5+x (x=0.0625, 0.12) fast ion conductors: Structures, stability and oxide ion migration pathways

International Nuclear Information System (INIS)

Tate, Matthew L.; Hack, Jennifer; Kuang, Xiaojun; McIntyre, Garry J.; Withers, Ray L.; Johnson, Mark R.; Radosavljevic Evans, Ivana

2015-01-01

A combined experimental and computational study of Bi 1−x Nb x O 1.5+x (x=0.0625 and 0.12) has been carried out using laboratory X-ray, neutron and electron diffraction, impedance measurements and ab-initio molecular dynamics. We demonstrate that Bi 0.9375 Nb 0.0625 O 1.5625 , previously reported to adopt a cubic fluorite-type superstructure, can form two different polymorphs depending on the synthetic method: a metastable cubic phase is produced by quenching; while slower cooling yields a stable material with a tetragonal √2×√2×1 superstructure, which undergoes a reversible phase transition into the cubic form at ~680 °C on subsequent reheating. Neutron diffraction reveals that the tetragonal superstructure arises mainly from ordering in the oxygen sublattice, with Bi and Nb remaining disordered, although structured diffuse scattering observed in the electron diffraction patterns suggests a degree of short-range ordering. Both materials are oxide ion conductors. On thermal cycling, Bi 0.88 Nb 0.12 O 1.62 exhibits a decrease in conductivity of approximately an order of magnitude due to partial transformation into the tetragonal phase, but still exhibits conductivity comparable to yttria-stabilised zirconia (YSZ). Ab-initio molecular dynamics simulations performed on Bi 0.9375 Nb 0.0625 O 1.5625 show that oxide ion diffusion occurs by O 2− jumps between edge- and corner-sharing OM 4 groups (M=Bi, Nb) via tetrahedral □M 4 and octahedral □M 6 vacancies. - Graphical abstract: Oxide ion migration in tetragonal Bi 0.9375 Nb 0.0625 O 1.5625 occurs by O 2− jumps between edge- and corner-sharing OM 4 groups (M=Bi, Nb) via tetrahedral M 4 and octahedral M 6 vacancies. - Highlights: • Bi 0.9375 Nb 0.0625 O 1.5625 adopts a tetragonal √2×√2×1 fluorite superstructure. • Superstructure is due to ordering in the O-sublattice, with Bi/Nb disordered. • Bi 0.9375 Nb 0.0625 O 1.5625 is a good oxide ion conductor. • O 2− jump between OM 4 groups (M

Characterization of composite metal-ceramic of nickel-oxide cerium doped gadolinium; Caracterizacao de compositos ceramica-metal de niquel e oxido de cerio dopado com gadolinio

Energy Technology Data Exchange (ETDEWEB)

Silva, M.L.A. da, E-mail: maria.andrade@pro.unifacs.br [Universidade Salvador (UNIFACS), BA (Brazil). Escola de Engenharia, Arquitetura e TI; Universidade Federal da Bahia (UFBA), BA (Brazil); Varela, M.C.R.S. [Universidade Federal da Bahia (UFBA), BA (Brazil)

2016-07-01

Composite nickel doped cerium oxide are used in SOFC anode materials. In this study we evaluated the effect of the presence of gadolinium on the properties of composite nickel and ceria and. The supports were synthesized by sol-gel method. The impregnation with nickel nitrate was taken sequentially, followed by calcination. The materials were characterized by X-ray diffraction, measurement of specific surface area, temperature programmed reduction, Raman spectroscopy. The presence of gadolinium retained the fluorite structure of ceria by forming a solid solution, also not influencing significantly on the specific surface area of the support. On the other hand, there was a decrease in the area catalysts, which can be attributed to sintering of nickel. Furthermore, addition of gadolinium favored the formation of intrinsic and extrinsic vacancies in cerium oxide, which leads to an increase in the ionic conductivity of the solid, desirable property for an SOFC anode catalyst. (author)

Incorporation of uranium in pyrochlore oxides and pressure-induced phase transitions

Energy Technology Data Exchange (ETDEWEB)

Zhang, F.X., E-mail: zhangfx@umich.edu [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Lang, M.; Tracy, C.; Ewing, R.C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Gregg, D.J.; Lumpkin, G.R. [Institute of Materials Engineering, ANSTO, Locked Bag 2001, Kirrawee DC 2232, NSW (Australia)

2014-11-15

Uranium-doped gadolinium zirconates with pyrochlore structure were studied at ambient and high-pressure conditions up to 40 GPa. The bonding environment of uranium in the structure was determined by x-ray photoelectron and Raman spectroscopies and x-ray diffraction. The uranium valence for samples prepared in air is mainly U{sup 6+}, but U{sup 4+} is present in pyrochlores fabricated in an argon atmosphere. Rietveld refinement of the XRD pattern suggests that uranium ions in pyrochlores are on the 16d site in 6-fold coordination with oxygen. At pressures greater than 22 GPa, the pyrochlore structure transformed to a cotunnite-type phase. The cotunnite high-pressure phase transformed to a defect fluorite structure on the release of pressure. - Graphical abstract: In U-bearing pyrochlore, U ions mainly occupy the 16d site and replace the smaller Zr{sup 4+}, part of the oxygen will occupy the 8b site, which is empty to most pyrochlores. At pressure of 22 GPa, the pyrochlore lattice is not stable and transforms to a cotunnite-type structure. The high-pressure structure is not stable and transform to a fluorite or back to the pyrochlore structure when pressure is released. - Highlights: • We found that U ions mainly occupy the smaller cation site in U-bearing pyrochlore. • Pyrochlore structure is not stable at pressure of more than 20 GPa. • The quenched sample has a pyrochlore or a disordered fluorite structure.

Structure and mechanical properties of swift heavy ion irradiated tungsten-bearing delta-phase oxides Y{sub 6}W{sub 1}O{sub 12} and Yb{sub 6}W{sub 1}O{sub 12}

Energy Technology Data Exchange (ETDEWEB)

Tang, M., E-mail: mtang@lanl.gov [Materials Science and Technology Division, Mail-Stop G755, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Wynn, T.A. [Materials Physics and Application Division, Mail-Stop K771, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Patel, M.K.; Won, J. [Materials Science and Technology Division, Mail-Stop G755, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Monnet, I. [CIMAP, CEA-CNRS-ENSICAEN-Universite de Caen Normandie, Bd Henri Becquerel, BP 5133, F-14070, Caen Cedex 5 (France); Pivin, J.C. [Centre de Spectrometrie Nucleaire et de Spectrometrie de Masse, CNRS-IN2P3-Universite Paris Sud, UMR 8609, Bat. 108, 91405 Orsay (France); Mara, N.A. [Materials Physics and Application Division, Mail-Stop K771, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Sickafus, K.E. [Materials Science and Technology Division, Mail-Stop G755, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

2012-06-15

We report on the relationship between structure and mechanical properties of complex oxides whose structures are derivatives of fluorite, following irradiation with swift heavy ion (92 MeV Xe) which approximately simulates fission product irradiation, where the electronic energy loss dominates. The two compounds of interest in this paper are Y{sub 6}W{sub 1}O{sub 12} and Yb{sub 6}W{sub 1}O{sub 12}. These compounds possess an ordered, fluorite derivative crystal structure known as the delta ({delta}) phase, a rhombohedral structure belonging to space group R3{sup Macron}. Structural changes induced by irradiation were examined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD investigations indicated an irradiation-induced amorphization in these compounds. This result is consistent with our previous study on Y{sub 6}W{sub 1}O{sub 12} under displacive radiation environment in which the nuclear energy loss is dominant. High resolution TEM also revealed that individual ion tracks was amorphized. The mechanical properties of both irradiated compounds, were determined by cross-sectional nano-indentation measurements as a function of ion penetration depth. The decreases in Young's modulus, E, and hardness, H (both by about 40% at the irradiated surface) suggest amorphization beyond simple defect accumulation occurs under this irradiation condition.

Nano-crystals of cerium–hafnium binary oxide: Their size-dependent structure

Energy Technology Data Exchange (ETDEWEB)

Raitano, Joan M. [Department of Applied Physics and Applied Mathematics, Materials Science and Engineering Program, Columbia University, New York, NY 10027 (United States); Khalid, Syed [National Synchrotron Light Source, Brookhaven National Laboratory, Upton, NY 11973 (United States); Marinkovic, Nebojsa [Chemical Engineering Department, Columbia University, 500 W 120th St, Mudd 801, New York, NY 10027 (United States); Chan, Siu-Wai, E-mail: sc174@columbia.edu [Department of Applied Physics and Applied Mathematics, Materials Science and Engineering Program, Columbia University, New York, NY 10027 (United States)

2015-09-25

Highlights: • (1 − x)CeO{sub 2}–xHfO{sub 2} was precipitated (0 < x < 1) and calcined in air. • For x ⩽ 0.14, crystallites ⩽140 nm in size exhibit only the fluorite structure. • This low hafnia solubility is attributable to no auto-reduction (Ce{sup 3+} = 0). • The low solubility is also due to the high temperature required for homogenization. • Coarsening is lessened as Hf{sup 4+} ions slow cation diffusion in these crystallites. - Abstract: Cerium oxide (CeO{sub 2}, “ceria”) and hafnium oxide (HfO{sub 2}, “hafnia”) were aqueously co-precipitated and subsequently calcined to allow for homogenization. The size of the (1−x)CeO{sub 2}–xHfO{sub 2} crystallites, determined by the Scherrer equation, varied from 140 nm for x = 0 to 15 nm for x = 0.73. For x ⩽ 0.14, only cubic structures are visible in X-ray diffractograms, and the lattice parameters are consistent with the values expected for structurally cubic solid solutions of hafnia in ceria. At x = 0.26, tetragonal and monoclinic phases nucleated with the former not being observed in the bulk phase diagram for ceria–hafnia. Therefore, the solubility limit of the cubic structure is between x = 0.14 and x = 0.26 for 40–61 nm crystallites, the sizes of these respective compositions. More specifically, for the 40 nm crystallites of x = 0.26 (1 − x)CeO{sub 2}–xHfO{sub 2}, 15% of the hafnia remains in a structurally cubic solid solution with ceria based on the observed cubic lattice parameter. The compositional domain for the cubic fluorite structure in this study is narrower than other nanostructured (1 − x)CeO{sub 2}–xHfO{sub 2} studies, especially studies with crystallite sizes less than 10 nm, but wider than observed in the bulk and helps to expand the size regime over which the relationship between crystallite size and phase stability is known. The extent of this cubic-structure domain is mainly attributable to the intermediate crystallite size and the roughly zero Ce{sup 3

Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

Energy Technology Data Exchange (ETDEWEB)

Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

1995-06-01

This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

Order-disorder phase transformations in quaternary pyrochlore oxide system: Investigated by X-ray diffraction, transmission electron microscopy and Raman spectroscopic techniques

International Nuclear Information System (INIS)

Radhakrishnan, A.N.; Prabhakar Rao, P.; Sibi, K.S.; Deepa, M.; Koshy, Peter

2009-01-01

Order-disorder transformations in a quaternary pyrochlore oxide system, Ca-Y-Zr-Ta-O, were studied by powder X-ray diffraction (XRD) method, transmission electron microscope (TEM) and FT-NIR Raman spectroscopic techniques. The solid solutions in different ratios, 4:1, 2:1, 1:1, 1:2, 1:4, 1:6, of CaTaO 3.5 and YZrO 3.5 were prepared by the conventional high temperature ceramic route. The XRD results and Rietveld analysis revealed that the crystal structure changed from an ordered pyrochlore structure to a disordered defect fluorite structure as the ratios of the solid solutions of CaTaO 3.5 and YZrO 3.5 were changed from 4:1 to 1:4. This structural transformation in the present system is attributed to the lowering of the average cation radius ratio, r A /r B as a result of progressive and simultaneous substitution of larger cation Ca 2+ for Y 3+ at A sites and smaller cation Ta 5+ for Zr 4+ at B sites. Raman spectroscopy and TEM analysis corroborated the XRD results. - Graphical abstract: Selected area electron diffraction (SAED) patterns showed highly ordered diffraction maxima with characteristic superlattice weak diffraction spots of the pyrochlore structure for (a) Ca 0.6 7Y 1.33 Zr 1.33 Ta 0.33 O 7 (C2YZT2) and bright diffraction maxima arranged in a ring pattern of the fluorite structure for (b) Ca 0.29 7Y 1.71 Zr 1.71 Ta 0.29 O 7 (CY6Z6T).

A robust NiO-Sm0.2Ce0.8O1.9 anode for direct-methane solid oxide fuel cell

KAUST Repository

Tian, Dong

2015-07-02

In order to directly use methane without a reforming process, NiO-Sm0.2Ce0.8O1.9 (NiO-SDC) nanocomposite anode are successfully synthesized via a one-pot, surfactant-assisted co-assembly approach for direct-methane solid oxide fuel cells. Both NiO with cubic phase and SDC with fluorite phase are obtained at 550 °C. Both NiO nanoparticles and SDC nanoparticles are highly monodispersed in size with nearly spherical shapes. Based on the as-synthesized NiO-SDC, two kinds of single cells with different micro/macro-porous structure are successfully fabricated. As a result, the cell performance was improved by 40%-45% with the new double-pore NiO-SDC anode relative to the cell performance with the conventional NiO-SDC anode due to a wider triple-phase-boundary (TPB) area. In addition, no significant degradation of the cell performance was observed after 60 hours, which means an increasing of long term stability. Therefore, the as-synthesized NiO-SDC nanocomposite is a promising anode for direct-methane solid oxide fuel cells.

Formation and decomposition of some rare earth (RE = La, Ce, Pr) hydroxides and oxides by homogeneous precipitation

International Nuclear Information System (INIS)

Ozawa, Masakuni; Onoe, Ryota; Kato, Hajime

2006-01-01

Formation and thermal decomposition of rare earth (RE = La, Ce, Pr) hydroxides and oxides by homogeneous precipitation using hexamethylenetetramine. The precipitatates were examined using thermal gravimetry and differential thermal analysis, infrared spectrometry and X-ray diffraction. The as-precipitated powders from the present process were La(OH) 3 , CeO 2 , Pr(OH) 3 . In the case of Ce, a cubic fluorite phase of cerium dioxide was directly obtained. The lanthanum trihydroxide decomposed to oxides via three steps. Two-step dehydration decomposition behavior at 340 and 500 o C was observed as La(OH) 3 → LaOOH + H 2 O and 2LaOOH → La 2 O 3 + H 2 O. The activation energy (ΔH) for dehydration was 240 and 244 kJ/mol, respectively. The additional decomposition of carbonate-containing species was observed at 670 o C with ΔH of 390 kJ/mol. Pr(OH) 3 did not show additional TGA profile of carbonate decomposition. Since no carbonate species form in solution during the HMT precipitation (hydrolysis of this molecule), the difference between La and Pr depends on the strength of basicity in the reaction with CO 2 after precipitation

A COMPARATIVE STUDY AND ANALYSIS OF FULL ADDER

OpenAIRE

Deepika*, Ankur Gupta, Ashwani Panjeta

2016-01-01

In Electronics adders are used widely. An adder performance is analysed using trems delay and power comsumption. This paper contains various adders simulated using Mentor graphics in180 nm technology and their comparsion using power delay product

Sequential evolution of different phases in metastable Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 (0.0 ≤ x ≤ 2.0) system: crucial role of reaction conditions.

Science.gov (United States)

Shukla, Rakesh; Sayed, Farheen N; Phapale, Suhas; Mishra, Ratikant; Tyagi, Avesh K

2013-07-15

The Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 (0.0 ≤ x ≤ 2.0) series was synthesized by the gel combustion method. This system exhibited the presence of a fluorite-type phase, along with a narrow biphasic region, depending upon the Ce/Gd content in the sample. Thermal stability of these new compounds under oxidizing and reducing conditions has been investigated. The products obtained on decomposition of Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 in oxidizing and reducing conditions were found to be entirely different. It was observed that in air the fluorite-type solid solutions of Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 composition undergo phase separation into perovskite GdAlO3 and fluorite-type solid solutions of Gd-Ce-Zr-O or Ce-Zr-Al-O depending upon the extent of Ce and Al substitution. On the other hand, Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 samples on heating under reducing conditions show a phase separation to CeAlO3 perovskite and a defect-fluorite of Gd2Zr2O7. The extent of metastability for a typical composition of Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O7 (nano), Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O(6.6) (heated under reduced conditions), Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O7 (heated in air at 1200 °C) has been experimentally determined employing a high temperature Calvet calorimeter. On the basis of thermodynamic stability data, it could be inferred that the formation of a more stable compound in the presence of two competing cations (i.e., Gd(3+) and Ce(3+)) is guided by the crystallographic stability.

Band Gap Transition Studies of U:ThO2 Using Cathodoluminescence

Science.gov (United States)

2014-03-27

regarding x-ray fluorescence. 2.1 Atomic Properties of Ux:Th1−xO2 Thorium and uranium dioxide are metal oxides with the fluorite crystal structure...thorium oxide is a material upon which few studies have been performed. The goal of this research is to determine how the insertion of uranium atoms into...doped thorium oxide crystal, 041 TU, with uranium mass concentration of 22.7% before chemical cleaning. Mass pre-cleaning: 0.341 g. 7 Figure 1.5

Bi{sub 1−x}Nb{sub x}O{sub 1.5+x} (x=0.0625, 0.12) fast ion conductors: Structures, stability and oxide ion migration pathways

Energy Technology Data Exchange (ETDEWEB)

Tate, Matthew L. [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia); Hack, Jennifer [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); Institut Laue-Langevin, Grenoble (France); Kuang, Xiaojun [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); McIntyre, Garry J. [Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia); Withers, Ray L. [Research School of Chemistry, Australian National University, Canberra, ACT (Australia); Johnson, Mark R. [Institut Laue-Langevin, Grenoble (France); Radosavljevic Evans, Ivana, E-mail: ivana.radosavljevic@durham.ac.uk [Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom); Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia)

2015-05-15

A combined experimental and computational study of Bi{sub 1−x}Nb{sub x}O{sub 1.5+x} (x=0.0625 and 0.12) has been carried out using laboratory X-ray, neutron and electron diffraction, impedance measurements and ab-initio molecular dynamics. We demonstrate that Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625}, previously reported to adopt a cubic fluorite-type superstructure, can form two different polymorphs depending on the synthetic method: a metastable cubic phase is produced by quenching; while slower cooling yields a stable material with a tetragonal √2×√2×1 superstructure, which undergoes a reversible phase transition into the cubic form at ~680 °C on subsequent reheating. Neutron diffraction reveals that the tetragonal superstructure arises mainly from ordering in the oxygen sublattice, with Bi and Nb remaining disordered, although structured diffuse scattering observed in the electron diffraction patterns suggests a degree of short-range ordering. Both materials are oxide ion conductors. On thermal cycling, Bi{sub 0.88}Nb{sub 0.12}O{sub 1.62} exhibits a decrease in conductivity of approximately an order of magnitude due to partial transformation into the tetragonal phase, but still exhibits conductivity comparable to yttria-stabilised zirconia (YSZ). Ab-initio molecular dynamics simulations performed on Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} show that oxide ion diffusion occurs by O{sup 2−} jumps between edge- and corner-sharing OM{sub 4} groups (M=Bi, Nb) via tetrahedral □M{sub 4} and octahedral □M{sub 6} vacancies. - Graphical abstract: Oxide ion migration in tetragonal Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} occurs by O{sup 2−} jumps between edge- and corner-sharing OM{sub 4} groups (M=Bi, Nb) via tetrahedral M{sub 4} and octahedral M{sub 6} vacancies. - Highlights: • Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} adopts a tetragonal √2×√2×1 fluorite superstructure. • Superstructure is due to ordering in the O-sublattice, with Bi

A model for the oxygen potential of oxide fuels at high burnup

Energy Technology Data Exchange (ETDEWEB)

Garcia, P; Piron, J P [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France); Baron, D [Direction des Etudes et Recherches, Electricite de France, Moret-dur-Loing (France)

1997-08-01

Using Lindemer`s analysis as a starting point, a comprehensive description of the chemical state of the fluorite fuel matrix along with the most abundant fission products has been developed. The model was then implemented within the framework of an upgraded version of the SOLGASMIX program known as SAGE. In addition to approximately seventy solid compounds, three different mixture phases are modelled. The first one is the gaseous phase and comprises roughly sixty different compounds. The second is made up of noble metals such as Mo, Ru, Tc, Pd. The third mixture phase is a representation of the fluorite fuel matrix. Since SAGE is a code which calculates chemical equilibria by minimizing the Gibbs energy of the system, it is essential that reliable free energies of formation be used as data. This is relatively straightforward with regard to most compounds and thermochemical data are readily available in the open literature. As regards the fluorite phase however, the basic hypothesis is that it is possible to model the effect of defects such as interstitials (in the hyperstoichiometric phase) and vacancies (in the hypostoichiometric phase) by assuming the existence of hypothetical solute compounds such as U{sub 2}O{sub 4.5} that stabilize the hyperstoichiometric phase. As rare earths (Re) of valence two or three are dissolved in the matrix, the hypothetical compounds Re{sub 4/3}O{sub 2} and URe{sub 2}O{sub 6} are chosen to reflect the behavior of the ternay system. This description accurately predicts the hypostoichiometric region of the phase diagram but underestimate the increase in oxygen potential in the hyperstoichiometric region. 26 refs, 10 figs, 1 tab.

A model for the oxygen potential of oxide fuels at high burnup

International Nuclear Information System (INIS)

Garcia, P.; Piron, J.P.; Baron, D.

1997-01-01

Using Lindemer's analysis as a starting point, a comprehensive description of the chemical state of the fluorite fuel matrix along with the most abundant fission products has been developed. The model was then implemented within the framework of an upgraded version of the SOLGASMIX program known as SAGE. In addition to approximately seventy solid compounds, three different mixture phases are modelled. The first one is the gaseous phase and comprises roughly sixty different compounds. The second is made up of noble metals such as Mo, Ru, Tc, Pd. The third mixture phase is a representation of the fluorite fuel matrix. Since SAGE is a code which calculates chemical equilibria by minimizing the Gibbs energy of the system, it is essential that reliable free energies of formation be used as data. This is relatively straightforward with regard to most compounds and thermochemical data are readily available in the open literature. As regards the fluorite phase however, the basic hypothesis is that it is possible to model the effect of defects such as interstitials (in the hyperstoichiometric phase) and vacancies (in the hypostoichiometric phase) by assuming the existence of hypothetical solute compounds such as U 2 O 4.5 that stabilize the hyperstoichiometric phase. As rare earths (Re) of valence two or three are dissolved in the matrix, the hypothetical compounds Re 4/3 O 2 and URe 2 O 6 are chosen to reflect the behavior of the ternay system. This description accurately predicts the hypostoichiometric region of the phase diagram but underestimate the increase in oxygen potential in the hyperstoichiometric region. 26 refs, 10 figs, 1 tab

Atomistic simulations of the radiation resistance of oxides

International Nuclear Information System (INIS)

Chartier, A.; Van Brutzel, L.; Crocombette, J.-P.

2012-01-01

Fluorite compounds such as urania and ceria, or related compounds such as pyrochlores and also spinels show different behaviors under irradiations, which ranges from perfect radiation resistance to crystalline phase change or even complete amorphization depending on their structure and/or their composition. Displacement cascades – dedicated to the understanding of the ballistic regime and performed by empirical potentials molecular dynamics simulations – have revealed that the remaining damages of the above mentioned oxides are reduced to point defects unlike what is observed in zircon and zirconolite, which directly amorphize during the cascade. The variable behavior of these point defects is the key of the various responses of these materials to irradiations. This behavior can be investigated by two specific molecular dynamics methodologies that will be reviewed here: (i) the method of point defects accumulation as a function of temperature that gives access to the dose effects and to the critical doses for amorphization; (ii) the study Frenkel pairs life-time – i.e. their time of recombination as function of temperature – that may be used as a tool to understand the results obtained in displacements cascades or to identify the microscopic mechanisms responsible for the amorphization/re-crystallization during the point defects accumulations.

Performance of cubic ZrO{sub 2} doped CeO{sub 2}: First-principles investigation on elastic, electronic and optical properties of Ce{sub 1−x} Zr{sub x}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tian, Dong [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Zeng, Chunhua, E-mail: zchh2009@126.com [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Science, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Wang, Hua, E-mail: wanghuaheat@hotmail.com [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Luo, Hongchun [Faculty of Science, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Cheng, Xianming [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Xiang, Chao [College of Mechanical and Electrical Engineering, Yangtze Normal University, Fuling 408100, Chongqing (China); Wei, Yonggang; Li, Kongzhai; Zhu, Xing [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan (China)

2016-06-25

The structural, elastic, electronic and optical properties of Ce{sub 1−x} Zr{sub x}O{sub 2} (x = 0, 0.25, 0.5, 0.75, 1) fluorite type oxides are studied by researchers using the method of density functional theory (DFT) + U method. The calculated equilibrium lattice parameter, cell volume, elastic and optical properties for CeO{sub 2} and ZrO{sub 2} are all in good agreement with the available experimental data and other theoretical results. It is found that Ce substituted by Zr leads to the formation of the pseudo-cubic fluorite-type structure. With doping concentration × increasing, the lattice parameter, cell volume and the bond length of d{sub Ce−O} and d{sub Zr−O} decrease linearly. It is interesting to find that the hardness of materials increase with Zr concentration increasing. For Ce{sub 0.75} Zr{sub 0.25} O{sub 2}, we also find that its ductility is good. Meanwhile, the range of the conduction band energy in the doped system becomes wider than that in the undoped system. The overlapping band phenomenon occur for all substitutions in Ce{sub 1−x} Zr{sub x}O{sub 2} (from x = 0.25 to x = 0.75), especially for the structure of Ce{sub 0.5} Zr{sub 0.5} O{sub 2} and Ce{sub 0.25} Zr{sub 0.75} O{sub 2}, its second band gaps almost disappear. Based on the dielectric functions obtained, it is shown that the static dielectric constant ε{sub 0} and refractive index n{sub 0} obviously decrease with Zr concentration increasing. After discussing, we know that CeO{sub 2} is suitable as a useful high-refractive index film material in single and multilayered optical coatings, whereas ZrO{sub 2} can be used as gate-dielectric materials in metal-oxide semiconductor (MOS) devices, in metallurgy and as a thermal barrier coating in engines. - Highlights: • Structural, and optical properties of fluorite type oxides are studied; • Ce substituted by Zr leads to formation of pseudo-cubic fluorite-type structure; • Hardness of materials are increased with Zr

Facile hydrothermal synthesis of CeO 2 nanopebbles

Indian Academy of Sciences (India)

Cerium oxide (CeO2) nanopebbles have been synthesized using a facile hydrothermal method. X-ray diffraction pattern (XRD) and transmission electron microscopy analyses confirm the presence of CeO2 nanopebbles. XRD shows the formation of cubic fluorite CeO2 and the average particle size estimated from the ...

Formation and decomposition of some rare earth (RE = La, Ce, Pr) hydroxides and oxides by homogeneous precipitation

Energy Technology Data Exchange (ETDEWEB)

Ozawa, Masakuni [Ceramics Research Laboratory, Nagoya Institute of Technology, Tajimi, 507-0071 Gifu (Japan)]. E-mail: ozawa@crl.nitech.ac.jp; Onoe, Ryota [Ceramics Research Laboratory, Nagoya Institute of Technology, Tajimi, 507-0071 Gifu (Japan); Kato, Hajime [Ceramics Research Laboratory, Nagoya Institute of Technology, Tajimi, 507-0071 Gifu (Japan)

2006-02-09

Formation and thermal decomposition of rare earth (RE = La, Ce, Pr) hydroxides and oxides by homogeneous precipitation using hexamethylenetetramine. The precipitatates were examined using thermal gravimetry and differential thermal analysis, infrared spectrometry and X-ray diffraction. The as-precipitated powders from the present process were La(OH){sub 3}, CeO{sub 2}, Pr(OH){sub 3}. In the case of Ce, a cubic fluorite phase of cerium dioxide was directly obtained. The lanthanum trihydroxide decomposed to oxides via three steps. Two-step dehydration decomposition behavior at 340 and 500 {sup o}C was observed as La(OH){sub 3} {sup {yields}} LaOOH + H{sub 2}O and 2LaOOH {sup {yields}} La{sub 2}O{sub 3} + H{sub 2}O. The activation energy ({delta}H) for dehydration was 240 and 244 kJ/mol, respectively. The additional decomposition of carbonate-containing species was observed at 670 {sup o}C with {delta}H of 390 kJ/mol. Pr(OH){sub 3} did not show additional TGA profile of carbonate decomposition. Since no carbonate species form in solution during the HMT precipitation (hydrolysis of this molecule), the difference between La and Pr depends on the strength of basicity in the reaction with CO{sub 2} after precipitation.

Air, aqueous and thermal stabilities of Ce3+ ions in cerium oxide nanoparticle layers with substrates

KAUST Repository

Naganuma, Tamaki

2014-01-01

Abundant oxygen vacancies coexisting with Ce3+ ions in fluorite cerium oxide nanoparticles (CNPs) have the potential to enhance catalytic ability, but the ratio of unstable Ce3+ ions in CNPs is typically low. Our recent work, however, demonstrated that the abundant Ce3+ ions created in cerium oxide nanoparticle layers (CNPLs) by Ar ion irradiation were stable in air at room temperature. Ce valence states in CNPs correlate with the catalytic ability that involves redox reactions between Ce3+ and Ce4+ ions in given application environments (e.g. high temperature in carbon monoxide gas conversion and immersion conditions in biomedical applications). To better understand the mechanism by which Ce3+ ions achieve stability in CNPLs, we examined (i) extra-long air-stability, (ii) thermal stability up to 500 °C, and (iii) aqueous stability of Ce 3+ ions in water, buffer solution and cell culture medium. It is noteworthy that air-stability of Ce3+ ions in CNPLs persisted for more than 1 year. Thermal stability results showed that oxidation of Ce 3+ to Ce4+ occurred at 350 °C in air. Highly concentrated Ce3+ ions in ultra-thin CNPLs slowly oxidized in water within 1 day, but stability was improved in the cell culture medium. Ce 3+ stability of CNPLs immersed in the medium was associated with phosphorus adsorption on the Ce3+ sites. This study also illuminates the potential interaction mechanisms of stable Ce3+ ions in CNPLs. These findings could be utilized to understand catalytic mechanisms of CNPs with abundant oxygen vacancies in their application environments. © The Royal Society of Chemistry 2014.

Contribution to the study of french pitchblendes

International Nuclear Information System (INIS)

Geffroy, J.; Sarcia, J.A.

1955-01-01

The authors first review the characteristics of uraninite-pitchblende, as deduced of present literature. They set apart from typical pitchblende a black oxide aspect, which probably corresponds to neo-formations, and a 'para-pitchblende' aspect, which they relate to deep sur-oxidation of normal pitchblende. They insist on the easy replacement of pitchblende by silica. and give indications as to changes in vein stones (fluorite, quartz, etc...). A detailed study of paragenesis and successions in french uranium districts follows (including discussion of uranium of uranium-bearing coals). The authors attempt to classify french pitchblende veins. They are chiefly epithermal and poor in satellite ores. Three types of deposits are identified: massive - pitchblende type, silica type, fluorite type. These deposits, as those of Portugal, are included in granite, Central-European peri-batholitic types where uranium associates which Ni, Co, Bi and Ag, are in France both rare and poor. Finally, the authors attempt to bring out in the european Hercynian area a particular distribution of paragenetic types. (authors) [fr

Electric-Loading Enhanced Kinetics in Oxide Ceramics: Pore Migration, Sintering and Grain Growth: Final Report

Energy Technology Data Exchange (ETDEWEB)

Chen, I-Wei [Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science & Engineering

2018-02-02

Solid oxide fuel cells and solid oxide electrolysis cells rely on solid electrolytes in which a large ionic current dominates. This project was initiated to investigate microstructural changes in such devices under electrochemical forces, because nominally insignificant processes may couple to the large ionic current to yield non-equilibrium phenomena that alter the microstructure. Our studies had focused on yttria-stabilized cubic zirconia (YSZ) widely used in these devices. The experiments have revealed enhanced grain growth at higher temperatures, pore and gas bubble migration at all temperatures, and the latter also lead to enhanced sintering of highly porous ceramics into fully dense ceramics at unprecedentedly low temperatures. These results have shed light on kinetic processes that fall completely outside the realm of classical ceramic processing. Other fast-oxygen oxide ceramics closely related to, and often used in conjunction with zirconia ceramics, have also be investigated, as are closely related scientific problems in zirconia ceramics. These include crystal structures, defects, diffusion kinetics, oxygen potentials, low temperature sintering, flash sintering, and coarsening theory, and all have resulted in greater clarity in scientific understanding. The knowledge is leveraged to provide new insight to electrode kinetics and near-electrode mixed conductivity and to new materials. In the following areas, our research has resulted in completely new knowledge that defines the state-of-the-art of the field. (a) Electrical current driven non-equilibrium phenomena, (b) Enhanced grain growth under electrochemically reducing conditions, (c) Development of oxygen potential polarization in electrically loaded electrolyte, (d) Low temperature sintering and grain growth, and (e) Structure, defects and cation kinetics of fluorite-structured oxides. Our research has also contributed to synthesis of new energy-relevant electrochemical materials and new understanding

A wet-chemical approach to perovskite and fluorite-type nanoceramics: synthesis and processing

NARCIS (Netherlands)

Veldhuis, Sjoerd

2015-01-01

In thesis the low-temperature, wet-chemical approach to various functional inorganic oxide materials is described. The main focus of this research is to control the material’s synthesis from liquid precursor to metal oxide powder or thin film; while understanding its formation mechanism. In

Recent progress in the development of anode materials for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Cowin, Peter I.; Petit, Christophe T.G.; Lan, Rong; Tao, Shanwen [Department of Chemical and Process Engineering, University of Strathclyde, Glasgow G1 1XJ (United Kingdom); Irvine, John T.S. [School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST (United Kingdom)

2011-05-15

The field of research into solid oxide fuel cell (SOFC) anode materials has been rapidly moving forward. In the four years since the last in-depth review significant advancements have been made in the reduction of the operating temperature and improvement of the performance of SOFCs. This progress report examines the developments in the field and looks to draw conclusions and inspiration from this research. A brief introduction is given to the field, followed by an overview of the principal previous materials. A detailed analysis of the developments of the last 4 years is given using a selection of the available literature, concentrating on metal-fluorite cermets and perovskite-based materials. This is followed by a consideration of alternate fuels for use in SOFCs and their associated problems and a short discussion on the effect of synthesis method on anode performance. The concluding remarks compile the significant developments in the field along with a consideration of the promise of future research. The recent progress in the development of anode materials for SOFCs based on oxygen ion conducting electrolytes is reviewed. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The pressure-induced structural response of rare earth hafnate and stannate pyrochlore from 0.1-50 GPa

Science.gov (United States)

Turner, K. M.; Rittman, D.; Heymach, R.; Turner, M.; Tracy, C.; Mao, W. L.; Ewing, R. C.

2017-12-01

Complex oxides with the pyrochlore (A2B2O7) and defect-fluorite ((A,B)4O7) structure-types undergo structural transformations under high-pressure. These compounds are under consideration for applications including as a proposed waste-form for actinides generated in the nuclear fuel cycle. High-pressure transformations in rare earth hafnates (A2Hf2O7, A=Sm, Eu, Gd, Dy, Y, Yb) and stannates (A2Sn2O7, A=Nd, Gd, Er) were investigated to 50 GPa by in situ Raman spectroscopy and synchrotron x-ray diffraction (XRD). Rare-earth hafnates form the pyrochlore structure for A=La-Tb and the defect-fluorite structure for A=Dy-Lu. Lanthanide stannates form the pyrochlore structure. Raman spectra revealed that at ambient pressure all compositions have pyrochlore-type short-range order. Stannate compositions show a larger degree of pyrochlore-type short-range ordering relative to hafnates. In situ high-pressure synchrotron XRD showed that rare earth hafnates and stannates underwent a pressure-induced phase transition to a cotunnite-like (Pnma) structure that begins between 18-25 GPa in hafnates and between 30-33 GPa in stannates. The phase transition is not complete at 50 GPa, and upon decompression, XRD indicates that all compositions transform to defect-fluorite with an amorphous component. In situ Raman spectroscopy showed that disordering in stannates and hafnates occurs gradually upon compression. Pyrochlore-structured hafnates retain short-range order to a higher pressure (30 GPa vs. <10 GPa) than defect-fluorite-structured hafnates. Hafnates and stannates decompressed from 50 GPa show Raman spectra consistent with weberite-type structures, also reported in irradiated stannates. The second-order Birch-Murnaghan equation of state fit gives a bulk modulus of 250 GPa for hafnate compositions with the pyrochlore structure, and 400 GPa for hafnate compositions with the defect-fluorite structure. Stannates have a lower bulk modulus relative to hafnates (between 80-150 GPa

Brine history indicated by argon, krypton, chlorine, bromine, and iodine analyses of fluid inclusions from the Mississippi Valley type lead-fluorite-barite deposits at Hansonburg, New Mexico

Science.gov (United States)

Böhlke, J.K.; Irwin, J.J.

1992-01-01

Argon, krypton, chlorine, bromine, and iodine were measured in a homogeneous population of high-salinity hydrothermal fluid inclusions from the Tertiary-age Mississippi Valley-type (MVT) lead-fluorite-barite deposits at Hansonburg, New Mexico to establish new types of evidence for the history of both the fluid and the major dissolved salts. Noble gases and halogens in fluid inclusions containing 10−10–10−9 L of brine (Cl= 3 molal) were analyzed by laser microprobe noble-gas mass spectrometry (lmngms) on neutron-irradiated samples.The concentrations of36Ar (4.7 × 10−8 molal) and84Kr1.8 × 10−9 molal) in the fluid inclusions are equal to those of fresh surface waters in equilibrium with air at approximately20 ± 5°. The mole ratios ofBr/Cl (1.2 × 10−4) andI/Cl (1–2 × 10−6) are among the lowest measured in any natural waters, similar to those of modern brines formed by dissolution of Permian NaCl-bearing evaporites in southeast New Mexico.40Ar/36Ar ratios (600) are twice that of air, and indicate that the fluid inclusions had excess radiogenic40Ar (1.4 × 10−5 molal) when trapped. The amount of excess40Ar appears to be too large to have been acquired with Cl by congruent dissolution of halite-bearing evaporites, and possibly too small to have been acquired with Pb by congruent dissolution of granitic basement rocks with Proterozoic KAr ages.From thelmngms data, combined with published Pb and S isotope data, we infer the following sequence of events in the history of the Hansonburg MVT hydrothermal brine: (1) the brine originated as relatively dilute meteoric water, and it did not gain or lose atmospheric Ar or Kr after recharge; (2) the originally dilute fluid acquired the bulk of its Cl and sulfate in the subsurface after recharge by dissolving halite-bearing Permian? marine evaporites; (3) the high salinity brine then acquired most of its Pb and excess radiogenic40Ar from interactions with aquifer rocks other than evaporites, possibly clastic

Obtaining of ceria - samaria - gadolinia ceramics for application as solid oxide fuel cell (SOFC) electrolyte

International Nuclear Information System (INIS)

Arakaki, Alexander Rodrigo

2010-01-01

Cerium oxide (CeO 2 ) when doped with rare earth oxides has its ionic conductivity enhanced, enabling its use as electrolyte for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC), which is operated in temperatures between 500 e 700 degree C. The most effective additives or dopants for ionic conductivity improvement are (samarium oxide - Sm 2 O 3 ) and gadolinia (gadolinium oxide - Gd 2 O 3 ), fixing the concentration between 10 and 20 molar%. In this work, Ce 0,8 (SmGd) 0,2 O 1,9 powders have been synthesized by hydroxide, carbonate and oxalate coprecipitation routes. The hydrothermal treatment has been studied for powders precipitated with ammonium hydroxide. A concentrate of rare earths containing 90wt% of CeO 2 and other containing 51% of Sm 2 O 3 and 30% of Gd 2 O 3 , both prepared from monazite processing, were used as starting materials. These concentrates were used due the lower cost compared to pure commercial materials and the chemical similarity of others rare earth elements. Initially, the coprecipitation and calcination conditions were defined. The process efficiency was verified by ceramic sinterability evaluation. The results showed that powders calcined in the range of 450 and 800 degree C presented high specific surface area (90 - 150 m 2 .g -1 ) and fluorite cubic structure, indicating the solid solution formation. It was observed, by scanning electron microscopy, that morphology of particles and agglomerates is a function of precipitant agent. The dilatometric analysis indicated the higher rate of shrinkage at temperatures around 1300-1350 degree C. High densification values (>95% TD) was obtained at temperatures above 1400 degree C. Synthesis by hydroxides coprecipitation followed by hydrothermal treatment demonstrated to be a promising route for crystallization of ceria nano powders at low temperatures (200 degree C). High values of specific surface area were reached with the employment of hydrothermal treatment (about 100 m 2 .g -1

Remarkable changes in the photoluminescent properties of Y2Ce2O7:Eu(3+) red phosphors through modification of the cerium oxidation states and oxygen vacancy ordering.

Science.gov (United States)

Raj, Athira K V; Prabhakar Rao, P; Sreena, T S; Sameera, S; James, Vineetha; Renju, U A

2014-11-21

A new series of red phosphors based on Eu(3+)-doped yttrium cerate [Y1.9Ce2O7:0.1Eu(3+), Y2Ce1.9O7:0.1Eu(3+) and Y2Ce2-xO7:xEu(3+) (x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.50)] was prepared via a conventional solid-state method. The influence of the substitution of Eu(3+) at the aliovalent site on the photoluminescent properties was determined by powder X-ray diffraction, FT Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy with energy-dispersive spectroscopy, UV-visible absorption spectroscopy, photoluminescence spectroscopy and lifetime measurements. The substitution of Eu(3+) at the Ce(4+) site induces a structural transition from a defect fluorite to a C-type structure, which increases the oxygen vacancy ordering and the distortion of the Eu(3+) environment, and decreases the formation of Ce(3+) states. In contrast, phosphors with isovalent substitution at the Y(3+) site exhibit the biphasic nature of defect fluorite and a C-type structure, thereby increasing the number of Ce(3+) oxidation states. These modifications resulted in remarkable changes in the photoluminescent properties of Y2Ce1.9O7:0.1Eu(3+) red phosphors, with emission intensities 3.8 times greater than those of the Ce0.9O2:0.1Eu(3+) and Y1.9Ce2O7:0.1Eu(3+). The photoluminescent properties of Y2Ce2-xO7:xEu(3+) were studied at different Eu(3+) concentrations under excitation with blue light. These phosphors emit intense red light due to the (5)D0-(7)F2 transition under excitation at 466 nm and no concentration quenching is observed with up to 50 mol% Eu(3+). They show increased lifetimes in the range 0.62-0.72 ms at Eu(3+) concentrations. The cation ordering linked to the oxygen vacancy ordering led to the uniform distribution of Eu(3+) ions in the lattice, thus allowing higher doping concentrations without quenching and consequently increasing the lifetime of the (5)D0 states. Our results demonstrate that significant improvements in

Contribution to the development of the MARS beamline to study oxide dispersion strengthened steels (ODS) irradiated with neutrons using synchrotron source: secondary phases evolution under irradiation

International Nuclear Information System (INIS)

Menut, Denis

2016-01-01

X-Ray Diffraction (XRD) coupled with X-ray Absorption Fine Structure (XAFS) analyses at the MARS beamline of the synchrotron SOLEIL facility were used to study the microstructural evolution of oxides phases found in oxide dispersion strengthened steels (ODS) irradiated in Material Testing Reactors. Two hold generations of ODS steel grades (DY and MA957) irradiated up to high fluencies (∼75 dpa) were studied. These experiments have required specific developments, in particular a dedicated sample holder. An important milestone was overcome integrating the MARS beamline to the nuclearized facilities accessible for CEA. First, XRD analysis provide new results concerning intermediate sizes of precipitates (around 100 nm) essentially from crystallographic point of view, the nano-sized oxides (from 1 to 10 nm) being not detected, due to the material itself, sample preparation as thin foil and experimental set-up calibration. Secondly, XAFS analysis is not a discriminating technique as soon as the absorber atom is involved in the chemical composition of various precipitates found in ODS. Nevertheless, the stability of the Ti with a coordination number of 5 is evidenced whatever the irradiation conditions. As our experimental study was not able to detect the nano-sized oxides, an alternative way is to perform modeling approach of the behavior of massive oxides under irradiation, compared to experimental analyses under ion irradiations. We have shown that the defect fluorite is an intermediate phase of the crystal-to-amorphous phase transition of the pyrochlore oxide structure, whatever the irradiation conditions and the ratio of the cationic radii, the Ti coordination number remaining around 5 in the amorphous state. (author) [fr

Thermochemistry of rare earth doped uranium oxides Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} (Ln = La, Y, Nd)

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lei; Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu

2015-10-15

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10–50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO{sub 1.5}, UO{sub 2} and UO{sub 3} in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} is similar to that of UO{sub 2} to UO{sub 3} for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U{sup 5+}, U{sup 6+}, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements. - Highlights: • We synthesize, characterize Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} solid solutions (Ln = La, Y, Nd). • Formation enthalpies become more exothermic with increasing rare earth content. • Oxidation enthalpy of Ln{sub x}U{sub 1−x}O{sub 2−0.5x+y} is similar to that of UO{sub 2} to UO{sub 3}. • Direct calorimetric measurements are in good agreement with free energy data.

Analysing the Repellents Using EDXRF Method

International Nuclear Information System (INIS)

Khin Mi Mi; Khin Yi; Sein Htoon

2004-05-01

Determination of elemental contents in neem oil was evaluated using EDXRF.The comparsion on elemental concentrations of mosquito repellents cream, lotion and neem oil had been made. Where the neem oil was applied to the exposed body, it was found that the neem oil gives the protection action from the bites of mosquitoes

Atmospheric dust deposition on soils around an abandoned fluorite mine (Hammam Zriba, NE Tunisia).

Science.gov (United States)

Djebbi, Chaima; Chaabani, Fredj; Font, Oriol; Queralt, Ignasi; Querol, Xavier

2017-10-01

The present study focuses on the eolian dispersion and dust deposition, of major and trace elements in soils in a semi-arid climate, around an old fluorite (CaF 2 ) and barite (BaSO 4 ) mine, located in Hammam Zriba in Northern Tunisia. Ore deposits from this site contain a high amount of metal sulphides constituting heavy metal pollution in the surrounding environment. Samples of waste from the surface of mine tailings and agricultural topsoil samples in the vicinity of the mine were collected. The soil samples and a control sample from unpolluted area, were taken in the direction of prevailing northwest and west winds. Chemical analysis of these solids was performed using both X-ray fluorescence and X-ray diffraction. To determine the transfer from mine wastes to the soils, soluble fraction was performed by inductively coupled plasma and ionic chromatography. The fine grained size fraction of the un-restored tailings, still contained significant levels of barium, strontium, sulphur, fluorine, zinc and lead with mean percentages (wt%) of 30 (calculated as BaO), 13 (as SrO), 10 (as SO 3 ), 4 (F), 2 (Zn) and 1.2 (Pb). Also, high concentrations of cadmium (Cd), arsenic (As) and mercury (Hg) were found with an averages of 36, 24 and 1.2mgkg -1 , respectively. As a result of the eolian erosion of the tailings and their subsequent wind transport, the concentrations of Ba, Sr, S, F, Zn and Pb were extremely high in the soils near to the tailings dumps, with 5%, 4%, 7%, 1%, 0.8% and 0.2%, respectively. Concentration of major pollutants decreases with distance, but they were high even in the farthest samples. Same spatial distribution was observed for Cd, As and Hg. While, the other elements follow different spatial patterns. The leaching test revealed that most elements in the mining wastes, except for the anions, had a low solubility despite their high bulk concentrations. According the 2003/33/CE Decision Threshold, some of these tailings samples were considered as

Californium oxygen system for 1.50 < O/Cf < 1.72

International Nuclear Information System (INIS)

Turcotte, R.P.; Haire, R.G.

1975-01-01

The californium-oxygen system was studied as a function of temperature, oxygen pressure, and stoichiometry by manometric and x-ray diffraction methods. The results establish rhombohedral Cf 7 O 12 as the stable compound obtained by heating Cf 2 O 3 in air. The isobaric oxidation-reduction cycles Cf 2 O 3 → Cf 7 O 12 → Cf 2 O 3 , observed in constant rate of heating (cooling) experiments, occur with large hysteresis. A close parallel to other fluorite related lanthanide and actinide oxide systems is established. (auth)

Oxidative Precipitation of Manganese from Acid Mine Drainage by Potassium Permanganate

Directory of Open Access Journals (Sweden)

Regeane M. Freitas

2013-01-01

Full Text Available Although oxidative precipitation by potassium permanganate is a widely recognised process for manganese removal, research dealing with highly contaminated acid mine drainage (AMD has yet to be performed. The present study investigated the efficiency of KMnO4 in removing manganese from AMD effluents. Samples of AMD that originated from inactive uranium mine in Brazil were chemically characterised and treated by KMnO4 at pH 3.0, 5.0, and 7.0. Analyses by Raman spectroscopy and geochemical modelling using PHREEQC code were employed to assess solid phases. Results indicated that the manganese was rapidly oxidised by KMnO4 in a process enhanced at higher pH. The greatest removal, that is, 99%, occurred at pH 7.0, when treated waters presented manganese levels as low as 1.0 mg/L, the limit established by the Brazilian legislation. Birnessite (MnO2, hausmannite (Mn3O4, and manganite (MnOOH were detected by Raman spectroscopy. These phases were consistently identified by the geochemical model, which also predicted phases containing iron, uranium, manganese, and aluminium during the correction of the pH as well as bixbyite (Mn2O3, nsutite (MnO2, pyrolusite (MnO2, and fluorite (CaF2 following the KMnO4 addition.

X-ray diffraction study of the Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore disordering sequence under irradiation

Energy Technology Data Exchange (ETDEWEB)

Soulié, Aurélien, E-mail: aurelien.soulie@cea.fr [CEA, DEN, Service de Recherches de Métallurgie Physique, Université Paris-Saclay, F-91191 Gif sur Yvette (France); CEA, DEN, Service de Recherches de Métallurgie Appliqué, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Menut, Denis [CEA, DEN, Service de Recherches de Métallurgie Appliqué, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Crocombette, Jean-Paul [CEA, DEN, Service de Recherches de Métallurgie Physique, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Chartier, Alain [CEA, DEN, Service de la Corrosion et du Comportement des Matériaux dans leur Environnement, Laboratoire de Modélisation, de Thermodynamique et de Thermochimie, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Sellami, Neila [Univ. Paris Sud, ICMMO-SP2M, Bât. 410, F-91405 Orsay (France); Sattonnay, Gaël [Univ. Paris-Sud, CSNSM, CNRS, IN2P3, Bât. 108, F-91405 Orsay (France); Monnet, Isabelle [CIMAP, CEA, CNRS, Université de Caen, BP 5133, F-14070 Caen Cedex 5 (France); and others

2016-11-15

The disordering sequence of Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore, a nano-oxide phase that strengthens ODS steels under irradiation is studied in the experimental and modeling framework. XRD analysis has been performed considering both swift heavy ion and low energy/low mass ion irradiations. The simulation within molecular dynamics of Frenkel pair accumulation proves able to reproduce the variation of the amorphization fluence with temperature. XRD patterns calculated from the simulations reproduce well the patterns observed experimentally in the literature. Both experiments and calculations point to a first transition from pyrochlore to fluorite before an eventual amorphization. For swift heavy ion irradiations with 93 MeV Xe ions, tracks of direct impact amorphization are visible by HRTEM. Advanced refinement shows that one third of the pyrochlore impacted by an ion transforms into fluorite, while two third are directly amorphized. - Highlights: • A comparison between swift heavy ion and low energy/low mass ion irradiation of Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore is performed. • Simulations of the irradiation with Molecular dynamics reproduce the amorphization dose at low energy/mass ion irradiation. • Advanced refinement of X-ray diffraction patterns gives the evolution of phase fractions in pyrochlore under irradiation. • The disordering sequence a transition from pyrochlore to defect fluorite before an eventual amorphization.

Structural, morphological, and electrical properties of doped ceria as a solid electrolyte for intermediate-temperature solid oxide fuel cells

KAUST Repository

Stojmenović, M.

2015-03-11

The solid solutions of CeO2 with one or more rare-earth oxides among Yb2O3, Sm2O3, and Gd2O3 are synthesized by either modified glycine nitrate procedure (MGNP) or self-propagating reaction at room temperature (SPRT). The overall mole fraction of rare-earth oxide dopants was x = 0.2. The characterization was committed by XRPD, TEM, BET, and Raman Spectroscopy methods. According to XRPD and Raman spectroscopy, the obtained products presented the single-phase solid solutions with basic fluorite-type CeO2 structure, regardless on the number and the concentration of dopants. Both XRPD and TEM analysis evidenced the nanometer particle dimensions. The defect model was applied to calculate lattice parameters of single-, co-, and multi-doped solids. The sintering of the sample nanopowders was performed at 1550 °C, in air atmosphere. The sintered samples were characterized by XRPD, SEM, and complex impedance methods. The sintering did not affect the concentration ratios of the constituents. The highest conductivity at 700 °C amounting to 2.14 × 10−2 and 1.92 × 10−2 Ω−1 cm−1 was measured for the sample Ce0.8Sm0.08Gd0.12O2−δ, synthesized by SPRT and MGNP methods, respectively. The corresponding activation energies of conductivity, measured in the temperature range 500–700 °C, amounted to 0.24 and 0.23 eV.

Structural, morphological, and electrical properties of doped ceria as a solid electrolyte for intermediate-temperature solid oxide fuel cells

KAUST Repository

Stojmenović, M.; Zunic, Milan; Gulicovski, J.; Bajuk-Bogdanović, D.; Holclajtner-Antunović, I.; Dodevski, V.; Mentus, S.

2015-01-01

The solid solutions of CeO2 with one or more rare-earth oxides among Yb2O3, Sm2O3, and Gd2O3 are synthesized by either modified glycine nitrate procedure (MGNP) or self-propagating reaction at room temperature (SPRT). The overall mole fraction of rare-earth oxide dopants was x = 0.2. The characterization was committed by XRPD, TEM, BET, and Raman Spectroscopy methods. According to XRPD and Raman spectroscopy, the obtained products presented the single-phase solid solutions with basic fluorite-type CeO2 structure, regardless on the number and the concentration of dopants. Both XRPD and TEM analysis evidenced the nanometer particle dimensions. The defect model was applied to calculate lattice parameters of single-, co-, and multi-doped solids. The sintering of the sample nanopowders was performed at 1550 °C, in air atmosphere. The sintered samples were characterized by XRPD, SEM, and complex impedance methods. The sintering did not affect the concentration ratios of the constituents. The highest conductivity at 700 °C amounting to 2.14 × 10−2 and 1.92 × 10−2 Ω−1 cm−1 was measured for the sample Ce0.8Sm0.08Gd0.12O2−δ, synthesized by SPRT and MGNP methods, respectively. The corresponding activation energies of conductivity, measured in the temperature range 500–700 °C, amounted to 0.24 and 0.23 eV.

Chemical thermodynamic representations of and

International Nuclear Information System (INIS)

Besmann, T.M.; Lindemer, T.B.

1985-01-01

All available oxygen potential-temperature-composition data for the calcium fluorite-structure sup(**) phase were retrieved from the literature and utilized in the development of a binary solid solution representation of the phase. The data and phase relations are found to be best described by a solution of [Pusub(4/3)O 2 ] and [PuO 2 ] with a temperature dependent interaction energy. The fluorite-structure is assumed to be represented by a combination of the binaries and , and thus treated as a solution of [Pusub(4/3)O 2 ], [PuO 2 ], [UO 2 ], and either [U 2 Osub(4.5)] or [U 3 O 7 ]. The resulting equations well reproduce the large amount of oxygen potential-temperature-composition data for the mixed oxide system, all of which were also retrieved from the literature. These models are the first that appear to display the appropriate oxygen potential-temperature-composition and phase relation behavior over the entire range of existence for the phases. (orig.)

Defining chemical expansion: the choice of units for the stoichiometric expansion coefficient

DEFF Research Database (Denmark)

Marrocchelli, Dario; Chatzichristodoulou, Christodoulos; Bishop, Sean R.

2014-01-01

Chemical expansion refers to the spatial dilation of a material that occurs upon changes in its composition. When this dilation is caused by a gradual, iso-structural increase in the lattice parameter with composition, it is related to the composition change by the stoichiometric expansion coeffi...... are provided for changes in oxygen content in fluorite, perovskite, and Ruddlesden-Popper (K2NiF4) phase materials used in solid oxide fuel cells....

Lattice thermal expansion and solubility limits of neodymium-doped ceria

International Nuclear Information System (INIS)

Zhang, Jinhua; Ke, Changming; Wu, Hongdan; Yu, Jishun; Wang, Jingran

2016-01-01

Nd x Ce 1−x O 2−0.5x (x=0–1.0) powders were prepared by reverse coprecipitation-calcination method and characterized by XRD. The crystal structure of product powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value. An empirical equation simulating the lattice parameter of neodymium doped ceria was established based on the experimental data. The lattice parameters of the fluorite structure solid solutions increased with extensive adoption of Nd 3+ , and the heating temperature going up. The average thermal expansion coefficients of neodymium doped ceria with fluorite structure are higher than 13.5×10 −6 °C −1 from room temperature to 1200 °C. - Graphical abstract: The crystal structure of Nd x Ce 1−x O 2−0.5x (x=0–1.0) powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value.

Interactions of NO{sub 2} at ambient temperature with cerium-zirconium mixed oxides supported on SBA-15

Energy Technology Data Exchange (ETDEWEB)

Levasseur, Benoit; Ebrahim, Amani M. [The City College of New York and The Graduate School of CUNY 160 Convent Ave, New York, NY 10031 (United States); Burress, Jacob [NIST Center for Neutron Research, National Institute of Standards and Technology 100 Bureau Drive, Gaithersburg, MD 20899 (United States); Bandosz, Teresa J., E-mail: tbandosz@ccny.cuny.edu [The City College of New York and The Graduate School of CUNY 160 Convent Ave, New York, NY 10031 (United States)

2011-12-15

Highlights: Black-Right-Pointing-Pointer Ce{sub 1-y}Zr{sub y}O{sub 2-x} mixed oxides were highly dispersed in mesoporous silica SBA-15. Black-Right-Pointing-Pointer A strong increase in the NO{sub 2} adsorption capacity was observed on composites. Black-Right-Pointing-Pointer The insertion of Zr{sup 4+} in ceria fluorite structure promotes the reduction of Ce{sup 4+} into Ce{sup 3+}. Black-Right-Pointing-Pointer Ce{sup 3+} and -OH groups were found to be the main active centers for NO{sub x} retention. Black-Right-Pointing-Pointer The structure remains quite stable after exposure to NO{sub 2} in ambient conditions. - Abstract: New silica-based composites were obtained using a slow precipitation of mixed oxide Ce{sub 1-x}Zr{sub x}O{sub 2} on the surface of mesoporous silica, SBA-15. The samples were tested as NO{sub 2} adsorbents in dynamic conditions at room temperature. The surface of the initial and exhausted materials was characterized using N{sub 2} sorption, XRD, TEM, potentiometric titration, and thermal analysis before and after exposure to NO{sub 2}. In comparison with unsupported Ce{sub 1-x}Zr{sub x}O{sub 2} mixed oxides, a significant increase in the NO{sub 2} adsorption capacity was observed. This is due to the high dispersion of active oxide phase on the surface of SBA-15. A linear trend was found between the NO{sub 2} adsorption capacity and the amount of Zr(OH){sub 4} added to the structure. Introduction of Zr{sup 4+} cations to ceria contributes to an increase in the amount of Ce{sup 3+}, which is the active center for the NO{sub 2} adsorption, and to an increase in the density of -OH groups. These groups are found to be involved in the retention of both NO{sub 2} and NO on the surface. After exposure to NO{sub 2}, an acidification of the surface caused by the oxidation of the cerium as well as the formation of nitrite and nitrates took place. The structure of the composites appears not to be affected by reactive adsorption of NO{sub 2}.

Synthesis, characterization and thermal expansion studies on thorium-praseodymium mixed oxide solid solutions

International Nuclear Information System (INIS)

Panneerselvam, G.; Antony, M.P.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2010-01-01

Full text: Thorium-praseodymium mixed oxide solid solutions containing 15, 25, 40 and 55 mole percent of praseodymia were synthesized by mixing the solutions of thorium nitrate in water and praseodymium oxide (Pr 6 O 11 ) in conc. HNO 3 . Subsequently, their hydroxides were co-precipitated by the addition of aqueous ammonia. Further the precipitate was dried at 50 deg C, calcined at 600 deg C for 4 hours and sintered at 1200 deg C for 6 h in air. X-ray diffraction measurements were performed for phase identification and lattice parameter derivation. Single-phase fluorite structure was observed for all the compositions. Bulk and theoretical densities of solid solutions were also determined by immersion and X-ray techniques. Thermal expansion coefficients and percentage linear thermal expansion of the solid solutions were determined using high temperature X-ray diffraction technique in the temperature range 300 to 1700 K for the first time. The room temperature lattice constants estimated for above compositions are 0.5578, 0.5565, 0.5545 and 0.5526 nm, respectively. The mean linear thermal expansion coefficients for the solid solutions are 15.48 x 10 -6 K -1 , 18.35 x 10 -6 K -1 , 22.65 x 10 -6 K -1 and 26.95 x 10 -6 K -1 , respectively. The percentage linear thermal expansions in this temperature range are 1.68, 1.89, 2.21 and 2.51 respectively. It is seen that the solid solutions are stable up to 1700 K. It is also seen that the effect and nature of the dopant are the important parameters influencing the thermal expansion of the ThO 2 . The lattice parameter of the solid solutions exhibited a decreasing trend with respect to praseodymia addition. The percentage linear thermal expansion of the solid solutions increases steadily with increasing temperature

Rapid, cool sintering of wet processed yttria-stabilized zirconia ceramic electrolyte thin films

OpenAIRE

Park, Jun-Sik; Kim, Dug-Joong; Chung, Wan-Ho; Lim, Yonghyun; Kim, Hak-Sung; Kim, Young-Beom

2017-01-01

Here we report a photonic annealing process for yttria-stabilized zirconia films, which are one of the most well-known solid-state electrolytes for solid oxide fuel cells (SOFCs). Precursor films were coated using a wet-chemical method with a simple metal-organic precursor solution and directly annealed at standard pressure and temperature by two cycles of xenon flash lamp irradiation. The residual organics were almost completely decomposed in the first pre-annealing step, and the fluorite cr...

Synthesis and crystal structure of the first Sc-Nb-O-N phases

Energy Technology Data Exchange (ETDEWEB)

Orthmann, Steven; Lerch, Martin [Institut fuer Chemie, Technische Universitaet Berlin (Germany)

2017-11-17

Synthesis of phase-pure materials in the system Sc-Nb-O-N is challenging. In this contribution we report on the preparation of the first scandium niobium oxide nitrides via reaction of water-saturated gaseous ammonia or an ammonia-oxygen mixture with amorphous scandium niobium oxides. Two new phases were obtained: rutile-type ScNb{sub 4}O{sub 7}N{sub 3}, which crystallizes in space group P4{sub 2}/mnm, and an anion-deficient fluorite-type Sc{sub 2}Nb(O,N,⬜){sub 6} phase crystallizing in space group Fm anti 3m. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Lattice thermal expansion and solubility limits of neodymium-doped ceria

Energy Technology Data Exchange (ETDEWEB)

Zhang, Jinhua, E-mail: jhzhang1212@126.com [The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China); State Key laboratory of Geological Process and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); Ke, Changming [The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China); Wu, Hongdan [College of Resources and Enviromental Engineering, Wuhan University of Science and Technology, Wuhan 430081 (China); Yu, Jishun [State Key laboratory of Geological Process and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); Wang, Jingran [The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China)

2016-11-15

Nd{sub x}Ce{sub 1−x}O{sub 2−0.5x} (x=0–1.0) powders were prepared by reverse coprecipitation-calcination method and characterized by XRD. The crystal structure of product powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value. An empirical equation simulating the lattice parameter of neodymium doped ceria was established based on the experimental data. The lattice parameters of the fluorite structure solid solutions increased with extensive adoption of Nd{sup 3+}, and the heating temperature going up. The average thermal expansion coefficients of neodymium doped ceria with fluorite structure are higher than 13.5×10{sup −6} °C{sup −1} from room temperature to 1200 °C. - Graphical abstract: The crystal structure of Nd{sub x}Ce{sub 1−x}O{sub 2−0.5x} (x=0–1.0) powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value.

Geochemistry of the furnace magnetite bed, Franklin, New Jersey, and the relationship between stratiform iron oxide ores and stratiform zinc oxide-silicate ores in the New Jersey highlands

Science.gov (United States)

Johnson, C.A.; Skinner, B.J.

2003-01-01

The New Jersey Highlands terrace, which is an exposure of the Middle Proterozoic Grenville orogenic belt located in northeastern United States, contains stratiform zinc oxide-silicate deposits at Franklin and Sterling Hill and numerous massive magnetite deposits. The origins of the zinc and magnetite deposits have rarely been considered together, but a genetic link is suggested by the occurrence of the Furnace magnetite bed and small magnetite lenses immediately beneath the Franklin zinc deposit. The Furnace bed was metamorphosed and deformed along with its enclosing rocks during the Grenvillian orogeny, obscuring the original mineralogy and obliterating the original rock fabrics. The present mineralogy is manganiferous magnetite plus calcite. Trace hydrous silicates, some coexisting with fluorite, have fluorine contents that are among the highest ever observed in natural assemblages. Furnace bed calcite has ??13C values of -5 ?? 1 per mil relative to Peedee belemnite (PDB) and ??18O values of 11 to 20 per mil relative to Vienna-standard mean ocean water (VSMOW). The isotopic compositions do not vary as expected for an original siderite layer that decarbonated during metamorphism, but they are consistent with nearly isochemical metamorphism of an iron oxide + calcite protolith that is chemically and minerlogically similar to iron-rich sediments found near the Red Sea brine pools and isotopically similar to Superior-type banded iron formations. Other magniferous magnite + calcite bodies occur at approximately the same stratigraphic position as far 50 km from the zinc deposits. A model is presented in which the iron and zinc deposits formed along the western edge of a Middle Proterozoic marine basin. Zinc was transported by sulfate-stable brines and was precipitated under sulfate-stable conditions as zincian carbonates and Fe-Mn-Zn oxides and silicates. Whether the zincian assemblages settled from the water column or formed by replacement reactions in shallowly

Synchronous and Asynchronous ATM Multiplexor Properties Comparsion

OpenAIRE

Jan Zabka

2006-01-01

The article is aimed to ATM multiplexor computer model utilisation. Based on simulation runs we try to review aspects of use a synchronous and asynchronous ATM multiplexors. ATM multiplexor is the input queuing model with three inputs. Synchronous multiplexor works without an input priority. Multiplexor inputs are served periodically. Asynchronous multiplexor model supports several queuing and priority mechanisms. CLR and CTD are basic performance parameters. Input cell flows are genera...

First-principles study of dielectric properties of cerium oxide

International Nuclear Information System (INIS)

Yamamoto, Takenori; Momida, Hiroyoshi; Hamada, Tomoyuki; Uda, Tsuyoshi; Ohno, Takahisa

2005-01-01

We have theoretically investigated the dielectric properties of fluorite CeO 2 as well as hexagonal and cubic Ce 2 O 3 by using first-principles pseudopotentials techniques within the local density approximation. Calculated electronic and lattice dielectric constants of CeO 2 are in good agreement with previous theoretical and experimental results. For Ce 2 O 3 , the hexagonal phase has a lattice dielectric constant comparable to that of CeO 2 , whereas the cubic phase has a much smaller one. We have concluded that the enhancement of the dielectric constant in CeO 2 epitaxially grown on Si is not due to its lattice expansion experimentally observed nor regular formation of oxygen vacancies in CeO 2

Effect of polyvinylpyrrolidone on cerium oxide nanoparticle characteristics prepared by a facile heat treatment technique

Directory of Open Access Journals (Sweden)

Anwar Ali Baqer

Full Text Available An aqueous medium composed of polyvinylpyrrolidone (PVP and cerium nitrates at calcination temperature was utilised in the production of cerium oxide (CeO2 semiconductor nanoparticles. A variety of analytical approaches was utilized to examine the structural, morphological and optical characteristics of the resulting nanoparticles. Differential thermal (DTA and thermogravimetric (TGA analyses, indicated that the best calcination temperatures for achieving CeO2 nanoparticle production were more than 485 °C. The results from Fourier-transform infrared (FTIR verified the formation of a crystalline structure after calcination procedures were performed to remove residual organic compounds. Additionally, results from X-ray diffraction (XRD analysis confirmed the cubic fluorite structure of the CeO2 produced. Samples were also analysed by energy dispersive spectroscopy (EDXA which indicated the existence of O and Ce in the samples. Field emission scanning electron microscopy (FESEM was used in the characterisation of nanoparticle morphological features. Transmission electron microscopy (TEM was employed to estimate typical nanoparticle and distribution within sample. This analysis indicated that mean particle sizes were inversely correlated with PVP concentration, with nanoparticle sizes ranging between 12 ± 7 nm at 0.03 g/mL PVP and 6 ± 2 nm at 0.05 g/mL PVP. These results corroborated those obtained by XRD analysis. A UV–vis spectrophotometer was utilised in the demonstration of optical properties and to examine the band gap energy of samples. The potential UV-shielding properties of the nanoparticles were demonstrated by the observed blue shift of the estimated optical energy band, i.e. from 3.35 to 3.43 eV, whilst PL spectra results indicated that decreasing particle size was associated with diminishing photoluminescence intensity. Keywords: Cerium oxide nanoparticles, Heat treatment technique, Structural properties, Optical

Reducción carbotérmica de pirolusita para la obtención de ferromanganeso y escoria, adecuados al desarrollo de materiales de soldadura

OpenAIRE

Cruz-Crespo, A.; García-Sánchez, L. L.; Quintana-Puchol, R.; Perdomo-González, L.; Gómez-Pérez, C. R.; Jiménez-Vielsa, G. E.; Cores-Sánchez, A.

2004-01-01

The high carbon ferromanganese obtained by means of carbothermic reduction in an electric arc furnace of direct current is proposed. The ideal composition of slag oxides to achieve a flux to be used in the submerged arc welding (SAW) is established. Calculation for charge components (pirolusite, coke, steel wool, lime, rutile and fluorite) for no fluxes technology for FeMn is carried out taking into account the welding fluxes characteristics of the SiO₂-MnO-CaO system. ...

The most common types of injuries in judo

OpenAIRE

Ječmínek, Jan

2014-01-01

Title: The most common types of injuries in judo Objectives: The aim of this study was to determine the most common injuries that occur during training and judo competitions. Identify treatment options, prevention and identify most common causes of injury. Methods: The chosen method was theoretical and empirical, ie collecting data and information from other publications and conduct its own research. Selecting what is relevant for judo injuries and comparsion whith author's experience and res...

Three new Anthraquinones, one new Benzochromene and one new Furfural glycoside from Lasianthus acuminatissimus.

Science.gov (United States)

Huang, Teng; Ming, Jianxin; Zhong, Jialiang; Zhong, Youquan; Wu, Huaqiang; Liu, Hongdong; Li, Bin

2018-06-01

Three new anthraquinones, lasianthurin B (1), C (2), lasianthuoside D (3), a new benzochromene, lasianthurin D (4), and a new furfural glycoside, lasianthuoside E (5), together with one known compound 4- hydroxymethyl-2-furaldehyde (6) were isolated from an alcohol extract of the root of Lasianthus acuminatissimus. Their structures were elucidated on the basis of extensive spectroscopic data analysis (including 1D, 2D NMR, X-ray, and MS experiments) and comparsion to literature data.

Remote Sensing, Geology and Geochemistry on the GVIII Uranium Mineralization, Gabal Gattar, North Eastern Desert, Egypt

International Nuclear Information System (INIS)

Elkholy, D.M.; Elhusseiny, M.O.; Saleh, W.H.; Elzalaky, M.A.

2012-01-01

GVIII- uranium occurrence of Gabal Gattar is located at the intersection of Lat. 27° 05' 56 a nd Long. 33° 16' 33 t o the south of GH-uranium occurrence. This occurrence is hosted in the alkali feldspar granite of Gabal Gattar. It is dissected by NNE-SSW, ENE-WSW and NW-SE faults and fractures. The granite is strongly altered in the zones of these faults and fractures. This granite is composed of K-feldspars, quartz, plagioclase and biotite as essential minerals and zircon, apatite, fluorite as accessories. The secondary minerals are chlorite, sericite, muscovite and iron oxides. The main alterations along the fault and fracture zones are hematitization, silicification, kaolintiization, chloritization and fluoritization that increase at the zones of intersection.The Advanced Spacebome Thermal Emission and Reflection Radiometer (ASTER) discriminated and mapped the hematitized zones in the studied granitic rocks predicting iron oxides as pathfinder minerals that be helpful in localizing high uranium concentration. The compilated and integrated data as alteration zones, geological and structural features using Geographic Information System (GIS) played an important role in correlating, manipulating, visualizing and extracting the information getting a better result for interpretation and evaluation of this occurrence. The study granite is geochemically, alkali- feldspar granite to syenogranite originated from weakly peraluminous magma of alkaline affinity and of within plate tectonic setting due to crustal relaxation. This granite shows many geochemical characterestics similar to the A-type granite, high contents of SiO 2 , (Na 2 O + K 2 O), Rb, Nb, Y, low contents of MgO, CaO and Sr and apparently F-rich granite.Radiometric measurements of GVIII U-occurrence show that the study granite records uranium values between 15 and 28 ppm, while the anomalies record uranium values range from 400 to more than 30000 ppm. Surfacial yellow secondary uranium

Mineralogical and geochemical characteristics of uranium-rich fluoriteinEl-Missikat mineralized granite,Central Eastern Desert, Egypt

Directory of Open Access Journals (Sweden)

Mohamed Fahmy Raslan

2009-12-01

Full Text Available A unique, highly radioactive variety of fluor it emineral has been recorded in the uranium occurrence of El-Missikat sheared granite pluton. In this occurrence, the uranium assumes different forms, including its presence as discrete, visible, secondary minerals, rare uraninite and its association with the jasperoid and silica veinlets. However,in some other parts of the sheared zone, the uranium was found to be solely incorporated with fluorite crystals,filling veinlet sand fractures with out any other manife station.This paper focuses ont her elevant mineralogical and geochemical characteristics of this unique fluorite variety.In addition to an investigation with binocular and polarizing microscopes, the separated fluorite grains were analyzed usingan environmental scanning electronmicroscope(ESEM and a field-emission scanning electron microscope.In addition to this,some fluorite crystals were subjected to electron microprobe analyses. While the fluorite accounted for as much as 20% of the sheared granite samples studied, it was found to range from 82 to 96 % in the different size fractions of the separated heavy mineral content. In some parts of the separated fluorite crystals,uranium inquantities of up to 2200 ppm was found to be heterogeneously distributed in the fluoritelattice,regardless of its coloration.

Crystal structure of fluorite-related Ln3SbO7 (Ln=La–Dy) ceramics studied by synchrotron X-ray diffraction and Raman scattering

International Nuclear Information System (INIS)

Siqueira, K.P.F.; Borges, R.M.; Granado, E.; Malard, L.M.; Paula, A.M. de; Moreira, R.L.; Bittar, E.M.; Dias, A.

2013-01-01

Ln 3 SbO 7 (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) ceramics were synthesized by solid-state reaction in optimized conditions of temperature and time to yield single-phase ceramics. The crystal structures of the obtained ceramics were investigated by synchrotron X-ray diffraction, second harmonic generation (SHG) and Raman scattering. All samples exhibited fluorite-type orthorhombic structures with different oxygen arrangements as a function of the ionic radius of the lanthanide metal. For ceramics with the largest ionic radii (La–Nd), the ceramics crystallized into the Cmcm space group, while the ceramics with intermediate and smallest ionic radii (Sm–Dy) exhibited a different crystal structure belonging to the same space group, described under the Ccmm setting. The results from SHG and Raman scattering confirmed these settings and ruled out any possibility for the non-centrosymmetric C222 1 space group describing the structure of the small ionic radii ceramics, solving a recent controversy in the literature. Besides, the Raman modes for all samples are reported for the first time, showing characteristic features for each group of samples. - Graphical abstract: Raman spectrum for La 3 SbO 7 ceramics showing their 22 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. - Highlights: • Ln 3 SbO 7 ceramics belonging to the space groups Cmcm and Ccmm are synthesized. • SXRD, SHG and Raman scattering confirmed the orthorhombic structures. • Ccmm instead of C222 1 is the correct one based on SHG and Raman data

Preparation of thin layer materials with macroporous microstructure for SOFC applications

International Nuclear Information System (INIS)

Marrero-Lopez, D.; Ruiz-Morales, J.C.; Pena-Martinez, J.; Canales-Vazquez, J.; Nunez, P.

2008-01-01

A facile and versatile method using polymethyl methacrylate (PMMA) microspheres as pore formers has been developed to prepare thin layer oxide materials with controlled macroporous microstructure. Several mixed oxides with fluorite and perovskite-type structures, i.e. doped zirconia, ceria, ferrites, manganites, and NiO-YSZ composites have been prepared and characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and mercury porosimetry. The synthesised materials are nanocrystalline and present a homogeneous pore distribution and relatively high specific surface area, which makes them interesting for SOFC and catalysis applications in the intermediate temperature range. - Graphical abstract: Thin films materials of mixed oxides with potential application in SOFC devices have been prepared with macroporous microstructure using PMMA microspheres as pore formers. Display Omitted

Enhancement of the chemical stability in confined δ-Bi2O3

DEFF Research Database (Denmark)

Sanna, Simone; Esposito, Vincenzo; Andreasen, Jens Wenzel

2015-01-01

Bismuth-oxide-based materials are the building blocks for modern ferroelectrics1, multiferroics2, gas sensors3, light photocatalysts4 and fuel cells5,6. Although the cubic fluorite δ-phase of bismuth oxide (δ-Bi2O3) exhibits the highest conductivity of known solid-state oxygen ion conductors5, its...... instability prevents use at low temperature7–10. Here we demonstrate the possibility of stabilizing δ-Bi2O3 using highly coherent interfaces of alternating layers of Er2O3-stabilized δ-Bi2O3 and Gd2O3-doped CeO2. Remarkably, an exceptionally high chemical stability in reducing conditions and redox cycles...

Synthesis, Characterization and Thermal Diffusivity of Holmium and Praseodymium Zirconates

OpenAIRE

Stopyra M.; Niemiec D.; Moskal G.

2016-01-01

A2B2O7 oxides with pyrochlore or defected fluorite structure are among the most promising candidates for insulation layer material in thermal barrier coatings. The present paper presents the procedure of synthesis of holmium zirconate Ho2Zr2O7 and praseodymium zirconate Pr2Zr2O7 via Polymerized-Complex Method (PCM). Thermal analysis of precursor revealed that after calcination at relatively low temperature (700°C) fine-crystalline, single-phase material is obtained. Thermal diffusivity was me...

Effect of dose rate on the translocation yield in rat spermatogonia

International Nuclear Information System (INIS)

Vyglenov, A.; Rudnitski, T.; Kokhmanska-Tvardovska, A.

1987-01-01

The effectiveness of chronic gamma-irradiation with dose rate 1.10 -4 Gy/min on the yield of reciprocal translocations in rat spermatogonia was studied. Comparsion was made with acute gamma-irradiation at emissive power 1,23 Gy/min. Emissive power decrease by four orders reduced 12 times the extent of genetic injury - from 34,9 down to 3 translocations per cellx10 -5 /cGy. In this respect, the rat is close to the laboratory mouse

Ni-doped (CeO2−δ)–YSZ mesoarchitectured with nanocrystalline framework: the effect of thermal treatment on structure, surface chemistry and catalytic properties in the partial oxidation of methane (CPOM)

International Nuclear Information System (INIS)

Somacescu, Simona; Florea, Mihaela; Osiceanu, Petre; Calderon-Moreno, Jose Maria; Ghica, Corneliu; Serra, Jose Manuel

2015-01-01

Ni-doped (CeO 2−δ )–YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure (∼18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer—Emmett—Teller, BET; Temperature—Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N 2 sorption measurements highlighted that the mesoporous structure is formed at 600 °C and remains stable at 800 °C. At 900 °C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 °C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce 3+  + Ce 4+ ) with high percentage of Ce 3+ valence state ∼35 % and (Ni 3+ and Ni 2+ ) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.Graphical Abstract

Ni-doped (CeO{sub 2−δ})–YSZ mesoarchitectured with nanocrystalline framework: the effect of thermal treatment on structure, surface chemistry and catalytic properties in the partial oxidation of methane (CPOM)

Energy Technology Data Exchange (ETDEWEB)

Somacescu, Simona, E-mail: ssimona@icf.ro [Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry (Romania); Florea, Mihaela [University of Bucharest, Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry (Romania); Osiceanu, Petre; Calderon-Moreno, Jose Maria [Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry (Romania); Ghica, Corneliu [National Institute of Materials Physics (Romania); Serra, Jose Manuel [Universidad Politécnica de Valencia - Consejo Superior de Investigaciones Científicas, Instituto de Tecnología Química (Spain)

2015-11-15

Ni-doped (CeO{sub 2−δ})–YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure (∼18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer—Emmett—Teller, BET; Temperature—Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N{sub 2} sorption measurements highlighted that the mesoporous structure is formed at 600 °C and remains stable at 800 °C. At 900 °C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 °C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce{sup 3+} + Ce{sup 4+}) with high percentage of Ce{sup 3+} valence state ∼35 % and (Ni{sup 3+} and Ni{sup 2+}) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.Graphical Abstract.

A petrographic study of Precambrian quartzites from Goa coast

Digital Repository Service at National Institute of Oceanography (India)

Wagle, B.G.; Rajamanickam, G.V.

tourmaline, topaz, zircon, rutile, fluorite, apatite and hornblende lead to a source of acidic composition. The introduction of tourmaline and fluorite in the wacke, the grade of metamorphism and the source of the wacke have been discussed...

Electronic, elastic, acoustic and optical properties of cubic TiO2: A DFT approach

International Nuclear Information System (INIS)

Mahmood, Tariq; Cao, Chuanbao; Tahir, Muhammad; Idrees, Faryal; Ahmed, Maqsood; Tanveer, M.; Aslam, Imran; Usman, Zahid; Ali, Zulfiqar; Hussain, Sajad

2013-01-01

The electronic, elastic, acoustic and optical properties of cubic phases TiO 2 fluorite and pyrite are investigated using the first principles calculations. We have employed five different exchange–correlation functions within the local density and generalized gradient approximations using the ultrasoft plane wave pseudopotential method. The calculated band structures of cubic-TiO 2 elucidate that the TiO 2 fluorite and pyrite are direct and indirect semiconductors in contrast to the previous findings. From our studied properties such as bulk and shear moduli, elastic constants C 44 and Debye temperature for TiO 2 fluorite and pyrite, we infer that both the cubic phases are not superhard materials and the pyrite phase is harder than fluorite. The longitudinal and transversal acoustic wave speeds for both phases in the directions [100], [110] and [111] are determined using the pre-calculated elastic constants. In addition, we also calculate the optical properties such as dielectric function, absorption spectrum, refractive index and energy loss function using the pre-optimized structure. On the observation of optical properties TiO 2 fluorite phase turn out to be more photocatalytic than pyrite

Uranium-contaminated soils: Ultramicrotomy and electron beam analysis

International Nuclear Information System (INIS)

Buck, E.C.; Dietz, N.L.; Bates, J.K.; Cunnane, J.C.

1994-01-01

Uranium contaminated soils from the Fernald Operation Site, Ohio, have been examined by a combination of optical microscopy, scanning electron microscopy with backscattered electron detection (SEM/BSE), and analytical electron microscopy (AEM). A method is described for preparing of transmission electron microscopy (TEM) thin sections by ultramicrotomy. By using these thin sections, SEM and TEM images can be compared directly. Uranium was found in iron oxides, silicates (soddyite), phosphates (autunites), and fluorite. Little uranium was associated with clays. The distribution of uranium phases was found to be inhomogeneous at the microscopic level

High ionic conductivity in confined bismuth oxide-based heterostructures

Directory of Open Access Journals (Sweden)

Simone Sanna

2016-12-01

Full Text Available Bismuth trioxide in the cubic fluorite phase (δ-Bi2O3 exhibits the highest oxygen ionic conductivity. In this study, we were able to stabilize the pure δ-Bi2O3 at low temperature with no addition of stabilizer but only by engineering the interface, using highly coherent heterostructures made of alternative layers of δ-Bi2O3 and Yttria Stabilized Zirconia (YSZ, deposited by pulsed laser deposition. The resulting [δ-Bi2O3/YSZ] heterostructures are found to be stable over a wide temperature range (500-750 °C and exhibits stable high ionic conductivity over a long time comparable to the value of the pure δ-Bi2O3, which is approximately two orders of magnitude higher than the conductivity of YSZ bulk.

High ionic conductivity in confined bismuth oxide-based heterostructures

DEFF Research Database (Denmark)

Sanna, Simone; Esposito, Vincenzo; Christensen, Mogens

2016-01-01

Bismuth trioxide in the cubic fluorite phase (δ-Bi2O3) exhibits the highest oxygen ionic conductivity. In this study, we were able to stabilize the pure -Bi2O3 at low temperature with no addition of stabilizer but only by engineering the interface, using highly coherent heterostructures made...... of alternative layers of δ-Bi2O3 and Yttria Stabilized Zirconia (YSZ), deposited by pulsed laser deposition. The resulting [δ-Bi2O3=YSZ] heterostructures are found to be stable over a wide temperature range (500-750 °C) and exhibits stable high ionic conductivity over a long time comparable to the value...... of the pure δ-Bi2O3, which is approximately two orders of magnitude higher than the conductivity of YSZ bulk....

Mineralogical Characterization of The Alteration Facies at Gabal El-Missikat Area, Central Eastern Desert, Egypt

International Nuclear Information System (INIS)

El-Sherif, A.M.

2013-01-01

The present study deals with the petrographical, mineralogical and geochemical characteristics of the alteration facies zones recognized around the shear zone at Gabal El-Missikat area, Central Eastern Desert, Egypt. Petrographically, the fresh granitic samples are composed mainly of quartz, K-feldspars (microcline and microcline perthite), plagioclase, biotite. The secondary minerals are sericite, kaolinite, muscovite, chlorite and epidote as well as zircon, apatite, fluorite, titanite and iron oxides as accessory minerals. Two alteration facies zones are recognized and namely as propylitic and advanced argillic. The propylitic facies zone is composed mainly of sericite with minor kaolinite, muscovite, quartz, relics of plagioclases, chlorite and rare epidote as well as zircon, hematite, goethite, magnetite, ilmenite, ilmenorutile, rutile, titanite, apatite, columbite and fluorite and secondary uranium minerals, the advanced argillic facies zone is composed mainly of kaolinite with minor sericite, quartz, muscovite, chlorite and rare epidote as well as zircon, hematite, goethite, magnetite, ilmenite, ilmenorutile, rutile, titanite, apatite and garnet of spessartine type as accessory minerals. The identified minerals in the studied two alteration facies zones can be grouped into three mineral groups which are: the primary minerals (pyrite, magnetite, galena, columbite and gold), the secondary minerals (uranophane, kasolite and wulfenite) and the gangue minerals (anhydrite, barite, celestine, hematite, goethite and fluorite). The identified mineral assemblage of the studied propylitic alteration facies zone may be attributed to strongly alkaline hydrothermal solutions at ph value of more than 7 with temperature varying between 350 and 450°C, while the advanced argillic alteration facies zone is essentially associated with strongly acidic hydrothermal solutions at ph value less than 7 with temperature varying between 150 and 400°C

COMPARSION EFFECTIVENES METHODS REPEIR CROWN TEETH IN DOGS

OpenAIRE

CHOOHNO V.S.

2008-01-01

Methods of dogs’ crown teeth restoration with using of anchor pin with light curable composite, glass fiber pin with light curable composite, stump crown with prosthetic crown were approved. Their effectiveness was compared. Greater reliability was shown by methods of stump crown with prosthetic crown, when using of which there was no that restoration damage in all cases, but there was no cosmetics effect. Restoration methods with using anchor pin with light curable composite and glass fiber ...

Geochemical pattern of rare-earth elements from ore deposits of Sete Barras and Volta Grande-PR

International Nuclear Information System (INIS)

Ronchi, L.H.; Dardenne, M.A.

1987-01-01

The fluorite ore deposits of Volta Grande and Sete Barras in Parana show similar REE distribution patterns. Fluorite ores from other regions in Parana e Santa Catarina show marked differences in the REE pattern which suggest different modes of origin. (author) [pt

Hydrogeochemistry of co-occurring geogenic arsenic, fluoride and iodine in groundwater at Datong Basin, northern China

Energy Technology Data Exchange (ETDEWEB)

Pi, Kunfu; Wang, Yanxin, E-mail: yx.wang@cug.edu.cn; Xie, Xianjun, E-mail: xjxie@cug.edu.cn; Su, Chunli; Ma, Teng; Li, Junxia; Liu, Yaqing

2015-12-30

Highlights: • Co-mobilization of As, F and I was identified at Datong Basin. • Both As and I are released via reductive dissolution of Fe minerals. • Some amounts of As and I may be sequestered by FeS precipitates. • Intensive evaporation promotes retention of As but mobilization of F and I. - Abstract: Abnormal levels of co-occurring arsenic (As), fluorine (F) and iodine (I) in groundwater at Datong Basin, northern China are geochemically unique. Hydrochemical, {sup 18}O and {sup 2}H characteristics of groundwater were analyzed to elucidate their mobilization processes. Aqueous As, F and I ranged from 5.6 to 2680 μg/L, 0.40 to 3.32 mg/L and 10.1 to 186 μg/L, respectively. High As, F and I groundwater was characterized by moderately alkaline, high HCO{sub 3}{sup −}, Fe(II), HS{sup −} and DOC concentrations with H{sub 3}AsO{sub 3}, F{sup −} and I{sup −} as the dominant species. The plots of δ{sup 18}O values and Cl/Br ratios versus Cl{sup −} concentration demonstrate build-up of more oxidizing conditions and precipitation of carbonate minerals induced by vertical recharge and intensive evaporation facilitate As retention to Fe (hydr) oxides, but enhance F and I mobilization from host minerals. Under reducing conditions, As and I can be simultaneously released via reductive dissolution of Fe (hydr) oxides and reduction of As(V) and I(V) while F migration may be retarded due to effects of dissolution-precipitation equilibria between carbonate minerals and fluorite. With the prevalence of sulfate-reducing condition and lowering of HCO{sub 3}{sup −} concentration, As and I may be sequestered by Fe(II) sulfides and F is retained to fluorite and on clay mineral surfaces.

Hydrogeochemistry of co-occurring geogenic arsenic, fluoride and iodine in groundwater at Datong Basin, northern China

International Nuclear Information System (INIS)

Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Su, Chunli; Ma, Teng; Li, Junxia; Liu, Yaqing

2015-01-01

Highlights: • Co-mobilization of As, F and I was identified at Datong Basin. • Both As and I are released via reductive dissolution of Fe minerals. • Some amounts of As and I may be sequestered by FeS precipitates. • Intensive evaporation promotes retention of As but mobilization of F and I. - Abstract: Abnormal levels of co-occurring arsenic (As), fluorine (F) and iodine (I) in groundwater at Datong Basin, northern China are geochemically unique. Hydrochemical, "1"8O and "2H characteristics of groundwater were analyzed to elucidate their mobilization processes. Aqueous As, F and I ranged from 5.6 to 2680 μg/L, 0.40 to 3.32 mg/L and 10.1 to 186 μg/L, respectively. High As, F and I groundwater was characterized by moderately alkaline, high HCO_3"−, Fe(II), HS"− and DOC concentrations with H_3AsO_3, F"− and I"− as the dominant species. The plots of δ"1"8O values and Cl/Br ratios versus Cl"− concentration demonstrate build-up of more oxidizing conditions and precipitation of carbonate minerals induced by vertical recharge and intensive evaporation facilitate As retention to Fe (hydr) oxides, but enhance F and I mobilization from host minerals. Under reducing conditions, As and I can be simultaneously released via reductive dissolution of Fe (hydr) oxides and reduction of As(V) and I(V) while F migration may be retarded due to effects of dissolution-precipitation equilibria between carbonate minerals and fluorite. With the prevalence of sulfate-reducing condition and lowering of HCO_3"− concentration, As and I may be sequestered by Fe(II) sulfides and F is retained to fluorite and on clay mineral surfaces.

Charge Distribution and Local Structure and Speciation in the UO2+x and PuO2+x Binary Oxides for x

International Nuclear Information System (INIS)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; Den Auwer, Christophe J.; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Tait, C. Drew; Veirs, D. Kirk; Villella, Phillip M.; Wastin, Franck

2005-01-01

The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO2+x (0.00pxp0.20) and PuO2+x/PuO2+x*y(OH)2y * zH2O have been determined by U/Pu LIII XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75A ? ) U?O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO2+x system, which does not show a separate phase at its x ? 0:25 endpoint, also displays (1) oxo groups at longer 1.9A ? distances consistent with Pu(V+d), (2) a multisite Pu?O distribution even when x is close to zero indicative of the formation of stable species with H2O and its hydrolysis products with O2*, and (3) a highly disordered, spectroscopically invisible Pu?Pu component. The structure and bonding in AnO2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements

Carbothermic reduction of pyrolusite for obtaining carbon bearing ferromanganese and slags, adequated to the development of welding materials

International Nuclear Information System (INIS)

Cruz-Crespo, A.; Garcia-Sanchez, L. L.; Quintana-Puchol, R.; Perdomo Gonzalez, L.; Gomez-Perez, C. R.; Jimenez-Vielsa, G. E.; Cores-Sanchez, A.

2004-01-01

The high carbon ferromanganese obtained by means of carbothermic reduction in an electric arc furnace of direct current is proposed. the ideal composition of slag oxides to achieve a flux to be used in the submerged arc welding (SAW) is established. Calculation for charge components (pyrolusite, coke, steel wool, lime, rutile and fluorite) for no fluxes technology for FeMn is carried out taking into account the welding fluxes characteristics of the SiO 2 -MnO-CaO system. Change materials reduction experiments to obtain FeMn and slag are used to develop a SAW flux. (Author) 21 refs

Interface formation and defect structures in epitaxial La2Zr2O7 thin films on (111) Si

International Nuclear Information System (INIS)

Seo, J.W.; Fompeyrine, J.; Guiller, A.; Norga, G.; Marchiori, C.; Siegwart, H.; Locquet, J.-P.

2003-01-01

We have studied the growth of epitaxial La 2 Zr 2 O 7 thin films on (111) Si. Although the interface structure can be strongly affected by the Si oxidation during the deposition process, epitaxial growth of La 2 Zr 2 O 7 was obtained. A detailed study by means of transmission electron microscopy reveals two types of structures (pyrochlore and fluorite) with the same average chemical composition but strong differences in reactivity and interface formation. The structural complexity of the ordered pyrochlore structure seems to prevent excess oxygen diffusion and interfacial SiO 2 formation

Carbothermic reduction of pyrolusite for obtaining carbon bearing ferromanganese and slags, adequated to the development of welding materials; Reduccion carbotermica de pirolusita para la obtencion de ferromanganeso y escoria, adecuados al desarrollo de materiales de soldadura

Energy Technology Data Exchange (ETDEWEB)

Cruz-Crespo, A.; Garcia-Sanchez, L. L.; Quintana-Puchol, R.; Perdomo Gonzalez, L.; Gomez-Perez, C. R.; Jimenez-Vielsa, G. E.; Cores-Sanchez, A.

2004-07-01

The high carbon ferromanganese obtained by means of carbothermic reduction in an electric arc furnace of direct current is proposed. the ideal composition of slag oxides to achieve a flux to be used in the submerged arc welding (SAW) is established. Calculation for charge components (pyrolusite, coke, steel wool, lime, rutile and fluorite) for no fluxes technology for FeMn is carried out taking into account the welding fluxes characteristics of the SiO{sub 2}-MnO-CaO system. Change materials reduction experiments to obtain FeMn and slag are used to develop a SAW flux. (Author) 21 refs.

Molten salt reactors. Synthesis of studies realized between 1973 and 1983. Experimental loop file

International Nuclear Information System (INIS)

1983-03-01

Four test loops were developed for the experimental study of a molten salt reactor with lead salt direct contact. A molten salt loop, completely in graphite, including the pump, showed that this material is convenient for salt containment and circulation. Reactor components like flowmeters, electromagnetic pumps, pressure gauge, valves developed for liquid sodium, were tested with liquid lead. A water-mercury loop was built for lead-molten salt simulation studies. Finally a lead-salt loop (COMPARSE) was built to study the behaviour of salt particles carried by lead in the heat exchanger. [fr

Charge Distribution and Local Structure and Speciation in the UO2+x and PuO2+x Binary Oxides for x <= 0.25

Energy Technology Data Exchange (ETDEWEB)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; Den Auwer, Christophe J.; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Tait, C DREW.; Veirs, D. Kirk; Villella, Phillip M.; Wastin, Franck

2005-02-01

The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO2+x (0.00pxp0.20) and PuO2+x/PuO2+x*y(OH)2y * zH2O have been determined by U/Pu LIII XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75A ? ) U?O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO2+x system, which does not show a separate phase at its x ? 0:25 endpoint, also displays (1) oxo groups at longer 1.9A ? distances consistent with Pu(V+d), (2) a multisite Pu?O distribution even when x is close to zero indicative of the formation of stable species with H2O and its hydrolysis products with O2*, and (3) a highly disordered, spectroscopically invisible Pu?Pu component. The structure and bonding in AnO2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements.

Application of SR Methods for the Study of Nanocomposite Materials for Hydrogen Energy

Science.gov (United States)

Sadykov, V. A.; Pavlova, S. N.; Vinokurov, Z. S.; Shmakov, A. N.; Eremeev, N. F.; Fedorova, Yu. E.; Yakimchuk, E. P.; Kriventsov, V. V.; Bolotov, V. A.; Tanashev, Yu. Yu.; Sadovskaya, E. M.; Cherepanova, S. V.; Zolotarev, K. V.

This work summarizes results of synchrotron radiation (SR) studies of the real/defect structure of nanocrystalline/nanocomposite oxide materials, which determines their functional properties in hydrogen energy field as catalysts and mixed ionic electronic conductors (cathodes and anodes of solid oxide fuel cells, oxygen separation membranes). For nanocrystalline ceria-zirconia mixed oxide prepared via modified Pechini route using ethanol solution of reagents, a high spatial uniformity of cations distribution between domains along with the oxygen sublattice deficiency revealed by full-profile Rietveld refinement of SR diffraction data provide structure disordering enhancing oxygen mobility. For PrNi0.5Co0.5O3-δ - Ce0.9Y0.1O2-δ nanocomposite extensive transfer of Pr cations into fluorite domains generates a new path of fast oxygen diffusion along chains of Pr3+ - Pr4+ cations as directly proved by analysis of the unit cell relaxation after changing pO2 in perfect agreement with data obtained by oxygen isotope heteroexchange.

Rapid, cool sintering of wet processed yttria-stabilized zirconia ceramic electrolyte thin films.

Science.gov (United States)

Park, Jun-Sik; Kim, Dug-Joong; Chung, Wan-Ho; Lim, Yonghyun; Kim, Hak-Sung; Kim, Young-Beom

2017-09-29

Here we report a photonic annealing process for yttria-stabilized zirconia films, which are one of the most well-known solid-state electrolytes for solid oxide fuel cells (SOFCs). Precursor films were coated using a wet-chemical method with a simple metal-organic precursor solution and directly annealed at standard pressure and temperature by two cycles of xenon flash lamp irradiation. The residual organics were almost completely decomposed in the first pre-annealing step, and the fluorite crystalline phases and good ionic conductivity were developed during the second annealing step. These films showed properties comparable to those of thermally annealed films. This process is much faster than conventional annealing processes (e.g. halogen furnaces); a few seconds compared to tens of hours, respectively. The significance of this work includes the treatment of solid-state electrolyte oxides for SOFCs and the demonstration of the feasibility of other oxide components for solid-state energy devices.

Characterizing the relationship between hyperstoichiometry, defect structure and local corrosion kinetics of uranium dioxide

International Nuclear Information System (INIS)

He Heming; Qin, Z.; Shoesmith, D.W.

2010-01-01

The ability of the UO 2 fluorite structure to accommodate large amounts of interstitial oxygen in various lattice sites leads to the formation of hyper-stoichiometric phases. The defect structures occurring in hyper-stoichiometric UO 2+x over the range 0.02 ≤ x ≤ 0.1 have been characterized by SEM/EDX and Raman analyses. The results demonstrate that as the nominal stoichiometry increases from 2.002 to 2.1, the diversity of defective structures existing on the UO 2+ surface also increases. Scanning electrochemical microscopy (SECM) measurements combined with a theoretical model were used to determine the rate constant for the reduction of the redox mediator ferrocene methanol, acting as a cathodic oxidant to corrode the four UO 2+x specimens. The rate constant was found to vary with location on the surface. Stoichiometric locations, with a well defined fluorite structure, exhibited very low corrosion rates. Higher rates were observed at more non-stoichiometric locations with the highest rates being obtained on locations exhibiting tetragonal distortions as their composition approached UO 2.33 . The distribution of rates increases with the degree of nominal non-stoichiometry as the diversity of microstructures existing on the UO 2+x surface increases.

Manganese

International Nuclear Information System (INIS)

Fayziev, A.R.

2002-01-01

Present article is devoted to manganese content in fluoride. The manganese content of some geologic deposits of Tajikistan was determined by means of chemical analysis. The mono mineral samples of fluorite of 5 geologic deposits of various mineralogical and genetic type was studied. The manganese content in fluorite of geologic deposits of various mineralogical and genetic type was defined.

Evaluation of aqueous geochemistry of fluoride enriched groundwater: A case study of the Patan district, Gujarat, Western India

Directory of Open Access Journals (Sweden)

Pankaj Kumar

2017-10-01

Saturation index for selected minerals suggests that most of the samples are oversaturated with calcite and undersaturated with fluorite. Calcite precipitation leads to the removal of Ca2+ from solution thus allowing more fluorite to dissolve. These released Ca2+ ions combine with CO32− ions to further enhance the precipitation of CaCO3.

Catalytic oxidation using nitrous oxide

Directory of Open Access Journals (Sweden)

Juan Carlos Beltran-Prieto

2017-01-01

Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

Synthesis and characterization of Ce{sub 1-x}SmXO{sub 2-(x/2)} as solid electrolyte for application in IT-SOFCs; Sintese e caracterizacao de Ce{sub 1-x}SmXO{sub 2-(x/2)} como eletrolito solido para aplicacao em IT-SOFCs

Energy Technology Data Exchange (ETDEWEB)

Nicodemo, J.P.; Martinelli, A.E.; Nascimento, R.M. [Universidade Federal do Rio Grande do Norte (DECM/UFRN), Natal, RN (Brazil). Dept. de Engenharia de Materiais], e-mail: juli_pivotto@yahoo.com.br; Melo, D.M.A. [Universidade Federal do Rio Grande do Norte (DQ/UFRN), Natal, RN (Brazil). Dept. de Quimica; Cela, B. [Universidade Federal do Rio Grande do Norte (PPGCEM/UFRN), Natal, RN (Brazil). Programa de Pos-Graduacao em Ciencia e Engenharia de Materiais; Macedo, D.A. [Universidade Federal do Rio Grande do Norte (PPGEM/UFRN), Natal, RN (Brazil). Programa de Pos-Graduacao em Engenharia Mecanica

2008-07-01

Mixed rare earth doped CeO{sub 2} oxide-based have been extensively studied for use in solid electrolytes for fuel cells. Ceramics-based CeO{sub 2} have high ionic conductivity and enable the operation of solid oxide fuel cells (SOFCs) in intermediate temperatures, in the range of 500 to 750 deg C. In this work, was investigated the Sm{sub 2}O{sub 3} doped CeO{sub 2} by Pechini method to obtain Ce{sub 0,9}Sm{sub 0,1}O{sub 1,95}. The resulting powders were characterized by the chemical composition (EDS) and crystallographic (XRD), thermal analysis (TG/ATD and DTG), and particles morphology (SEM). After calcinations of 500 and 700 deg C for 2 hours were obtained nanosized powders with crystalline structure of cubic phase type fluorite fully formed. (author)

Pair Distribution Function Analysis of Structural Disorder by Nb5+ Inclusion in Ceria: Evidence for Enhanced Oxygen Storage Capacity from Under-Coordinated Oxide.

Science.gov (United States)

Hiley, Craig I; Playford, Helen Y; Fisher, Janet M; Felix, Noelia Cortes; Thompsett, David; Kashtiban, Reza J; Walton, Richard I

2018-02-07

Partial substitution of Ce 4+ by Nb 5+ is possible in CeO 2 by coinclusion of Na + to balance the charge, via hydrothermal synthesis in sodium hydroxide solution. Pair distribution function analysis using reverse Monte Carlo refinement reveals that the small pentavalent substituent resides in irregular coordination positions in an average fluorite lattice, displaced away from the ideal cubic coordination toward four oxygens. This results in under-coordinated oxygen, which explains significantly enhanced oxygen storage capacity of the materials of relevance to redox catalysis used in energy and environmental applications.

Mineralogy of Non-Silicified Fossil Wood

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George E. Mustoe

2018-03-01

Full Text Available The best-known and most-studied petrified wood specimens are those that are mineralized with polymorphs of silica: opal-A, opal-C, chalcedony, and quartz. Less familiar are fossil woods preserved with non-silica minerals. This report reviews discoveries of woods mineralized with calcium carbonate, calcium phosphate, various iron and copper minerals, manganese oxide, fluorite, barite, natrolite, and smectite clay. Regardless of composition, the processes of mineralization involve the same factors: availability of dissolved elements, pH, Eh, and burial temperature. Permeability of the wood and anatomical features also plays important roles in determining mineralization. When precipitation occurs in several episodes, fossil wood may have complex mineralogy.

Uranium-contaminated soils: Ultramicrotomy and electron beam analysis

International Nuclear Information System (INIS)

Buck, E.C.; Dietz, N.L.; Bates, J.K.; Cunnane, J.C.

1994-02-01

Uranium-contaminated soils from the U.S. Department of Energy (DOE) Fernald Site, Ohio, have been examined by a combination of scanning electron microscopy with backscattered electron imaging (SEM/BSE) and analytical electron microscopy (AEM). The inhomogeneous distribution of particulate uranium phases in the soil required the development of a method for using ultramicrotomy to prepare transmission electron microscopy (TEM) thin sections of the SEM mounts. A water-miscible resin was selected that allowed comparison between SEM and TEM images, permitting representative sampling of the soil. Uranium was found in iron oxides, silicates (soddyite), phosphates (autunites), and fluorite (UO 2 ). No uranium was detected in association with phyllosilicates in the soil

Virtual Compton Scattering at Jefferson Lab

International Nuclear Information System (INIS)

Laveissiere, G.

2003-01-01

The presentation, subtitled 'Extraction of Proton Generalized Polarisabilities at Q2=1.0 and 1.9 GeV2 using a Dispersion Relations Formalism' highlighted activities in the following areas: Electroproduction of photons experiment: analysis below and above π 0 production threshold; Proton Generalized Polarisabilities extraction above π 0 production threshold, specifics of the Jlab E93050 experiment, Cross section results and dispersion relations fit at the Q2 = 0.923 GeV2 and Q2 = 1.760 GeV2 levels; and ending with a comparsion of structure functions and dispersion relations parameters analysis

17O solid-state NMR spectroscopy of A2B2O7 oxides: quantitative isotopic enrichment and spectral acquisition?

Science.gov (United States)

Fernandes, Arantxa; Moran, Robert F; Sneddon, Scott; Dawson, Daniel M; McKay, David; Bignami, Giulia P M; Blanc, Frédéric; Whittle, Karl R; Ashbrook, Sharon E

2018-02-13

The potential of 17 O NMR spectroscopy for the investigation of A 2 B 2 O 7 ceramic oxides important in the encapsulation of radioactive waste is demonstrated, with post-synthetic enrichment by exchange with 17 O 2 gas. For Y 2 Sn 2 O 7 , Y 2 Ti 2 O 7 and La 2 Sn 2 O 7 pyrochlores, enrichment of the two distinct O species is clearly non quantitative at lower temperatures (∼700 °C and below) and at shorter times, despite these being used in prior work, with preferential enrichment of OA 2 B 2 favoured over that of OA 4 . At higher temperatures, the 17 O NMR spectra suggest that quantitative enrichment has been achieved, but the integrated signal intensities do not reflect the crystallographic 1 : 6 (O1 : O2) ratio until corrected for differences in T 1 relaxation rates and, more importantly, the contribution of the satellite transitions. 17 O NMR spectra of Y 2 Zr 2 O 7 and Y 2 Hf 2 O 7 defect fluorites showed little difference with any variation in enrichment temperature or time, although an increase in the absolute level of enrichment (up to ∼7.5%) was observed at higher temperature. DFT calculations show that the six distinct resonances observed cannot be assigned unambiguously, as each has contributions from more than one of the five possible next nearest neighbour environments. For La 2 Ti 2 O 7 , which adopts a layered perovskite-like structure, little difference in the spectral intensities is observed with enrichment time or temperature, although the highest absolute levels of enrichment (∼13%) were obtained at higher temperature. This work demonstrates that 17 O NMR has the potential to be a powerful probe of local structure and disorder in oxides, but that considerable care must be taken both in choosing the conditions for 17 O enrichment and the experimental acquisition parameters if the necessary quantitative measurements are to be obtained for more complex systems.

The use of fluoride as a natural tracer in water and the relationship to geological features: Examples from the Animas River Watershed, San Juan Mountains, Silverton, Colorado

Science.gov (United States)

Bove, D.J.; Walton-Day, K.; Kimball, B.A.

2009-01-01

Investigations within the Silverton caldera, in southwestern Colorado, used a combination of traditional geological mapping, alteration-assemblage mapping, and aqueous geochemical sampling that showed a relationship between geological and hydrologic features that may be used to better understand the provenance and evolution of the water. Veins containing fluorite, huebnerite, and elevated molybdenum concentrations are temporally and perhaps genetically associated with the emplacement of high-silica rhyolite intrusions. Both the rhyolites and the fluorite-bearing veins produce waters containing elevated concentrations of F-, K and Be. The identification of water samples with elevated F/Cl molar ratios (> 10) has also aided in the location of water draining F-rich sources, even after these waters have been diluted substantially. These unique aqueous geochemical signatures can be used to relate water chemistry to key geological features and mineralized source areas. Two examples that illustrate this relationship are: (1) surface-water samples containing elevated F-concentrations (> 1.8 mg/l) that closely bracket the extent of several small high-silica rhyolite intrusions; and (2) water samples containing elevated concentrations of F-(> 1.8 mg/ l) that spatially relate to mines or areas that contain late-stage fluorite/huebnerite veins. In two additional cases, the existence of high F-concentrations in water can be used to: (1) infer interaction of the water with mine waste derived from systems known to contain the fluorite/huebnerite association; and (2) relate changes in water quality over time at a high elevation mine tunnel to plugging of a lower elevation mine tunnel and the subsequent rise of the water table into mineralized areas containing fluorite/huebnerite veining. Thus, the unique geochemical signature of the water produced from fluorite veins indicates the location of high-silica rhyolites, mines, and mine waste containing the veins. Existence of high F

P-T path fluid evolution in the Gross Spitzkoppe granite stock, Namibia

Directory of Open Access Journals (Sweden)

Stephen Frindt

2002-01-01

Full Text Available The Gross Spitzkoppe granite stock (GSS is a zoned 30 km^2 epizonal intrusion that consists of three main granites: 1 medium-grained biotite granite (marginal, 2 a coarse-grained biotite granite, and 3 a central, porphyritic granite. The stock contains pegmatites as banded marginal stockscheiders and isolated pockets composed of large alkali feldspar and quartz, dark mica, interstitial fluorite, and euhedral topaz and beryl crystals. In the porphyritic granite there are local wolframite-bearing greisens and hydrothermal fluorite and topaz-rich veins.Fluid inclusion studies were conducted on: 1 topaz and quartz crystals from the marginal stockscheider; 2 quartz, topaz, fluorite and beryl crystals from isolated pegmatites; 3 topaz from a miarolitic pegmatite; 4 beryl and quartz veins from greisenized porphyritic granite; and 5 fluorite from a late fluorite vein inthe coarse-grained biotite granite. Preliminary data indicate the presence of three compositionally distinct primary and pseudosecondary inclusion types that are of late magmatic-hydrothermal origin.Type 1. Low salinity (0–10 eq. wt% NaCl H2O (± CO2 inclusions that homogenize to the liquid phase in the temperature range of 300 to 550˚C. These inclusions are from quartz, topaz and beryl. Inclusions in fluorite from the fluorite vein homogenize at ~170˚C and have a salinity of ca. 1–2 eq. wt% NaCl.Type 2. Saline (25–30 eq. wt% NaCl halite-bearing H2O (± CO2 inclusions that homogenize to the liquid phase in the temperature range of 300 to 400˚C. These inclusions are from quartz.Type 3. Low salinity (0–3 eq. wt% NaCl H2O-CO2 inclusions that homogenize to vapor phase in the temperature range of 330 to 550˚C. These inclusions are from quartz and topaz.Hydrothermal fluids from greisen minerals are represented by type 1 and type 2 H2O inclusions. They are predominantly of low salinity (~8 eq. wt% NaCl and homogenize to the liquid phase in the temperature range of 300 to 500�

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

International Nuclear Information System (INIS)

Raison, P.E.

2001-01-01

Presented are studies involving the incorporation of americium and curium in zirconia-based materials. First explored was the pseudo ternary system AmO 2 -ZrO 2 -Y 2 O 3 . It was determined that selected Y-CSZ materials can incorporate significant quantities of americium oxide and remain cubic single-phase. The cell parameters of these fluorite-type products were established to be linear with the AmO 2 content. The Cm 2 O 3 -ZrO 2 system was also investigated. It was found that at 25 mol% of CmO 1.5 , the Cm(III) stabilized zirconia in its cubic form (a = 5.21 ±0.01 Angstrom). At higher and lower concentrations, diphasic materials were encountered. At 50 mol% of CmO 1.5 , a pyrochlore oxide - Cm 2 Zr 2 O 7 - is formed (a = 10.63 ±0.02 Angstrom). (author)

The Enzymatic Oxidation of Graphene Oxide

Science.gov (United States)

Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

2011-01-01

Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

The Li–Si–(O)–N system revisited: Structural characterization of Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O

Energy Technology Data Exchange (ETDEWEB)

Casas-Cabanas, M. [CIC energiGUNE, Parque Tecnológico de Álava, Albert Einstein 48, ED.CIC, 01510 Miñano (Spain); Santner, H. [Institut de Ciència de Materials de Barcelona (CSIC) Campus UAB, 08193 Bellaterra, Catalonia (Spain); Palacín, M.R., E-mail: rosa.palacin@icmab.es [Institut de Ciència de Materials de Barcelona (CSIC) Campus UAB, 08193 Bellaterra, Catalonia (Spain)

2014-05-01

A systematic study of the Li–Si–(O)–N system is presented. The synthetic conditions to prepare Li{sub 2}SiN{sub 2}, Li{sub 5}SiN{sub 3}, Li{sub 18}Si{sub 3}N{sub 10}, Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are described and the structure of the last two compounds has been solved for the first time. While Li{sub 21}Si{sub 3}N{sub 11} crystallizes as a superstructure of the anti-fluorite structure with Li and Si ordering, Li{sub 7}SiN{sub 3}O exhibits the anti-fluorite structure with both anion and cation disorder. - Graphical abstract: A systematic study of the Li–Si–(O)–N system is presented. Li{sub 21}Si{sub 3}N{sub 11} crystallizes as a superstructure of the anti-fluorite structure with Li and Si ordering, Li{sub 7}SiN{sub 3}O exhibits the anti-fluorite structure with both anion and cation disorder. - Highlights: • Li{sub 2}SiN{sub 2}, Li{sub 5}SiN{sub 3}, Li{sub 18}Si{sub 3}N{sub 10}, Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are prepared. • The structures of Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are presented. • Li{sub 21}Si{sub 3}N{sub 11} exhibits an anti-fluorite superstructure with Li and Si ordering.

The competing oxide and sub-oxide formation in metal-oxide molecular beam epitaxy

International Nuclear Information System (INIS)

Vogt, Patrick; Bierwagen, Oliver

2015-01-01

The hetero-epitaxial growth of the n-type semiconducting oxides β-Ga 2 O 3 , In 2 O 3 , and SnO 2 on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga 2 O, In 2 O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO 2 , somewhat lower for In 2 O 3 , and the lowest for Ga 2 O 3 . Our findings can be generalized to further oxides that possess related sub-oxides

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

Energy Technology Data Exchange (ETDEWEB)

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru [Institute of Chemistry FEBRAS, 159, Pr. 100-letya Vladivostoka, Vladivostok 690022 (Russian Federation); Uvarov, N.F. [Institute of Solid State Chemistry and Mechanochemistry, SB RAS, 18, Kutateladze Str., Novosibirsk 630128 (Russian Federation); Slobodyuk, A.B.; Polyantsev, M.M.; Merkulov, E.B. [Institute of Chemistry FEBRAS, 159, Pr. 100-letya Vladivostoka, Vladivostok 690022 (Russian Federation); Ulihin, A.S. [Institute of Solid State Chemistry and Mechanochemistry, SB RAS, 18, Kutateladze Str., Novosibirsk 630128 (Russian Federation); Goncharuk, V.K. [Institute of Chemistry FEBRAS, 159, Pr. 100-letya Vladivostoka, Vladivostok 690022 (Russian Federation)

2017-05-15

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K, these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.

Structural Characteristics of Bimetallic Catalysts Supported on Nano-Ceria

Directory of Open Access Journals (Sweden)

J. F. Bozeman

2011-01-01

Full Text Available Cu-Pt bimetal catalysts supported on nanocrystalline CeO2 (nano-ceria are synthesized via the low-cost sol-gel approach followed by impregnation processing. The average particle size of the catalytic composites is 63 nm. Ceria nanopowders sequentially impregnated in copper solution and then in Pt solution transformed into Pt-skin-structured Cu-Pt/ceria nanocomposite, based on the surface elemental and bulk compositional analyses. The ceria supporter has a fluorite structure, but the structure of Cu and Pt catalytic contents, not detected by X-ray diffraction spectroscopy due to the low loading level, is yet conclusive. The bimetallic catalytic nanocomposites may potentially serve as sulfur-tolerant anode in solid oxide fuel cells.

Bone tumours in children and juveniles

International Nuclear Information System (INIS)

Meister, P.

1978-01-01

The auther stresses the importance 1) of clinical data (e.g. age of the patient, localisation of the lesion, type and duration of the symptoms), 2) of radiographic findings and 3) of anatomicopathological changes which must all be taken into account especially in the judgment of bone tumours. Radiographic examination is of importance here also as a morphological method as it gives a picture of the 'mosaic' of a bone change. Biopsy material alone may contain only isolated parts with ambiguous histological findings, so that the true nature of the bone lesion can only be recognized by comparsion with the X-ray findings. (orig.) [de

Tin-antimony oxide oxidation catalysts

Energy Technology Data Exchange (ETDEWEB)

Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

1998-12-15

Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

Sputtered tin oxide and titanium oxide thin films as alternative transparent conductive oxides

Energy Technology Data Exchange (ETDEWEB)

Boltz, Janika

2011-12-12

Alternative transparent conductive oxides to tin doped indium oxide have been investigated. In this work, antimony doped tin oxide and niobium doped titanium oxide have been studied with the aim to prepare transparent and conductive films. Antimony doped tin oxide and niobium doped titanium oxide belong to different groups of oxides; tin oxide is a soft oxide, while titanium oxide is a hard oxide. Both oxides are isolating materials, in case the stoichiometry is SnO{sub 2} and TiO{sub 2}. In order to achieve transparent and conductive films free carriers have to be generated by oxygen vacancies, by metal ions at interstitial positions in the crystal lattice or by cation doping with Sb or Nb, respectively. Antimony doped tin oxide and niobium doped titanium oxide films have been prepared by reactive direct current magnetron sputtering (dc MS) from metallic targets. The process parameters and the doping concentration in the films have been varied. The films have been electrically, optically and structurally analysed in order to analyse the influence of the process parameters and the doping concentration on the film properties. Post-deposition treatments of the films have been performed in order to improve the film properties. For the deposition of transparent and conductive tin oxide, the dominant parameter during the deposition is the oxygen content in the sputtering gas. The Sb incorporation as doping atoms has a minor influence on the electrical, optical and structural properties. Within a narrow oxygen content in the sputtering gas highly transparent and conductive tin oxide films have been prepared. In this study, the lowest resistivity in the as deposited state is 2.9 m{omega} cm for undoped tin oxide without any postdeposition treatment. The minimum resistivity is related to a transition to crystalline films with the stoichiometry of SnO{sub 2}. At higher oxygen content the films turn out to have a higher resistivity due to an oxygen excess. After post

Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

Science.gov (United States)

Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

2017-06-01

The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

High pressure phase transitions and compressibilities of Er2Zr2O7 and Ho2Zr2O7

Science.gov (United States)

Zhang, F. X.; Lang, M.; Becker, U.; Ewing, R. C.; Lian, J.

2008-01-01

Phase stability and compressibility of rare earth zirconates with the defect-fluorite structure were investigated by in situ synchrotron x-ray diffraction. A sluggish defect-fluorite to a cotunnitelike phase transformation occurred at pressures of ˜22 and ˜30GPa for Er2Zr2O7 and Ho2Zr2O7, respectively. Enhanced compressibility was found for the high pressure phase as a result of increasing cation coordination number and cation-anion bond length.

High Pressure Phase Transitions and Compressibilities of Er2Zr2O7 and Ho2Zr2O7

Energy Technology Data Exchange (ETDEWEB)

Zhang,F.; Lang, M.; Becker, U.; Ewing, R.; Lian, J.

2008-01-01

Phase stability and compressibility of rare earth zirconates with the defect-fluorite structure were investigated by in situ synchrotron x-ray diffraction. A sluggish defect-fluorite to a cotunnitelike phase transformation occurred at pressures of {approx} 22 and {approx} 30 GPa for Er2Zr2O7 and Ho2Zr2O7, respectively. Enhanced compressibility was found for the high pressure phase as a result of increasing cation coordination number and cation-anion bond length.

Evolution of mineralizing brines in the east Tennessee Mississippi Valley-type ore field

Energy Technology Data Exchange (ETDEWEB)

Kesler, S.E.; Gesink, J.A.; Haynes, F.M. (Univ. of Michingan, Ann Arbor (USA))

1989-05-01

The east Tennessee Mississippi Valley-type (MVT) ore field contains barite-fluorite and sphalterite deposits in a continuous paleoaquifer consisting of breccia zones in the Upper Cambrian-Lower Ordovician Knox Group. Paragenetic observations and fluid inclusion compositions in these deposits indicate that the Knox paleoaquifer was invaded first by Ca-rich brines (Ca:Na about 1) that deposited fluorite and barite, and later by Na-Ca brines (Ca:Na = 0.1 to 0.5) that deposited sphalerite. Geologic relation sindicate that these brines were derived from the southeast, in the area of the Middle Ordovician Servier foreland shale basin, and that imposed by fluorite solubility indicate further that all original connate water in the Sevier basin was required to deposit the estimated flourite reserves of the ore field.Thus, the later, sphalerite-depositing brines represent recycled meteoric water from the Sevier basin or connate brines from underlying (Cambrian) shales.

Optical properties and electronic transitions of zinc oxide, ferric oxide, cerium oxide, and samarium oxide in the ultraviolet and extreme ultraviolet

DEFF Research Database (Denmark)

Pauly, N; Yubero, F; Espinós, J P

2017-01-01

Optical properties and electronic transitions of four oxides, namely zinc oxide, ferric oxide, cerium oxide, and samarium oxide, are determined in the ultraviolet and extreme ultraviolet by reflection electron energy loss spectroscopy using primary electron energies in the range 0.3-2.0 ke...

Properties of ceria doped with gadolinia via microwave-assisted hydrothermal synthesis

International Nuclear Information System (INIS)

Carregosa, J.D.C.; Oliveira, R.M.P.B.; Macedo, D.A.; Nascimento, R.M.

2016-01-01

The solid solution of CeO_2 doped with Gd"3"+ (CGO) is a promising candidate for electrolyte in Solid Oxide Full Cells (SOFCs) operating in intermediate and low temperatures. The reduction of the working temperature of these energy conversion devices is the great technological challenge to its marketing. In this work, nanocrystalline powders of Ce_1_-_xGd_xO_2_-_x_/_2 with x=0, x=0.1 e x=0.2 were obtained via microwave-hydrothermal synthesis at low temperature and times of synthesis (10 and 20 min at 120° C). The powders were analyzed by TG-DTA, DRX and dilatometry. The results showed characteristic peaks of the cubic fluorite-type structure, referring to the cerium oxide (CeO_2), without the presence of secondary peaks. It was also observed that the samples processed at levels of 10 and 20 minutes showed distinct behaviors in contrast to the concentrations of Gd"3"+. (author)

Properties of ceria doped with gadolinia via microwave-assisted hydrothermal synthesis; Propriedades de ceria dopada com gadolinia via sintese hidrotermal assistida por micro-ondas

Energy Technology Data Exchange (ETDEWEB)

Carregosa, J.D.C.; Oliveira, R.M.P.B. [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil); Macedo, D.A. [Universidade Federal da Paraiba (UFPB), Joao Pessoa, PB (Brazil); Nascimento, R.M., E-mail: jdcovello@hotmail.com [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil)

2016-07-01

The solid solution of CeO{sub 2} doped with Gd{sup 3+} (CGO) is a promising candidate for electrolyte in Solid Oxide Full Cells (SOFCs) operating in intermediate and low temperatures. The reduction of the working temperature of these energy conversion devices is the great technological challenge to its marketing. In this work, nanocrystalline powders of Ce{sub 1-x}Gd{sub x}O{sub 2-x/2} with x=0, x=0.1 e x=0.2 were obtained via microwave-hydrothermal synthesis at low temperature and times of synthesis (10 and 20 min at 120° C). The powders were analyzed by TG-DTA, DRX and dilatometry. The results showed characteristic peaks of the cubic fluorite-type structure, referring to the cerium oxide (CeO{sub 2}), without the presence of secondary peaks. It was also observed that the samples processed at levels of 10 and 20 minutes showed distinct behaviors in contrast to the concentrations of Gd{sup 3+}. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2001-07-01

Presented are studies involving the incorporation of americium and curium in zirconia-based materials. First explored was the pseudo ternary system AmO{sub 2}-ZrO{sub 2}-Y{sub 2}O{sub 3}. It was determined that selected Y-CSZ materials can incorporate significant quantities of americium oxide and remain cubic single-phase. The cell parameters of these fluorite-type products were established to be linear with the AmO{sub 2} content. The Cm{sub 2}O{sub 3}-ZrO{sub 2} system was also investigated. It was found that at 25 mol% of CmO{sub 1.5}, the Cm(III) stabilized zirconia in its cubic form (a = 5.21 {+-}0.01 Angstrom). At higher and lower concentrations, diphasic materials were encountered. At 50 mol% of CmO{sub 1.5}, a pyrochlore oxide - Cm{sub 2}Zr{sub 2}O{sub 7} - is formed (a = 10.63 {+-}0.02 Angstrom). (author)

Solid oxide fuel cells fueled with reducible oxides

Science.gov (United States)

Chuang, Steven S.; Fan, Liang Shih

2018-01-09

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing the solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.

Shock Compression Response of Calcium Fluoride (CaF2)

Science.gov (United States)

Root, Seth

2017-06-01

The fluorite crystal structure is a textbook lattice that is observed for many systems, such as CaF2, Mg2 Si, and CeO2. Specifically, CaF2 is a useful material for studying the fluorite system because it is readily available as a single crystal. Under static compression, CaF2 is known to have at least three solid phases: fluorite, cotunnite, and a Ni2 In phase. Along the Hugoniot CaF2 undergoes a fluorite to cotunnite phase transition, however, at higher shock pressures it is unknown whether CaF2 undergoes another solid phase transition or melts directly from the cotunnite phase. In this work, we conducted planar shock compression experiments on CaF2 using Sandia's Z-machine and a two-stage light gun up to 900 GPa. In addition, we use density functional theory (DFT) based quantum molecular dynamics (QMD) simulations to provide insight into the CaF2 state along the Hugoniot. In collaboration with: Michael Desjarlais, Ray Lemke, Patricia Kalita, Scott Alexander, Sandia National Laboratories. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL850.

Development and simulation of various methods for neutron activation analysis

International Nuclear Information System (INIS)

Otgooloi, B.

1993-01-01

Simple methods for neutron activation analysis have been developed. The results on the studies of installation for determination of fluorine in fluorite ores directly on the lorry by fast neutron activation analysis have been shown. Nitrogen in organic materials was shown by N 14 and N 15 activation. The description of the new equipment 'FLUORITE' for fluorate factory have been shortly given. Pu and Be isotope in organic materials, including in wheat, was measured. 25 figs, 19 tabs. (Author, Translated by J.U)

Depressing effect of phenoxyl acetic acids on flotation of minerals containing Ca2+/Mg2+ gangues

Institute of Scientific and Technical Information of China (English)

无

2007-01-01

Phenoxyl acetic acids were applied to determine their depressing effect on minerals containing Ca2+/Mg2+ gangues. Calcite,mixture of calcite and fluorite, and nickel ore were used in the flotation. And the depression mechanism was studied by the determination of contact angle, zeta potential, adsorptive capacity of collector, and IR analysis as well. It is found that 0.1 mmol/L of phenoxyl acetic acid derived from pyrogallol or gallic acid exhibits strong depressing ability on calcite in almost zero yields at pH value of 9.8, and calcite can be depressed in the flotation of calcite/fluorite mixture for approximate 87% yield of fluorite. The flotation result of practical nickel ore containing serpentine indicates that these two depressants may also show better depression performance to serpentine than traditional depressants such as sodium fluosilicate and carboxylmethyl cellulose. Analysis for the depression mechanism reveals that there exists strong chemical interaction between the depressants and minerals.

The XPS study of the structure of uranium-containing ceramics

Directory of Open Access Journals (Sweden)

Teterin Anton Yu.

2010-01-01

Full Text Available The samples of the (Ca0.5GdU0.5Zr2O7 and (Ca0.5GdU0.5(ZrTiO7 ceramics with the fluorite and pyrochlore structures used as matrixes for the long-lived high-level radioactive waste disposal were studied with the X-ray photoelectron spectroscopy method. On the basis of the X-ray photoelectron spectroscopy parameters of the outer and core electrons from the binding energy range of 0-1250 eV the oxidation states of the included metal ions were determined, the quantitative elemental and ionic analysis was done, and the orderliness (monophaseness was evaluated. The obtained data agree with the X-ray diffraction and the scanning electron microscopy results.

Design of high quality doped CeO2 solid electrolytes with nanohetero structure

International Nuclear Information System (INIS)

Mori, T.; Ou, D.R.; Ye, F.; Drennan, J.

2006-01-01

Doped cerium (CeO 2 ) compounds are fluorite related oxides which show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, a considerable interest has been shown in application of these materials for low (400-650 o C) temperature operation of solid oxide fuel cells (SOFCs). In this paper, our experimental data about the influence of microstructure at the atomic level on electrochemical properties were reviewed in order to develop high quality doped CeO 2 electrolytes in fuel cell applications. Using this data in the present paper, our original idea for a design of nanodomain structure in doped CeO 2 electrolytes was suggested. The nanosized powders and dense sintered bodies of M doped CeO 2 (M:Sm,Gd,La,Y,Yb, and Dy) compounds were fabricated. Also nanostructural features in these specimens were introduced for conclusion of relationship between electrolytic properties and domain structure in doped CeO 2 . It is essential that the electrolytic properties in doped CeO 2 solid electrolytes reflect in changes of microstructure even down to the atomic scale. Accordingly, a combined approach of nanostructure fabrication, electrical measurement and structure characterization was required to develop superior quality doped CeO 2 electrolytes in the fuel cells. (author)

Effects of Oxidation on Oxidation-Resistant Graphite

Energy Technology Data Exchange (ETDEWEB)

Windes, William [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Rebecca [Idaho National Lab. (INL), Idaho Falls, ID (United States); Carroll, Mark [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-05-01

The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidation rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.

Self-assembled manganese oxide structures through direct oxidation

KAUST Repository

Zhao, Chao; Wang, Qingxiao; Yang, Yang; Zhang, Bei; Zhang, Xixiang

2012-01-01

The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

Self-assembled manganese oxide structures through direct oxidation

KAUST Repository

Zhao, Chao

2012-12-01

The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

Directory of Open Access Journals (Sweden)

Jacques C. Védrine

2016-01-01

Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

Simulation of 3D mesoscale structure formation in concentrated aqueous solution of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19). Application of dynamic mean-field density functional theory

NARCIS (Netherlands)

van Vlimmeren, BAC; Maurits, NM; Zvelindovsky, AV; Sevink, GJA; Fraaije, JGEM

1999-01-01

We simulate the microphase separation dynamics of aqueous solutions of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19) by a dynamic variant of mean-field density functional theory for

Polyaniline: Aniline oxidation with strong and weak oxidants under various acidity

Energy Technology Data Exchange (ETDEWEB)

Bláha, Michal, E-mail: blaha@imc.cas.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokeš, Jan [Charles University, Faculty of Mathematics and Physics, 180 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)

2017-06-15

Aniline was oxidized with three strong inorganic oxidants (ammonium peroxydisulfate, cerium(IV) sulfate, potassium dichromate), two weak inorganic oxidants (iron(III) chloride, silver nitrate), and one organic oxidant (p-benzoquinone) in aqueous solutions of methanesulfonic acid (MSA) of various concentration. Whereas oxidation of aniline with ammonium peroxydisulfate yielded high-molecular-weight conducting polyaniline (PANI) in the whole acidity range, the oxidation with cerium(IV) sulfate led also to a single product close to PANI with considerably lower molecular weight and lower conductivity. Potassium dichromate gave PANI only at high concentration of MSA. The use of iron(III) chloride yielded composite mixtures of PANI and low-molecular-weight aniline oligomers. The oxidation of aniline with silver nitrate led to composites of silver and an organic part, which was constituted either by aniline oligomers or conducting polyaniline or both. p-Benzoquinone as oxidant produced mainly aniline oligomers with poor conductivity and 2,5-dianilino-p-benzoquinone-like structure detected in FTIR and Raman spectra when oxidation proceeded with weak oxidants. A general model of oxidation with strong and weak oxidants was formulated. - Highlights: • Comparison of aniline oxidation with oxidants of different redox potential. • UV–vis, FTIR and Raman spectroscopies combined with size-exclusion chromatography. • The contents of polymer and oligomers were analyzed and discussed. • General model of aniline oxidation with strong and weak oxidants was formulated.

Oxidative Decarboxylation of Levulinic Acid by Cupric Oxides

Directory of Open Access Journals (Sweden)

Lu Lin

2010-11-01

Full Text Available In this paper, cupric oxides was found to effectively oxidize levulinic acid (LA and lead to the decarboxylation of levulinic acid to 2-butanone. The effects of cupric oxide dosage, reaction time and initial pH value were investigated in batch experiments and a plausible mechanism was proposed. The results showed that LA decarboxylation over cupric oxides at around 300 °C under acidic conditions produced the highest yield of butanone (67.5%. In order to elucidate the catalytic activity of cupric oxides, XRD, AFM, XPS and H2-TPR techniques was applied to examine their molecular surfaces and their effects on the reaction process.

Oxide ceramics

International Nuclear Information System (INIS)

Ryshkewitch, E.; Richerson, D.W.

1985-01-01

The book explores single-phase ceramic oxide systems from the standpoint of physical chemistry and technology. This second edition also focuses on advances in technology since publication of the original edition. These include improvements in raw materials and forming and sintering techniques, and the major role that oxide ceramics have had in development of advanced products and processes. The text is divided into five major sections: general fundamentals of oxide ceramics, advances in aluminum oxide technology, advances in zirconia technology, and advances in beryllium oxide technology

Uranium oxidation: characterization of oxides formed by reaction with water

International Nuclear Information System (INIS)

Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

1983-01-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

Ultrasound assisted green synthesis of cerium oxide nanoparticles using Prosopis juliflora leaf extract and their structural, optical and antibacterial properties

Directory of Open Access Journals (Sweden)

Arunachalam Thirunavukkarasu

2018-03-01

Full Text Available Cerium oxide nanoparticles (CONPs were prepared using ultrasound assisted leaf extract of Prosopis juliflora acting as a reducing as well as stabilizing agent. The synthesized CONPs were characterized by ultraviolet-visible absorption spectroscopy (UV-Vis, particle size analyzer (PSA, Fourier transform infrared spectroscopy (FT-IR, Raman spectroscopy, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS and high-resolution transmission electron microscopy (HRTEM. From the UV-Vis analysis, the optical band gap of the prepared CONPs (Eg = 3.62 eV was slightly increased as compared to the bulk ceria (Eg = 3.19 eV. The phytochemicals in the extract reduced the particle size to 3.7 nm ± 0.3 nm, as it is evident from the PSA. FT-IR results confirmed the Ce-O stretching bands by showing the peaks at 452 cm-1. The Raman spectrumshowed a characteristic peak shift for CONPs at 461.2 cm-1. XRD analysis revealed the cubic fluorite structure of the synthesizednanoparticles with the lattice constant, a of 5.415 Å and unit cell volume, V of 158.813 Å3. XPS signals were used to determine the concentration of Ce3+ and Ce4+ in the prepared CONPs and it was found that major amount of cerium exist in the Ce4+ state. HRTEM images showed spherical shaped particles with an average size of 15 nm. Furthermore, the antibacterial activity of the prepared CONPs was evaluated and their efficacies were compared with the conventional antibiotics using disc diffusion assay against a set of Gram positive (G+ bacteria (Staphylococcus aureus, Streptococcus pneumonia and Gram negative (G- bacteria (Pseudomonas aeruginosa, Proteus vulgaris. The results suggested that CONPs showed antibacterial activity with significant variations due to the differences in the membrane structure and cell wall composition among the two groups tested.

ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

Energy Technology Data Exchange (ETDEWEB)

Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

1977-12-11

The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

Alumina composites for oxide/oxide fibrous monoliths

International Nuclear Information System (INIS)

Cruse, T. A.; Polzin, B. J.; Picciolo, J. J.; Singh, D.; Tsaliagos, R. N.; Goretta, K. C.

2000-01-01

Most work on ceramic fibrous monoliths (FMs) has focused on the Si 3 N 4 /BN system. In an effort to develop oxidation-resistant FMs, several oxide systems have recently been examined. Zirconia-toughened alumina and alumina/mullite appear to be good candidates for the cell phase of FMs. These composites offer higher strength and toughness than pure alumina and good high-temperature stability. By combining these oxides, possibly with a weaker high-temperature oxide as the cell-boundary phase, it should be possible to product a strong, resilient FM that exhibits graceful failure. Several material combinations have been examined. Results on FM fabrication and microstructural development are presented

Study of the gamma spectrum of 16N with a BGO detector, for the purpose of calibration and of determining the fluorine grade of mineral samples

International Nuclear Information System (INIS)

Castro-Garcia, M.P.; Alonso-Sanchez, T.; Rey-Ronco, M.A.

2013-01-01

The study of 16 N's gamma spectrum has two main uses: calibrating gamma detectors in a high energy range, and determining the fluorine grade of mineral samples of fluorite. This article examines and compares the gamma ray spectrum of 16 N as recorded by a Bi 4 GeO 12 detector, as well as the resolution of this detector at high energy levels, and the signal-background relationship of an experimental laboratory cyclic activation unit. 16 N is the product of the reaction 9-F-19(n,α)7-N-16, which takes place during the neutron activation of mineral samples of fluorspar, and its production depends, among other factors, upon the grade of fluorite. The technique used in this study is cyclic-type neutron activation for recording delayed gamma rays, carried out with an americium-beryllium neutron source with an activity of 1 Ci. Lastly, a correlation is established between the area below the peak amount of 16 N emitted by the sample, and the sample's fluorite grade. (author)

Structural Phase Transition and Compressibility of CaF2 Nanocrystals under High Pressure

Directory of Open Access Journals (Sweden)

Jingshu Wang

2018-05-01

Full Text Available The structural phase transition and compressibility of CaF2 nanocrystals with size of 23 nm under high pressure were investigated by synchrotron X-ray diffraction measurement. A pressure-induced fluorite to α-PbCl2-type phase transition starts at 9.5 GPa and completes at 20.2 GPa. The phase-transition pressure is lower than that of 8 nm CaF2 nanocrystals and closer to bulk CaF2. Upon decompression, the fluorite and α-PbCl2-type structure co-exist at the ambient pressure. The bulk modulus B0 of the 23 nm CaF2 nanocrystals for the fluorite and α-PbCl2-type phase are 103(2 and 78(2 GPa, which are both larger than those of the bulk CaF2. The CaF2 nanocrystals exhibit obviously higher incompressibility compare to bulk CaF2. Further analysis demonstrates that the defect effect in our CaF2 nanocrystals plays a dominant role in the structural stability.

Wadi Ladid Al-JI,Dan Alkali Feldspar Granites and Associated Pegmatites, North Eastern Eser, Egypt:Geology,Mineralogy and Radioactivity

International Nuclear Information System (INIS)

Abu Steet, A.A.; Ayoub, R.R.; Bakhit, A.F.

2013-01-01

This article deals with the geology, structure, mineralogy and radioactivity of the alkali feldspar granites at wadi Ladid al-Ji,dan, north Eastern Desert of Egypt. Geologically, the area consists mainly of alkali feldspar granites. These granites are medium to coarse grained, pink to red in colour and form numbers of moderate to relatively high elevated outcrops. These rocks are altered in some parts due to secondary processes especially along the fault zones and contacts. The area displays primary and secondary structures. Primary structures comprise layering, volcanic flows, vesicular tops of lavas and volcanic bombs. The secondary structures are represented by exfoliation, joints and faults. The granites are dissected by several sets of joints predominating in the N-S direction, dipping 84°-88° mainly to west; E-W direction, dipping 70°-75° mainly to south and NW-SE direction, dipping 80°-82° to SW direction. The majority of joints are tension ones. These tension joints are commonly filled with quartz, feldspars, epidote, iron oxides, manganese oxides and aplite. The studied area is dissected by major regional faults. Along the fault zones; the granites are marked by fault breccia and alteration features, especially silicification, hematitization, kaolinitization and chloritization. The area is cutting by faults trending mainly in N-S, NE-SW and NNW-SSE directions. The average uranium and thorium contents of the alkali feldspar granites are 12 and 23 ppm and reaches up to 36 and 37 ppm in the normal pegmatites. In the anomalous pegmatites the maximum values recorded are 91 and 72 ppm. Generally, the averages of uranium and thorium contents in the studied pegmatites are higher than that of the world and Egyptian uraniferous pegmatites. The high uranium content in alkali feldspar granites is related to the presence of some accessory minerals such as zircon, fluorite and apatite but the high uranium content in the pegmatites is related to the presence of

Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

Science.gov (United States)

Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

2013-09-24

A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

The effect of B-site substitution on structural transformation and ionic conductivity in Ho2(ZryTi1−y)2O7

International Nuclear Information System (INIS)

Shafique, Muhammad; Kennedy, Brenden J.; Iqbal, Yaseen; Ubic, Rick

2016-01-01

Compounds in the pyrochlore system Ho 2 (Zr y Ti 1−y ) 2 O 7 exhibit an order-disorder transition from pyrochlore to a defect-fluorite type structure. Compositions in this system were prepared via mechanical milling, followed by a two-step sintering process. Structural characterization was carried out via Rietveld refinements using neutron powder diffraction data, supported by X-ray diffraction to determine the phase and location of the pyrochlore-fluorite transformation. Unit-cell parameters were determined for the whole series using Rietveld refinements as well as the Nelson–Riley function. The neutron refinement results confirmed that the cation disorder was independent of the anion Frenkel disorder. The relation between the x-parameter in the oxygen 48f position and anion Frenkel disorder was found to be linear for the pyrochlore structure. The ionic conductivity studies were undertaken via AC impedance analysis to determine the electronic behaviour and its relation to the structural change in the temperature range 300°C–700 °C. The trends in ionic conductivity and activation energy were explained structurally via neutron powder diffraction and X-ray diffraction data. The pyrochlore-fluorite boundary composition (at y = 0.5) exhibited the lowest activation energy and highest ionic conductivity. - Highlights: • Ho 2 (Zr y Ti 1-y ) 2 O 7 structure changed from ordered pyrochlore to defect-fluorite at y = 0.6. • Ho 2 (Zr 0.5 Ti 0.5 ) 2 O 7 exhibited high ionic conductivity and low activation energy. • Doping improved stability in ionic conductivity behaviour at lower temperature.

Oxidized Lipoprotein as a Major Vessel Cell Proliferator in Oxidized Human Serum.

Directory of Open Access Journals (Sweden)

Yoshiro Saito

Full Text Available Oxidative stress is correlated with the incidence of several diseases such as atherosclerosis and cancer, and oxidized biomolecules have been determined as biomarkers of oxidative stress; however, the detailed molecular relationship between generated oxidation products and the promotion of diseases has not been fully elucidated. In the present study, to clarify the role of serum oxidation products in vessel cell proliferation, which is related to the incidence of atherosclerosis and cancer, the major vessel cell proliferator in oxidized human serum was investigated. Oxidized human serum was prepared by free radical exposure, separated using gel chromatography, and then each fraction was added to several kinds of vessel cells including endothelial cells and smooth muscle cells. It was found that a high molecular weight fraction in oxidized human serum specifically induced vessel cell proliferation. Oxidized lipids were contained in this high molecular weight fraction, while cell proliferation activity was not observed in oxidized lipoprotein-deficient serum. Oxidized low-density lipoproteins induced vessel cell proliferation in a concentration-dependent manner. Taken together, these results indicate that oxidized lipoproteins containing lipid oxidation products function as a major vessel cell proliferator in oxidized human serum. These findings strongly indicate the relevance of determination of oxidized lipoproteins and lipid oxidation products in the diagnosis of vessel cell proliferation-related diseases such as atherosclerosis and cancer.

Anaerobic sulfide-oxidation in marine colorless sulfur-oxidizing bacteria

Digital Repository Service at National Institute of Oceanography (India)

LokaBharathi, P.A.; Nair, S.; Chandramohan, D.

Colorless sulfur-oxidizing bacteria are ubiquitous in Indian waters and have the ability to oxidize sulfide under anaerobic conditions. These bacteria can not only mediate the sulfur cycle oxidatively but also the nitrogen cycle reductively without...

Magnetic susceptibilities of Ca/sub y/U/sub 1-y/O/sub 2+x/ solid solutions

International Nuclear Information System (INIS)

Hinatsu, Y.; Fujino, T.

1988-01-01

Magnetic susceptibilities of Ca/sub y/U/sub 1-y/O/sub 2+x/ solid solutions with fluorite structure were measured from 4.2 K to room temperature. An antiferromagnetic transition was observed for all the solid solutions examined in this study (y ≤ 0.33). The Neel temperature of the oxygen-hypostoichiometric solid solutions (x 2 solid solutions, but different from that of (U,Th)O 2 solid solutions. The effective magnetic moment decreased with increasing calcium concentration, which indicates the oxidation of uranium in the solid solutions. From the analysis of the magnetic susceptibility data, it was found that the oxidation state of uranium was either tetravalent or pentavalent. The Neel temperature of the hyperstoichiometric solid solutions (x > 0) did not change appreciably with calcium concentrations. From the comparison of the magnetic susceptibility data of the hypostoichiometric solid solutions with those of the hyperstoichiometric solid solutions, the effect of oxygen vacancies is more significant than that of interstitial oxygens on the decrease of magnetic interactions between uranium ions

Interactions between iron oxides and copper oxides under hydrothermal conditions

Energy Technology Data Exchange (ETDEWEB)

McGarvey, G B; Owen, D G

1995-08-01

Under hydrothermal conditions, magnetite and hematite have been shown to undergo interconversion reactions, the extent of which is controlled in part by the presence of copper oxides. In oxygenated water, the degree to which magnetite was oxidized to hematite was found to be dependent on the presence of CuO or Cu{sub 2}O. When these materials were absent, the oxidation of magnetite was limited by the dissolved oxygen in the aqueous system. Participation of the copper oxides in the oxidation process was confirmed by more complete conversion of magnetite was also influenced by the presence of the copper oxides. In addition to driving the reduction to completion, the presence of the copper oxides also exerted a strong influence over the morphology of the magnetite that formed. (author). 13 refs., 1 tab., 3 figs.

Progress report - Physical and Environmental Sciences - Physics Division, 1996 January 1 to December 31

International Nuclear Information System (INIS)

Powell, B.M.

1997-04-01

This document is the last Progress Report for the Neutron and Condensed Matter Science Branch, at Chalk River Labs of Atomic Energy of Canada Limited. The materials science program continued to include measurements of stress as a major component, but the determination of phase diagrams for specific alloys was also a prominent activity. Studies were made of two types of unusual magnetic materials. The magnetic properties of several oxide pyrochlore were investigated and spin waves were measured in the magnetic semiconductor, chalcopyrite. The crystal structures of the deuterated anti fluorite were determined and the reorientation of the ammonium ion was refined in detail. Differential scanning calorimetry measurements were used to investigate whether spontaneous phase separation into chiral domains occurs for mixtures of DPPC of opposite chirality. A new Neutron Velocity Selector was commissioned

Progress report - Physical and Environmental Sciences - Physics Division, 1996 January 1 to December 31

Energy Technology Data Exchange (ETDEWEB)

Powell, B.M. (ed.)

1997-04-01

This document is the last Progress Report for the Neutron and Condensed Matter Science Branch, at Chalk River Labs of Atomic Energy of Canada Limited. The materials science program continued to include measurements of stress as a major component, but the determination of phase diagrams for specific alloys was also a prominent activity. Studies were made of two types of unusual magnetic materials. The magnetic properties of several oxide pyrochlore were investigated and spin waves were measured in the magnetic semiconductor, chalcopyrite. The crystal structures of the deuterated anti fluorite were determined and the reorientation of the ammonium ion was refined in detail. Differential scanning calorimetry measurements were used to investigate whether spontaneous phase separation into chiral domains occurs for mixtures of DPPC of opposite chirality. A new Neutron Velocity Selector was commissioned.

SrWO4 at high pressures

International Nuclear Information System (INIS)

Grzechnik, A.; Crichton, W.A.; Hanfland, M.

2005-01-01

Room-temperature high-pressure behaviour of SrWO 4 scheelite (I4 1 /a, Z=4) has been studied to 20.7 GPa in a diamond anvil cell using synchrotron angle-dispersive X-ray powder diffraction. Above 10 GPa, it transforms to the fergusonite structure (I2/a, Z=4). Both scheelite and fergusonite types are ordered superstructures of fluorite (Fm anti 3m, Z=4). There is no significant volume collapse at the scheelite-fergusonite phase transition. However, the compression data including both phases of strontium tungstate cannot be fitted by a common Birch-Murnaghan equation of state. An onset of decomposition into component oxides occurs at about 15 GPa. The pressure-induced transformations are irreversible. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

SrWO{sub 4} at high pressures

Energy Technology Data Exchange (ETDEWEB)

Grzechnik, A. [Departamento de Fisica de la Materia Condensada, Universidad del Pais Vasco, Apdo. 644, Bilbao 48080 (Spain); European Synchrotron Radiation Facility, B.P. 220, 38043 Grenoble cedex (France); Crichton, W.A.; Hanfland, M. [European Synchrotron Radiation Facility, B.P. 220, 38043 Grenoble cedex (France)

2005-11-01

Room-temperature high-pressure behaviour of SrWO{sub 4} scheelite (I4{sub 1}/a, Z=4) has been studied to 20.7 GPa in a diamond anvil cell using synchrotron angle-dispersive X-ray powder diffraction. Above 10 GPa, it transforms to the fergusonite structure (I2/a, Z=4). Both scheelite and fergusonite types are ordered superstructures of fluorite (Fm anti 3m, Z=4). There is no significant volume collapse at the scheelite-fergusonite phase transition. However, the compression data including both phases of strontium tungstate cannot be fitted by a common Birch-Murnaghan equation of state. An onset of decomposition into component oxides occurs at about 15 GPa. The pressure-induced transformations are irreversible. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Radiation-induced cationic polymerization of limonene oxide, α-pinene oxide, and β-pinene oxide

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1984-01-01

After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weight. A cationic mechanism is evidenced by the strongly retarding effect of tri-n-propylamine on the polymerization rate. At 25 0 C, limonene oxide gives the highest polymerization rates, an average conversion of 36% per Mrad being obtained in comparison with values of 5.7 and 7.3% per Mrad for the α-pinene and β-pinene oxides, respectively. Similarly, the average anti DP/sub n/ decreases from 11.8 for the limonene oxide polymer to 5.6 and 4.0 for the α-pinene oxide and β-pinene oxide polymers, respectively. A high frequency of chain transfer to monomer is indicated in each case by the fact that the kinetic chain lengths are estimated to be on the order of a hundred times larger than the anti DP/sub n/ values. Structural characterization of the limonene oxide polymer by 1 H and 13 C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the α-pinene and β-pinene oxides show that in the polymerization of these monomers, the opening of the epoxide ring is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-dimethyl group in the main chain. The detection of isopropenyl end groups in the pinene oxide polymers is also consistent with this mode of propagation being followed by chain (proton) transfer to monomer

Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

Science.gov (United States)

Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-07-28

Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

Safeguards effectiveness evaluations in safeguards planning

International Nuclear Information System (INIS)

Al-Ayat, R.A.

1987-01-01

This paper describes analytic tools we developed to quantify the effectiveness of safeguards against theft of special nuclear material by insiders. These tools help identify vulnerabilities in existing safeguards, suggest potential improvements, and help assess the benefits of these upgrades prior to implementation. Alone, these tools are not sufficient for safeguards planning, since the cost of implementing all suggested upgrades almost always exceeds the available resources. This paper describes another tool we developed to allow comparsion of benefits of various upgrades to identify those upgrade packages that achieve the greatest improvement in protection for a given cost and to provide a priority ranking among cost-effective packages, thereby helping decision-makers select the upgrades to implement and highlight the mount of residual risk. 5 refs., 3 figs

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Selective carbon monoxide oxidation over Ag-based composite oxides

Energy Technology Data Exchange (ETDEWEB)

Guldur, C. [Gazi University, Ankara (Turkey). Chemical Engineering Department; Balikci, F. [Gazi University, Ankara (Turkey). Institute of Science and Technology, Environmental Science Department

2002-02-01

We report our results of the synthesis of 1 : 1 molar ratio of the silver cobalt and silver manganese composite oxide catalysts to remove carbon monoxide from hydrogen-rich fuels by the catalytic oxidation reaction. Catalysts were synthesized by the co-precipitation method. XRD, BET, TGA, catalytic activity and catalyst deactivation studies were used to identify active catalysts. Both CO oxidation and selective CO oxidation were carried out in a microreactor using a reaction gas mixture of 1 vol% CO in air and another gas mixture was prepared by mixing 1 vol% CO, 2 vol% O{sub 2}, 84 vol% H{sub 2}, the balance being He. 15 vol% CO{sub 2} was added to the reactant gas mixture in order to determine the effect of CO{sub 2}, reaction gases were passed through the humidifier to determine the effect of the water vapor on the oxidation reaction. It was demonstrated that metal oxide base was decomposed to the metallic phase and surface areas of the catalysts were decreased when the calcination temperature increased from 200{sup o}C to 500{sup o}C. Ag/Co composite oxide catalyst calcined at 200{sup o}C gave good activity at low temperatures and 90% of CO conversion at 180{sup o}C was obtained for the selective CO oxidation reaction. The addition of the impurities (CO{sub 2} or H{sub 2}O) decreased the activity of catalyst for selective CO oxidation in order to get highly rich hydrogen fuels. (author)

Oxidized limonene and oxidized linalool - concomitant contact allergy to common fragrance terpenes.

Science.gov (United States)

Bråred Christensson, Johanna; Karlberg, Ann-Therese; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Giménez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

2016-05-01

Limonene and linalool are common fragrance terpenes. Both oxidized R-limonene and oxidized linalool have recently been patch tested in an international setting, showing contact allergy in 5.2% and 6.9% of dermatitis patients, respectively. To investigate concomitant reactions between oxidized R-limonene and oxidized linalool in consecutive dermatitis patients. Oxidized R-limonene 3.0% (containing limonene hydroperoxides 0.33%) and oxidized linalool 6% (linalool hydroperoxides 1%) in petrolatum were tested in 2900 consecutive dermatitis patients in Australia, Denmark, Singapore, Spain, Sweden, and the United Kingdom. A total of 281 patients reacted to either oxidized R-limonene or oxidized linalool. Of these, 25% had concomitant reactions to both compounds, whereas 29% reacted only to oxidized R-limonene and 46% only to oxidized linalool. Of the 152 patients reacting to oxidized R-limonene, 46% reacted to oxidized linalool, whereas 35% of the 200 patients reacting to oxidized linalool also reacted to oxidized R-limonene. The majority of the patients (75%) reacted to only one of the oxidation mixtures, thus supporting the specificity of the reactions. The concomitant reactions to the two fragrance allergens suggest multiple sensitizations, which most likely reflect the exposure to the different fragrance materials in various types of consumer products. This is in accordance with what is generally seen for patch test reactions to fragrance materials. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

Energy Technology Data Exchange (ETDEWEB)

You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

2017-08-15

Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

OpenAIRE

Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

2012-01-01

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

Oxidation films morphology

International Nuclear Information System (INIS)

Paidassi, J.

1960-01-01

After studying the oxidation of several pure polyvalent metals (Fe, Cu, Mn, Ni, U) and of their oxides at high temperature and atmospheric pressure, the author suggests how to modify the usual representation of the oxide film (a piling of different oxide layers, homogeneous on a micrographic scale with a equi-axial crystallisation, free of mechanical tensions, with flat boundary surfaces) to have it nearer to reality. In this first part, the author exposes the study of the real micrographic structure of the oxidation film and gives examples of precipitation in the oxides during the cooling of the oxidised sample. (author) [fr

New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

Science.gov (United States)

Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

2018-05-01

The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

Science.gov (United States)

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Tungsten oxide nanowires grown on graphene oxide sheets as high-performance electrochromic material

International Nuclear Information System (INIS)

Chang, Xueting; Sun, Shibin; Dong, Lihua; Hu, Xiong; Yin, Yansheng

2014-01-01

Graphical abstract: Electrochromic mechanism of tungsten oxide nanowires-reduced graphene oxide composite. - Highlights: • A novel inorganic-nano-carbon hybrid composite was prepared. • The hybrid composite has sandwich-like structure. • The hybrid composite exhibited high-quality electrohcromic performance. - Abstract: In this work, we report the synthesis of a novel hybrid electrochromic composite through nucleation and growth of ultrathin tungsten oxide nanowires on graphene oxide sheets using a facile solvothermal route. The competition between the growth of tungsten oxide nanowires and the reduction of graphene oxide sheets leads to the formation of sandwich-structured tungsten oxide-reduced graphene oxide composite. Due to the strongly coupled effect between the ultrathin tungsten oxide nanowires and the reduced graphene oxide nanosheets, the novel electrochromic composite exhibited high-quality electrochromic performance with fast color-switching speed, good cyclic stability, and high coloration efficiency. The present tungsten oxide-reduced graphene oxide composite represents a new approach to prepare other inorganic-reduced graphene oxide hybrid materials for electrochemical applications

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

It has been suggested that oxidative stress, especially oxidative ...

African Journals Online (AJOL)

nabipour

2012-02-14

Feb 14, 2012 ... 1Department of Clinical Biochemistry, Faculty of Medicine, Bushehr University of Medical Sciences, Bushehr, Iran. 2Department of Cardiology ... oxidative modification of low-density lipoproteins (LDL), may play a causative role in ... the oxidation of lipids in the cell membrane especially the oxidation of LDL.

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

Science.gov (United States)

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

Science.gov (United States)

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

Oxidation kinetics of (B6O) boron oxide

International Nuclear Information System (INIS)

Makarov, V.S.; Solov'ev, N.E.; Ugaj, Ya.A.

1987-01-01

Reactivity of B 6 O to oxygen is investigated. It is shown that the process of B 6 O oxidation in the air in the temperature range 760-1150 K results in the maximum transformation degree equal to 0.35. At the initial stages oxidation proceeds in kinetic regime, at final stages - in diffusion one, and high viscosity of B 2 O 3 probably affects the oxidation process

Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks

Science.gov (United States)

Jones, J. Graham; Warner, C. G.

1972-01-01

Graham Jones, J., and Warner, C. G. (1972).Brit. J. industr. Med.,29, 169-177. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks. Occupational and medical histories, smoking habits, respiratory symptoms, chest radiographs, and ventilatory capacities were studied in 14 steelworkers employed as deseamers of steel ingots for periods of up to 16 years. The men were exposed for approximately five hours of each working shift to fume concentrations ranging from 1·3 to 294·1 mg/m3 made up mainly of iron oxide with varying proportions of chromium oxide and nickel oxide. Four of the men, with 14 to 16 years' exposure, showed radiological evidence of pneumoconiosis classified as ILO categories 2 or 3. Of these, two had pulmonary function within the normal range and two had measurable loss of function, moderate in one case and mild in the other. Many observers would diagnose these cases as siderosis but the authors consider that this term should be reserved for cases exposed to pure iron compounds. The correct diagnosis is mixed-dust pneumoconiosis and the loss of pulmonary function is caused by the effects of the mixture of metallic oxides. It is probable that inhalation of pure iron oxide does not cause fibrotic pulmonary changes, whereas the inhalation of iron oxide plus certain other substances obviously does. Images PMID:5021996

The 2016 oxide electronic materials and oxide interfaces roadmap

DEFF Research Database (Denmark)

Lorenz, M.; Rao, M. S. Ramachandra; Venkatesan, T.

2016-01-01

of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap......, Pentcheva, and Gegenwart. Finally, Miletto Granozio presents the European action ‘towards oxide-based electronics’ which develops an oxide electronics roadmap with emphasis on future nonvolatile memories and the required technologies.In summary, we do hope that this oxide roadmap appears as an interesting...

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †.

Science.gov (United States)

Afzal, Adeel; Dickert, Franz L

2018-04-20

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed.

Improved Understanding of In Situ Chemical Oxidation Contaminant Oxidation Kinetics

Science.gov (United States)

2007-12-01

natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE perchloroethylene HSO5− peroxymonosulfate PNDA p...properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and stability in the subsurface, and develop a standardized natural...chlorinated ethenes For contaminant oxidation by activated S2O82−, it is more difficult to develop a general description of kobs vs. T because there are

Fundamental aspects of Am and Cm in zirconia-based materials. Investigations using X-ray diffraction and Raman spectroscopy

International Nuclear Information System (INIS)

Raison, P.E.; Haire, R.G.; Assefa, Z.

2002-01-01

We have investigated incorporation of americium and curium in selected zirconia-based materials. Fundamental aspects were explored via X-ray diffraction and Raman spectroscopy. First explored was the pseudo ternary system, AmO 2 -ZrO 2 -Y 2 O 3 . It was found that stable, cubic solid solutions (Am x Zr 1-x Y y )O 2-2/y can be obtained for selected compositions. The cell parameters of the cubic phases were established as being linear with the AmO 2 content. For the Cm 2 O 3 -ZrO 2 system, it was determined that diphasic materials are produced, except for two compositions: 25 mol% and 50 mol% of CmO 1.5 . For these compositions a single-phase cubic fluorite type solid solution (a=5.21A±0.01) and a pyrochlore oxide Cm 2 Zr 2 O 7 (a=10.63A±0.02) are formed, respectively. The stability of pyrochlore oxides is also being investigated as a function of self-irradiation, using shorter-lived isotopes, one being the californium pyrochlore 249 Cf 2 Zr 2 O 7 . We obtained evidence that after six months of storage the pyrochlore oxide is undergoing structural change. Additional studies are in progress. (author)

Characterization of tin oxide nanoparticles synthesized via oxidation from metal

International Nuclear Information System (INIS)

Abruzzi, R.C.; Dedavid, B.A.; Pires, M.J.R.; Streicher, M.

2014-01-01

The tin oxide (SnO_2) is a promising material with great potential for applications such as gas sensors and catalysts. This oxide nanostructures show higher activation efficiency due to its larger effective surface. This paper presents the synthesis and characterization of the tin oxide in different conditions, via oxidation of pure tin with nitric acid. Results obtained from the characterization of SnO_2 powder by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDX), Particle size by Dynamic Light Scattering (DLS) and Infrared Spectroscopy (FTIR) indicated that the conditions were suitable for the synthesis to obtain manometric tin oxide granules with crystalline structure of rutile. (author)

Aging simulation of the tailings from Stava fluorite extraction by exposure to gamma rays

Directory of Open Access Journals (Sweden)

Gianluca Bella

Full Text Available Abstract Tailings storage facilities are disposal systems for storing the waste products of the mining industry consisting of a slurry mixture made of soil, rock and water that remain after the mineral values have been removed from the patent ore. Tailings dams are supposed to last forever, so after their deposition, tailings can experience aging processes with physical and chemical changes depending on the interactions between local conditions and source mineralogy. The consequences of these aging processes are increased interlocking of particles and oxidation processes, sometimes making previously safely held contaminants available and mobile. Among the long-term aging processes, the natural ionizing radiation (from radioactive isotopes of the soils, cosmic rays, and also ultraviolet rays from the sun can be considered, as proposed in the current research. Furthermore, in many countries, tailings are beginning to be re-used as backfill, landscaping material or feedstock for cement and concrete. So if any, the long-term physical and chemical modifications could affect the hydraulic and mechanical behaviour of tailings with relevant economic consequences. For these reasons, wet and dry silty samples of tailings spilled out after the failure of the Stava tailings dam (Trentino Alto Adige, Italy were exposed to gamma rays, as an accelerated aging technique to simulate the natural ionizing radiation, and then characterized. The modifications on physical and chemical properties were observed and, despite certain chemical stability, some physical changes were observed, particularly in terms of size particle distribution, inner porosity of the particles and specific surface.

Aging simulation of the tailings from Stava fluorite extraction by exposure to gamma rays

Energy Technology Data Exchange (ETDEWEB)

Bella, Gianluca; Barbero, Monica; Barpi, Fabrizio, E-mail: gianluca.bella@polito.it, E-mail: monica.barbero@polito.it, E-mail: fabrizio.barpi@polito.it [Politecnico di Torino - DISEG (Italy); Lameiras, Fernando Soares, E-mail: fsl@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil); Espósito, Terezinha de Jesus, E-mail: esposito@etg.ufmg.br [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Departamento de Transporte e Engenharia Geotécnica

2017-10-15

Tailings storage facilities are disposal systems for storing the waste products of the mining industry consisting of a slurry mixture made of soil, rock and water that remain after the mineral values have been removed from the patent ore. Tailings dams are supposed to last forever, so after their deposition, tailings can experience aging processes with physical and chemical changes depending on the interactions between local conditions and source mineralogy. The consequences of these aging processes are increased interlocking of particles and oxidation processes, sometimes making previously safely held contaminants available and mobile. Among the long-term aging processes, the natural ionizing radiation (from radioactive isotopes of the soils, cosmic rays, and also ultraviolet rays from the sun) can be considered, as proposed in the current research. Furthermore, in many countries, tailings are beginning to be re-used as backfill, landscaping material or feedstock for cement and concrete. So if any, the long-term physical and chemical modifications could affect the hydraulic and mechanical behaviour of tailings with relevant economic consequences. For these reasons, wet and dry silty samples of tailings spilled out after the failure of the Stava tailings dam (Trentino Alto Adige, Italy) were exposed to gamma rays, as an accelerated aging technique to simulate the natural ionizing radiation, and then characterized. The modifications on physical and chemical properties were observed and, despite certain chemical stability, some physical changes were observed, particularly in terms of size particle distribution, inner porosity of the particles and specific surface. (author)

CaSO4:Dy and/or Tm: study of its properties for dosimetry application

International Nuclear Information System (INIS)

Ferreira, M.M.

1979-01-01

In order obtain in practical and cheap solid state dosimeter with high sensitivity, a technique initially developed to cold press a mixture of suitable materials in their powder form sensitive to radiation. The material initially used was natural CaF 2 (fluorite) for this salt was extensively studied in radiation dosimetry since it shows a thermoluminescent (TL) effect after radiation. However, natural calcium fluorite shows two main disadvantages: its high senstivity to room light and the impossibility to control its impurity content due to its natural origin. Calcium sulphate was thus used as a good substitute of fluorite. Rare earths doped calcium sulphate shows a high TL sensitivity and is not disturbed by light. It is also easily obtained in the laboratory under controlled conditions so to get reproducible impurity content. The best dosimeters that can be produced with rare earth doped calcium sulphate are CaSO 4 :Dy and CaSO 4 :Tm. Calcium sulphate, simultaneously doped with Tm and Dy was produced and 100% increase was obtained in the TL sensitivity when compared with the individually are earth doped calcium sulphate. (Author) [pt

The oxidation; Okislenie

Energy Technology Data Exchange (ETDEWEB)

Nikitin, V I

1961-07-01

In this chapter of book author determine that alkylene tetra hydro-{gamma}-piron, oxidated by potassium permanganate in all cases of passed oxidation gave oxidation products, confirmatory their structure.

SANDIA MOUNTAIN WILDERNESS, NEW MEXICO.

Science.gov (United States)

Hedlund, D.C.; Kness, R.F.

1984-01-01

Geologic and mineral-resource investigations in the Sandia Mountains in New Mexico indicate that a small part of the area has a probable mineral-resource potential. Most of the mineral occurrences are small barite-fluorite veins that occur along faults on the eastern slope of the range. The barite veins in the Landsend area and in the Tunnel Spring area are classed as having a probable mineral-resource potential. Fluorite veins which occur at the La Luz mine contain silver-bearing galeana and the area near this mine is regarded as having a probable resource potential for silver. No energy resources were identified in this study.

Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Kung, H.H.; Kundalkar, B.; Kung, M.C.; Cheng, W.H.

1980-02-21

Adsorption, temperature-programed desorption, and pulse reaction studies of cis-2-butene and butadiene on spinel zinc ferrite by previously described methods provided evidence that the selectivity for oxidative dehydrogenation of butenes increases when zinc is added to the iron oxide catalyst because selective oxidation and complete oxidation proceed on separate sites, as they do on pure iron; because the density of sites for selective oxidation is higher and the density of sites for complete combustion is lower than on pure iron oxide; and because the activity of the combustion sites is lower.

Direct Coal Oxidation in Modified Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Deleebeeck, Lisa; Gil, Vanesa; Ippolito, Davide

2017-01-01

Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon-carbonate s......Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon......-carbonate slurry or anode layer. The nature of the coal affects both open circuit voltage and power output. Highest OCV and power densities were observed for bituminous coal and by adding manganese oxide or praseodymium-doped ceria to the carbon/carbonate mixture. Comparing the carbon black fueled performance...... bituminous coal (73 mW/cm2)....

Mechanism of 1, 1-d2 propene oxidation over oxide catalysts

International Nuclear Information System (INIS)

Portefaix, J.L.; Figueras, F.; Forissier, M.

1980-01-01

CD 2 CHCH 3 was oxidized over bismuth molybdate, tin-antimony mixed oxides and supported molybdenum and vanadium oxide catalysts. The deuterium retention is high ( > 90%) in the recovered propene. Percentage retentions of deuterium in the acrolein agree with literature data when bismuth molybdate is used as catalyst. On Sb-Sn-O and supported Mo and V oxides, no isotope effect is noticed for the abstraction of the second hydrogen from the olefin. The slow step of the reaction may therefore be different for the oxidation of propene on Bi-Mo-O and Sb-Sn-O. The ethanal produced by oxidation of CD 2 CHCH 3 contains only minor amounts of deuterium, whatever the catalyst used. It is suggested that partial oxidation of propene to acrolein and C-C bond rupture are parallel reactions which involve different intermediates. Possible mechanisms adapted from organic chemistry are presented to explain these findings. 4 tables

Oxidation phase growth diagram of vanadium oxides film fabricated by rapid thermal annealing

Institute of Scientific and Technical Information of China (English)

Tamura KOZO; Zheng-cao LI; Yu-quan WANG; Jie NI; Yin HU; Zheng-jun ZHANG

2009-01-01

Thermal evaporation deposited vanadium oxide films were annealed in air by rapid thermal annealing (RTP). By adjusting the annealing temperature and time, a series of vanadium oxide films with various oxidation phases and surface morphologies were fabricated, and an oxidation phase growth diagram was established. It was observed that different oxidation phases appear at a limited and continuous annealing condition range, and the morphologic changes are related to the oxidation process.

Frustration under pressure: Exotic magnetism in new pyrochlore oxides

Directory of Open Access Journals (Sweden)

C. R. Wiebe

2015-04-01

Full Text Available Pyrochlore structures, of chemical formula A2B2O7 (A and B are typically trivalent and tetravalent ions, respectively, have been the focus of much activity in the condensed matter community due to the ease of substitution of rare earth and transition metal ions upon the two interpenetrating corner-shared tetrahedral lattices. Over the last few decades, superconductivity, spin liquid states, spin ice states, glassy states in the absence of chemical disorder, and metal-insulator transitions have all been discovered in these materials. Geometric frustration plays a role in the relevant physics of all of these phenomena. In the search for new pyrochlore materials, it is the RA/RB cation radius ratio which determines the stability of the lattice over the defect fluorite structure in the lower limit. Under ambient pressure, the pyrochlores are stable for 1.36 ≤ RA/RB ≤ 1.71. However, using high pressure synthesis techniques (1-10 GPa of pressure, metastable pyrochlores exist up to RA/RB = 2.30. Many of these compounds are stable on a timescale of years after synthesis, and provide a means to greatly enhance exchange, and thus test theories of quantum magnetism and search for new phenomena. Within this article, we review new pyrochlore compounds synthesized via high pressure techniques and show how the ground states are extremely sensitive to chemical pressure.

Oxidation of urate by a therapeutic nitric oxide/air mixture

International Nuclear Information System (INIS)

Hicks, M.; Nguyen, L.; Day, R.; Rogers, P.

1996-01-01

Full text: Little is known about the potential toxicological consequences of therapeutic exposure of lung tissue to inhaled nitric oxide (NO). This route of administration is currently being successfully employed for the treatment of pulmonary hypertension and other lung pathologies including acute reperfusion injury in lung transplant patients. The toxicity of NO lies in its ability to act as an oxidant either in its own right or in concert with oxygen or with the superoxide free radical. One important interaction may be the reaction of these products with protective antioxidants in the lung epithelial lining fluid. One such antioxidant found in significant concentrations in both upper and lower airways is uric acid. In the present study, urate solutions (30μM) were exposed to a therapeutic concentration of NO gas, (35 ppm in air), for up to 90 minutes. Oxidative changes were followed spectrophotometrically and by HPLC. Significant loss of uric acid was observed with a concomitant formation of nitrite and allantoin, the stable oxidation product of NO and the major oxidation product of uric acid, respectively. No oxidation of urate was observed in the presence of air alone or when urate was incubated with nitrite. Uric acid oxidation could also be prevented by passing the NO / air stream through 10% KOH before the uric acid solution. This strategy removed trace amounts of higher oxides of nitrogen, (especially NO 2 ), from the NO / air stream. Thus, therapeutic inhalation of NO may deplete soluble antioxidants such as uric acid, especially during long-term chronic exposure unless care is taken to minimise formation of higher oxides of nitrogen

Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

International Nuclear Information System (INIS)

Finkeldei, Sarah Charlotte

2015-01-01

Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO 2 based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO 2 based pyrochlores. ZrO 2 - Nd 2 O 3 pellets with pyrochlore and defect

Effect of the Lithium Oxide Concentration on a Reduction of Lanthanide Oxides

International Nuclear Information System (INIS)

Choi, In-Kyu; Jeong, Myeong-Soo; Do, Jae-Bum; Seo, Chung-Seok

2007-01-01

The pyrochemical reduction process of spent oxide fuel is one of the options to handle spent PWR fuels in Korea. After spent oxide fuel is converted to a metallic form, fission products will be removed from the resultant uranium and higher actinide metals by an electrorefining process. The chemical behaviors of lanthanide oxides during the pyrochemical process has been extensively studied. It was also reported that about 30 to 50% of several lanthanide oxides were reduced to corresponding metals by an electrolytic reduction process having 1 wt% of a lithium oxide concentration. Korea Atomic Energy Research Institute (KAERI), however, has been used 3 wt% of lithium oxide to increase the applied current of the electrolytic reduction process. Though it was reported that U 3 O 8 was reduced to uranium metal having a high reduction yield at 3 wt% of the Li 2 O concentration, the effect of the lithium oxide concentration on the reduction of lanthanide oxides has not been clarified

Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

International Nuclear Information System (INIS)

Fossing, H.

1992-01-01

Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

Direct Coal Oxidation in Modified Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Deleebeeck, Lisa; Gil, Vanesa; Ippolito, Davide

2015-01-01

Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon-carbonate s......Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon......-carbonate slurry or anode layer. The nature of the coal affects both open circuit voltage and power output. Highest OCV and power densities were observed for bituminous coal and by adding manganese oxide or praseodymium-doped ceria to the carbon/carbonate mixture. Comparing the carbon black fueled performance...... bituminous coal (73 mW/cm2). © 2015 ECS - The Electrochemical Society...

Protein oxidation in aquatic foods

DEFF Research Database (Denmark)

Baron, Caroline P.

2014-01-01

The chapter discusses general considerations about protein oxidation and reviews the mechanisms involved in protein oxidation and consequences of protein oxidation on fish proteins. It presents two case studies, the first deals with protein and lipid oxidation in frozen rainbow trout......, and the second with oxidation in salted herring. The mechanisms responsible for initiation of protein oxidation are unclear, but it is generally accepted that free radical species initiating lipid oxidation can also initiate protein oxidation. The chapter focuses on interaction between protein and lipid...... oxidation. The protein carbonyl group measurement is the widely used method for estimating protein oxidation in foods and has been used in fish muscle. The chapter also talks about the impact of protein oxidation on protein functionality, fish muscle texture, and food nutritional value. Protein oxidation...

Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

Science.gov (United States)

2009-05-01

methyl tert butyl ether NAPL non-aqueous phase liquid NOD natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE...and persulfate; and Technical Objective 2, assess how soil properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and...to develop a general description of kobs vs. T because there are many reactions that can contribute to the concentration of the reactive intermediate

Oxidation Resistant Graphite Studies

Energy Technology Data Exchange (ETDEWEB)

W. Windes; R. Smith

2014-07-01

The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

Oxidizer Scoping Studies

Energy Technology Data Exchange (ETDEWEB)

Chancellor, Christopher John [Los Alamos National Laboratory

2016-11-07

The purpose of this report is to present the results of the acceptable knowledge (AK) review of oxidizers present in active waste streams, provide a technical analysis of the oxidizers, and report the results of the scoping study testing. This report will determine the fastest burning oxidizer to be used in the development of a Test Plan for Preparation and Testing of Sorbents Mixed with Oxidizer found in Transuranic Waste (DWT-TP-001). The companion report, DWT-RPT-002, Sorbent Scoping Studies, contains similar information for sorbents identified during the AK review of TRU waste streams. The results of the oxidizer and sorbent scoping studies will be used to inform the QL1 test plan. The QL1 test results will support the development of a basis of knowledge document that will evaluate oxidizing chemicals and sorbents in TRU waste and provide guidance for treatment.

The properties of protective oxide scales containing cerium on alloy 800H in oxidizing and oxidizing/sulphidizing environments

NARCIS (Netherlands)

Haanappel, V.A.C.; Haanappel, V.A.C.; Fransen, T.; Geerdink, Bert; Gellings, P.J.; Stroosnijder, M.F.

1991-01-01

The corrosion protection of oxide scales formed by electrophoretic deposition in a cerium-containing sol on Alloy 800H, a 32Ni-20Cr steel, followed by firing in air at 1123 K was studied in oxidizing and mixed oxidizing/sulphidizing environments at elevated temperatures. In particular, the influence

Spectrographic determination of impurities in high-purity tantalum oxide and niobium oxide

International Nuclear Information System (INIS)

Anderson, S.T.G.; Russell, G.M.

1990-01-01

The development of spectrographic methods by direct current arc excitation and carrier distillation for the determination of impurities in tantalum and niobium oxides are described. Iron, silicon, aluminium, titanium, calcium, silver, tin, magnesium, and manganese can be determined in tantalum oxide and niobium oxide in concentrations ranging from 3 to 300 p.p.m. Niobium can be determined in tantalum oxide in concentrations ranging from 10 to 300 p.p.m. Tantalum cannot be determined in niobium oxide, and tungsten cannot be determined in either matrix as a result of the absence of sensitive lines in the spectra of these elements. Relative standard deviations of analyte element concentrations are in the region of 0,18 for tantalum oxide samples, and 0,13 for niobium oxide samples. A detailed laboratory method is included. 4 figs., 4 tabs., 3 refs

Efficient synthesis of graphene oxide and the mechanisms of oxidation and exfoliation

Science.gov (United States)

Yuan, Rui; Yuan, Jing; Wu, Yanping; Chen, Lei; Zhou, Huidi; Chen, Jianmin

2017-09-01

An efficient method for the preparation of graphene oxide (GO) was descried through inducing the ultrasonic in the rate-determining step of oxidation processes. Both the transformation procedures and the detailed molecular behavior of parent graphene (PG), partially oxidized graphene (PGO) and GO in H2SO4 and aqueous solution were investigated by molecular dynamic simulation (MD) combining with experiments. The results obtained from MD simulation show that the addition of KMnO4 truly marked the beginning of the reaction which carried out from the border of PG flakes to the centre. This oxidation procedure was the rate-determining step and mainly contained three steps: the boundary carbon atoms oxidized, the distance of the corresponding interlayer enlarged and the oxidizing agent diffused into the unoxidized region, the processes was repeated until oxidized completely. So, the introducing ultrasonic in this section can accelerate not only the exfoliation of layers but also the diffusion of oxidizer and finally raises the oxidation efficiency dramatically. To further clarify these simulation results, the GO was prepared by the method mentioned above. The analyses results for the X-ray diffraction (XRD), Raman spectra and X-ray photoelectron spectroscopy (XPS) of the resulting GO show that the ultrasonic method could perfectly shortens the oxidation time from 12 h to 3 h and forms the higher degree of oxidation products with more carboxylic acid groups on its edges. Thus, this study provides a better understanding of the transformation procedures of graphite and proposes an efficient way to produce GOs suitable for various chemical modifications.

Green oxidations: Titanium dioxide induced tandem oxidation coupling reactions

OpenAIRE

Jeena, Vineet; Robinson, Ross S

2009-01-01

Summary The application of titanium dioxide as an oxidant in tandem oxidation type processes is described. Under microwave irradiation, quinoxalines have been synthesized in good yields from the corresponding ?-hydroxyketones.

Influence of rare earth oxides in the oxidation of chromia forming alloys

International Nuclear Information System (INIS)

Ramanathan, L.V.

1989-01-01

The influence of superficial application of rare earth oxides such as CeO sub(2), La sub(2)O sub(3), Nd sub(2)O sub(3), Sm sub(2)O sub(3), and Gd sub(2)O sub (3) to AISI 304 and 310 stainless steels, on their isothermal oxidation behavior at 900 sup(0) and 1000 sup(0)C, and cyclic oxidation behavior between 20 sup(0) and 1000 sup(0)C has been studied. The application of rare earth oxides (REO) has been found to increase the oxidation resistance at AISI 304. No significant improvements in oxidation resistance of AISI 310 were noted. The oxidation resistance of AISI 304 was highest in the presence of CeO sub(2) on its surface. The other REO in decreasing order of influence on oxidation resistance are La sub(2)O sub(3), Nd sub(2)O sub(3), Sm sub(2)O sub(3) and Gd sub(2)O sub(3). SEM investigations of the oxide scale morphology revealed that the improved resistance is probably due to the formation of a thin layer of fine grained compact Cr sub(2)O sub(3) and the higher adhesion of the scale to its increased plasticity. (author)

REDUPP. Second annual report

International Nuclear Information System (INIS)

Zetterstroem Evins, L.; Vaehaenen, M.

2013-05-01

Understanding the interactions between solid surface and fluid during the dissolution process is essential for developing a model for spent fuel dissolution. This project aims to enhance the understanding of the dissolution process of fluorite-type materials; these have the same crystal structure as nuclear fuel. CaF 2 , CeO 2 , ThO 2 and UO 2 are here used in dissolution studies during which the evolution of the solution and surface is monitored as the dissolution proceeds. For the UO 2 -experiments, the effect of natural groundwater on the dissolution of a surface emitting alpha radiation is investigated. The goal is to use the experimental results in combination with first-principles modelling to formulate a model describing the surfaces of dissolving fluorite-type materials. The project is on-going and this report presents the progress after two years. The experimental results reported here point towards effects of surface area and surface area to volume ratios, exposed grain boundaries, and bulk vs. 'local' solubility. The importance of well-controlled analytical conditions and high-resolution measurements are emphasized, in order to distinguish differences between effects of remnant fines, amorphous precipitates, grain boundaries, surface defects and crystallographic orientation of the exposed surfaces. The progress with regards to modelling shows that a surface model is formulated which can predict the surface formation energies of all crystal planes of the fluorite structure. It has been shown that this quantity can be related with the experimental surface stability during dissolution, and that for any material with the fluorite structure the same relation between computed surface stability and experimental stability (dissolution rate) will hold. The work on setting up a model of the dissolution process is ongoing; this kind of modelling is computationally very demanding as it requires a combination of molecular dynamics simulations and ab initio electronic

Lattice contraction and lattice deformation of UO{sub 2} and ThO{sub 2} doped with Gd{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Baena, Angela [Belgian Nuclear Research Centre (SCK-CEN), Institute for Nuclear Materials Science, Boeretang 200, B-2400 Mol (Belgium); KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, B-3001 Heverlee (Belgium); Cardinaels, Thomas; Govers, Kevin; Pakarinen, Janne [Belgian Nuclear Research Centre (SCK-CEN), Institute for Nuclear Materials Science, Boeretang 200, B-2400 Mol (Belgium); Binnemans, Koen [KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, B-3001 Heverlee (Belgium); Verwerft, Marc, E-mail: marc.verwerft@sckcen.be [Belgian Nuclear Research Centre (SCK-CEN), Institute for Nuclear Materials Science, Boeretang 200, B-2400 Mol (Belgium)

2015-12-15

The lattice deformations in two doped fluorite systems, (U{sub 1−x}Gd{sub x})O{sub 2.00} and (Th{sub 1−x}Gd{sub x})O{sub 2−x/2}, have been reassessed by precise X-ray and electron diffraction investigations and the results were interpreted using the Bond Valence Sum (BVS) approach. For the (U{sub 1−x}Gd{sub x})O{sub 2.00} system, the experimental findings and theoretical assessment confirm earlier work: the lattice keeps its fluorite structure with a unit cell parameter that contracts linearly with dopant concentration. The lattice contraction in the (Th{sub 1−x}Gd{sub x})O{sub 2−x/2} system has for the first time been analyzed up to the solubility limit. Similar as for (U{sub 1−x}Gd{sub x})O{sub 2.00}, the (Th{sub 1−x}Gd{sub x})O{sub 2−x/2} solid solution contracts linearly as a function of dopant concentration but additionally, it develops a superstructure which is closely related to the parent fluorite structure. An excess anion bixbyite trial model is proposed to describe this superstructure. - Highlights: • Lattice deformations of (U{sub 1−x}Gd{sub x})O{sub 2.00} & (Th{sub 1−x}Gd{sub x})O{sub 2−x/2} are not identical. • (U{sub 1−x}Gd{sub x})O{sub 2.00} retains its fluorite structure. • (Th{sub 1−x}Gd{sub x})O{sub 2−x/2} forms an excess-anion bixbyite structure. • (U{sub 1−x}Gd{sub x})O{sub 2.00} and (Th{sub 1−x}Gd{sub x})O{sub 2−x/2} contractions were evaluated with high precision.

Non-oxidative and oxidative torrefaction characterization and SEM observations of fibrous and ligneous biomass

International Nuclear Information System (INIS)

Chen, Wei-Hsin; Lu, Ke-Miao; Lee, Wen-Jhy; Liu, Shih-Hsien; Lin, Ta-Chang

2014-01-01

Highlights: • Non-oxidative and oxidative torrefaction of biomass is studied. • Two fibrous biomasses and two ligneous biomasses are tested. • SEM observations of four biomasses are provided. • Fibrous biomass is more sensitive to O 2 concentration than ligneous biomass. • The performance of non-oxidative torrefaction is better than that of oxidative torrefaction. - Abstract: Oxidative torrefaction is a method to reduce the operating cost of upgrading biomass. To understand the potential of oxidative torrefaction and its impact on the internal structure of biomass, non-oxidative and oxidative torrefaction of two fibrous biomass materials (oil palm fiber and coconut fiber) and two ligneous ones (eucalyptus and Cryptomeria japonica) at 300 °C for 1 h are studied and compared with each other. Scanning electron microscope (SEM) observations are also performed to explore the impact of torrefaction atmosphere on the lignocellulosic structure of biomass. The results indicate that the fibrous biomass is more sensitive to O 2 concentration than the ligneous biomass. In oxidative torrefaction, an increase in O 2 concentration decreases the solid yield. The energy yield is linearly proportional to the solid yield, which is opposite to the behavior of non-oxidative torrefaction. The performance of non-oxidative torrefaction is better than that of oxidative torrefaction. As a whole, ligneous biomass can be torrefied in oxidative environments at lower O 2 concentrations, whereas fibrous biomass is more suitable for non-oxidative torrefaction

Synthesis of graphene oxide through different oxidation degrees for solar cells

Science.gov (United States)

Zhang, Xiaoshan; Wang, Huan; Huang, Tianjiao; Wen, Lingling; Zhou, Liya

2018-03-01

Graphene is known as an electro-chemical material and widely used in electro-chemical devices, especially in solar cell. Decreasing the thickness of the layer is a critical way to improve the electrochemical property of solar cells as far as possible. Among the various oxidation approaches, presented herein is a facile approach, which is easier, less cost and more effective, environmental benign with the greener processing and without any requirement for post purification, towards the synthesis of graphene oxide (GO) with different oxidation degrees by potassium ferrate (K2FeO4). A modified method using less amount of oxidizing agent is reported herein. It is the pretreatment of the synthesis of graphite, which maintains the thermal cycle of the system. This novel reports to compound GO with controlled oxidation degrees can not only increase the quantity of oxygen-containing functional groups on GO surface, increase space between graphene oxide layer and facilitate the dispersion of graphene in aqueous solution. Thus, the modified method shows prospect for large-scale production of graphene oxide and its novel application, in addition to its derivative and market potential for solar cells.

Anodic oxidation

CERN Document Server

Ross, Sidney D; Rudd, Eric J; Blomquist, Alfred T; Wasserman, Harry H

2013-01-01

Anodic Oxidation covers the application of the concept, principles, and methods of electrochemistry to organic reactions. This book is composed of two parts encompassing 12 chapters that consider the mechanism of anodic oxidation. Part I surveys the theory and methods of electrochemistry as applied to organic reactions. These parts also present the mathematical equations to describe the kinetics of electrode reactions using both polarographic and steady-state conditions. Part II examines the anodic oxidation of organic substrates by the functional group initially attacked. This part particular

Oxidative Stress in Neurodegeneration

Directory of Open Access Journals (Sweden)

Varsha Shukla

2011-01-01

Full Text Available It has been demonstrated that oxidative stress has a ubiquitous role in neurodegenerative diseases. Major source of oxidative stress due to reactive oxygen species (ROS is related to mitochondria as an endogenous source. Although there is ample evidence from tissues of patients with neurodegenerative disorders of morphological, biochemical, and molecular abnormalities in mitochondria, it is still not very clear whether the oxidative stress itself contributes to the onset of neurodegeneration or it is part of the neurodegenerative process as secondary manifestation. This paper begins with an overview of how oxidative stress occurs, discussing various oxidants and antioxidants, and role of oxidative stress in diseases in general. It highlights the role of oxidative stress in neurodegenerative diseases like Alzheimer's, Parkinson's, and Huntington's diseases and amyotrophic lateral sclerosis. The last part of the paper describes the role of oxidative stress causing deregulation of cyclin-dependent kinase 5 (Cdk5 hyperactivity associated with neurodegeneration.

Cerium oxide and platinum nanoparticles protect cells from oxidant-mediated apoptosis

International Nuclear Information System (INIS)

Clark, Andrea; Zhu Aiping; Sun Kai; Petty, Howard R.

2011-01-01

Catalytic nanoparticles represent a potential clinical approach to replace or correct aberrant enzymatic activities in patients. Several diseases, including many blinding eye diseases, are promoted by excessive oxidant stress due to reactive oxygen species (ROS). Cerium oxide and platinum nanoparticles represent two potentially therapeutic nanoparticles that de-toxify ROS. In the present study, we directly compare these two classes of catalytic nanoparticles. Cerium oxide and platinum nanoparticles were found to be 16 ± 2.4 and 1.9 ± 0.2 nm in diameter, respectively. Using surface plasmon-enhanced microscopy, we find that these nanoparticles associate with cells. Furthermore, cerium oxide and platinum nanoparticles demonstrated superoxide dismutase catalytic activity, but did not promote hemolytic or cytolytic pathways in living cells. Importantly, both cerium oxide and platinum nanoparticles reduce oxidant-mediated apoptosis in target cells as judged by the activation of caspase 3. The ability to diminish apoptosis may contribute to maintaining healthy tissues.

Interface and oxide traps in high-κ hafnium oxide films

International Nuclear Information System (INIS)

Wong, H.; Zhan, N.; Ng, K.L.; Poon, M.C.; Kok, C.W.

2004-01-01

The origins of the interface trap generation and the effects of thermal annealing on the interface and bulk trap distributions are studied in detail. We found that oxidation of the HfO 2 /Si interface, removal of deep trap centers, and crystallization of the as-deposited film will take place during the post-deposition annealing (PDA). These processes will result in the removal of interface traps and deep oxide traps and introduce a large amount of shallow oxide traps at the grain boundaries of the polycrystalline film. Thus, trade-off has to be made in considering the interface trap density and oxide trap density when conducting PDA. In addition, the high interface trap and oxide trap densities of the HfO 2 films suggest that we may have to use the SiO 2 /HfO 2 stack or hafnium silicate structure for better device performance

Oxidation mechanisms occurring in wines

OpenAIRE

Oliveira, Carla Maria; Ferreira, António César Silva; Freitas, Victor De; Silva, Artur M. S.

2011-01-01

The present review aims to show the state of the art on the oxidation mechanisms occurring in wines, as well as the methods to monitor, classify and diagnose wine oxidation. Wine oxidation can be divided in enzymatic oxidation and non-enzymatic oxidation. Enzymatic oxidation almost entirely occurs in grape must and is largely correlated with the content of hydroxycinnamates, such as caffeoyltartaric acid and paracoumaroyltartaric acid, and flavan-3-ols. Non-enzymatic oxidation, al...

Oxidation of uraninite

International Nuclear Information System (INIS)

Janeczek, J.; Ewing, R.C.

1993-06-01

Samples of uraninite and pitchblende annealed at 1200 degrees C in H 2 , and untreated pitchblende were sequentially oxidized in air at 180-190 degrees C, 230 degrees C, and 300 degrees C. Uraninite and untreated pitchblende oxidized to the U 4 O 9 -type oxide, and their x-ray symmetry remained isometric up to 300 degrees C. Reduced pitchblende, after oxidation to UO 2+x and U 4 O 9 -type oxides, transformed into α-U 3 O 8 at 300 degrees C. Two major mechanisms control uraninite and untreated pitchblende stability during oxidation: 1. Th and/or lanthanide elements maintain charge balance and block oxygen interstitials near impurity cations; 2. the uraninite structure saturates with respect to excess and radiation-induced oxygen interstitials. Untreated pitchblende during oxidation behaved similarly to irradiated UO 2 in spent nuclear fuel; whereas, reduced pitchblende resembled non-irradiated UO 2 . An analysis of the data in the literature, as well as our own efforts (XRD, EMPA, SEM, AEM) to identify U 3 O 7 in samples form Cigar Lake, Canada, failed to provide conclusive evidence of the natural occurrence of tetragonal αU 3 O 7 . Most probably, reported occurrences of U 3 O 7 are mixtures of isometric uraninites of slightly different compositions, 45 refs

Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

Science.gov (United States)

Javanaud, Cedric; Michotey, Valerie; Guasco, Sophie; Garcia, Nicole; Anschutz, Pierre; Canton, Mathieu; Bonin, Patricia

2011-11-01

Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Thermally exfoliated graphite oxide

Science.gov (United States)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

2011-01-01

A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

Science.gov (United States)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Oxidant/antioxidant balance in animal nutrition and health: the role of protein oxidation

Directory of Open Access Journals (Sweden)

Pietro eCeli

2015-10-01

Full Text Available This review examines the role that oxidative stress, and protein oxidation in particular, plays in nutrition, metabolism and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functional modifications. Protein oxidation seems to be involved in pathological conditions such as respiratory diseases and parasitic infection; however some studies also suggest that protein oxidation plays a crucial role in the regulation of important physiological functions such as reproduction, nutrition, metabolism, lactation, gut health and neonatal physiology. As the characterization of the mechanisms by which oxidative stress may influence metabolism and health is attracting considerable scientific interest, the aim of this review is to present veterinary scientists and clinicians with various aspects of oxidative damage to proteins.

High temperature oxidation test of oxide dispersion strengthened (ODS) steel claddings

International Nuclear Information System (INIS)

Narita, Takeshi; Ukai, Shigeharu; Kaito, Takeji; Ohtsuka, Satoshi; Matsuda, Yasushi

2006-07-01

In a feasibility study of ODS steel cladding, its high temperature oxidation resistance was evaluated. Although addition of Cr is effective for preventing high temperature oxidation, excessively higher amount of Cr leads to embrittlement due to the Cr-rich α' precipitate formation. In the ODS steel developed by the Japan Atomic Energy Agency (JAEA), the Cr content is controlled in 9Cr-ODS martensite and 12Cr-ODS ferrite. In this study, high temperature oxidation test was conducted for ODS steels, and their results were compared with that of conventional austenitic stainless steel and ferritic-martensitic stainless steel. Following results were obtained in this study. (1) 9Cr-ODS martensitic and 12Cr-ODS ferritic steel have superior high temperature oxidation resistance compared to 11mass%Cr PNC-FMS and even 17mass% SUS430 and equivalent to austenitic PNC316. (2) The superior oxidation resistance of ODS steel was attributed to earlier formation of the protective alpha-Cr 2 O 3 layer at the matrix and inner oxide scale interface. The grain size of ODS steel is finer than that of PNC-FMS, so the superior oxidation resistance of ODS steel can be attributed to the enhanced Cr-supplying rate throughout the accelerated grain boundary diffusion. Finely dispersed Y 2 O 3 oxide particles in the ODS steel matrix may also stabilized the adherence between the protective alpha-Cr 2 O 3 layer and the matrix. (author)

"A New Class of Creep Resistant Oxide/Oxide Ceramic Matrix Composites"

Energy Technology Data Exchange (ETDEWEB)

Dr. Mohit Jain, Dr. Ganesh Skandan, Prof. Roger Cannon, Rutgers University

2007-03-30

Despite recent progress in the development of SiC-SiC ceramic matrix composites (CMCs), their application in industrial gas turbines for distributed energy (DE) systems has been limited. The poor oxidation resistance of the non-oxide ceramics warrants the use of envrionmental barrier coatings (EBCs), which in turn lead to issues pertaining to life expectancy of the coatings. On the other hand, oxide/oxide CMCs are potential replacements, but their use has been limited until now due to the poor creep resistance at high temperatures, particularly above 1200 oC: the lack of a creep resistant matrix has been a major limiting factor. Using yttrium aluminum garnet (YAG) as the matrix material system, we have advanced the state-of-the-art in oxide/oxide CMCs by introducing innovations in both the structure and composition of the matrix material, thereby leading to high temperature matrix creep properties not achieved until now. An array of YAG-based powders with a unique set of particle characteristics were produced in-house and sintered to full density and compressive creep data was obtained. Aided in part by the composition and the microstructure, the creep rates were found to be two orders of magnitude smaller than the most creep resistant oxide fiber available commercially. Even after accounting for porosity and a smaller matrix grain size in a practical CMC component, the YAG-based matrix material was found to creep slower than the most creep resistant oxide fiber available commercially.

An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

Science.gov (United States)

Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

2015-09-14

Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts.

Industrial use of SPring-8 in fuel cell development

International Nuclear Information System (INIS)

Sugiura, Masahiro

2007-01-01

The study of fuel cells by using synchrotron radiation from SPring-8 was reviewed for polymer electrolyte fuel cells (PEFCs; also called proton exchange membrane fuel cells), solid oxide fuel cells (SOFCs), and fuel cell-related materials. PEFCs use a solid polymer as an electrolyte and porous carbon electrodes containing a platinum catalyst. Measurements of Pt particles in the cathode catalyst by x-ray absorption near-edge structure (XANES) showed that the decrease of the particle size of Pt particles caused an increased of the number of 5d orbital holes of Pt atoms. Oxidization processes of Pt particles were measured by time-resolved dispersive x-ray absorption fine structure (XAFS). Measurements by time-gating quick scan XAFS together with dispersive XAFS revealed the reduction-oxidation process of Pt nanoparticles under the operation condition of PEFCs. SOFCs use a hard, non-porous ceramic compound as the electrolyte. SOFCs are operated at very high temperatures - around 1,000degC. Oxides having perovskite and fluorite structures are one of the most promising materials for electrolyte of SOFCs operated at reduced temperatures. The local structures of doped ceria and lanthanum gallate compounds were studied by extended XAFS. It was indicated from the measurements of ionic conductivity of these compounds that the local structure seriously affected oxide ionic conduction. Residual thermal stresses in the electrolyte of the anode-supported planar SOFCs were measured by high-energy x-rays. The crystal structure and electron density distribution of hydrogen storage alloys were measured by x-ray diffraction. (Y.K.)

Thermochemical modeling of the plutonium and uranium-plutonium dioxides

International Nuclear Information System (INIS)

Besmann, T.M.; Lindemer, T.B.

1984-01-01

The chemical thermodynamic properties of the actinide oxides have long been of interest for nuclear fuel design and for predicting fuel behavior under accident conditions. The result of such interest has been the publication of many studies over several decades containing thousands of measurements. The calcium fluorite structure and phases have been intensely studied, with in excess of 1000 data points having been determined. The object of the current work is to develop quantitative models of and which accurately describe the oxygen potential-temperature-composition behavior of the phases. The entire available data base of oxygen potential-temperature-composition values were extracted for use in the development of the models for the plutonia and mixed oxide phases. With perhaps the exception of Babelot et al., little effort has been made to utilize the large existing data base in such analyses. These data were instrumental in developing our models for the oxides, indicating the appropriate oxygen potential-composition relationships and providing for the determination of parametric values. The modeling approach used by us is fundamentally simple, utilizing the assumption that the complex oxides can be described as solutions of oxides with invariant stoichiometries. The chemical thermodynamic models for and described here are among the first to make extensive use of the large oxygen potential-temperature-composition data base which exists for these systems. These relatively simple models should be easily applied to the design of fuel compositions the analysis of behavior during burnup, and the development of codes for accident analysis. 5 references

Mineral characterisation of Don Pao rare earth deposit in Vietnam

International Nuclear Information System (INIS)

XuanBen, T.

1998-01-01

Full text: The Don Pao Rare Earth Deposit was discovered in 1959 in Phon Tho district, about 450km North-West of Hanoi capital. Geological work was conducted between 1959-95, resulting in 60 ore bodies of various sizes being identified. The ore bodies are irregularly shaped nests, lenses and veins hosted in the shear zone, at the margin of a Paeleogene aged syenite massif. The mineral composition of Don Pao Deposit is very complex, consisting of more than 50 minerals. Among them, basnaesite, parisite, fluorite and barite are the main constituent minerals of the ore. All the minerals were identified by the modern methods of mineralogical studies. Based on the constituent mineral ratios, four ore types have been distinguished in the deposit: 1. Rare earth ore containing over 5 percent of RE 2 O 3 . 2. Rare Earth-Barite ore containing 0.5 to 30 percent of RE 2 O 3 . 3. Rare Earth-Barite-Fluorite ore containing 1 to 5 percent of RE 2 O 3 . 4. Rare Earth bearing Fluorite ore containing 1 to 5 percent of RE 2 O 3 . According to the benefication test, the ores in Don Pao can be enriched to a concentrate of 60 percent of RE 2 O 3 with a recover of 75 percent

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

OpenAIRE

Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

2014-01-01

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

Oxidation of zirconium alloys in steam: influence of tetragonal zirconia on oxide growth mechanism

International Nuclear Information System (INIS)

Godlewski, J.

1990-07-01

The oxidation of zirconium alloys in presence of steam, presents after a 'parabolic' growth law, an acceleration of the oxidation velocity. This phenomenon limits the use of zirconium alloys as nuclear fuel cladding element. In order to determine the physico-chemical process leading to this kinetic transition, two approaches have been carried out: the first one has consisted to determine the composition of the oxide layer and its evolution with the oxidation time; and the second one to determine the oxygen diffusion coefficients in the oxide layers of pre- and post-transition as well as their evolution with the oxidation time. The composition of the oxide layers has been determined by two analyses techniques: the X-ray diffraction and the laser Raman spectroscopy. This last method has allowed to confirm the presence of tetragonal zirconium oxide in the oxide layers. Analyses carried out by laser Raman spectroscopy on oxides oblique cuttings have revealed that the tetragonal zirconium oxide is transformed in monoclinic phase during the kinetic transition. A quantitative approach has allowed to corroborate the results obtained by these two techniques. In order to determine the oxygen diffusion coefficients in the oxides layers, two diffusion treatments have been carried out: 1)under low pressure with D 2 18 O 2 ) under high pressure in an autoclave with H 2 18 O. The oxygen 18 concentration profiles have been obtained by two analyses techniques: the nuclear microprobe and the secondary ions emission spectroscopy. The obtained profiles show that the mass transport is made by the volume and particularly by the grain boundaries. The corresponding diffusion coefficients have been calculated with the WHIPPLE and LE CLAIRE solution. The presence of tetragonal zirconium oxide, its relation with the kinetic transition, and the evolution of the diffusion coefficients with the oxidation time, are discussed in terms of internal stresses in the oxide layer and of the oxide layer

Sputtered indium oxide films

International Nuclear Information System (INIS)

Gillery, F.H.

1986-01-01

A method is described for depositing on a substrate multiple layer films comprising at least one primary layer of a metal oxide and at least one primary layer of a metal other than the metal of the oxide layer. The improvement described here comprises improving the adhesion between the metal oxide and metal layers by depositing between the layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers. An article of manufacture is described comprising a nonmetallic substrate, and deposited thereon in any order: a. at least one coating layer of metal; b. at least one coating layer of an oxide of a metal other than the metal of the metal layer; and c. deposited between the metal and metal oxide layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers

Studies on O/M ratio determination in uranium oxide, plutonium oxide and uranium-plutonium mixed oxide

International Nuclear Information System (INIS)

Sampath, S.; Chawla, K.L.

1975-01-01

Thermogravimetric studies were carried out in unsintered and sintered samples of uranium oxide, plutonium oxide and uranium-plutonium mixed oxide under different atmospheric conditions (air, argon and moist argon/hydrogen). Moisture loss was found to occur below 200 0 C for uranium dioxide samples, upto 700 0 C for sintered plutonium dioxide and negligible for sintered samples. The O/M ratios for non-stoichiometric uranium dioxide (sintered and unsintered), plutonium dioxide and mixed uranium and plutonium oxides (sintered) could be obtained with a precision of +- 0.002. Two reference states UOsub(2.000) and UOsub(2.656) were obtained for uranium dioxide and the reference state MOsub(2.000) was used for other cases. For unsintered plutonium dioxide samples, accurate O/M ratios could not be obtained of overlap of moisture loss with oxygen loss/gain. (author)

Actinide oxide photodiode and nuclear battery

Energy Technology Data Exchange (ETDEWEB)

Sykora, Milan; Usov, Igor

2017-12-05

Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxides are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.

Porous ceramics out of oxides

International Nuclear Information System (INIS)

Bakunov, V.S.; Balkevich, V.L.; Vlasov, A.S.; Guzman, I.Ya.; Lukin, E.S.; Poluboyarinov, D.N.; Poliskij, R.Ya.

1977-01-01

A review is made of manufacturing procedures and properties of oxide ceramics intended for high-temperature thermal insulation and thermal protection applications. Presented are structural characteristics of porous oxide refractories and their properties. Strength and thermal conductivity was shown to depend upon porosity. Described is a procedure for manufacturing porous ceramic materials from aluminium oxide, zirconium dioxide, magnesium oxide, beryllium oxide. The thermal resistance of porous ceramics from BeO is considerably greater than that of other high-refractoriness oxides. Listed are areas of application for porous materials based on oxides

Thermal oxidation of silicon with two oxidizing species

International Nuclear Information System (INIS)

Vild-Maior, A.A.; Filimon, S.

1979-01-01

A theoretical model for the thermal oxidation of silicon in wet oxygen is presented. It is shown that the presence of oxygen in the oxidation furnace has an important effect when the water temperature is not too high (less than about 65 deg C). The model is in good agreement with the experimental data. (author)

Staphylococcal response to oxidative stress

Directory of Open Access Journals (Sweden)

Rosmarie eGaupp

2012-03-01

Full Text Available Staphylococci are a versatile genus of bacteria that are capable of causing acute and chronic infections in diverse host species. The success of staphylococci as pathogens is due in part to their ability to mitigate endogenous and exogenous oxidative and nitrosative stress. Endogenous oxidative stress is a consequence of life in an aerobic environment; whereas, exogenous oxidative and nitrosative stress are often due to the bacteria’s interaction with host immune systems. To overcome the deleterious effects of oxidative and nitrosative stress, staphylococci have evolved protection, detoxification, and repair mechanisms that are controlled by a network of regulators. In this review, we summarize the cellular targets of oxidative stress, the mechanisms by which staphylococci sense oxidative stress and damage, oxidative stress protection and repair mechanisms, and regulation of the oxidative stress response. When possible, special attention is given to how the oxidative stress defense mechanisms help staphylococci control oxidative stress in the host.

SPH based modelling of oxide and oxide film formation in gravity die castings

International Nuclear Information System (INIS)

Ellingsen, K; M'Hamdi, M; Coudert, T

2015-01-01

Gravity die casting is an important casting process which has the capability of making complicated, high-integrity components for e.g. the automotive industry. Oxides and oxide films formed during filling affect the cast product quality. The Smoothed particle hydrodynamics (SPH) method is particularly suited to follow complex flows. The SPH method has been used to study filling of a gravity die including the formation and transport of oxides and oxide films for two different filling velocities. A low inlet velocity leads to a higher amount of oxides and oxide films in the casting. The study demonstrates the usefulness of the SPH method for an increased understanding of the effect of different filling procedures on the cast quality. (paper)

Review Of Plutonium Oxidation Literature

International Nuclear Information System (INIS)

Korinko, P.

2009-01-01

A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles ( 250 (micro)m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

Synthesis of Graphene Oxide by Oxidation of Graphite with Ferrate(VI) Compounds: Myth or Reality?

Science.gov (United States)

Sofer, Zdeněk; Luxa, Jan; Jankovský, Ondřej; Sedmidubský, David; Bystroň, Tomáš; Pumera, Martin

2016-09-19

It is well established that graphene oxide can be prepared by the oxidation of graphite using permanganate or chlorate in an acidic environment. Recently, however, the synthesis of graphene oxide using potassium ferrate(VI) ions has been reported. Herein, we critically replicate and evaluate this new ferrate(VI) oxidation method. In addition, we test the use of potassium ferrate(VI) for the synthesis of graphene oxide under various experimental routes. The synthesized materials are analyzed by a number of analytical methods in order to confirm or disprove the possibility of synthesizing graphene oxide by the ferrate(VI) oxidation route. Our results confirm the unsuitability of using ferrate(VI) for the oxidation of graphite on graphene oxide because of its high instability in an acidic environment and low oxidation power in neutral and alkaline environments. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation of Ethylene Carbonate on Li Metal Oxide Surfaces

DEFF Research Database (Denmark)

Østergaard, Thomas M.; Giordano, Livia; Castelli, Ivano Eligio

2018-01-01

Understanding the reactivity of the cathode surface is of key importance to the development of batteries. Here, density functional theory is applied to investigate the oxidative decomposition of the electrolyte component, ethylene carbonate (EC), on layered LixMO(2) oxide surfaces. We compare...

Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

Science.gov (United States)

Renaud, Gilles

Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having

Oxidation of zirconium-aluminum alloys

International Nuclear Information System (INIS)

Cox, B.

1967-10-01

Examination of the processes occurring during the oxidation of Zr-1% A1, Zr-3% A1, and Zr-1.5% A1-0.5% Mo alloys has shown that in steam rapid oxidation occurs predominantly around the Zr 3 A1 particles, which at low temperatures appear to be relatively unattacked. The unoxidised particles become incorporated in the oxide, and become fully oxidised as the film thickens. This rapid localised oxidation is preceded by a short period of uniform film growth, during which the oxide film thickness does not exceed ∼200A-o. Thus the high oxidation rates can probably be ascribed to aluminum in solution in the zirconium matrix, although its precise mode of operation has not been determined. Once the solubility limit of aluminum is exceeded, the size, distribution and number of intermetallic particles affects the oxidation rate merely by altering the distribution of regions of metal giving high oxidation rates. The controlling process during the early stages of oxidation is electron transport and not ionic transport. Thus, the aluminum in the oxide film is presumably increasing the ionic conductivity more than the electronic. The oxidation rates in atmospheric pressure steam are very high and their irregular temperature dependence suggests that the oxidation rate will be pressure dependent. This was confirmed, in part, by a comparison with oxidation in moist air. It was found that the rate of development of white oxide around intermetallic particles was considerably reduced by the decrease in the partial pressure of H 2 O; the incubation period was not much different, however. (author)

Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

Science.gov (United States)

Tojo, Tomohiro; Shinohara, Masaki; Fujisawa, Kazunori; Muramatsu, Hiroyuki; Hayashi, Takuya; Ahm Kim, Yoong; Endo, Morinobu

2012-10-01

Through coating with graphene oxides, we have developed a chemical route to the bulk production of long, thin manganese oxide (MnO2) nanowires that have high electrical conductivity. The average diameter of these hybrid nanowires is about 25 nm, and their average length is about 800 nm. The high electrical conductivity of these nanowires (ca. 189.51+/-4.51 µS) is ascribed to the homogeneous coating with conductive graphene oxides as well as the presence of non-bonding manganese atoms. The growth mechanism of the nanowires is theoretically supported by the initiation of morphological conversion from graphene oxide to wrapped structures through the formation of covalent bonds between manganese and oxygen atoms at the graphene oxide edge.

Oxidative stress

Directory of Open Access Journals (Sweden)

Osredkar Joško

2012-05-01

Full Text Available The human organism is exposed to the influence of various forms of stress, either physical, psychological or chemical, which all have in common that they may adversely affect our body. A certain amount of stress is always present and somehow directs, promotes or inhibits the functioning of the human body. Unfortunately, we are now too many and too often exposed to excessive stress, which certainly has adverse consequences. This is especially true for a particular type of stress, called oxidative stress. All aerobic organisms are exposed to this type of stress because they produce energy by using oxygen. For this type of stress you could say that it is rather imperceptibly involved in our lives, as it becomes apparent only at the outbreak of certain diseases. Today we are well aware of the adverse impact of radicals, whose surplus is the main cause of oxidative stress. However, the key problem remains the detection of oxidative stress, which would allow us to undertake timely action and prevent outbreak of many diseases of our time. There are many factors that promote oxidative stress, among them are certainly a fast lifestyle and environmental pollution. The increase in oxidative stress can also trigger intense physical activity that is directly associated with an increased oxygen consumption and the resulting formation of free radicals. Considering generally positive attitude to physical activity, this fact may seem at first glance contradictory, but the finding has been confimed by several studies in active athletes. Training of a top athlete daily demands great physical effort, which is also reflected in the oxidative state of the organism. However, it should be noted that the top athletes in comparison with normal individuals have a different defense system, which can counteract the negative effects of oxidative stress. Quite the opposite is true for irregular or excessive physical activity to which the body is not adapted.

Nitric oxide: a physiologic messenger.

Science.gov (United States)

Lowenstein, C J; Dinerman, J L; Snyder, S H

1994-02-01

To review the physiologic role of nitric oxide, an unusual messenger molecule that mediates blood vessel relaxation, neurotransmission, and pathogen suppression. A MEDLINE search of articles published from 1987 to 1993 that addressed nitric oxide and the enzyme that synthesizes it, nitric oxide synthase. Animal and human studies were selected from 3044 articles to analyze the clinical importance of nitric oxide. Descriptions of the structure and function of nitric oxide synthase were selected to show how nitric oxide acts as a biological messenger molecule. Biochemical and physiologic studies were analyzed if the same results were found by three or more independent observers. Two major classes of nitric oxide synthase enzymes produce nitric oxide. The constitutive isoforms found in endothelial cells and neurons release small amounts of nitric oxide for brief periods to signal adjacent cells, whereas the inducible isoform found in macrophages releases large amounts of nitric oxide continuously to eliminate bacteria and parasites. By diffusing into adjacent cells and binding to enzymes that contain iron, nitric oxide plays many important physiologic roles. It regulates blood pressure, transmits signals between neurons, and suppresses pathogens. Excess amounts, however, can damage host cells, causing neurotoxicity during strokes and causing the hypotension associated with sepsis. Nitric oxide is a simple molecule with many physiologic roles in the cardiovascular, neurologic, and immune systems. Although the general principles of nitric oxide synthesis are known, further research is necessary to determine what role it plays in causing disease.

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

International Nuclear Information System (INIS)

Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

2010-01-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

Energy Technology Data Exchange (ETDEWEB)

Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

2010-07-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide.

Science.gov (United States)

Zhong, Rui; Zhang, Zhao; Zhao, Hongguo; He, Xianru; Wang, Xin; Zhang, Rui

2018-05-30

Graphene oxide (GO), modified with anti-aging agent p -phenylenediamine (PPD), was added into nitrile rubber (NBR) in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR), Raman, and X-ray diffraction (XRD). Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA) show an increased storage modulus (G') and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn⁻Wall⁻Ozawa (FWO) equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO⁻PPD. In addition, mechanical properties (tensile strength and elongation at break) of both before and after aged NBR/GO⁻PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

Catalytic Oxidation of Cyanogen Chloride over a Monolithic Oxidation Catalyst

National Research Council Canada - National Science Library

Campbell, Jeffrey

1997-01-01

The catalytic oxidation of cyanogen chloride was evaluated over a monolithic oxidation catalyst at temperatures between 200 and 300 deg C in air employing feed concentrations between 100 and 10,000 ppm...

Reversible solid oxide fuel cells (R-SOFCs) with chemically stable proton-conducting oxides

KAUST Repository

Bi, Lei

2015-07-01

Proton-conducting oxides offer a promising way of lowering the working temperature of solid oxide cells to the intermediate temperate range (500 to 700. °C) due to their better ionic conductivity. In addition, the application of proton-conducting oxides in both solid oxide fuel cells (SOFCs) and sold oxide electrolysis cells (SOECs) provides unique advantages compared with the use of conventional oxygen-ion conducting conductors, including the formation of water at the air electrode site. Since the discovery of proton conduction in some oxides about 30. years ago, the development of proton-conducting oxides in SOFCs and SOECs (the reverse mode of SOFCs) has gained increased attention. This paper briefly summarizes the development in the recent years of R-SOFCs with proton-conducting electrolytes, focusing on discussing the importance of adopting chemically stable materials in both fuel cell and electrolysis modes. The development of electrode materials for proton-conducting R-SOFCs is also discussed. © 2015 Elsevier B.V.

Oxidant/Antioxidant Balance in Animal Nutrition and Health: The Role of Protein Oxidation.

Science.gov (United States)

Celi, Pietro; Gabai, Gianfranco

2015-01-01

This review examines the role that oxidative stress (OS), and protein oxidation in particular, plays in nutrition, metabolism, and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functional modifications. Protein oxidation seems to be involved in pathological conditions, such as respiratory diseases and parasitic infection; however, some studies also suggest that protein oxidation plays a crucial role in the regulation of important physiological functions, such as reproduction, nutrition, metabolism, lactation, gut health, and neonatal physiology. As the characterization of the mechanisms by which OS may influence metabolism and health is attracting considerable scientific interest, the aim of this review is to present veterinary scientists and clinicians with various aspects of oxidative damage to proteins.

Copper-mediated oxidative degradation of catecholamines and oxidative damage of protein

Energy Technology Data Exchange (ETDEWEB)

Goncalves, P.R.; Harria, M.I.N.; Felix, J.M.; Hoffmann, M.E. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Biologia

1997-12-31

Full text. Degradative oxidation of catecholamines has been a matter of large interest in recent years due to the evidences associating their autoxidation with the etiology of neurotoxic and cardiotoxic processes. In this work we present data on the degradative oxidation of catecholamines of physiological importance: isoproterenol (IP), epinephrine (EP), norepinephrine (NEP), deoxyepinephrine (DEP) and dopamine (DA). The degradative oxidation of the catecholamines was followed by measurement of spectral changes and oxygen consumption by neutral aqueous solutions. The data show that Cu{sup 2+} strongly accelerated the rate of catecholamine oxidation, following the decreasing order; EP>DEP>IP>NEP>DA. The production of superoxide anion radical during catecholamine oxidation was very slow, even in the presence of Cu{sup 2+}. The ability of IP to induce damages on bovine serum albumin (BSA) was determined by measuring the formation of carbonyl-groups in the protein, detected by reduction with tritiated Na BH{sub 4}. The incubation of BSA with IP (50-500{mu}M), in the presence of 100{mu}M Cu{sup 2+} leaded to an increased and dose dependent {sup 3} H-incorporation by the oxidized protein. The production of oxidative damage by IP/Cu{sup 2+} was accompanied by marked BSA fragmentation, detected by SDS-polyacrylamide gel dependent (25-400{mu}M IP) des appearance of the original BSA band and appearance of smaller fragments spread in the gel, when incubation has been done in the presence of 100{mu}M Cu{sup 2+}. These results suggest that copper-catalysed oxidative degradation of proteins induced by catecholamines might be critically involved in the toxic action of these molecules

Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

International Nuclear Information System (INIS)

Dzhordano, N.; Bart, D.; Madzhori, R.

1984-01-01

A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

PREFACE: Semiconducting oxides Semiconducting oxides

Science.gov (United States)

Catlow, Richard; Walsh, Aron

2011-08-01

Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

Synthesis and characterization of charge-substituted garnets YCaLnGa5O12 (Ln = Ce,Pr,Tb)

International Nuclear Information System (INIS)

Gramsch, S.A.

1993-01-01

A low temperature method is described for the preparation of the new garnet compounds YCaLnGa 5 O l2 (Ln=Ce, Pr, Th). In this set of compounds (Ca 2+ + Ln 4+ ) replaces 2 Y 3+ in the parent gallium based garnet Y 3 Ga 5 O l2 in order to stabilize as effectively as possible the Ln 4+ species in the eight-coordinate ''A'' site of the garnet structure. Characterization of the oxides by x-ray powder diffraction and thermogravimetric analysis is discussed with regard to the structural relationship of the substituted compound to the parent material. The tetravalent ions Pr 4+ and Tb 4+ exhibit increased thermal stability in reducing conditions as compared to the Ln 4+ states in the fluorite (LnO 2 ) and perovskite (BaLnO 3 ) type structures. This result is discussed with reference to the complex crystal chemistry of these systems

Mechanism and Thermochemistry of Coal Char Oxidation and Desorption of Surface Oxides

DEFF Research Database (Denmark)

Levi, Gianluca; Causà, Mauro; Lacovig, Paolo

2017-01-01

The present study investigates the coal char combustion by a combination of thermochemical and X-ray photoemission spectroscopy (XPS) analyses. Thermoanalytical methods (differential thermogravimetry, differential scanning calorimetry, and temperature-programmed desorption) are used to identify...... the key reactive steps that occur upon oxidation and heating of coal char (chemisorption, structural rearrangement and switchover of surface oxides, and desorption) and their energetics. XPS is used to reveal the chemical nature of the surface oxides that populate the char surface and to monitor...... functionalities prevail. The rearrangement of epoxy during preoxidation goes together with activation of the more stable and less reactive carbon sites. Results are in good agreement with semi-lumped kinetic models of carbon oxidation, which include (1) formation of "metastable" surface oxides, (2) complex...

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

Science.gov (United States)

Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

Rare earth oxide doping in oxide cathodes

International Nuclear Information System (INIS)

Engelsen, Daniel den; Gaertner, Georg

2006-01-01

The effect on life performance and poisoning with O 2 by doping oxide cathodes with rare earth oxides and pseudo rare earth oxides, notably yttria, is qualitatively explained in terms of electrolysis of BaO during emission of electrons. Doped cathodes show less electrolysis and consume therefore less Ba during life: consequently, doped cathodes have a better life performance. However, the lower Ba-production makes doped cathodes more sensitive to oxygen poisoning. The experimentally found relation between conductivity and yttria concentration was the motive to propose a new model for the crystal imperfections in BaO. In this new imperfection model most Y 3+ -ions will combine with barium vacancies, therefore, the increase of the conductivity is modest and also the effect on the position of the Fermi level is modest. By assuming a combination of bulk and surface conductivity, the agreement between experiment and theory can be improved further

Effects of stress on the oxide layer thickness and post-oxidation creep strain of zircaloy-4

International Nuclear Information System (INIS)

Lim, Sang Ho; Yoon, Young Ku

1986-01-01

Effects of compressive stress generated in the oxide layer and its subsequent relief on oxidation rate and post-oxidation creep characteristics of zircaloy-4 were investigated by oxidation studies in steam with and without applied tensile stress and by creep testing at 700 deg C in high purity argon. The thickness of oxide layer increased with the magnitude of tensile stress applied during oxidation at 650 deg C in steam whereas similar phenomenon was not observed during oxidation at 800 deg C. Zircaloy-4 specimens oxidized at 600 deg C in steam without applied stress exhibited higher creep strain than that shown by unoxidized specimens when creep-tested in argon. Zircaloy-4 specimens oxidized at 600 deg C steam under the applied stress of 8.53MPa and oxidized at 800 deg C under the applied stress of 0 and 8.53MPa exhibited lower strain than that shown by unoxidized specimen. The above experimental results were accounted for on the basis of interactions among applied stress during oxidation, compressive stress generated in the oxide layer and elasticity of zircaloy-4 matrix. (Author)

Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

International Nuclear Information System (INIS)

Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

2001-01-01

The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

Characterization and uranium bioleaching performance of mixed iron- and sulfur-oxidizers versus iron-oxidizers

International Nuclear Information System (INIS)

Qian Li; Jing Sun; Dexin Ding; Qingliang Wang; Wenge Shi; Eming Hu; Xiaoyu Jiang; University of South China, Hengyang; Xingxing Wang

2017-01-01

In order to develop and apply mixed iron- and sulfur-oxidizers in uranium bioleaching, the characteristics of a mixed iron- and sulfur-oxidizing consortium (Consortium ISO) were comparatively investigated versus an iron-oxidizing consortium (Consortium IO). The results showed, the Consortium ISO exerted stronger oxidative ability and acid-producing ability than Consortium IO did. The synergy of sulfur-oxidizers and iron-oxidizers could change the structure and properties of the passivation substance, and work positively for eliminating the accumulation of passivation substance. In the bioleaching process, the uranium bioleaching experiments showed the recovery percentage of uranium reached 99.5% with Consortium ISO, 6.3% more than that of Consortium IO. (author)

Thin zirconium oxides

International Nuclear Information System (INIS)

Oviedo, Cristina

2000-01-01

Polycrystalline Zr and two pure Zr single-crystal samples, one oriented with the normal to the surface parallel to the c-axis of the hcp structure (Z1) and the other with the normal perpendicular to c (Z2), were oxidised at 10 -8 , 10 -7 and 10 -6 Torr and room temperature. Oxidation kinetics, composition and thicknesses of the oxide films formed in each case were analyzed using XPS (X-ray Photoelectron Spectroscopy) as the main technique. The oxidation kinetics followed logarithmic laws in all cases. The deconvolution of XPS Zr3d peaks indicated the formation of two Zr-O compounds before the formation of ZrO 2 . Varying the photoelectrons take-off angle, the compound distribution inside the oxide films could be established. Thus, it was confirmed that the most external oxide, in contact with the gas, was ZrO 2 . The thickness of the films grown at the different pressures was determined. In the polycrystalline samples, thicknesses between 15 and 19 ± 2Angstroem were obtained for pressures between 10 -8 and 10 -6 Torr, in close coincidence with the determined ones for Z2. The thicknesses measured in Z1 were smaller, reaching 13 ± 2Angstroem for the oxidations performed at 10 -6 Torr. (author)

Selection of a Commercial Anode Oxide Coating for Electro-oxidation of Cyanide

Directory of Open Access Journals (Sweden)

Lanza Marcos Roberto V.

2002-01-01

Full Text Available This paper presents a study of the performance of two commercial dimensionally stable anode (DSA® oxide coatings in the electrochemical process for cyanide oxidation. The coatings studied were 70TiO2/30RuO2 and 55Ta2O5/45IrO2, on Ti substrate. The efficiency of both materials in the electro-oxidation of free cyanide was compared using linear voltammetry and electrolysis at constant potential. The 70TiO2/30RuO2 electrode shows a better performance in the electro-oxidation of free cyanide.

Staged membrane oxidation reactor system

Science.gov (United States)

Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

2012-09-11

Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

Global DNA methylation and oxidative stress biomarkers in workers exposed to metal oxide nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Liou, Saou-Hsing; Wu, Wei-Te; Liao, Hui-Yi [National Institute of Environmental Health Sciences, National Health Research Institutes, Zhunan, Miaoli County, Taiwan (China); Chen, Chao-Yu; Tsai, Cheng-Yen; Jung, Wei-Ting [Department of Chemistry, Fu Jen Catholic University, New Taipei City, Taiwan (China); Lee, Hui-Ling, E-mail: huilinglee3573@gmail.com [Department of Chemistry, Fu Jen Catholic University, New Taipei City, Taiwan (China)

2017-06-05

Highlights: • Global methylation and oxidative DNA damage levels in nanomaterial handling workers were assessed. • 8-isoprostane in exhaled breath condensate of workers exposed to nanoparticles was higher. • 8-OHdG was negatively correlated with global methylation. • Exposure to metal oxide nanoparticles may lead to global methylation and DNA oxidative damage. - Abstract: This is the first study to assess global methylation, oxidative DNA damage, and lipid peroxidation in workers with occupational exposure to metal oxide nanomaterials (NMs). Urinary and white blood cell (WBC) 8-hydroxydeoxyguanosine (8-OHdG), and exhaled breath condensate (EBC) 8-isoprostane were measured as oxidative stress biomarkers. WBC global methylation was measured as an epigenetic alteration. Exposure to TiO{sub 2}, SiO{sub 2,} and indium tin oxide (ITO) resulted in significantly higher oxidative biomarkers such as urinary 8-OHdG and EBC 8-isoprostane. However, significantly higher WBC 8-OHdG and lower global methylation were only observed in ITO handling workers. Significant positive correlations were noted between WBC and urinary 8-OHdG (Spearman correlation r = 0.256, p = 0.003). Furthermore, a significant negative correlation was found between WBC 8-OHdG and global methylation (r = −0.272, p = 0.002). These results suggest that exposure to metal oxide NMs may lead to global methylation, DNA oxidative damage, and lipid peroxidation.

Oxide ultrathin films science and technology

CERN Document Server

Pacchioni, Gianfranco

2012-01-01

A wealth of information in one accessible book. Written by international experts from multidisciplinary fields, this in-depth exploration of oxide ultrathin films covers all aspects of these systems, starting with preparation and characterization, and going on to geometrical and electronic structure, as well as applications in current and future systems and devices. From the Contents: Synthesis and Preparation of Oxide Ultrathin Films Characterization Tools of Oxide Ultrathin Films Ordered Oxide Nanostructures on Metal Surfaces Unusual Properties of Oxides and Other Insulators in the Ultrathin Limit Silica and High-K Dielectrics Thin Films in Microelectronics Oxide Passive Films and Corrosion Protection Oxide Films as Catalytic Materials and as Models of Real Catalysts Oxide Films in Spintronics Oxide Ultrathin Films in Solid Oxide Fuel Cells Transparent Conducting and Chromogenic Oxide Films as Solar Energy Materials Oxide Ultrathin Films in Sensor Applications Ferroelectricity in Ultrathin Film Capacitors T...

METAL OXIDE NANOPARTICLES

Energy Technology Data Exchange (ETDEWEB)

FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

2007-10-01

This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide

Directory of Open Access Journals (Sweden)

Rui Zhong

2018-05-01

Full Text Available Graphene oxide (GO, modified with anti-aging agent p-phenylenediamine (PPD, was added into nitrile rubber (NBR in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR, Raman, and X-ray diffraction (XRD. Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA show an increased storage modulus (G’ and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG and differential scanning calorimetry (DSC. Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn–Wall–Ozawa (FWO equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO–PPD. In addition, mechanical properties (tensile strength and elongation at break of both before and after aged NBR/GO–PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

On the Design of Oxide Films, Nanomaterials, and Heterostructures for Solar Water Oxidation Photoanodes

Science.gov (United States)

Kronawitter, Coleman Xaver

Photoelectrochemistry and its associated technologies show unique potential to facilitate the large-scale production of solar fuels—those energy-rich chemicals obtained through conversion processes driven by solar energy, mimicking the photosynthetic process of green plants. The critical component of photoelectrochemical devices designed for this purpose is the semiconductor photoelectrode, which must be optically absorptive, chemically stable, and possess the required electronic band alignment with respect to the redox couple of the electrolyte to drive the relevant electrochemical reactions. After many decades of investigation, the primary technological obstacle remains the development of photoelectrode structures capable of efficient and stable conversion of light with visible frequencies, which is abundant in the solar spectrum. Metal oxides represent one of the few material classes that can be made photoactive and remain stable to perform the required functions. The unique range of functional properties of oxides, and especially the oxides of transition metals, relates to their associated diversity of cation oxidation states, cation electronic configurations, and crystal structures. In this dissertation, the use of metal oxide films, nanomaterials, and heterostructures in photoelectrodes enabling the solar-driven oxidation of water and generation of hydrogen fuel is examined. A range of transition- and post-transition-metal oxide material systems and nanoscale architectures is presented. The first chapters present results related to electrodes based on alpha-phase iron(III) oxide, a promising visible-light-active material widely investigated for this application. Studies of porous films fabricated by physical vapor deposition reveal the importance of structural quality, as determined by the deposition substrate temperature, on photoelectrochemical performance. Heterostructures with nanoscale feature dimensionality are explored and reviewed in a later chapter

The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

Science.gov (United States)

Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

2016-05-01

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanisms of electrochemical reduction and oxidation of nitric oxide

NARCIS (Netherlands)

Vooys, de A.C.A.; Beltramo, G.L.; Riet, van B.; Veen, van J.A.R.; Koper, M.T.M.

2004-01-01

A summary is given of recent work on the reactivity of nitric oxide on various metal electrodes. The significant differences between the reactivity of adsorbed NO and NO in solution are pointed out, both for the reduction and the oxidation reaction(s). Whereas adsorbed NO can be reduced only to

Oxidation-resistant cermet

Science.gov (United States)

Phillips, W. M.

1977-01-01

Chromium metal alloys and chromium oxide ceramic are combined to produce cermets with oxidation-resistant properties. Application of cermets includes use in hot corrosive environments requiring strong resistive materials.

Development of hierarchically porous cobalt oxide for enhanced photo-oxidation of indoor pollutants

Energy Technology Data Exchange (ETDEWEB)

Cheng, J. P., E-mail: chengjp@zju.edu.cn [Zhejiang University, State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering (China); Shereef, Anas; Gray, Kimberly A., E-mail: k-gray@northwestern.edu [Northwestern University, Center for Catalysis and Surface Science (United States); Wu, Jinsong [Northwestern University, Department of Materials Science and Engineering (United States)

2015-03-15

Porous cobalt oxide was successfully prepared by precipitation of cobalt hydroxide followed by low temperature thermal decomposition. The morphologies of the resultant oxides remained as the corresponding hydroxides, although the morphology of cobalt hydroxides was greatly influenced by the precursor salts. The cobalt oxides with average crystal size less than 20 nm were characterized by X-ray diffraction, scanning electron microscope, BET surface area, and XPS analysis. The photocatalytic activities of the various cobalt oxides morphologies were investigated by comparing the photo-degradation of acetaldehyde under simulated solar illumination. Relative to their low order structures and reference titania samples, the hierarchical nanostructures of cobalt oxide showed excellent abilities to rapidly degrade acetaldehyde, a model air pollutant. This was attributed to the unique nature of these hierarchical cobalt oxide nanoassemblies, which contained many catalytically active reaction sites and open pores.

Dissolving method for nuclear fuel oxide

International Nuclear Information System (INIS)

Tomiyasu, Hiroshi; Kataoka, Makoto; Asano, Yuichiro; Hasegawa, Shin-ichi; Takashima, Yoichi; Ikeda, Yasuhisa.

1996-01-01

In a method of dissolving oxides of nuclear fuels in an aqueous acid solution, the oxides of the nuclear fuels are dissolved in a state where an oxidizing agent other than the acid is present together in the aqueous acid solution. If chlorate ions (ClO 3 - ) are present together in the aqueous acid solution, the chlorate ions act as a strong oxidizing agent and dissolve nuclear fuels such as UO 2 by oxidation. In addition, a Ce compound which generates Ce(IV) by oxidation is added to the aqueous acid solution, and an ozone (O 3 ) gas is blown thereto to dissolve the oxides of nuclear fuels. Further, the oxides of nuclear fuels are oxidized in a state where ClO 2 is present together in the aqueous acid solution to dissolve the oxides of nuclear fuels. Since oxides of the nuclear fuels are dissolved in a state where the oxidizing agent is present together as described above, the oxides of nuclear fuels can be dissolved even at a room temperature, thereby enabling to use a material such as polytetrafluoroethylene and to dissolve the oxides of nuclear fuels at a reduced cost for dissolution. (T.M.)

Direct oxide reducing method

International Nuclear Information System (INIS)

Tokiwai, Moriyasu.

1995-01-01

Calcium oxides and magnetic oxides as wastes generated upon direct reduction are subjected to molten salt electrolysis, and reduced metallic calcium and magnesium are separated and recovered. Then calcium and magnesium are used recyclically as the reducing agent upon conducting direct oxide reduction. Even calcium oxides and magnesium oxides, which have high melting points and difficult to be melted usually, can be melted in molten salts of mixed fluorides or chlorides by molten-salt electrolysis. Oxides are decomposed by electrolysis, and oxygen is removed in the form of carbon monoxide, while the reduced metallic calcium and magnesium rise above the molten salts on the side of a cathode, and then separated. Since only carbon monoxide is generated as radioactive wastes upon molten salt electrolysis, the amount of radioactive wastes can be greatly reduced, and the amount of the reducing agent used can also be decreased remarkably. (N.H.)

Oxidation of pyrite: Consequences and significance

Directory of Open Access Journals (Sweden)

Dimitrijević Mile D.

2002-01-01

Full Text Available This paper presents the most important studies on the oxidation of pyrite particularly in aqueous solutions. The consequences of pyrite oxidation was examined, as well as its importance, from both the technical-technological and environmental points of view. The oxidation of pyrite was considered in two parts. The spontaneous oxidation of pyrite in nature was described in the first part, with this part comprising pyrite oxidation in deposits depots and mines. It is explained how way natural electrochemical processes lead to the decomposition of pyrite and other minerals associated with pyrite. The oxidation of pyrite occurring during technological processes such as grinding, flotation and leaching, was shown in the second part. Particular emphasis was placed on the oxidation of pyrite during leaching. This part includes the leaching of sulphide and oxide ores, the leaching of pyrite coal and the leaching of refractory gold-bearing ores (pressure oxidation, bacterial oxidation, oxidation by means of strong oxidants and the electrolysis of pyrite suspensions. Various mechanisms of pyrite oxidation and of the galvanic interaction of pyrite with other sulphide minerals are shown.

Oxidant/Antioxidant Balance in Animal Nutrition and Health: The Role of Protein Oxidation

OpenAIRE

Celi, Pietro; Gabai, Gianfranco

2015-01-01

This review examines the role that oxidative stress (OS), and protein oxidation in particular, plays in nutrition, metabolism, and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functi...

Oxidant/antioxidant balance in animal nutrition and health: the role of protein oxidation

OpenAIRE

Pietro eCeli; Pietro eCeli; Gianfranco eGabai

2015-01-01

This review examines the role that oxidative stress, and protein oxidation in particular, plays in nutrition, metabolism and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functional m...

Does oxidative stress shorten telomeres?

NARCIS (Netherlands)

Boonekamp, Jelle J.; Bauch, Christina; Mulder, Ellis; Verhulst, Simon

Oxidative stress shortens telomeres in cell culture, but whether oxidative stress explains variation in telomere shortening in vivo at physiological oxidative stress levels is not well known. We therefore tested for correlations between six oxidative stress markers and telomere attrition in nestling

Wet-cupping removes oxidants and decreases oxidative stress.

Science.gov (United States)

Tagil, Suleyman Murat; Celik, Huseyin Tugrul; Ciftci, Sefa; Kazanci, Fatmanur Hacievliyagil; Arslan, Muzeyyen; Erdamar, Nazan; Kesik, Yunus; Erdamar, Husamettin; Dane, Senol

2014-12-01

Wet-cupping therapy is one of the oldest known medical techniques. Although it is widely used in various conditions such as acute\\chronic inflammation, infectious diseases, and immune system disorders, its mechanism of action is not fully known. In this study, we investigated the oxidative status as the first step to elucidate possible mechanisms of action of wet cupping. Wet cupping therapy is implemented to 31 healthy volunteers. Venous blood samples and Wet cupping blood samples were taken concurrently. Serum nitricoxide, malondialdehyde levels and activity of superoxide dismutase and myeloperoxidase were measured spectrophotometrically. Wet cupping blood had higher activity of myeloperoxidase, lower activity of superoxide dismutase, higher levels of malondialdehyde and nitricoxide compared to the venous blood. Wet cupping removes oxidants and decreases oxidative stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fiber type-specific nitric oxide protects oxidative myofibers against cachectic stimuli.

Directory of Open Access Journals (Sweden)

Zengli Yu

2008-05-01

Full Text Available Oxidative skeletal muscles are more resistant than glycolytic muscles to cachexia caused by chronic heart failure and other chronic diseases. The molecular mechanism for the protection associated with oxidative phenotype remains elusive. We hypothesized that differences in reactive oxygen species (ROS and nitric oxide (NO determine the fiber type susceptibility. Here, we show that intraperitoneal injection of endotoxin (lipopolysaccharide, LPS in mice resulted in higher level of ROS and greater expression of muscle-specific E3 ubiqitin ligases, muscle atrophy F-box (MAFbx/atrogin-1 and muscle RING finger-1 (MuRF1, in glycolytic white vastus lateralis muscle than in oxidative soleus muscle. By contrast, NO production, inducible NO synthase (iNos and antioxidant gene expression were greatly enhanced in oxidative, but not in glycolytic muscles, suggesting that NO mediates protection against muscle wasting. NO donors enhanced iNos and antioxidant gene expression and blocked cytokine/endotoxin-induced MAFbx/atrogin-1 expression in cultured myoblasts and in skeletal muscle in vivo. Our studies reveal a novel protective mechanism in oxidative myofibers mediated by enhanced iNos and antioxidant gene expression and suggest a significant value of enhanced NO signaling as a new therapeutic strategy for cachexia.

Trends for Methane Oxidation at Solid Oxide Fuel Cell Conditions

DEFF Research Database (Denmark)

Kleis, Jesper; Jones, Glenn; Abild-Pedersen, Frank

2009-01-01

First-principles calculations are used to predict a plausible reaction pathway for the methane oxidation reaction. In turn, this pathway is used to obtain trends in methane oxidation activity at solid oxide fuel cell (SOFC) anode materials. Reaction energetics and barriers for the elementary...... the Ni surfaces to other metals of interest. This allows the reactivity over the different metals to be understood in terms of two reactivity descriptors, namely, the carbon and oxygen adsorption energies. By combining a simple free-energy analysis with microkinetic modeling, activity landscapes of anode...

Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

KAUST Repository

Wang, Zhenwei

2015-04-20

In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

Insulating gallium oxide layer produced by thermal oxidation of gallium-polar GaN: Insulating gallium oxide layer produced by thermal oxidation of gallium-polar GaN

Energy Technology Data Exchange (ETDEWEB)

Hossain, T. [Kansas State Univ., Manhattan, KS (United States); Wei, D. [Kansas State Univ., Manhattan, KS (United States); Nepal, N. [Naval Research Lab. (NRL), Washington, DC (United States); Garces, N. Y. [Naval Research Lab. (NRL), Washington, DC (United States); Hite, J. K. [Naval Research Lab. (NRL), Washington, DC (United States); Meyer, H. M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Eddy, C. R. [Naval Research Lab. (NRL), Washington, DC (United States); Baker, Troy [Nitride Solutions, Wichita, KS (United States); Mayo, Ashley [Nitride Solutions, Wichita, KS (United States); Schmitt, Jason [Nitride Solutions, Wichita, KS (United States); Edgar, J. H. [Kansas State Univ., Manhattan, KS (United States)

2014-02-24

We report the benefits of dry oxidation of n -GaN for the fabrication of metal-oxide-semiconductor structures. GaN thin films grown on sapphire by MOCVD were thermally oxidized for 30, 45 and 60 minutes in a pure oxygen atmosphere at 850 °C to produce thin, smooth GaO_x layers. Moreover, the GaN sample oxidized for 30 minutes had the best properties. Its surface roughness (0.595 nm) as measured by atomic force microscopy (AFM) was the lowest. Capacitance-voltage measurements showed it had the best saturation in accumulation region and the sharpest transition from accumulation to depletion regions. Under gate voltage sweep, capacitance-voltage hysteresis was completely absent. The interface trap density was minimum (D_it = 2.75×10¹⁰ cm^–2eV^–1) for sample oxidized for 30 mins. These results demonstrate a high quality GaO_x layer is beneficial for GaN MOSFETs.

Selective oxidation

International Nuclear Information System (INIS)

Cortes Henao, Luis F.; Castro F, Carlos A.

2000-01-01

It is presented a revision and discussion about the characteristics and factors that relate activity and selectivity in the catalytic and not catalytic partial oxidation of methane and the effect of variables as the temperature, pressure and others in the methane conversion to methanol. It thinks about the zeolites use modified for the catalytic oxidation of natural gas

Inhibiting mitochondrial β-oxidation selectively reduces levels of nonenzymatic oxidative polyunsaturated fatty acid metabolites in the brain.

Science.gov (United States)

Chen, Chuck T; Trépanier, Marc-Olivier; Hopperton, Kathryn E; Domenichiello, Anthony F; Masoodi, Mojgan; Bazinet, Richard P

2014-03-01

Schönfeld and Reiser recently hypothesized that fatty acid β-oxidation is a source of oxidative stress in the brain. To test this hypothesis, we inhibited brain mitochondrial β-oxidation with methyl palmoxirate (MEP) and measured oxidative polyunsaturated fatty acid (PUFA) metabolites in the rat brain. Upon MEP treatment, levels of several nonenzymatic auto-oxidative PUFA metabolites were reduced with few effects on enzymatically derived metabolites. Our finding confirms the hypothesis that reduced fatty acid β-oxidation decreases oxidative stress in the brain and β-oxidation inhibitors may be a novel therapeutic approach for brain disorders associated with oxidative stress.

A salt diapir-related Mississippi Valley-type deposit: the Bou Jaber Pb-Zn-Ba-F deposit, Tunisia: fluid inclusion and isotope study

Science.gov (United States)

Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.

2016-08-01

The Bou Jaber Ba-F-Pb-Zn deposit is located at the edge of the Bou Jaber Triassic salt diapir in the Tunisia Salt Diapir Province. The ores are unconformity and fault-controlled and occur as subvertical column-shaped bodies developed in dissolution-collapse breccias and in cavities within the Late Aptian platform carbonate rocks, which are covered unconformably by impermeable shales and marls of the Fahdene Formation (Late Albian-Cenomanian age). The host rock is hydrothermally altered to ankerite proximal to and within the ore bodies. Quartz, as fine-grained bipyramidal crystals, formed during hydrothermal alteration of the host rocks. The ore mineral assemblage is composed of barite, fluorite, sphalerite, and galena in decreasing abundance. The ore zones outline distinct depositional events: sphalerite-galena, barite-ankerite, and fluorite. Fluid inclusions, commonly oil-rich, have distinct fluid salinities and homogenization temperatures for each of these events: sphalerite-galena (17 to 24 wt% NaCl eq., and Th from 112 to 136 °C); ankerite-barite (11 to 17 wt% NaCl eq., and Th from 100 to 130 °C); fluorite (19 to 21 wt% NaCl eq., Th from 140 to 165 °C). The mean temperature of the ore fluids decreased from sphalerite (125 °C) to barite (115 °C) and increased during fluorite deposition (152 °C); then decreased to ˜110 °C during late calcite precipitation. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of fluid inclusions in fluorite are metal rich (hundreds to thousands ppm Pb, Zn, Cu, Fe) but the inclusions in barite are deficient in Pb, Zn, Cu, Fe. Inclusions in fluorite have Cl/Br and Na/Br ratios of several thousand, consistent with dissolution of halite while the inclusions analysed in barite have values lower than seawater which are indicative of a Br-enriched brine derived from evaporation plus a component of halite dissolution. The salinity of the barite-hosted fluid inclusions is less than obtained simply by the

Oxidation effect on templating of metal oxide nanoparticles within block copolymers

International Nuclear Information System (INIS)

Akcora, Pinar; Briber, Robert M.; Kofinas, Peter

2009-01-01

Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.

The oxidation of acid azo dye AY 36 by a manganese oxide containing mine waste

International Nuclear Information System (INIS)

Clarke, Catherine E.; Kielar, Filip; Johnson, Karen L.

2013-01-01

Highlights: ► This study looks at the oxidative breakdown of the amine containing dye acid yellow 36 by a Mn oxide containing mine waste. ► The oxidation proceeds by successive one electron transfers between the dye molecule and the Mn oxide minerals. ► The initial decolorization of the dye is rapid, but does not involve the cleavage of the azo bond. -- Abstract: The oxidative breakdown of acid azo dye acid yellow 36 (AY 36) by a Mn oxide containing mine tailings is demonstrated. The oxidation reaction is pH dependent with the rate of decolorization increasing with decreasing pH. The oxidation reaction mechanism is initiated at the amino moiety and proceeds via successive, one electron transfers from the dye to the Mn oxide minerals. The reaction pathway involves the formation of a number of colorless intermediate products, some of which hydrolyze in a Mn oxide-independent step. Decolorization of the dye is rapid and is observed before the cleavage of the azo-bond, which is a slower process. The terminal oxidation products were observed to be p-benzoquinone and 3-hydroxybenzenesulfonate. The reaction order of the initial decolorization was determined to be pseudo fractional order with respect to pH and pseudo first order with respect to dye concentration and Mn tailings’ surface area

Oxidation of tritium by hopcalite bed

Energy Technology Data Exchange (ETDEWEB)

Nishikawa, Masabumi; Shinnai, Kohsuke; Matsunaga, Sohichi; Kinoshita, Yoshihiko

1984-08-01

Oxidation by the catalyst bed with a metal oxide and subsequent adsorption to the porous dehydrative reagents is supposed to be effective process for scavenging tritium from an inert atmosphere. Use of spongy copper oxide or wires of copper oxide is not recommended to use as the metal oxide catalyst from the view point of mass transfer because of sintering and of limited effective surface area. Use of hopcalites and copper oxide-kieselguhr are examined in this study and it is concluded that hopcalites are more suitable as the metal oxide catalyst because they not only remain the oxidation power on hydrogen isotopes even at an ambient temperature, but also show a negligible drop in oxidation performances with repeated regeneration. The effective temperature is about 400/sup 0/C for hopcalites and 300-600/sup 0/C for copper oxide-kieselguhr to use as the oxidation bed of tritium.

Oxidation of tritium by hopcalite bed

International Nuclear Information System (INIS)

Nishikawa, Masabumi; Shinnai, Kohsuke; Matsunaga, Sohichi; Kinoshita, Yoshihiko

1984-01-01

Oxidation by the catalyst bed with a metal oxide and subsequent adsorption to the porous dehydrative reagents is supposed to be effective process for scavenging tritium from an inert atmosphere. Use of spongy copper oxide or wires of copper oxide is not recommended to use as the metal oxide catalyst from the view point of mass transfer because of sintering and of limited effective surface area. Use of hopcalites and copper oxide-kieselguhr are examined in this study and it is concluded that hopcalites are more suitable as the metal oxide catalyst because they not only remain the oxidation power on hydrogen isotopes even at an ambient temperature, but also show a negligible drop in oxidation performances with repeated regeneration. The effective temperature is about 400 0 C for hopcalites and 300--600 0 C for copper oxide-kieselguhr to use as the oxidation bed of tritium. (author)

Method of producing homogeneous mixed metal oxides and metal--metal oxide mixtures

International Nuclear Information System (INIS)

Quinby, T.C.

1978-01-01

Metal powders, metal oxide powders, and mixtures thereof of controlled particle size are provided by reacting an aqueous solution containing dissolved metal values with excess urea. Upon heating, urea reacts with water from the solution to leave a molten urea solution containing the metal values. The molten urea solution is heated to above about 180 0 C, whereupon metal values precipitate homogeneously as a powder. The powder is reduced to metal or calcined to form oxide particles. One or more metal oxides in a mixture can be selectively reduced to produce metal particles or a mixture of metal and metal oxide particles

Electro-catalytic oxidation of reactive Orange 107 using cerium doped oxides of Nd3+ nanoparticle

International Nuclear Information System (INIS)

Rajkumar, K.; Muthukumar, M.; Mangalaraja, R.V.

2011-01-01

A new rare earth doped cerium oxide powder was used as a catalyst to investigate the removal of colour and TOC from simulated wastewater of Reactive Orange 107. The electro oxidation process was carried out in the reactor in presence of an electrolyte NaCl. Graphite electrode was used as anode and cathode and electrolysis were carried out at a current density of 34.96 mAcm -2 with a catalyst concentration of 0.05g L -1 . In order to find the efficiency of nanocatalyst, experiments were also conducted without catalyst. From the experiment, it was found that complete colour removal was achieved on electrocatalytic oxidation as well as electro oxidation. When comparing the above processes, catalytic oxidation shows more efficient than electro oxidation. With respect to the degradation of the dye, catalytic oxidation shows more TOC removal than the oxidation taken place without catalyst. It infers that even though the electro-catalytic oxidation process achieves complete decolouration but it does not achieve complete mineralisation. The FTIR and GCMS studies confirmed the formation of by-products. (author)

Method of producing homogeneous mixed metal oxides and metal-metal oxide mixtures

International Nuclear Information System (INIS)

Quinby, T.C.

1980-01-01

A method for preparing particulate metal or metal oxide of controlled partile size comprises contacting an an aqueous solution containing dissolved metal values with excess urea at a temperature sufficient to cause urea to react with water to provide a molten urea solution containing the metal values; heating the molten urea solution to cause the metal values to precipitate, forming a mixture containing precipitated metal values; heating the mixture containing precipitated metal values to evaporate volatile material leaving a dry powder containing said metal values. The dry powder can be calcined to provide particulate metal oxide or reduced to provide particulate metal. Oxide mixtures are provided when the aqueous solution contains values of more than one metal. Homogeneousmetal-metal oxide mistures for preparing cermets can be prepared by selectively reducing at least one of the metal oxides. (auth)

Supported versus colloidal zinc oxide for advanced oxidation processes

Science.gov (United States)

Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

2017-07-01

Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

Chemistry of reference waters of the crystalline basement of Northern Switzerland for safety assessment studies

International Nuclear Information System (INIS)

Pearson, F.J. Jr.; Scholtis, A.

1993-08-01

The chemistry of groundwater in formations being considered as host rocks for nuclear waste repositories must be known to assess the performance of those repositories, and as media for laboratory experiments. Two potential repository siting areas in the crystalline basement of northern Switzerland are being assessed. This report gives the chemistry of water in both areas for reference use in this assessment. The western area is in the region defined by the Kaisten, Leuggern, Boettstein, and Zurzach boreholes. The western reference water is based on samples from the Leuggern, Boettstein, and Zurzach boreholes. Kaisten water is of higher salinity (1.3 g/l). The concentration ranges of the reference water include Kaisten values, however. High quality samples and analyses, particularly from long term sampling at Zurzach and Leuggern, define the concentration ranges of many trace elements. The definition of this water assumes saturation with respect to calcite, baryte, fluorites, chalcedony, and kaolinite. The reference pe is based on the assumption that dissolved iron concentrations are controlled by the solubility of the mineral goethite, and is consistent with other redox indicators such as the measured Pt-electrode potential and the ratio of dissolved As(V) to As(III). The eastern area is characterized by the Siblingen boreholes. The eastern reference water is a Na-HCO 3 -SO 4 -(Cl) type with a total dissolved solids content of about 0.5 g/l. Only three samples taken during borehole drilling are available to define this water, so it can be specified in less detail and with less precision than the western water. Its definition assumes saturation with respect to calcite, baryte, and fluorites. The samples permit only a broad definition of its oxidation potential and content of redox-sensitive metals such as Fe, As, Mn, and U. Trace element data for the most part are lacking. (author) figs., tabs., 28 refs

Precursors for use in vapour and solution phase thermolysis routes to II-VI thin films and nanodispersed oxide materials

International Nuclear Information System (INIS)

Chunggaze, M.

1999-12-01

-7 are formed in the vapour phase from (3) and (4). Compounds (3), (4) and (7) also form significant quantities of diethyl diselenide (EtSe 2 Et), as detected by GC-MS; whereas (5) and (6) do not. A series of precursors with pendant amine functions have also been synthesised in an effort to reduce the degree of association seen in the simple parent diethyl-dithiocarbamates. The preparation of nanocrystalline titanium dioxide and cerium oxide powders, which are used in dye-sensitised photovoltaic cells (Graetzel cells) and as catalysts respectively were prepared by the thermolysis of a series of suitable single source precursor in a thermolysing/passivating solvent such as tri-octyl-phosphine oxide (TOPO). The nano-particulate oxides formed have the unique property of being coated with TOPO and hence are stable in the solid form without leading to aggregation and are re-dispersible in organic solvents. The oxides formed were generally amorphous in nature and required further annealing to induce crystallinity. Other routes to preparing nano-porous titanium dioxide such as aerosol assisted CVD were also used in an attempt to deposit nano-porous films of titanium dioxide. Cerium oxide particles were synthesised at relatively low thermolysis temperatures (200-300 deg C) and were characterised to exist in the fluorite phase (CeO 2 ). The interaction of TOPO with the precursor was found to aid in lowering the thermolysing temperatures as well as favour the growth of the CeO 2 particles. Lowering the thermolysis temperature to 100 deg C allowed for the preparation of the pyramidal Ce 2 O 3 particles. (author)

Poly(ethylene oxide)–Poly(propylene oxide)-Based Copolymers for ...

African Journals Online (AJOL)

Amphiphilic poly(ethylene oxide)–poly(propylene oxide) (PEO–PPO)-based copolymers are thermoresponsive materials having aggregation properties in aqueous medium. As hydrosolubilizers of poorly water-soluble drugs and improved stability of sensitive agents, these materials have been investigated for improvement ...

Effect of yttrium on the oxide scale adherence of pre-oxidized silicon-containing heat-resistant alloy

International Nuclear Information System (INIS)

Yan Jingbo; Gao Yimin; Shen Yudi; Yang Fang; Yi Dawei; Ye Zhaozhong; Liang Long; Du Yingqian

2011-01-01

Highlights: → AE experiment shows yttrium has a beneficial effect on the pre-oxidized HP40 alloy. → Yttrium facilitates the formation of internal oxide after 10 h of oxidation. → Internal oxide changes the rupture behaviour of the oxide scale. → Twins form in the internal oxide and improve the binding strength of the scale. - Abstract: This paper investigates the effect of the rare earth element yttrium on the rupture behaviour of the oxide scale on the silicon-containing heat-resistant alloy during cooling. After 10 h of oxidation, yttrium is found to facilitate the formation of internal oxides (silica) at the scale-matrix interface. Due to the twinning observed by scanning transmission electron microscopy (STEM) in silica, the critical strain value for the scale failure can be dramatically improved, and the formation of cracks at the scale-matrix interface is inhibited.

Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

Science.gov (United States)

Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2015-12-01

The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our results provide new empirical data that should allow for more precise quantitative constraints on atmospheric pO2 based on the sedimentary rock record. 1Anbar, A.D. et al., 2007. Science, 317, i. 5846: 1903-1906. 2Williamson & Rimstidt, 1994. Geochim. et Cosmochim

Molecular theory of graphene oxide.

Science.gov (United States)

Sheka, Elena F; Popova, Nadezhda A

2013-08-28

Applied to graphene oxide, the molecular theory of graphene considers its oxide as a final product in the succession of polyderivatives related to a series of oxidation reactions involving different oxidants. The graphene oxide structure is created in the course of a stepwise computational synthesis of polyoxides of the (5,5) nanographene molecule governed by an algorithm that takes into account the molecule's natural radicalization due to the correlation of its odd electrons, the extremely strong influence of the structure on properties, and a sharp response of the molecule behavior on small actions of external factors. Taking these together, the theory has allowed for a clear, transparent and understandable explanation of the hot points of graphene oxide chemistry and suggesting reliable models of both chemically produced and chemically reduced graphene oxides.

Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

Energy Technology Data Exchange (ETDEWEB)

Swaminathan, Srinivasan, E-mail: swaminathan@kist.re.kr [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul 136 791 (Korea, Republic of); Krishna, Nanda Gopala [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Kim, Dong-Ik, E-mail: dongikkim@kist.re.kr [High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul 136 791 (Korea, Republic of)

2015-10-30

Highlights: • Initial oxidation characteristics of Cu-bearing austenitic stainless steel at 650 °C were studied. • Strong segregation and oxidation of Mn and Nb were found in the entire oxide scale. • Surface coverage by metallic Cu-rich precipitates increases with exposure time. • Chemical heterogeneity of oxide scale revealed initial oxidation to be non-selective. • Fe-Cr and Mn-Cr mixed oxides were realized along with binary oxides of Fe, Cr and Mn. - Abstract: Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr{sub 2}O{sub 4} and MnCr{sub 2}O{sub 4} along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

A novel hydrogen oxidizer amidst the sulfur-oxidizing Thiomicrospira lineage

Science.gov (United States)

Hansen, Moritz; Perner, Mirjam

2015-01-01

Thiomicrospira species are ubiquitously found in various marine environments and appear particularly common in hydrothermal vent systems. Members of this lineage are commonly classified as sulfur-oxidizing chemolithoautotrophs. Although sequencing of Thiomicrospira crunogena's genome has revealed genes that encode enzymes for hydrogen uptake activity and for hydrogenase maturation and assembly, hydrogen uptake ability has so far not been reported for any Thiomicrospira species. We isolated a Thiomicrospira species (SP-41) from a deep sea hydrothermal vent and demonstrated that it can oxidize hydrogen. We show in vivo hydrogen consumption, hydrogen uptake activity in partially purified protein extracts and transcript abundance of hydrogenases during different growth stages. The ability of this strain to oxidize hydrogen opens up new perspectives with respect to the physiology of Thiomicrospira species that have been detected in hydrothermal vents and that have so far been exclusively associated with sulfur oxidation. PMID:25226028

Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

Energy Technology Data Exchange (ETDEWEB)

Finkeldei, Sarah Charlotte

2015-07-01

Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO{sub 2} based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO{sub 2} based pyrochlores. ZrO{sub 2} - Nd{sub 2}O{sub 3} pellets

Fatty acid omega-oxidation as a rescue pathway for fatty acid oxidation disorders in humans

NARCIS (Netherlands)

Wanders, Ronald J. A.; Komen, Jasper; Kemp, Stephan

2011-01-01

Fatty acids (FAs) can be degraded via different mechanisms including alpha-, beta- and omega-oxidation. In humans, a range of different genetic diseases has been identified in which either mitochondrial FA beta-oxidation, peroxisomal FA beta-oxidation or FA alpha-oxidation is impaired. Treatment

High Temperature Oxidation Behavior of Zirconium Alloy with Nano structured Oxide Layer in Air Environment

International Nuclear Information System (INIS)

Park, Y. J.; Kim, J. W.; Park, J. W.; Cho, S. O.

2016-01-01

If the temperature of the cladding materials increases above 1000 .deg. C, which can be caused by a loss of coolant accident (LOCA), Zr becomes an auto-oxidation catalyst and hence produces a huge amount of hydrogen gas from water. Therefore, many investigations are being carried out to prevent (or reduce) the hydrogen production from Zr-based cladding materials in the nuclear reactors. Our team has developed an anodization technique by which nanostructured oxide can be formed on various flat metallic elements such as Al, Ti, and Zr-based alloy. Anodization is a simple electrochemical technique and requires only a power supply and an electrolyte. In this study, Zr-based alloys with nanostructured oxide layers were oxidized by using Thermogravimetry analysis (TGA) and compared with the pristine one. It reveals that the nanostructured oxide layer can prevent oxidation of substrate metal in air. Oxidation behavior of the pristine Zr-Nb-Sn alloy and the Zr-Nb-Sn alloy with nanostructured oxide layer evaluated by measuring weight gain (TGA). In comparison with the pristine Zr-Nb-Sn alloy, weight gain of the Zr-Nb-Sn alloy with nanostructured oxide layer is lower than 10% even for 12 hours oxidation in air.

Zinc oxide overdose

Science.gov (United States)

Zinc oxide is an ingredient in many products. Some of these are certain creams and ointments used ... prevent or treat minor skin burns and irritation. Zinc oxide overdose occurs when someone eats one of ...

Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature

OpenAIRE

Lili Zhang; Xinxin Yu; Hongrui Hu; Yang Li; Mingzai Wu; Zhongzhu Wang; Guang Li; Zhaoqi Sun; Changle Chen

2015-01-01

Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4?7H2O. By adjusting reaction temperature, ?-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from ?-Fe2O3 to Fe3O4 via ?-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide ...

Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application

Science.gov (United States)

Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik

2017-09-01

Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.

W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

Science.gov (United States)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Electrochemical Thinning for Anodic Aluminum Oxide and Anodic Titanium Oxide

Energy Technology Data Exchange (ETDEWEB)

Lee, In Hae; Jo, Yun Kyoung; Kim, Yong Tae; Tak, Yong Sug; Choi, Jin Sub [Inha University, Incheon (Korea, Republic of)

2012-05-15

For given electrolytes, different behaviors of anodic aluminum oxide (AAO) and anodic titanium oxide (ATO) during electrochemical thinning are explained by ionic and electronic current modes. Branched structures are unavoidably created in AAO since the switch of ionic to electronic current is slow, whereas the barrier oxide in ATO is thinned without formation of the branched structures. In addition, pore opening can be possible in ATO if chemical etching is performed after the thinning process. The thinning was optimized for complete pore opening in ATO and potential-current behavior is interpreted in terms of ionic current-electronic current switching.

Molecular water oxidation catalysis

CERN Document Server

Llobet, Antoni

2014-01-01

Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most importan

Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

International Nuclear Information System (INIS)

Morss, L.R.

1992-01-01

The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects

DEFF Research Database (Denmark)

Harthøj, Anders; Holt, Tobias; Møller, Per

2015-01-01

This work evaluates the performance of cobalt/cerium oxide (Co/CeO2) composite coatings and pure Co coatings to be used for solid oxide fuel cell (SOFC) interconnects. The coatings are electroplated on the ferritic stainless steels Crofer 22 APU and Crofer 22H. Coated and uncoated samples...

Oxidative phosphorylation revisited

DEFF Research Database (Denmark)

Nath, Sunil; Villadsen, John

2015-01-01

The fundamentals of oxidative phosphorylation and photophosphorylation are revisited. New experimental data on the involvement of succinate and malate anions respectively in oxidative phosphorylation and photophosphorylation are presented. These new data offer a novel molecular mechanistic...

Oxidative Ce"3"+ sequestration by fungal manganese oxides with an associated Mn(II) oxidase activity

International Nuclear Information System (INIS)

Zheng, Haisu; Tani, Yukinori; Naitou, Hirotaka; Miyata, Naoyuki; Tojo, Fuyumi

2016-01-01

Sequestration of Ce"3"+ by biogenic manganese oxides (BMOs) formed by a Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2, was examined at pH 6.0. In anaerobic Ce"3"+ solution, newly formed BMOs exhibited stoichiometric Ce"3"+ oxidation, where the molar ratio of Ce"3"+ sequestered (Ce_s_e_q) relative to Mn"2"+ released (Mn_r_e_l) was maintained at approximately two throughout the reaction. A similar Ce"3"+ sequestration trend was observed in anaerobic treatment of BMOs in which the associated Mn(II) oxidase was completely inactivated by heating at 85 °C for 1 h or by adding 50 mM NaN_3. Aerobic Ce"3"+ treatment of newly formed BMO (enzymatically active) resulted in excessive Ce"3"+ sequestration over Mn"2"+ release, yielding Ce_s_e_q/Mn_r_e_l > 200, whereas heated or poisoned BMOs released a significant amount of Mn"2"+ with lower Ce"3"+ sequestration efficiency. Consequently, self-regeneration by the Mn(II) oxidase in newly formed BMO effectively suppressed Mn"2"+ release and enhanced oxidative Ce"3"+ sequestration under aerobic conditions. Repeated treatments of heated or poisoned BMOs under aerobic conditions confirmed that oxidative Ce"3"+ sequestration continued even after most Mn oxide was released from the solid phase, indicating auto-catalytic Ce"3"+ oxidation at the solid phase produced through primary Ce"3"+ oxidation by BMO. From X-ray diffraction analysis, the resultant solid phases formed through Ce"3"+ oxidation by BMO under both aerobic and anaerobic conditions consisted of cerianite with crystal sizes of 5.00–7.23 Å. Such nano-sized CeO_2 (CeO_2_,_B_M_O) showed faster auto-catalytic Ce"3"+ oxidation than that on well-crystalized cerianite under aerobic conditions, where the normalized pseudo-first order rate constants for auto-catalytic Ce"3"+ oxidation on CeO_2_,_B_M_O was two orders of magnitude higher. Consequently, we concluded that Ce"3"+ contact with BMOs sequesters Ce"3"+ through two oxidation paths: primary Ce"3

The catalytic activity of several tungsten oxides for the oxidation of propene

International Nuclear Information System (INIS)

De Rossi, S.; Schiavello, M.; Rome Univ.; Iguchi, E.; Tilley, R.J.D.

1976-01-01

A study has been made of the catalytic oxidation of propene over the oxides WO 3 , WOsub(2,95), WOsub(2,90), WOsub(2,72) and Wo 2 , which were selected because they possess specific features of chemical and structural interest rather than for their catalytic ability. It was found that the oxides WOsub(2,95), WOsub(2,90) and WOsub(2,72) all selectively produce acrolein in small amounts. The oxides WO 3 and WO 2 were non-selective and rather inactive. The results are discussed in terms of a mechanism involving both variable valence in the crystal and the specific structural geometry of these compounds. (orig.) [de

Oxidative Stress in BPH

Directory of Open Access Journals (Sweden)

Murat Savas

2009-01-01

The present study has shown that there were not relationship between potency of oxidative stress and BPH. Further well designed studies should be planned to find out whether the oxidative stress-related parameters play role in BPH as an interesting pathology in regard of the etiopathogenesis. Keywords: benign prostatic hyperplasia, oxidative stress, prostate

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

Science.gov (United States)

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Selective propene oxidation on mixed metal oxide catalysts

International Nuclear Information System (INIS)

James, David William

2002-01-01

Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

Uranium Metal to Oxide Conversion by Air Oxidation –Process Development

Energy Technology Data Exchange (ETDEWEB)

Duncan, A

2001-12-31

Published technical information for the process of metal-to-oxide conversion of uranium components has been reviewed and summarized for the purpose of supporting critical decisions for new processes and facilities for the Y-12 National Security Complex. The science of uranium oxidation under low, intermediate, and high temperature conditions is reviewed. A process and system concept is outlined and process parameters identified for uranium oxide production rates. Recommendations for additional investigations to support a conceptual design of a new facility are outlined.

Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst

Energy Technology Data Exchange (ETDEWEB)

Hong, Do Young; Vislovskiy, Vladislav P.; Yoo, Jin S.; Chang, Jong San [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Sang Eon [Inha University, Incheon (Korea, Republic of); Park, Min Seok [Mongolia International University, Ulaanbaatar (Mongolia)

2005-11-15

This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

Plutonium oxides and uranium and plutonium mixed oxides. Carbon determination

International Nuclear Information System (INIS)

Anon.

Determination of carbon in plutonium oxides and uranium plutonium mixed oxides, suitable for a carbon content between 20 to 3000 ppm. The sample is roasted in oxygen at 1200 0 C, the carbon dioxide produced by combustion is neutralized by barium hydroxide generated automatically by coulometry [fr

Electrochemistry of hydrous oxide films

International Nuclear Information System (INIS)

Burke, L.D.; Lyons, M.E.G.

1986-01-01

The formation, acid-base properties, structural aspects, and transport processes of hydrous oxide films are discussed. Classical and nonclassical theoretical models of the oxide-solution interface are compared. Monolayer oxidation, behavior, and crystal growth of oxides on platinum, palladium, gold, iridium, rhodium, ruthenium, and some non-noble metals, including tungsten, are reviewed and compared

Selective oxidation of benzene and cyclohexane using amorphous microporous mixed oxides; Selektive Oxidation von Benzol und Cyclohexan mit amorphen mikroporoesen Mischoxiden

Energy Technology Data Exchange (ETDEWEB)

Stoeckmann, M.

2000-07-01

Phenol was to be produced by direct oxidation of benzene with environment-friendly oxidants like hydrogen peroxide, oxygen, or ozone. Catalysts were amorphous microporous mixed oxides whose properties can be selected directly in the sol-gel synthesis process. Apart from benzene, also cyclohexane was oxidized with ozone using AMM catalysts in order to get more information on the potential of ozone as oxidant in heterogeneously catalyzed reactions. [German] Ziel dieser Arbeit war die Herstellung von Phenol durch die Direktoxidation von Benzol mit umweltfreundlichen Oxidationsmitteln wie Wasserstoffperoxid, Sauerstoff oder Ozon. Als Katalysatoren dienten amorphe mikroporoese Mischoxide, da deren Eigenschaften direkt in der Synthese durch den Sol-Gel-Prozess gezielt eingestellt werden koennen. Neben Benzol wurde auch Cyclohexan mit Ozon unter der Verwendung von AMM-Katalysatoren oxidiert, um das Potential von Ozon als Oxiationsmittel in heterogen katalysierten Reaktionen naeher zu untersuchen. (orig.)

Oxidative DNA damage and oxidative stress in lead-exposed workers.

Science.gov (United States)

Dobrakowski, M; Pawlas, N; Kasperczyk, A; Kozłowska, A; Olewińska, E; Machoń-Grecka, A; Kasperczyk, S

2017-07-01

There are many discrepancies among the results of studies on the genotoxicity of lead. The aim of the study was to explore lead-induced DNA damage, including oxidative damage, in relation to oxidative stress intensity parameters and the antioxidant defense system in human leukocytes. The study population consisted of 100 male workers exposed to lead. According to the blood lead (PbB) levels, they were divided into the following three subgroups: a group with PbB of 20-35 μg/dL (low exposure to lead (LE) group), a group with a PbB of 35-50 µg/dL (medium exposure to lead (ME) group), and a group with a PbB of >50 μg/dL (high exposure to lead (HE) group). The control group consisted of 42 healthy males environmentally exposed to lead (PbB lead exposure induces DNA damage, including oxidative damage, in human leukocytes. The increase in DNA damage was accompanied by an elevated intensity of oxidative stress.

Oxidative stress-mediated antibacterial activity of graphene oxide and reduced graphene oxide in Pseudomonas aeruginosa

OpenAIRE

Gurunathan, Sangiliyandi; Han,Jae Woong; Abdal Daye,Ahmed; Eppakayala,Vasuki; Kim,Jin-Hoi

2012-01-01

Sangiliyandi Gurunathan, Jae Woong Han, Ahmed Abdal Dayem, Vasuki Eppakayala, Jin-Hoi KimDepartment of Animal Biotechnology, Konkuk University, Seoul, South KoreaBackground: Graphene holds great promise for potential use in next-generation electronic and photonic devices due to its unique high carrier mobility, good optical transparency, large surface area, and biocompatibility. The aim of this study was to investigate the antibacterial effects of graphene oxide (GO) and reduced graphene oxid...

CATALYTIC OXIDATION OF ALCOHOLS AND EPOXIDATION OF OLEFINS WITH HYDROGEN PEROXIDE AS OXIDANT

Science.gov (United States)

Hydrogen peroxide (H2O2) is an ideal oxidant of choice for these oxidations due to economic and environmental reasons by giving water as a by-product. Two catalysts used are vanadium phosphorus oxide (VPO) and Fe3+/montmorillonite-K10 catalyst prepared by ion-exchange method at a...

Nanoroses of nickel oxides: Synthesis, electron tomography study, and application in CO oxidation and energy storage

KAUST Repository

Fihri, Aziz; Sougrat, Rachid; Baby, Rakhi Raghavan; Rahal, Raed; Cha, Dong Kyu; Hedhili, Mohamed N.; Bouhrara, Mohamed; Alshareef, Husam N.; Polshettiwar, Vivek

2012-01-01

Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron

Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

1994-10-01

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu₂O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu₂O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu₂O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N₂ and CO₂. At the end of each reaction, the catalyst was found to be Cu₂O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

Oxidative desulfurization of benzene fraction on transition metal oxides

Science.gov (United States)

Boikov, E. B.; Vishnetskaya, M. V.

2013-02-01

It is established that molecular oxygen is able to oxidize thiophene selectively in a mixture with benzene on V2O5 · MoO3. The introduction of thiophene inhibits the oxidation of benzene. It is shown that the conversion of thiophene during operation of the catalyst is reduced at first and then increases until it reaches its initial value.

Nanoparticular metal oxide/anatase catalysts

DEFF Research Database (Denmark)

2010-01-01

The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

The oxidative hypothesis of senescence

Directory of Open Access Journals (Sweden)

Gilca M

2007-01-01

Full Text Available The oxidative hypothesis of senescence, since its origin in 1956, has garnered significant evidence and growing support among scientists for the notion that free radicals play an important role in ageing, either as "damaging" molecules or as signaling molecules. Age-increasing oxidative injuries induced by free radicals, higher susceptibility to oxidative stress in short-lived organisms, genetic manipulations that alter both oxidative resistance and longevity and the anti-ageing effect of caloric restriction and intermittent fasting are a few examples of accepted scientific facts that support the oxidative theory of senescence. Though not completely understood due to the complex "network" of redox regulatory systems, the implication of oxidative stress in the ageing process is now well documented. Moreover, it is compatible with other current ageing theories (e.g., those implicating the mitochondrial damage/mitochondrial-lysosomal axis, stress-induced premature senescence, biological "garbage" accumulation, etc. This review is intended to summarize and critically discuss the redox mechanisms involved during the ageing process: sources of oxidant agents in ageing (mitochondrial -electron transport chain, nitric oxide synthase reaction- and non-mitochondrial- Fenton reaction, microsomal cytochrome P450 enzymes, peroxisomal β -oxidation and respiratory burst of phagocytic cells, antioxidant changes in ageing (enzymatic- superoxide dismutase, glutathione-reductase, glutathion peroxidase, catalase- and non-enzymatic glutathione, ascorbate, urate, bilirubine, melatonin, tocopherols, carotenoids, ubiquinol, alteration of oxidative damage repairing mechanisms and the role of free radicals as signaling molecules in ageing.

The study of the oxidation of the natural flavonol fisetin confirmed quercetin oxidation mechanism

International Nuclear Information System (INIS)

Ramešová, Šárka; Sokolová, Romana; Degano, Ilaria

2015-01-01

Highlights: • The oxidation mechanisms of fisetin and quercetin were compared. • The oxidation product of fisetin was identified even if it was not stable. • A benzofuranon derivative is the common oxidation product of flavonols. • Fisetin decomposes in solution during minutes handled in the presence of air. - Abstract: Oxidation of the bioactive flavonoid fisetin was studied under inert atmosphere and under ambient conditions. The presence of fast subsequent chemical reactions following the electron transfer was supported by in situ spectroelectrochemistry and identification of products by HPLC-DAD and HPLC–ESI-MS/MS. In the absence of oxygen, 2,6-dihydroxy-2-(3′,4′-dihydroxybenzoyl)-benzofuran-3(2H)-one was identified as the only oxidation product of fisetin. This product was found also as the main oxidation product in the presence of oxygen. The oxidation pathway leading to formation of a benzofuranone derivative can be considered as common for flavonols containing C2-C3 double bond, C3-OH group and dihydroxy-substituted phenyl moiety in its structure. This product was not stable and decomposed further even in contact with oxygen coming from eluents during chromatography. Two oxidation pathways occur under ambient conditions. DFT calculations support the result.

Ytterbia doped nickel–manganese mixed oxide catalysts for liquid phase oxidation of benzyl alcohol

Directory of Open Access Journals (Sweden)

S.S.P. Sultana

2017-11-01

Full Text Available Nickel–manganese mixed oxides doped with 1, 3, 5 mol% ytterbia have been prepared by co-precipitation method and used in the catalytic oxidation of benzyl alcohol. Catalytic activity of these oxides calcined at 400 °C and 500 °C was studied for selective oxidation of benzyl alcohol to the corresponding aldehyde using molecular oxygen as an oxidizing agent. The results showed that thermally stable 5 mol% ytterbia doped nickel–manganese oxide [Yb2O3-(5%-Ni6MnO8] exhibited highest catalytic performance when it was calcined at 400 °C. A 100% conversion of the benzyl alcohol was achieved with >99% selectivity to benzaldehyde within a reaction period of 5 h at 100 °C. The mixed oxide prepared has been characterized by scanning election microscopy (SEM and energy dispersive X-ray analysis (EDXA, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, thermogravimetric analysis (TGA, Brunauer–Emmett–Teller (BET and temperature programed reduction (H2-TPR.

High temperature oxidation resistant cermet compositions

Science.gov (United States)

Phillips, W. M. (Inventor)

1976-01-01

Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

Hydrogen oxidation in Azospirillum brasilense

Energy Technology Data Exchange (ETDEWEB)

Tibelius, K.

1984-01-01

Hydrogen oxidation by Azospirillum brasilense Sp7 was studied in N/sub 2/-fixing and NH/sub 4//sup +/-grown batch cultures. The K/sub m/ for H/sub 2/ of O/sub 2/-dependent H/sup 3/H oxidation in whole cells was 9 uM. The rates of H/sup 3/H and H/sub 2/ oxidation were very similar, indicating that the initial H/sub 2/ activation step in the overall H/sub 2/ oxidation reaction was not rate-limiting and that H/sup 3/H oxidation was a valid measure of H/sub 2/-oxidation activity. Hydrogen-oxidation activity was inhibited irreversibly by air. In N-free cultures the O/sub 2/ optima for O/sub 2/-dependent H/sub 2/ oxidation, ranging from 0.5-1.25% O/sub 2/ depending on the phase of growth, were significantly higher than those of C/sub 2/H/sub 2/ reduction, 0.15-0.35%, suggesting that the H/sub 2/-oxidation system may have a limited ability to aid in the protection of nitrogenase against inactivation by O/sub 2/. Oxygen-dependent H/sub 2/ oxidation was inhibited by NO/sub 2//sup +/, NO, CO, and C/sub 2/H/sub 2/ with apparent K/sub 1/ values of 20, 0.4, 28, and 88 uM, respectively. Hydrogen-oxidation activity was 50 to 100 times higher in denitrifying cultures when the terminal electron acceptor for growth was N/sub 2/O rather than NO/sub 3//sup -/, possibly due to the irreversible inhibition of hydrogenase by NO/sub 2//sup -/ and NO in NO/sub 3//sup -/-grown cultures.

Contribution to characteristics of uranium oxides

International Nuclear Information System (INIS)

Fritsche, R.; Dahlkamp, F.J.

2001-01-01

Uranium oxides from pegmatitic, metamorphic and metasomatic uranium occurrences were investigated with the objective to check for differences in their physico-chemical properties and, whether such properties are sufficiently distinct to be applied as an exploration tool. Research methods included microscopy, electron microprobe and X-ray diffractometry amended by determinations of reflectance, Vickers hardness, unit-cell dimension and oxidation grade. Tentative research results are as follows: (a) U-oxides (uraninites) of pegmatites always contain significant amounts of Th (1,5-10 wt.% ThO2). (b) U-oxides from metasomatic environments have high, but variable contents of Fe, Ca, Ti, Si and Th (around 10 wt.%), Th being low. (c) U-oxides crystallised during metamorphism contain minor impurities of the above listed elements (total of oxides < 2 wt.%). (d) Redistributed U-oxides have elevated amounts of these elements. (e) Unit-cell dimensions of U-oxides tend to reflect a complex function of formation temperature, oxidation grade and the influence of incorporated elements caused by their radius and electro-negativity. (f) A global negative correlation of unit-cell dimension and oxidation grade of uranium oxides is indicated but based on widely varying ratios of the two parameters. (g) Colloform U-oxide (pitchblende) is characterised by elevated Ca-contents (1-5 wt.% CaO) and an almost complete lack of Th (< 1 wt.% ThO2). (h) Idiomorphic U-oxide (uraninite) is commonly low in Ca (< 1.5 wt.% CaO) but contains relatively high Th values. (i) The reflectance of U-oxides generally correlates positively with Vickers hardness and unit-cell dimension, but the incorporation of other elements in the lattice of U-oxides may cause strong interference. (author)

Oxidation of propane with oxygen, nitrous oxide and oxygen/nitrous oxide mixture over Co- and Fe-zeolites

Czech Academy of Sciences Publication Activity Database

Novoveská, K.; Bulánek, R.; Wichterlová, Blanka

2005-01-01

Roč. 100, 3-4 (2005), s. 315-319 ISSN 0920-5861 R&D Projects: GA ČR(CZ) GA104/03/1120 Institutional research plan: CEZ:AV0Z40400503 Keywords : propene * propane oxidation * nitrous oxide * Fe-ZSM-5 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.365, year: 2005

N-Oxide-N-oxide interactions and Cl...Cl halogen bonds in pentachloropyridine N-oxide: the many-body approach to interactions in the crystal state.

Science.gov (United States)

Wzgarda-Raj, Kinga; Rybarczyk-Pirek, Agnieszka J; Wojtulewski, Sławomir; Palusiak, Marcin

2018-02-01

Pentachloropyridine N-oxide, C 5 Cl 5 NO, crystallizes in the monoclinic space group P2 1 /c. In the crystal structure, molecules are linked by C-Cl...Cl halogen bonds into infinite ribbons extending along the crystallographic [100] direction. These molecular aggregates are further stabilized by very short intermolecular N-oxide-N-oxide interactions into herringbone motifs. Computations based on quantum chemistry methods allowed for a more detailed description of the N-oxide-N-oxide interactions and Cl...Cl halogen bonds. For this purpose, Hirshfeld surface analysis and the many-body approach to interaction energy were applied.

[Isolation and identification of Mn oxidizing bacterium Aminobacter sp. H1 and its oxidation mechanism].

Science.gov (United States)

Yan, Ping; Jiang, Li-Ying; Chen, Jian-Meng; He, Zhi-Min; Xiao, Shao-Dan; Jiang, Yi-Feng

2014-04-01

A bacterium with high manganese oxidizing activity was isolated from a biological manganese removal filter and named as H1. Based on its characteristics and the analysis of 16S rDNA sequence, the strain H1 belonged to the genus Aminobacter sp. and its manganese oxidizing ability had never been reported. In this paper, the microbiologic properties of the strain H1, the manganese oxidation mechanisms and characteristics of biogenic manganese oxides were investigated. The results showed that the maximal tolerant Mn concentration of strain H1 was 50 mmol x L(-1), and Mn(II) could be completely removed by strain H1 when the concentration was lower than 10 mmol x L(-1). Strain H1 could oxidize Mn2+ by both the production of manganese oxidizing activity factor and alkaline metabolites during growth, which were synthesized in the cell and then secreted into extracellular culture medium. During the oxidation process, the intermediate of soluble Mn(III) was detected. SEM showed that the biogenic manganese oxides were amorphous and poorly-crystalline, and it closely combined with bacteria. The components of the biogenic manganese oxides produced by strain H1 were identified as MnCO3, MnOOH, Mn3O4 and MnO2 by XRD, XPS and SEM-EDX.

Metal oxide nanorod arrays on monolithic substrates

Energy Technology Data Exchange (ETDEWEB)

Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

2018-01-02

A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can include a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.

Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

DEFF Research Database (Denmark)

Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

2001-01-01

The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

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)

Reduction of graphene oxide by aniline with its concomitant oxidative polymerization.

Science.gov (United States)

Xu, Li Qun; Liu, Yi Liang; Neoh, Koon-Gee; Kang, En-Tang; Fu, Guo Dong

2011-04-19

Graphene oxide (GO) nanosheets are readily reduced by aniline above room temperature in an aqueous acid medium, with the aniline simultaneously undergoing oxidative polymerization to produce the reduced graphene oxide-polyaniline nanofiber (RGO-PANi) composites. The resulting RGO-PANi composites and RGO (after dissolution of PANi) were characterized by XPS, XRD analysis, TGA, UV-visible absorption spectroscopy, and TEM. It was also found that the RGO-PANi composites exhibit good specific capacitance during galvanostatic charging-discharging when used as capacitor electrodes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lipid oxidation. Part 2. Oxidation products of olive oil methyl esters.

Science.gov (United States)

Pokorný, J; Tài, P; Parízková, H; Smidrkalová, E; El-Tarras, M F; Janícek, G

1976-01-01

Olive oil was converted into methyl esters which were autoxidized at 60 degrees C. The composition of oxidized products was determined by the comparison of infrared spectra and NMR spectra of the original and acetylated samples, the sample reduced with potassium iodide and the acetylated reduced sample. Oxidized products were separated by preparative thin layer chromatography on silica gel and characterized by selective detection and by infrared spectrometry of the fractions. The oxidation products consisted of hydroperoxido butyl oleate, substituted hydroperoxides, mono- and disubstituted monomeric derivatives and a small amount of oligomers.