Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy.

PubMed

Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

2018-01-25

We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy ΔG ⧧ of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute ΔG ⧧ for hydride transfers from hydride donors to CO 2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted ΔG ⧧ ; this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.

The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

DTIC Science & Technology

2016-01-04

AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT...of both Aluminum Hydride Cluster Anions and Boron Aluminum Hydride Cluster Anions with Oxygen: Anionic Products The anionic products of reactions

An elasto-plastic fracture mechanics based model for assessment of hydride embrittlement in zircaloy cladding tubes

NASA Astrophysics Data System (ADS)

Nilsson, Karl-Fredrik; Jakšić, Nikola; Vokál, Vratko

2010-01-01

This paper describes a finite element based fracture mechanics model to assess how hydrides affect the integrity of zircaloy cladding tubes. The hydrides are assumed to fracture at a low load whereas the propagation of the fractured hydrides in the matrix material and failure of the tube is controlled by non-linear fracture mechanics and plastic collapse of the ligaments between the hydrides. The paper quantifies the relative importance of hydride geometrical parameters such as size, orientation and location of individual hydrides and interaction between adjacent hydrides. The paper also presents analyses for some different and representative multi-hydride configurations. The model is adaptable to general and complex crack configurations and can therefore be used to assess realistic hydride configurations. The mechanism of cladding failure is by plastic collapse of ligaments between interacting fractured hydrides. The results show that the integrity can be drastically reduced when several radial hydrides form continuous patterns.

Fundamental experiments on hydride reorientation in zircaloy

NASA Astrophysics Data System (ADS)

Colas, Kimberly B.

In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and remain constant in the tensile direction during the second precipitation regime. This could be due to the fact that the face of reoriented hydride platelet is in compression once these platelets have grown to a sufficient size. The second goal of this study was to perform a spatially resolved study of the effect of a stress concentration such as a notch or a crack on hydride reorientation. Using SEM and image analysis, it was found that a sharp crack induces a different hydride microstructure than a blunt notch. In the case of sharp crack, hydrides are more localized and align more with the defect than for blunt notches. The hydride connectivity also increases close to a stress concentration which will assist in crack propagation during DHC. Using TEM, the microstructure of hydrides grown near crack tips were observed to be similar to that of circumferential hydrides grown in the bulk. The orientation relationship studied with SEM and micro-X-ray diffraction was found to be in most cases δ(111)// α(0002) for hydrides grown both near and far from stress concentrations. Using the same micro-X-ray diffraction technique local hydride and matrix elastic strains were measured and observed to vary significantly from grain to grain. It was however observed that hydrides grown close to the stress concentration are in tension in the face of the platelet, similar to reoriented hydrides, while those grown far from the stress concentration are in tension, similar to circumferential hydrides. The orders of magnitude of the measured strains in the hydrides and the zirconium matrix compared well to those predicted by finite element models. This study shows that it is possible to study hydride dissolution and precipitation in-situ using time-dependent techniques. It was found that the precipitation temperature is lowered by hydride reorientation. The evolution of hydride strains during precipitation was found to be different for unstressed, stressed and reoriented hydrides. The reoriented hydride fraction and connectivity increase with number of cycles which could lead to more dangerous microstructure for storage of spent fuel. Pre-existing cracks were also found to affect hydride connectivity and morphology which directly impacts DHC and fuel integrity. (Abstract shortened by UMI.).

Method for preparing porous metal hydride compacts

DOEpatents

Ron, M.; Gruen, D.M.; Mendelsohn, M.H.; Sheft, I.

1980-01-21

A method for preparing porous metallic-matrix hydride compacts which can be repeatedly hydrided and dehydrided without disintegration. A mixture of a finely divided metal hydride and a finely divided matrix metal is contacted with a poison which prevents the metal hydride from dehydriding at room temperature and atmospheric pressure. The mixture of matrix metal and poisoned metal hydride is then compacted under pressure at room temperature to form porous metallic-matrix hydride compacts.

Method for preparing porous metal hydride compacts

DOEpatents

Ron, Moshe; Gruen, Dieter M.; Mendelsohn, Marshall H.; Sheft, Irving

1981-01-01

A method for preparing porous metallic-matrix hydride compacts which can be repeatedly hydrided and dehydrided without disintegration. A mixture of a finely divided metal hydride and a finely divided matrix metal is contacted with a poison which prevents the metal hydride from dehydriding at room temperature and atmospheric pressure. The mixture of matrix metal and poisoned metal hydride is then compacted under pressure at room temperature to form porous metallic-matrix hydride compacts.

Vanadium Respiration by Geobacter metallireducens: Novel Strategy for In Situ Removal of Vanadium from Groundwater

PubMed Central

Ortiz-Bernad, Irene; Anderson, Robert T.; Vrionis, Helen A.; Lovley, Derek R.

2004-01-01

Vanadium can be an important contaminant in groundwaters impacted by mining activities. In order to determine if microorganisms of the Geobacteraceae, the predominant dissimilatory metal reducers in many subsurface environments, were capable of reducing vanadium(V), Geobacter metallireducens was inoculated into a medium in which acetate was the electron donor and vanadium(V) was the sole electron acceptor. Reduction of vanadium(V) resulted in the production of vanadium(IV), which subsequently precipitated. Reduction of vanadium(V) was associated with cell growth with a generation time of 15 h. No vanadium(V) was reduced and no precipitate was formed in heat-killed or abiotic controls. Acetate was the most effective of all the electron donors evaluated. When acetate was injected into the subsurface to enhance the growth and activity of Geobacteraceae in an aquifer contaminated with uranium and vanadium, vanadium was removed from the groundwater even more effectively than uranium. These studies demonstrate that G. metallireducens can grow via vanadium(V) respiration and that stimulating the activity of Geobacteraceae, and hence vanadium(V) reduction, can be an effective strategy for in situ immobilization of vanadium in contaminated subsurface environments. PMID:15128571

A classical but new kinetic equation for hydride transfer reactions.

PubMed

Zhu, Xiao-Qing; Deng, Fei-Huang; Yang, Jin-Dong; Li, Xiu-Tao; Chen, Qiang; Lei, Nan-Ping; Meng, Fan-Kun; Zhao, Xiao-Peng; Han, Su-Hui; Hao, Er-Jun; Mu, Yuan-Yuan

2013-09-28

A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions.

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice

PubMed Central

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal. PMID:26962395

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice.

PubMed

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal.

Assessment of total and organic vanadium levels and their bioaccumulation in edible sea cucumbers: tissues distribution, inter-species-specific, locational differences and seasonal variations.

PubMed

Liu, Yanjun; Zhou, Qingxin; Xu, Jie; Xue, Yong; Liu, Xiaofang; Wang, Jingfeng; Xue, Changhu

2016-02-01

The objective of this study is to investigate the levels, inter-species-specific, locational differences and seasonal variations of vanadium in sea cucumbers and to validate further several potential factors controlling the distribution of metals in sea cucumbers. Vanadium levels were evaluated in samples of edible sea cucumbers and were demonstrated exhibit differences in different seasons, species and sampling sites. High vanadium concentrations were measured in the sea cucumbers, and all of the vanadium detected was in an organic form. Mean vanadium concentrations were considerably higher in the blood (sea cucumber) than in the other studied tissues. The highest concentration of vanadium (2.56 μg g(-1)), as well as a higher degree of organic vanadium (85.5 %), was observed in the Holothuria scabra samples compared with all other samples. Vanadium levels in Apostichopus japonicus from Bohai Bay and Yellow Sea have marked seasonal variations. Average values of 1.09 μg g(-1) of total vanadium and 0.79 μg g(-1) of organic vanadium were obtained in various species of sea cucumbers. Significant positive correlations between vanadium in the seawater and V org in the sea cucumber (r = 81.67 %, p = 0.00), as well as between vanadium in the sediment and V org in the sea cucumber (r = 77.98 %, p = 0.00), were observed. Vanadium concentrations depend on the seasons (salinity, temperature), species, sampling sites and seawater environment (seawater, sediment). Given the adverse toxicological effects of inorganic vanadium and positive roles in controlling the development of diabetes in humans, a regular monitoring programme of vanadium content in edible sea cucumbers can be recommended.

Leaching characteristics of vanadium in mine tailings and soils near a vanadium titanomagnetite mining site.

PubMed

Yang, Jinyan; Tang, Ya; Yang, Kai; Rouff, Ashaki A; Elzinga, Evert J; Huang, Jen-How

2014-01-15

A series of column leaching experiments were performed to understand the leaching behaviour and the potential environmental risk of vanadium in a Panzhihua soil and vanadium titanomagnetite mine tailings. Results from sequential extraction experiments indicated that the mobility of vanadium in both the soil and the mine tailings was low, with <1% of the total vanadium readily mobilised. Column experiments revealed that only <0.1% of vanadium in the soil and mine tailing was leachable. The vanadium concentrations in the soil leachates did not vary considerably, but decreased with the leachate volume in the mine tailing leachates. This suggests that there was a smaller pool of leachable vanadium in the mine tailings compared to that in the soil. Drought and rewetting increased the vanadium concentrations in the soil and mine tailing leachates from 20μgL(-1) to 50-90μgL(-1), indicating the potential for high vanadium release following periods of drought. Experiments with soil columns overlain with 4, 8 and 20% volume mine tailings/volume soil exhibited very similar vanadium leaching behaviour. These results suggest that the transport of vanadium to the subsurface is controlled primarily by the leaching processes occurring in soils. Copyright © 2013 Elsevier B.V. All rights reserved.

[Oxidative Stress Level of Vanadium-exposed Workers].

PubMed

Wei, Teng-da; Li, Shun-pin; Liu, Yun-xing; Tan, Chun-ping; Li, Juan; Zhang, Zu-hui; Lan, Ya-jia; Zhang, Qin

2015-11-01

To determine the oxidative stress level in peripheral blood of vanadium-exposed workers, as an indication of population health effect of vanadium on human neurobehavioral system. 86 vanadium-exposed workers and 65 non-exposed workers were recruited by cluster sampling. A questionnaire was administered to collect demographic and occupational exposure information. Serum activity of superoxide dismutase (SOD), inducible nitric oxide synthase (iNOS) and malonaldehyde (MDA) contents were detected by kit assay. The differences in oxidative stress level between vanadium-exposed and non-exposed workers were compared. Vanadium-exposed workers had higher levels of MDA contents than the controls. The total superoxide dismutase(T-SOD) activity in vanadium-exposed workers was significantly lower than that in the controls, which was associated with lowered levels of manganese superoxide dismutase (Mn-SOD) activity. No changes in serum levels of cupro-zinc superoxide dismutase (CuZn-SOD) was found in vanadium-exposed workers. No difference in iNOS activity was found between vanadium-exposed workers and controls. Vanadium exposure increases free radical production in serum and reduces antioxidant capacity. But the relationship between vanadium exposure and iNOS damage remains uncertain.

Cyclopentadiene-mediated hydride transfer from rhodium complexes.

PubMed

Pitman, C L; Finster, O N L; Miller, A J M

2016-07-12

Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

Quantifying the stress fields due to a delta-hydride precipitate in alpha-Zr matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tummala, Hareesh; Capolungo, Laurent; Tome, Carlos N.

This report is a preliminary study on δ-hydride precipitate in zirconium alloy performed using 3D discrete dislocation dynamics simulations. The ability of dislocations in modifying the largely anisotropic stress fields developed by the hydride particle in a matrix phase is addressed for a specific dimension of the hydride. The influential role of probable dislocation nucleation at the hydride-matrix interface is reported. Dislocation nucleation around a hydride was found to decrease the shear stress (S 13) and also increase the normal stresses inside the hydride. We derive conclusions on the formation of stacks of hydrides in zirconium alloys. The contribution ofmore » mechanical fields due to dislocations was found to have a non-negligible effect on such process.« less

The presence of vanadium in groundwater of southeastern extreme the pampean region Argentina Relationship with other chemical elements.

PubMed

Fiorentino, Carmen E; Paoloni, Juan D; Sequeira, Mario E; Arosteguy, Pedro

2007-08-15

Changes in the quality of groundwater resources are related to the presence and concentration of contaminants, especially trace elements such as arsenic, boron, fluoride and vanadium. Vanadium is a rare element naturally abundant, generally found in combination with other elements. Vanadium pentoxide is known to have aneugenic effects. Thus, a study was carried out to assess the presence of vanadium in the groundwater of the southeastern pampean region of Argentina, which constitutes the main water supply for the local population. Statistical and correlational analyses were applied to identify possible interrelationships between vanadium and another chemical elements. Vanadium was found in all groundwater samples. The minimum and maximum vanadium concentrations found were 0.05 mg/l and 2.47 mg/l, respectively. Vanadium is significantly correlated with other trace elements such as arsenic, fluoride and boron. The interrelationship between vanadium and the presence of volcanic glass in sediments is not significant as expected.

Bioaccumulation of Vanadium by Vanadium-Resistant Bacteria Isolated from the Intestine of Ascidia sydneiensis samea.

PubMed

Romaidi; Ueki, Tatsuya

2016-06-01

Isolation of naturally occurring bacterial strains from metal-rich environments has gained popularity due to the growing need for bioremediation technologies. In this study, we found that the vanadium concentration in the intestine of the vanadium-rich ascidian Ascidia sydneiensis samea could reach 0.67 mM, and thus, we isolated vanadium-resistant bacteria from the intestinal contents and determined the ability of each bacterial strain to accumulate vanadium and other heavy metals. Nine strains of vanadium-resistant bacteria were successfully isolated, of which two strains, V-RA-4 and S-RA-6, accumulated vanadium at a higher rate than did the other strains. The maximum vanadium absorption by these bacteria was achieved at pH 3, and intracellular accumulation was the predominant mechanism. Each strain strongly accumulated copper and cobalt ions, but accumulation of nickel and molybdate ions was relatively low. These bacterial strains can be applied to protocols for bioremediation of vanadium and heavy metal toxicity.

Vanadium recycling in the United States in 2004

USGS Publications Warehouse

Goonan, Thomas G.

2011-01-01

As one of a series of reports that describe the recycling of metal commodities in the United States, this report discusses the flow of vanadium in the U.S. economy in 2004. This report includes a description of vanadium supply and demand in the United States and illustrates the extent of vanadium recycling and recycling trends. In 2004, apparent vanadium consumption, by end use, in the United States was 3,820 metric tons (t) in steelmaking and 232 t in manufacturing, of which 17 t was for the production of superalloys and 215 t was for the production of other alloys, cast iron, catalysts, and chemicals. Vanadium use in steel is almost entirely dissipative because recovery of vanadium from steel scrap is chemically impeded under the oxidizing conditions in steelmaking furnaces. The greatest amount of vanadium recycling is in the superalloy, other-alloy, and catalyst sectors of the vanadium market. Vanadium-bearing catalysts are associated with hydrocarbon recovery and refining in the oil industry. In 2004, 2,850 t of vanadium contained in alloy scrap and spent catalysts was recycled, which amounted to about 44 percent of U.S. domestic production. About 94 percent of vanadium use in the United States was dissipative (3,820 t in steel/4,050 t in steel+fabricated products).

Boron hydride polymer coated substrates

DOEpatents

Pearson, R.K.; Bystroff, R.I.; Miller, D.E.

1986-08-27

A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

Boron hydride polymer coated substrates

DOEpatents

Pearson, Richard K.; Bystroff, Roman I.; Miller, Dale E.

1987-01-01

A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

Release kinetics of vanadium from vanadium (III, IV and V) oxides: Effect of pH, temperature and oxide dose.

PubMed

Hu, Xingyun; Yue, Yuyan; Peng, Xianjia

2018-05-01

Batch experiments were performed to derive the rate laws for the proton-promoted dissolution of the main vanadium (III, IV and V) oxides at pH 3.1-10.0. The release rates of vanadium are closely related to the aqueous pH, and several obvious differences were observed in the release behavior of vanadium from the dissolution of V 2 O 5 and vanadium(III, IV) oxides. In the first 2hr, the release rates of vanadium from V 2 O 3 were r=1.14·([H + ]) 0.269 at pH 3.0-6.0 and r=0.016·([H + ]) -0.048 at pH 6.0-10.0; the release rates from VO 2 were r=0.362·([H + ]) 0.129 at pH 3.0-6.0 and r=0.017·([H + ]) -0.097 at pH 6.0-10.0; and the release rates from V 2 O 5 were r=0.131·([H + ]) -0.104 at pH 3.1-10.0. The release rates of vanadium from the three oxides increased with increasing temperature, and the effect of temperature was different at pH 3.8, pH 6.0 and pH 7.7. The activation energies of vanadium (III, IV and V) oxides (33.4-87.5kJ/mol) were determined at pH 3.8, pH6.0 and pH 7.7, showing that the release of vanadium from dissolution of vanadium oxides follows a surface-controlled reaction mechanism. The release rates of vanadium increased with increasing vanadium oxides dose, albeit not proportionally. This study, as part of a broader study of the release behavior of vanadium, can help to elucidate the pollution problem of vanadium and to clarify the fate of vanadium in the environment. Copyright © 2017. Published by Elsevier B.V.

Methods for making lithium vanadium oxide electrode materials

DOEpatents

Schutts, Scott M.; Kinney, Robert J.

2000-01-01

A method of making vanadium oxide formulations is presented. In one method of preparing lithium vanadium oxide for use as an electrode material, the method involves: admixing a particulate form of a lithium compound and a particulate form of a vanadium compound; jet milling the particulate admixture of the lithium and vanadium compounds; and heating the jet milled particulate admixture at a temperature below the melting temperature of the admixture to form lithium vanadium oxide.

THE COLORIMETRIC DETERMINATION OF VANADIUM IN NIOBIUM-VANADIUM ALLOYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Articolo, O.J.

1959-06-26

A procedure is described for the analysis of vanadium in niobium-- vanadium alloys in the range >0.1% vanadium with an accuracy of better than 3%. The method was applied to the analysis of niobium alloys in which the nominal per cent vanadium varied between 0.3 to 4.6%. The sample is dissolved in a mixture of nitric and hydrofluoric acid and then evaporated to fumes with sulfuric acid. The niobium is hydrolyzed with sulfurous acid and separated from the vanadium by filtration. Hydrogen peroxide is added to the filtrate to form a reddish brown complex with the vanadium. The optical densitymore » of the resulting solution is obtained at 450 m mu on a model B Beckman spectrophotometer. (auth)« less

Metal hydride composition and method of making

DOEpatents

Congdon, James W.

1995-01-01

A dimensionally stable hydride composition and a method for making such a composition. The composition is made by forming particles of a metal hydride into porous granules, mixing the granules with a matrix material, forming the mixture into pellets, and sintering the pellets in the absence of oxygen. The ratio of matrix material to hydride is preferably between approximately 2:1 and 4:1 by volume. The porous structure of the granules accommodates the expansion that occurs when the metal hydride particles absorb hydrogen. The porous matrix allows the flow of hydrogen therethrough to contact the hydride particles, yet supports the granules and contains the hydride fines that result from repeated absorption/desorption cycles.

Thermodynamic Hydricity of Transition Metal Hydrides

DOE PAGES

Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.; ...

2016-08-02

Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bondbreaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H -). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H 2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H 2more » in the presence of a base, and the potential-pK a method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Finally, methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO 2, and the production and oxidation of hydrogen.« less

DNA damage induction in human cells exposed to vanadium oxides in vitro.

PubMed

Rodríguez-Mercado, Juan J; Mateos-Nava, Rodrigo A; Altamirano-Lozano, Mario A

2011-12-01

Vanadium and vanadium salts cause genotoxicity and elicit variable biological effects depending on several factors. In the present study, we analyzed and compared the DNA damage and repair processes induced by vanadium in three oxidation states. We used human blood leukocytes in vitro and in a single cell gel electrophoresis assay at two pH values. We observed that vanadium(III) trioxide and vanadium(V) pentoxide produced DNA single-strand breaks at all of the concentrations (1, 2, 4, or 8 μg/ml) and treatment times (2, 4, or 6 h) tested. Vanadium(IV) tetraoxide treatment significantly increased DNA damage at all concentrations for 4 or 6 h of treatment but not for 2 h of treatment. The DNA repair kinetics indicated that most of the cells exposed to vanadium III and V for 4 h recovered within the repair incubation time of 90 min; however, those exposed to vanadium(IV) repaired their DNA within 120 min. The data at pH 9 indicated that vanadium(IV) tetraoxide induced DNA double-strand breaks. Our results show that the genotoxic effect of vanadium can be produced by any of its three oxidation states. However, vanadium(IV) induces double-strand breaks, and it is known that these lesions are linked with forming structural chromosomal aberrations. Copyright © 2011 Elsevier Ltd. All rights reserved.

1. VIEW OF A PORTION OF THE HYDRIDE PROCESSING LABORATORY. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. VIEW OF A PORTION OF THE HYDRIDE PROCESSING LABORATORY. OPERATIONS IN THE GLOVE BOX IN THE BACKGROUND OF THE PHOTOGRAPH INCLUDED HYDRIDING OF PLUTONIUM AND HYDRIDE SEPARATION. IN THE FOREGROUND, THE VACUUM MONITOR CONTROL PANEL MEASURED TEMPERATURES WITHIN THE GLOVEBOX. THE CENTER CONTROL PANEL REGULATED THE FURNACE INSIDE THE GLOVE BOX USED IN THE HYDRIDING PROCESSES. THIS EQUIPMENT WAS ESSENTIAL TO THE HYDRIDING PROCESS, AS WELL AS OTHER GLOVE BOX OPERATIONS. - Rocky Flats Plant, Plutonium Laboratory, North-central section of industrial area at 79 Drive, Golden, Jefferson County, CO

Tensile properties of titanium electrolytically charged with hydrogen

NASA Technical Reports Server (NTRS)

Smith, R. J.; Otterson, D. A.

1971-01-01

Yield strength, ultimate tensile strength, and elongation were studied for annealed titanium electrolytically charged with hydrogen. The hydrogen was present as a surface hydride layer. These tensile properties were generally lower for uncharged titanium than for titanium with a continuous surface hydride; they were greater for uncharged titanium than for titanium with an assumed discontinuous surface hydride. We suggest that the interface between titanium and titanium hydride is weak. And the hydride does not necessarily impair strength and ductility of annealed titanium. The possibility that oxygen and/or nitrogen can embrittle titanium hydride is discussed.

Effect of hydrogenation conditions on the microstructure and mechanical properties of zirconium hydride

NASA Astrophysics Data System (ADS)

Muta, Hiroaki; Nishikane, Ryoji; Ando, Yusuke; Matsunaga, Junji; Sakamoto, Kan; Harjo, Stefanus; Kawasaki, Takuro; Ohishi, Yuji; Kurosaki, Ken; Yamanaka, Shinsuke

2018-03-01

Precipitation of brittle zirconium hydrides deteriorate the fracture toughness of the fuel cladding tubes of light water reactor. Although the hydride embrittlement has been studied extensively, little is known about physical properties of the hydride due to the experimental difficulties. In the present study, to elucidate relationship between mechanical properties and microstructure, two δ-phase zirconium hydrides and one ε-phase zirconium hydride were carefully fabricated considering volume changes at the metal-to-hydride transformation. The δ-hydride that was fabricated from α-zirconium exhibits numerous inner cracks due to the large volume change. Analyses of the neutron diffraction pattern and electron backscatter diffraction (EBSD) data show that the sample displays significant stacking faults in the {111} plane and in the pseudo-layered microstructure. On the other hand, the δ-hydride sample fabricated from β-zirconium at a higher temperature displays equiaxed grains and no cracks. The strong crystal orientation dependence of mechanical properties were confirmed by indentation test and EBSD observation. The δ-hydride hydrogenated from α-zirconium displays a lower Young's modulus than that prepared from β-zirconium. The difference is attributed to stacking faults within the {111} plane, for which the Young's modulus exhibits the highest value in the perpendicular direction. The strong influence of the crystal orientation and dislocation density on the mechanical properties should be considered when evaluating hydride precipitates in nuclear fuel cladding.

High pressure hydriding of sponge-Zr in steam-hydrogen mixtures

NASA Astrophysics Data System (ADS)

Soo Kim, Yeon; Wang, Wei-E.; Olander, D. R.; Yagnik, S. K.

1997-07-01

Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400°C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2/H 2O above which massive hydriding occurs at 400°C is ˜ 200. The critical H 2/H 20 ratio is shifted to ˜2.5 × 103 at 350°C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ˜5 h at a hydriding rate of ˜10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale.

Effects of dietary vanadium in mallard ducks

USGS Publications Warehouse

White, D.H.; Dieter, M.P.

1978-01-01

Adult mallard ducks fed 0, 1, 10, or 100 ppm vanadyl sulfate in the diet were sacrificed after 12 wk on treatment; tissues were analyzed for vanadium. No birds died during the study and body weights did not change. Vanadium accumulated to higher concentrations in the bone and liver than in other tissues. Concentrations in bones of hens were five times those in bones of drakes, suggesting an interaction between vanadium and calcium mobilization in laying hens. Vanadium concentrations in most tissues were significantly correlated and increased with treatment level. Lipid metabolism was altered in laying hens fed 100 ppm vanadium. Very little vanadium accumulated in the eggs of laying hens.

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1991-01-01

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-06-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-04-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

Activated aluminum hydride hydrogen storage compositions and uses thereof

DOEpatents

Sandrock, Gary; Reilly, James; Graetz, Jason; Wegrzyn, James E.

2010-11-23

In one aspect, the invention relates to activated aluminum hydride hydrogen storage compositions containing aluminum hydride in the presence of, or absence of, hydrogen desorption stimulants. The invention particularly relates to such compositions having one or more hydrogen desorption stimulants selected from metal hydrides and metal aluminum hydrides. In another aspect, the invention relates to methods for generating hydrogen from such hydrogen storage compositions.

Hydriding process

DOEpatents

Raymond, J.W.; Taketani, H.

1973-12-01

BS>A method is described for hydriding a body of a Group IV-B metal, preferably zirconium, to produce a crack-free metal-hydride bedy of high hydrogen content by cooling the body at the beta to beta + delta boundary, without further addition of hydrogen, to precipitate a fine-grained delta-phase metal hydride in the beta + delta phase region and then resuming the hydriding, preferably preceded by a reheating step. (Official Gazette)

Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zidan, Ragaiy; Hardy, B. J.; Corgnale, C.

2016-01-31

The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce verymore » high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.« less

Metal hydride composition and method of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Congdon, J.W.

1995-08-22

A dimensionally stable hydride composition and a method for making such a composition are disclosed. The composition is made by forming particles of a metal hydride into porous granules, mixing the granules with a matrix material, forming the mixture into pellets, and sintering the pellets in the absence of oxygen. The ratio of matrix material to hydride is preferably between approximately 2:1 and 4:1 by volume. The porous structure of the granules accommodates the expansion that occurs when the metal hydride particles absorb hydrogen. The porous matrix allows the flow of hydrogen there through to contact the hydride particles, yetmore » supports the granules and contains the hydride fines that result from repeated absorption/desorption cycles. 3 figs.« less

Effect of tea polyphenols on production performance, egg quality, and hepatic antioxidant status of laying hens in vanadium-containing diets.

PubMed

Yuan, Z H; Zhang, K Y; Ding, X M; Luo, Y H; Bai, S P; Zeng, Q F; Wang, J P

2016-07-01

This study was conducted to determine the effect of tea polyphenols (TP) on production performance, egg quality, and hepatic-antioxidant status of laying hens in vanadium-containing diets. A total of 300 Lohman laying hens (67 wk old) were used in a 1 plus 3 × 3 experiment design in which hens were given either a diet without vanadium and TP supplementation (control) or diets supplemented with 5, 10, or 15 mg V/kg and TP (0, 600, 1,000 mg/kg) diets for 8 wk, which included 2 phases: a 5-wk accumulation phase and a 3-wk depletion phase. During the accumulation phase, dietary vanadium addition decreased (linear, P < 0.01) albumen height and Haugh unit (HU), and TP supplementation mitigated (linear effect, P < 0.01) this reduction effect induced by vanadium. Eggshell thickness (linear, P < 0.01), redness (linear and quadratic, P < 0.05), and yellowness (linear and quadratic, P < 0.05) were decreased by vanadium and increased by the effect of TP when a vanadium-containing diet was fed. In the depletion phase, the bleaching effect on eggshells induced by vanadium disappeared one wk after vanadium withdrawal. Eggshell thickness, eggshell strength, albumen height, and HU were lower (P < 0.05) in the 15 mg/kg vanadium group compared with the control diet until 2 wk post vanadium challenge, but hens fed 15 mg/kg vanadium and 600 mg/kg TP showed no difference from the control diet only after 1 wk withdrawal. In the liver, the activity of glutathione S-transferases and glutathione peroxidase was increased (linear, P < 0.01) with the TP addition at 5 wk in the accumulation phase in the vanadium-containing diet; the malondialdehyde content increased (linear effect, P = 0.02) with the addition of vanadium. The results indicate that supplementation of 10 and 15 mg/kg vanadium resulted in reduced albumen quality, bleaching effect on eggshell color, and antioxidant stress in the liver. The effect of TP addition can prevent laying hens from the adverse effect of vanadium on egg quality, liver antioxidant stress and shorten the recovery time. © 2016 Poultry Science Association Inc.

Vanadium distribution in rats and DNA cleavage by vanadyl complex: implication for vanadium toxicity and biological effects.

PubMed Central

Sakurai, H

1994-01-01

Vanadium ion is toxic to animals. However, vanadium is also an agent used for chemoprotection against cancers in animals. To understand both the toxic and beneficial effects we studied vanadium distribution in rats. Accumulation of vanadium in the liver nuclei of rats given low doses of compounds in the +4 or +5 oxidation state was greater than in the liver nuclei of rats given high doses of vanadium compounds or the vanadate (+5 oxidation state) compound. Vanadium was incorporated exclusively in the vanadyl (+4 oxidation state) form. We also investigated the reactions of vanadyl ion and found that incubation of DNA with vanadyl ion and hydrogen peroxide (H2O2) led to intense DNA cleavage. ESR spin trapping demonstrated that hydroxyl radicals are generated during the reactions of vanadyl ion and H2O2. Thus, we propose that the mechanism for vanadium-dependent toxicity and antineoplastic action is due to DNA cleavage by hydroxyl radicals generated in living systems. PMID:7843133

Aqueous vanadium ion dynamics relevant to bioinorganic chemistry: A review.

PubMed

Kustin, Kenneth

2015-06-01

Aqueous solutions of the four highest vanadium oxidation states exhibit four diverse colors, which only hint at the diverse reactions that these ions can undergo. Cationic vanadium ions form complexes with ligands; anionic vanadium ions form complexes with ligands and self-react to form isopolyanions. All vanadium species undergo oxidation-reduction reactions. With a few exceptions, elucidation of the dynamics of these reactions awaited the development of fast reaction techniques before the kinetics of elementary ligation, condensation, reduction, and oxidation of the aqueous vanadium ions could be investigated. As the biological roles played by endogenous and therapeutic vanadium expand, it is appropriate to bring the results of the diverse kinetics studies under one umbrella. To achieve this goal this review presents a systematic examination of elementary aqueous vanadium ion dynamics. Copyright © 2014 Elsevier Inc. All rights reserved.

Vanadium

USGS Publications Warehouse

Kelley, Karen D.; Scott, Clinton T.; Polyak, Désirée E.; Kimball, Bryn E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Vanadium is used primarily in the production of steel alloys; as a catalyst for the chemical industry; in the making of ceramics, glasses, and pigments; and in vanadium redox-flow batteries (VRBs) for large-scale storage of electricity. World vanadium resources in 2012 were estimated to be 63 million metric tons, which include about 14 million metric tons of reserves. The majority of the vanadium produced in 2012 was from China, Russia, and South Africa.Vanadium is extracted from several different types of mineral deposits and from fossil fuels. These deposits include vanadiferous titanomagnetite (VTM) deposits, sandstone-hosted vanadium (with or without uranium) deposits (SSV deposits), and vanadium-rich black shales. VTM deposits are the principal source of vanadium and consist of magmatic accumulations of ilmenite and magnetite containing 0.2 to 1 weight percent vanadium pentoxide (V2O5). SSV deposits are another important source; these deposits have average ore grades that range from 0.1 to greater than 1 weight percent V2O5. The United States has been and is currently the main producer of vanadium from SSV deposits, particularly those on the Colorado Plateau. Vanadium-rich black shales occur in marine successions that were deposited in epeiric (inland) seas and on continental margins. Concentrations in these shales regularly exceed 0.18 weight percent V2O5 and can be as high as 1.7 weight percent V2O5. Small amounts of vanadium have been produced from the Alum Shale in Sweden and from ferrophosphorus slag generated during the reduction of phosphate to elemental phosphorus in ore from shales of the Phosphoria Formation in Idaho and Wyoming. Because vanadium enrichment occurs in beds that are typically only a few meters thick, most of the vanadiferous black shales are not currently economic, although they may become an important resource in the future. Significant amounts of vanadium are recovered as byproducts of petroleum refining, and processing of coal, tar sands, and oil shales may be important future sources.Vanadium occurs in one of four oxidation states in nature: +2, +3, +4, and +5. The V3+ ion has an octahedral radius that is almost identical to that of (Fe3+) and (Al3+) and, therefore, it substitutes in ferromagnesian minerals. During weathering, much of the vanadium may partition into newly formed clay minerals, and it either remains in the +3 valence state or oxidizes to the +4 valence state, both of which are relatively insoluble. If erosion is insignificant but chemical leaching is intense, the residual material may be enriched in vanadium, as are some bauxites and laterites. During the weathering of igneous, residual, or sedimentary rocks, some vanadium oxidizes to the +5 valence state, especially in the intensive oxidizing conditions that are characteristic of arid climates.The average contents of vanadium in the environment are as follows: soils [10 to 500 parts per million (ppm)]; streams and rivers [0.2 to 2.9 parts per billion (ppb)]; and coastal seawater (0.3 to 2.8 ppb). Concentrations of vanadium in soils (548 to 7,160 ppm) collected near vanadium mines in China, the Czech Republic, and South Africa are many times greater than natural concentrations in soils. Additionally, if deposits contain sulfide minerals such as chalcocite, pyrite, and sphalerite, high levels of acidity may be present if sulfide dissolution is not balanced by the presence of acid-neutralizing carbonate minerals. Some of the vanadium-bearing deposit types, particularly some SSV and black-shale deposits, contain appreciable amounts of carbonate minerals, which lowers the acid-generation potential.Vanadium is a micronutrient with a postulated requirement for humans of less than 10 micrograms per day, which can be met through dietary intake. Primary and secondary drinking water regulations for vanadium are not currently in place in the United States. Vanadium toxicity is thought to result from an intake of more than 10 to 20 milligrams per day. Vanadium is essential for some biological processes and organisms. For example, some nitrogen-fixing bacteria require vanadium for producing enzymes necessary to convert nitrogen from the atmosphere into ammonia, which is a more biologically accessible form of nitrogen.

Hydrogen, lithium, and lithium hydride production

DOEpatents

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

2014-03-25

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

Uranium Hydride Nucleation and Growth Model FY'16 ESC Annual Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hill, Mary Ann; Richards, Andrew Walter; Holby, Edward F.

2016-12-20

Uranium hydride corrosion is of great interest to the nuclear industry. Uranium reacts with water and/or hydrogen to form uranium hydride which adversely affects material performance. Hydride nucleation is influenced by thermal history, mechanical defects, oxide thickness, and chemical defects. Information has been gathered from past hydride experiments to formulate a uranium hydride model to be used in a Canned Subassembly (CSA) lifetime prediction model. This multi-scale computer modeling effort started in FY’13, and the fourth generation model is now complete. Additional high-resolution experiments will be run to further test the model.

In situ hydride formation in titanium during focused ion milling.

PubMed

Ding, Rengen; Jones, Ian P

2011-01-01

It is well known that titanium and its alloys are sensitive to electrolytes and thus hydrides are commonly observed in electropolished foils. In this study, focused ion beam (FIB) milling was used to prepare thin foils of titanium and its alloys for transmission electron microscopy. The results show the following: (i) titanium hydrides were observed in pure titanium, (ii) the preparation of a bulk sample in water or acid solution resulted in the formation of more hydrides and (iii) FIB milling aids the precipitation of hydrides, but there were never any hydrides in Ti64 and Ti5553.

Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Auer, Henry; Guehne, Robin; Bertmer, Marko

Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms withmore » d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.« less

17. VIEW OF HYDRIDING SYSTEM IN BUILDING 881. THE HYDRIDING ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

17. VIEW OF HYDRIDING SYSTEM IN BUILDING 881. THE HYDRIDING SYSTEM WAS PART OF THE FAST ENRICHED URANIUM RECOVERY PROCESS. (11/11/59) - Rocky Flats Plant, General Manufacturing, Support, Records-Central Computing, Southern portion of Plant, Golden, Jefferson County, CO

Rechargeable metal hydrides for spacecraft application

NASA Technical Reports Server (NTRS)

Perry, J. L.

1988-01-01

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

Metal hydride compositions and lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Kwo; Nei, Jean

Heterogeneous metal hydride (MH) compositions comprising a main region comprising a first metal hydride and a secondary region comprising one or more additional components selected from the group consisting of second metal hydrides, metals, metal alloys and further metal compounds are suitable as anode materials for lithium ion cells. The first metal hydride is for example MgH.sub.2. Methods for preparing the composition include coating, mechanical grinding, sintering, heat treatment and quenching techniques.

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

Vanadium Recovery from Oil Fly Ash by Carbon Removal and Roast-Leach Process

NASA Astrophysics Data System (ADS)

Jung, Myungwon; Mishra, Brajendra

2018-02-01

This research mainly focuses on the recovery of vanadium from oil fly ash by carbon removal and the roast-leach process. The oil fly ash contained about 85% unburned carbon and 2.2% vanadium by weight. A vanadium-enriched product was obtained after carbon removal, and the vanadium content of this product was 19% by weight. Next, the vanadium-enriched product was roasted with sodium carbonate to convert vanadium oxides to water-soluble sodium metavanadate. The roasted sample was leached with water at 60°C, and the extraction percentage of vanadium was about 92% by weight. Several analytical techniques, such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), x-ray fluorescence (XRF), and thermogravimetric and differential thermal analysis (TG-DTA), were utilized for sample analyses. Thermodynamic modeling was also conducted with HSC chemistry software to explain the experimental results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Qingtao; Li, Liyu; Nie, Zimin

We will show a new method to differentiate the vanadium transport from concentration gradient and that from electric field. Flow batteries with vanadium and iron redox couples as the electro-active species were employed to investigate the transport behavior of vanadium ions in the presence of electric field. It was shown that electric field accelerated the positive-to-negative and reduced the negative-to-positive vanadium ions transport in charge process and affected the vanadium ions transport in an opposite way in discharge process. In addition, a method was designed to differentiate the concentration gradient-driven vanadium ions diffusion and electric field-driven vanadium ions migration. Simplifiedmore » mathematical model was established to simulate the vanadium ions transport in real charge-discharge operation of flow battery. The concentration gradient diffusion coefficients and electric-migration coefficients of V2+, V3+, VO2+, and VO2+ across Nafion membrane were obtained by fitting the experimental data.« less

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE PAGES

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang; ...

2017-08-02

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

Development of a component design tool for metal hydride heat pumps

NASA Astrophysics Data System (ADS)

Waters, Essene L.

Given current demands for more efficient and environmentally friendly energy sources, hydrogen based energy systems are an increasingly popular field of interest. Within the field, metal hydrides have become a prominent focus of research due to their large hydrogen storage capacity and relative system simplicity and safety. Metal hydride heat pumps constitute one such application, in which heat and hydrogen are transferred to and from metal hydrides. While a significant amount of work has been done to study such systems, the scope of materials selection has been quite limited. Typical studies compare only a few metal hydride materials and provide limited justification for the choice of those few. In this work, a metal hydride component design tool has been developed to enable the targeted down-selection of an extensive database of metal hydrides to identify the most promising materials for use in metal hydride thermal systems. The material database contains over 300 metal hydrides with various physical and thermodynamic properties included for each material. Sub-models for equilibrium pressure, thermophysical data, and default properties are used to predict the behavior of each material within the given system. For a given thermal system, this tool can be used to identify optimal materials out of over 100,000 possible hydride combinations. The selection tool described herein has been applied to a stationary combined heat and power system containing a high-temperature proton exchange membrane (PEM) fuel cell, a hot water tank, and two metal hydride beds used as a heat pump. A variety of factors can be used to select materials including efficiency, maximum and minimum system pressures, pressure difference, coefficient of performance (COP), and COP sensitivity. The targeted down-selection of metal hydrides for this system focuses on the system's COP for each potential pair. The values of COP and COP sensitivity have been used to identify pairs of highest interest for use in this application. The metal hydride component design tool developed in this work selects between metal hydride materials on an unprecedented scale. It can be easily applied to other hydrogen-based thermal systems, making it a powerful and versatile tool.

Thirty years through vanadium chemistry.

PubMed

Costa Pessoa, J

2015-06-01

The relevance of vanadium in biological systems is known for many years and vanadium-based catalysts have important industrial applications, however, till the beginning of the 80s research on vanadium chemistry and biochemistry did not receive much attention from the scientific community. The understanding of the broad bioinorganic implications resulting from the similarities between phosphate and vanadate(V) and the discovery of vanadium dependent enzymes gave rise to an enormous increase in interest in the chemistry and biological relevance of vanadium. Thereupon the last 30years corresponded to a period of enormous research effort in these fields, as well as in medicinal applications of vanadium and in the development of catalysts for use in fine-chemical synthesis, some of these inspired by enzymatic active sites. Since the 80s my group in collaboration with others made contributions, described throughout this text, namely in the understanding of the speciation of vanadium compounds in aqueous solution and in biological fluids, and to the transport of vanadium compounds in blood plasma and their uptake by cells. Several new types of vanadium compounds were also synthesized and characterized, with applications either as prospective therapeutic drugs or as homogeneous or heterogenized catalysts for the production of fine chemicals. The developments made are described also considering the international context of the evolution of the knowledge in the chemistry and bioinorganic chemistry of vanadium compounds during the last 30years. This article was compiled based on the Vanadis Award presentation at the 9th International Vanadium Symposium. Copyright © 2015 Elsevier Inc. All rights reserved.

Azimuthally anisotropic hydride lens structures in Zircaloy 4 nuclear fuel cladding: High-resolution neutron radiography imaging and BISON finite element analysis

NASA Astrophysics Data System (ADS)

Lin, Jun-Li; Zhong, Weicheng; Bilheux, Hassina Z.; Heuser, Brent J.

2017-12-01

High-resolution neutron radiography has been used to image bulk circumferential hydride lens particles in unirradiated Zircaloy 4 tubing cross section specimens. Zircaloy 4 is a common light water nuclear reactor (LWR) fuel cladding; hydrogen pickup, hydride formation, and the concomitant effect on the mechanical response are important for LWR applications. Ring cross section specimens with three hydrogen concentrations (460, 950, and 2830 parts per million by weight) and an as-received reference specimen were imaged. Azimuthally anisotropic hydride lens particles were observed at 950 and 2830 wppm. The BISON finite element analysis nuclear fuel performance code was used to model the system elastic response induced by hydride volumetric dilatation. The compressive hoop stress within the lens structure becomes azimuthally anisotropic at high hydrogen concentrations or high hydride phase fraction. This compressive stress anisotropy matches the observed lens anisotropy, implicating the effect of stress on hydride formation as the cause of the observed lens azimuthal asymmetry. The cause and effect relation between compressive stress and hydride lens anisotropy represents an indirect validation of a key BISON output, the evolved hoop stress associated with hydride formation.

[The vanadium compounds: chemistry, synthesis, insulinomimetic properties].

PubMed

Fedorova, E V; Buriakina, A V; Vorob'eva, N M; Baranova, N I

2014-01-01

The review considers the biological role of vanadium, its participation in various processes in humans and other mammals, and the anti-diabetic effect of its compounds. Vanadium salts have persistent hypoglycemic and antihyperlipidemic effects and reduce the probability of secondary complications in animals with experimental diabetes. The review contains a detailed description of all major synthesized vanadium complexes having antidiabetic activity. Currently, vanadium complexes with organic ligands are more effective and safer than the inorganic salts. Despite the proven efficacy of these compounds as the anti-diabetic agents in animal models, only one organic complex of vanadium is currently under the second phase of clinical trials. All of the considered data suggest that vanadium compound are a new promising class of drugs in modern pharmacotherapy of diabetes.

Method of producing a chemical hydride

DOEpatents

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

2007-11-13

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

49 CFR 173.311 - Metal hydride storage systems.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 2 2013-10-01 2013-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage systems...

49 CFR 173.311 - Metal hydride storage systems.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 2 2011-10-01 2011-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage systems...

49 CFR 173.311 - Metal hydride storage systems.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 2 2014-10-01 2014-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage systems...

Bioleaching of vanadium from barren stone coal and its effect on the transition of vanadium speciation and mineral phase

NASA Astrophysics Data System (ADS)

Wang, Xin; Lin, Hai; Dong, Ying-bo; Li, Gan-yu

2018-03-01

This study determined the optimal conditions required to obtain maximum vanadium extraction and examined the transition of mineral phases and vanadium speciation during the bioleaching process. Parameters including the initial pH value, initial Fe2+ concentration, solid load, and inoculum quantity were examined. The results revealed that 48.92wt% of the vanadium was extracted through bioleaching under optimal conditions. Comparatively, the chemical leaching yield (H2SO4, pH 2.0) showed a slower and milder increase in vanadium yield. The vanadium bioleaching yield was 35.11wt% greater than the chemical leaching yield. The Community Bureau of Reference (BCR) sequential extraction results revealed that 88.62wt% of vanadium existed in the residual fraction. The bacteria substantially changed the distribution of the vanadium speciation during the leaching process, and the residual fraction decreased to 48.44wt%. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) results provided evidence that the crystal lattice structure of muscovite was destroyed by the bacteria.

Why Antidiabetic Vanadium Complexes are Not in the Pipeline of "Big Pharma" Drug Research? A Critical Review.

PubMed

Scior, Thomas; Guevara-Garcia, Jose Antonio; Do, Quoc-Tuan; Bernard, Philippe; Laufer, Stefan

2016-01-01

Public academic research sites, private institutions as well as small companies have made substantial contributions to the ongoing development of antidiabetic vanadium compounds. But why is this endeavor not echoed by the globally operating pharmaceutical companies, also known as "Big Pharma"? Intriguingly, today's clinical practice is in great need to improve or replace insulin treatment against Diabetes Mellitus (DM). Insulin is the mainstay therapeutically and economically. So, why do those companies develop potential antidiabetic drug candidates without vanadium (vanadium- free)? We gathered information about physicochemical and pharmacological properties of known vanadium-containing antidiabetic compounds from the specialized literature, and converted the data into explanations (arguments, the "pros and cons") about the underpinnings of antidiabetic vanadium. Some discoveries were embedded in chronological order while seminal reviews of the last decade about the Medicinal chemistry of vanadium and its history were also listed for further understanding. In particular, the concepts of so-called "noncomplexed or free" vanadium species (i.e. inorganic oxido-coordinated species) and "biogenic speciation" of antidiabetic vanadium complexes were found critical and subsequently documented in more details to answer the question.

Physiological and anthocyanin biosynthesis genes response induced by vanadium stress in mustard genotypes with distinct photosynthetic activity.

PubMed

Imtiaz, Muhammad; Mushtaq, Muhammad Adnan; Nawaz, Muhammad Amjad; Ashraf, Muhammad; Rizwan, Muhammad Shahid; Mehmood, Sajid; Aziz, Omar; Rizwan, Muhammad; Virk, Muhammad Safiullah; Shakeel, Qaiser; Ijaz, Raina; Androutsopoulos, Vasilis P; Tsatsakis, Aristides M; Coleman, Michael D

2018-06-13

The present study aimed to elucidate the photosynthetic performance, antioxidant enzyme activities, anthocyanin contents, anthocyanin biosynthetic gene expression, and vanadium uptake in mustard genotypes (purple and green) that differ in photosynthetic capacity under vanadium stress. The results indicated that vanadium significantly reduced photosynthetic activity in both genotypes. The activities of the antioxidant enzymes were increased significantly in response to vanadium in both genotypes, although the purple exhibited higher. The anthocyanin contents were also reduced under vanadium stress. The anthocyanin biosynthetic genes were highly expressed in the purple genotype, notably the genes TT8, F3H, and MYBL2 under vanadium stress. The results indicate that induction of TT8, F3H, and MYBL2 genes was associated with upregulation of the biosynthetic genes required for higher anthocyanin biosynthesis in purple compared with the green mustard. The roots accumulated higher vanadium than shoots in both mustard genotypes. The results indicate that the purple mustard had higher vanadium tolerance. Copyright © 2018 Elsevier B.V. All rights reserved.

Homogeneous hydride formation path in α-Zr: Molecular dynamics simulations with the charge-optimized many-body potential

DOE PAGES

Zhang, Yongfeng; Bai, Xian-Ming; Yu, Jianguo; ...

2016-06-01

A formation path for homogeneous γ hydride formation in hcp α-Zr, from solid solution to the ζ and then the γ hydride, was demonstrated using molecular static calculations and molecular dynamic simulations with the charge-optimized many-body (COMB) potential. Hydrogen has limited solubility in α-Zr. Once the solubility limit is exceeded, the stability of solid solution gives way to that of coherent hydride phases such as the ζ hydride by planar precipitation of hydrogen. At finite temperatures, the ζ hydride goes through a partial hcp-fcc transformation via 1/3 <1¯100> slip on the basal plane, and transforms into a mixture of γmore » hydride and α-Zr. In the ζ hydride, slip on the basal plane is favored thermodynamically with negligible barrier, and is therefore feasible at finite temperatures without mechanical loading. The transformation process involves slips of three equivalent shear partials, in contrast to that proposed in the literature where only a single shear partial was involved. The adoption of multiple slip partials minimizes the macroscopic shape change of embedded hydride clusters and the shear strain accumulation in the matrix, and thus reduces the overall barrier needed for homogeneous γ hydride formation. In conclusion, this formation path requires finite temperatures for hydrogen diffusion without mechanical loading. Therefore, it should be effective at the cladding operating conditions.« less

A Twist on Facial Selectivity of Hydride Reductions of Cyclic Ketones: Twist-Boat Conformers in Cyclohexanone, Piperidone, and Tropinone Reactions

PubMed Central

2015-01-01

The role of twist-boat conformers of cyclohexanones in hydride reductions was explored. The hydride reductions of a cis-2,6-disubstituted N-acylpiperidone, an N-acyltropinone, and tert-butylcyclohexanone by lithium aluminum hydride and by a bulky borohydride reagent were investigated computationally and compared to experiment. Our results indicate that in certain cases, factors such as substrate conformation, nucleophile bulkiness, and remote steric features can affect stereoselectivity in ways that are difficult to predict by the general Felkin–Anh model. In particular, we have calculated that a twist-boat conformation is relevant to the reactivity and facial selectivity of hydride reduction of cis-2,6-disubstituted N-acylpiperidones with a small hydride reagent (LiAlH4) but not with a bulky hydride (lithium triisopropylborohydride). PMID:25372509

Hydride affinity scale of various substituted arylcarbeniums in acetonitrile.

PubMed

Zhu, Xiao-Qing; Wang, Chun-Hua

2010-12-23

Combined with the integral equation formalism polarized continuum model (IEFPCM), the hydride affinities of 96 various acylcarbenium ions in the gas phase and CH(3)CN were estimated by using the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-311++G(2df,2p)//B3LYP/6-31+G(d), and BLYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) methods for the first time. The results show that the combination of the BLYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) method and IEFPCM could successfully predict the hydride affinities of arylcarbeniums in MeCN with a precision of about 3 kcal/mol. On the basis of the calculated results from the BLYP method, it can be found that the hydride affinity scale of the 96 arylcarbeniums in MeCN ranges from -130.76 kcal/mol for NO(2)-PhCH(+)-CN to -63.02 kcal/mol for p-(Me)(2)N-PhCH(+)-N(Me)(2), suggesting most of the arylcarbeniums are good hydride acceptors. Examination of the effect of the number of phenyl rings attached to the carbeniums on the hydride affinities shows that the increase of the hydride affinities takes place linearly with increasing number of benzene rings in the arylcarbeniums. Analyzing the effect of the substituents on the hydride affinities of arylcarbeniums indicates that electron-donating groups decrease the hydride affinities and electron-withdrawing groups show the opposite effect. The hydride affinities of arylcarbeniums are linearly dependent on the sum of the Hammett substituent parameters σ(p)(+). Inspection of the correlation of the solution-phase hydride affinities with gas-phase hydride affinities and aqueous-phase pK(R)(+) values reveals a remarkably good correspondence of ΔG(H(-)A)(R(+)) with both the gas-phase relative hydride affinities only if the α substituents X have no large electron-donating or -withdrawing properties and the pK(R)(+) values even though the media are dramatically different. The solution-phase hydride affinities also have a linear relationship with the electrophilicity parameter E, and this dependence can certainly serve as one of the most effective ways to estimate the new E values from ΔG(H(-)A)(R(+)) or vice versa. Combining the hydride affinities and the reduction potentials of the arylcarbeniums, we obtained the bond homolytic dissociation Gibbs free energy changes of the C-H bonds in the corresponding hydride adducts in acetonitrile, ΔG(HD)(RH), and found that the effects of the substituent on ΔG(HD)(RH) are very small. Simple thermodynamic analytic platforms for the three C-H cleavage modes were constructed. It is evident that the present work would be helpful in understanding the nature of the stabilities of the carbeniums and mechanisms of the hydride transfers between carbeniums and other hydride donors.

Conversion and origin of normal and abnormal temperature dependences of kinetic isotope effect in hydride transfer reactions.

PubMed

Zhu, Xiao-Qing; Li, Xiu-Tao; Han, Su-Hui; Mei, Lian-Rui

2012-05-18

The effects of substituents on the temperature dependences of kinetic isotope effect (KIE) for the reactions of the hydride transfer from the substituted 5-methyl-6-phenyl-5,6-dihydrophenanthridine (G-PDH) to thioxanthylium (TX(+)) in acetonitrile were examined, and the results show that the temperature dependences of KIE for the hydride transfer reactions can be converted by adjusting the nature of the substituents in the molecule of the hydride donor. In general, electron-withdrawing groups can make the KIE to have normal temperature dependence, but electron-donating groups can make the KIE to have abnormal temperature dependence. Thermodynamic analysis on the possible pathways of the hydride transfer from G-PDH to TX(+) in acetonitrile suggests that the transfers of the hydride anion in the reactions are all carried out by the concerted one-step mechanism whether the substituent is an electron-withdrawing group or an electron-donating group. But the examination of Hammett-type free energy analysis on the hydride transfer reactions supports that the concerted one-step hydride transfer is not due to an elementary chemical reaction. The experimental values of KIE at different temperatures for the hydride transfer reactions were modeled by using a kinetic equation formed according to a multistage mechanism of the hydride transfer including a returnable charge-transfer complex as the reaction intermediate; the real mechanism of the hydride transfer and the root that why the temperature dependences of KIE can be converted as the nature of the substituents are changed were discovered.

Commercialization of the Chevron FCC vanadium trap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, J.V.; Kuehler, C.W.; Krishna, A.S.

1995-09-01

Vanadium, present to varying degrees in FCC feed, deposits on the catalyst virtually quantitatively in the cracking process. In resid operations, vanadium levels on catalyst can reach 10,000 ppm at typical catalyst make-up rates. Once on the catalyst, vanadium destroys the zeolite and restricts access to active sites. This reduces catalyst activity. A vanadium trap is a material that when introduced into the catalyst inventory selectively reacts with migrating vanadium, thus protecting the zeolite and other active components of the catalyst. The trap may be incorporated into the catalyst, or introduced as a separate particle. Only a limited amount ofmore » trap can be incorporated into the catalyst without limiting the amount of zeolite that can be included. Gulf began development of a vanadium trap during the early 1980`s. The work produced a variety of promising materials whose use as vanadium traps was subsequently patented. The work ultimately led to a formulation with a phase very active for trapping vanadium while still quite sulfur tolerant. Based on these results, an extensive pilot plant evaluation was undertaken by Chevron after the Chevron-Gulf merger to better simulate commercial operation. The paper describes pilot plant tests as well as 3 commercial tests of this vanadium trap.« less

Spatial distribution of vanadium and microbial community responses in surface soil of Panzhihua mining and smelting area, China.

PubMed

Cao, Xuelong; Diao, Muhe; Zhang, Baogang; Liu, Hui; Wang, Song; Yang, Meng

2017-09-01

Spatial distribution of vanadium in surface soils from different processing stages of vanadium-bearing titanomagnetite in Panzhihua mining and smelting area (China) as well as responses of microbial communities including bacteria and fungi to vanadium were investigated by fieldwork and laboratory incubation experiment. The vanadium contents in this region ranged from 149.3 to 4793.6 mg kg -1 , exceeding the soil background value of vanadium in China (82 mg kg -1 ) largely. High-throughput DNA sequencing results showed bacterial communities from different manufacturing locations were quite diverse, but Bacteroidetes and Proteobacteria were abundant in all samples. The contents of organic matter, available P, available S and vanadium had great influences on the structures of bacterial communities in soils. Bacterial communities converged to similar structure after long-term (240 d) cultivation with vanadium containing medium, dominating by bacteria which can tolerate or reduce toxicities of heavy metals. Fungal diversities decreased after cultivation, but Ascomycota and Ciliophora were still the most abundant phyla as in the original soil samples. Results in this study emphasize the urgency of investigating vanadium contaminations in soils and provide valuable information on how vanadium contamination influences bacterial and fungal communities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Controlled coordination in vanadium(V) dimethylhydrazido compounds.

PubMed

Sakuramoto, Takashi; Moriuchi, Toshiyuki; Hirao, Toshikazu

2016-11-01

The vanadium(V) dimethylhydrazido compounds were structurally characterized to elucidate the effect of the alkoxide ligands in the coordination environment of vanadium(V) hydrazido center. The single-crystal X-ray structure determination of the vanadium(V) dimethylhydrazido compound with isopropoxide ligands revealed a dimeric structure with the V(1)-N(1) distance of 1.680(5)Å, in which each vanadium atom is coordinated in a distorted trigonal-bipyramidal geometry (τ 5 =0.81) with the hydrazido and bridging isopropoxide ligands in the apical positions. On the contrary, nearly tetrahedral arrangement around the vanadium metal center (τ 4 =0.06) with the V(1)-N(1) distance of 1.660(2)Å was observed in the vanadium(V) dimethylhydrazido compound with tert-butoxide ligands. The introduction of the 2,2',2″-nitrilotriethoxide ligand led to a pseudo-trigonal-bipyramidal geometry (τ 5 =0.92) at the vanadium center with the V(1)-N(1) distance of 1.691(5)Å, wherein vanadium atom is pulled out of the plane formed by the nitrilotriethoxide oxygen atoms in the direction of the hydrazido nitrogen. The coordination from the apical ligand in the vanadium(V) dimethylhydrazido compound was found to result in the longer V(1)-N(1) distance. Copyright © 2016 Elsevier Inc. All rights reserved.

The toxicity of vanadium on gastrointestinal, urinary and reproductive system, and its influence on fertility and fetuses malformations.

PubMed

Wilk, Aleksandra; Szypulska-Koziarska, Dagmara; Wiszniewska, Barbara

2017-09-25

Vanadium is a transition metal that has a unique and beneficial effect on both humans and animals. For many years, studies have suggested that vanadium is an essential trace element. Its biological properties are of interest due to its therapeutic potential, including in the treatment of diabetes mellitus. Vanadium deficiencies can lead to a range of pathologies. However, excessive concentration of this metal can cause irreversible damage to various tissues and organs. Vanadium toxicity mainly manifests in gastrointestinal symptoms, including diarrhea, vomiting, and weight reduction. Vanadium also exhibits hepatotoxic and nephrotoxic properties, including glomerulonephritis and pyelonephritis. Vanadium compounds may also lead to partial degeneration of the seminiferous epithelium of the seminiferous tubules in the testes and can affect male fertility. This paper describes the harmful effects of vanadium on the morphology and physiology of both animal and human tissues, including the digestive system, the urinary tract, and the reproductive system. What is more, the following study includes data concerning the correlation between the above-mentioned metal and its influence on fertility and fetus malformations. Additionally, this research identifies the doses of vanadium which lead to pathological alterations becoming visible within tissues. Moreover, this study includes information about the protective efficacy of some substances in view of the toxicity of vanadium.

SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS..

EPA Science Inventory

Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride ...

Storing hydrogen in the form of light alloy hydrides

NASA Technical Reports Server (NTRS)

Freund, E.; Gillerm, C.

1981-01-01

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

Assessment of Dephosphorization During Vanadium Extraction Process in Converter

NASA Astrophysics Data System (ADS)

Chen, Lian; Diao, Jiang; Wang, Guang; Xie, Bing

2018-06-01

Dephosphorization during the vanadium extraction process in the converter was studied. The effects of the slag basicity and FeO content on the dephosphorization and the mineral phases in the phosphorus-containing vanadium slag are discussed. The results show that removal of phosphorus from the hot metal during the vanadium extraction process can be achieved by adding lime into the vanadium extraction converter. The highest dephosphorization rate was obtained at slag basicity of 1.93. The phosphorus distribution ratio increased with increasing FeO content up to 16-18% but decreased thereafter. Vanadium was present in the slag only as spinels rather than calcium vanadate. Phosphorus was still present in the form of calcium phosphate eutectic in calcium silicate. The present work proves that the vanadium extraction and dephosphorization processes are nonconflicting reactions.

Synthesis, Characterization, Antioxidant Status, and Toxicity Study of Vanadium-Rutin Complex in Balb/c Mice.

PubMed

Roy, Souvik; Majumdar, Sumana; Singh, Amit Kumar; Ghosh, Balaram; Ghosh, Nilanjan; Manna, Subhadip; Chakraborty, Tania; Mallick, Sougato

2015-08-01

A new trend was developed for the formation of a complex between vanadium and flavonoid derivatives in order to increase the intestinal absorption and to reduce the toxicity of vanadium compounds. The vanadium-rutin complex was characterized by several spectroscopic techniques like ultraviolet (UV)-visible, Fourier transform infrared (FTIR), NMR, mass spectrometry, and microscopic evaluation by scanning electron microscopy. The mononuclear complex was formed by the interaction between vanadium and rutin with 1:2 metal to ligand stoichiometry. Antioxidant activity of the complex was evaluated by 1,1-diphenyl-2 picrylhydrazyl, ferric-reducing power, and 2,2'-azin-obis 3-ethylbenzothiazoline-6-sulphonic acid methods. It was shown that radical scavenging activity and ferric-reducing potential of free rutin was lower as compared with vanadium-rutin complex. The study was also investigated for oral acute toxicity and 28 days repeated oral subacute toxicity study of vanadium-rutin complex in balb/c mice. The vanadium-rutin complex showed mortality at a dose of 120 mg/kg in the balb/c mice. In 28 days repeated oral toxicity study, vanadium-rutin complex was administered to both sex of balb/c mice at dose levels of 90, 45, and 20 ppm, respectively. In addition, subacute toxicity study of vanadium-rutin complex (at 90 ppm dose level) showed increase levels of white blood cell (WBC), total bilirubin, alanine aminotransferase (ALT), alkaline phosphatase (ALP), aspartate aminotransferase (AST), creatinine, and blood urea nitrogen and decrease level of total protein (TP) as compared with control group. Histopathological study of vanadium-rutin showed structural alteration in the liver, kidney, and stomach at 90 ppm dose level. No observed toxic level of vanadium-rutin complex at 20 ppm dose level could be good for further study.

Vanadium exposure-induced striatal learning and memory alterations in rats.

PubMed

Sun, Liping; Wang, Keyue; Li, Yan; Fan, Qiyuan; Zheng, Wei; Li, Hong

2017-09-01

Occupational and environmental exposure to vanadium has been associated with toxicities in reproductive, respiratory, and cardiovascular systems. The knowledge on whether and how vanadium exposure caused neurobehavioral changes remains incomplete. This study was designed to investigate the changes in learning and memory following drinking water exposure to vanadium, and to conduct the preliminary study on underlying mechanisms. Male Sprague-Dawley rats were exposed to vanadium dissolved in drinking water at the concentration of 0.0, 0.5, 1.0 and 2.0g/L, as the control, low-, medium-, and high- dose groups, respectively, for 12 weeks. The results by the Morris water maze test showed that the time for the testing animal to find the platform in the high exposed group was increased by 82.9% and 49.7%, as compared to animals in control and low-dose groups (p<0.05). There were significantly fewer rats in the medium- and high- dose groups than in the control group who were capable of crossing the platform (p<0.05). Quantitation of vanadium by atomic absorption spectrophotometry revealed a significant dose-dependent accumulation of vanadium in striatum (r=0.931, p<0.01). Histopathological examination further demonstrated a degenerative damage in vanadium-exposed striatum. Interestingly, with the increase of the dose of vanadium, the contents of neurotransmitter ACh, 5-HT and GABA in the striatum increased; however, the levels of Syn1 was significantly reduced in the exposed groups compared with controls (p<0.05). These data suggest that vanadium exposure apparently reduces the animals' learning ability. This could be due partly to vanadium's accumulation in striatum and the ensuing toxicity to striatal structure and synaptic plasticity. Further research is warranted for mechanistic understanding of vanadium-induced neurotoxicity. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrogen storage materials and method of making by dry homogenation

DOEpatents

Jensen, Craig M.; Zidan, Ragaiy A.

2002-01-01

Dry homogenized metal hydrides, in particular aluminum hydride compounds, as a material for reversible hydrogen storage is provided. The reversible hydrogen storage material comprises a dry homogenized material having transition metal catalytic sites on a metal aluminum hydride compound, or mixtures of metal aluminum hydride compounds. A method of making such reversible hydrogen storage materials by dry doping is also provided and comprises the steps of dry homogenizing metal hydrides by mechanical mixing, such as be crushing or ball milling a powder, of a metal aluminum hydride with a transition metal catalyst. In another aspect of the invention, a method of powering a vehicle apparatus with the reversible hydrogen storage material is provided.

Porous metal hydride composite and preparation and uses thereof

DOEpatents

Steyert, W.A.; Olsen, C.E.

1980-03-12

A composite formed from large pieces of aggregate formed from (1) metal hydride (or hydride-former) powder and (2) either metal powder or plastic powder or both is prepared. The composite has large macroscopic interconnected pores (much larger than the sizes of the powders which are used) and will have a very fast heat transfer rate and low windage loss. It will be useful, for example, in heat engines, hydrogen storage devices, and refrigerator components which depend for their utility upon both a fast rate of hydriding and dehydriding. Additionally, a method of preparing the composite and a method of increasing the rates of hydriding and dehydriding of metal hydrides are also given.

Porous metal hydride composite and preparation and uses thereof

DOEpatents

Steyert, William A.; Olsen, Clayton E.

1982-01-01

A composite formed from large pieces of aggregate formed from (1) metal hydride (or hydride-former) powder and (2) either metal powder or plastic powder or both is prepared. The composite has large macroscopic interconnected pores (much larger than the sizes of the powders which are used) and will have a very fast heat transfer rate and low windage loss. It will be useful, for example, in heat engines, hydrogen storage devices, and refrigerator components which depend for their utility upon both a fast rate of hydriding and dehydriding. Additionally, a method of preparing the composite and a method of increasing the rates of hydriding and dehydriding of metal hydrides are also given.

Gas-controlled dynamic vacuum insulation with gas gate

DOEpatents

Benson, David K.; Potter, Thomas F.

1994-06-07

Disclosed is a dynamic vacuum insulation comprising sidewalls enclosing an evacuated chamber and gas control means for releasing hydrogen gas into a chamber to increase gas molecule conduction of heat across the chamber and retrieving hydrogen gas from the chamber. The gas control means includes a metal hydride that absorbs and retains hydrogen gas at cooler temperatures and releases hydrogen gas at hotter temperatures; a hydride heating means for selectively heating the metal hydride to temperatures high enough to release hydrogen gas from the metal hydride; and gate means positioned between the metal hydride and the chamber for selectively allowing hydrogen to flow or not to flow between said metal hydride and said chamber.

Gas-controlled dynamic vacuum insulation with gas gate

DOEpatents

Benson, D.K.; Potter, T.F.

1994-06-07

Disclosed is a dynamic vacuum insulation comprising sidewalls enclosing an evacuated chamber and gas control means for releasing hydrogen gas into a chamber to increase gas molecule conduction of heat across the chamber and retrieving hydrogen gas from the chamber. The gas control means includes a metal hydride that absorbs and retains hydrogen gas at cooler temperatures and releases hydrogen gas at hotter temperatures; a hydride heating means for selectively heating the metal hydride to temperatures high enough to release hydrogen gas from the metal hydride; and gate means positioned between the metal hydride and the chamber for selectively allowing hydrogen to flow or not to flow between said metal hydride and said chamber. 25 figs.

The free-energy barrier to hydride transfer across a dipalladium complex

DOE PAGES

Ramirez-Cuesta, Anibal J.

2015-01-01

We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)(2)CH2}(2)Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model formore » the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.« less

In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

DOE PAGES

Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.; ...

2017-02-20

The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. Furthermore, these experimental resultsmore » can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.« less

METHOD OF FABRICATING A URANIUM-ZIRCONIUM HYDRIDE REACTOR CORE

DOEpatents

Weeks, I.F.; Goeddel, W.V.

1960-03-22

A method is described of evenly dispersing uranlum metal in a zirconium hydride moderator to produce a fuel element for nuclear reactors. According to the invention enriched uranium hydride and zirconium hydride powders of 200 mesh particle size are thoroughly admixed to form a mixture containing 0.1 to 3% by weight of U/sup 235/ hydride. The mixed powders are placed in a die and pressed at 100 tons per square inch at room temperature. The resultant compacts are heated in a vacuum to 300 deg C, whereby the uranium hydride deoomposes into uranium metal and hydrogen gas. The escaping hydrogen gas forms a porous matrix of zirconium hydride, with uramum metal evenly dispersed therethrough. The advantage of the invention is that the porosity and uranium distribution of the final fuel element can be more closely determined and controlled than was possible using prior methods of producing such fuel ele- ments.

Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution.

PubMed

Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S

2018-02-01

The ability of neutral transition-metal hydrides to serve as a source of hydride ion H - or proton H + is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H δ- ⋅⋅⋅ δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H δ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced magnetization in VxFe3-xO4 nanoparticles

NASA Astrophysics Data System (ADS)

Pool, V. L.; Kleb, M. T.; Chorney, C. L.; Arenholz, E.; Idzerda, Y. U.

2015-12-01

Nanoparticles of VxFe3-xO4 with up to 33% vanadium doping (x=0 to 1) and a 9 nm diameter are investigated in order to determine the site preference of the vanadium and the magnetic behavior of the nanoparticles. The iron and vanadium L23-edge X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (MCD) spectra are used to identify that vanadium initially substitutes into the tetrahedral iron site as V3+ and that the average iron moment is observed to increase with vanadium concentration up to 12.5% (x=.375). When the vanadium incorporation exceeds 12.5%, the XAS and MCD show that the vanadium begins substituting as V2+ in the octahedral coordination. This coincides with a rapid reduction of the average moment to zero by 25% (x=.75). The frequency-dependent alternating-current magnetic susceptibility (ACMS) displays a substantial increase in blocking temperature with vanadium concentration and indicated substantial variation in the strength of inter-particle interactions.

Investigation on the fates of vanadium and nickel during co-gasification of petroleum coke with biomass.

PubMed

Li, Jiazhou; Wang, Xiaoyu; Wang, Bing; Zhao, Jiantao; Fang, Yitian

2018-06-01

This study investigates the volatilization behaviors and mineral transformation of vanadium and nickel during co-gasification of petroleum coke with biomass. Moreover, the evolution of occurrence modes of vanadium and nickel was also determined by the method of sequential chemical extraction. The results show that the volatilities of vanadium and nickel in petroleum coke have a certain level of growth with an increase in the temperature. With the addition of biomass, their volatilities both show an obvious decrease. Organic matter and stable forms are the dominant chemical forms of vanadium and nickel. After gasification, organic-bound vanadium and nickel decompose completely and convert into other chemical forms. The crystalline phases of vanadium trioxide, coulsonite, nickel sulfide, and elemental nickel are clearly present in petroleum coke and biomass gasification ashes. When the addition of biomass reaches 60 wt%, the diffraction peaks of orthovanadate are found while that of vanadium trioxide disappear. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of Ultrasound-Assisted and Regular Leaching of Vanadium and Chromium from Roasted High Chromium Vanadium Slag

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Gao, Huiyang; Liu, Yajing; Zheng, Xiaole; Xue, Xiangxin

2018-02-01

Ultrasound-assisted leaching (UAL) was used for vanadium and chromium leaching from roasted material obtained by the calcification roasting of high-chromium-vanadium slag. UAL was compared with regular leaching. The effect of the leaching time and temperature, acid concentration, and liquid-solid ratio on the vanadium and chromium leaching behaviors was investigated. The UAL mechanism was determined from particle-size-distribution and microstructure analyses. UAL decreased the reaction time and leaching temperature significantly. Furthermore, 96.67% vanadium and less than 1% chromium were leached at 60°C for 60 min with 20% H2SO4 at a liquid-solid ratio of 8, which was higher than the maximum vanadium leaching rate of 90.89% obtained using regular leaching at 80°C for 120 min. Ultrasonic waves broke and dispersed the solid sample because of ultrasonic cavitation, which increased the contact area of the roasted sample and the leaching medium, the solid-liquid mass transfer, and the vanadium leaching rate.

Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review.

PubMed

Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael; Kausar, Nadeem; Mousa, Asem

2016-07-07

The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectrophotometric determination of vanadium in rutile and in mafic igneous rocks

USGS Publications Warehouse

Marinenko, John; Mei, Leung

1974-01-01

Minor and major levels of vanadium in rutile are separated from titanium and iron by sample fusion with sodium carbonate followed by water leach and filtration. The filtrate is then acidified with hydrochloric acid. Silicates are decomposed with a mixture of hydrofluoric and hydrochloric acids, and iron is separated by extraction of its chloride with diethyl ether. Sample vanadium in hydrochloric acid is then quantitatively reduced to vanadium(IV) with sulfurous acid. The remaining sulfur dioxide is expelled by heating. Vanadium (IV) then is reacted with excess of iron(III) at reduced acidity (pH 5) in the presence of 1,10-phenanthroline to yield the orange-red iron(II) 1,10-phenanthroline complex. Iron(II) generated by vanadium(IV) is a measure of total vanadium in the sample. The proposed method is free from elemental interferences because the color development cannot take place without the two redox reactions described above, and these are, under the outlined experimental conditions, quantitative only for vanadium.

SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS...

EPA Science Inventory

Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride s...

Metal Hydrides for High-Temperature Power Generation

DOE PAGES

Ronnebro, Ewa; Whyatt, Greg A.; Powell, Michael R.; ...

2015-08-10

Metal hydrides can be utilized for hydrogen storage and for thermal energy storage (TES) applications. By using TES with solar technologies, heat can be stored from sun energy to be used later which enables continuous power generation. We are developing a TES technology based on a dual-bed metal hydride system, which has a high-temperature (HT) metal hydride operating reversibly at 600-800°C to generate heat as well as a low-temperature (LT) hydride near room temperature that is used for hydrogen storage during sun hours until there is a need to produce electricity, such as during night time, a cloudy day, ormore » during peak hours. We proceeded from selecting a high-energy density, low-cost HT-hydride based on performance characterization on gram size samples, to scale-up to kilogram quantities and design, fabrication and testing of a 1.5kWh, 200kWh/m 3 bench-scale TES prototype based on a HT-bed of titanium hydride and a hydrogen gas storage instead of a LT-hydride. COMSOL Multiphysics was used to make performance predictions for cylindrical hydride beds with varying diameters and thermal conductivities. Based on experimental and modeling results, a bench-scale prototype was designed and fabricated and we successfully showed feasibility to meet or exceed all performance targets.« less

Hydride transfer catalysed by Escherichia coli and Bacillus subtilis dihydrofolate reductase: coupled motions and distal mutations.

PubMed

Hammes-Schiffer, Sharon; Watney, James B

2006-08-29

This paper reviews the results from hybrid quantum/classical molecular dynamics simulations of the hydride transfer reaction catalysed by wild-type (WT) and mutant Escherichia coli and WT Bacillus subtilis dihydrofolate reductase (DHFR). Nuclear quantum effects such as zero point energy and hydrogen tunnelling are significant in these reactions and substantially decrease the free energy barrier. The donor-acceptor distance decreases to ca 2.7 A at transition-state configurations to enable the hydride transfer. A network of coupled motions representing conformational changes along the collective reaction coordinate facilitates the hydride transfer reaction by decreasing the donor-acceptor distance and providing a favourable geometric and electrostatic environment. Recent single-molecule experiments confirm that at least some of these thermally averaged equilibrium conformational changes occur on the millisecond time-scale of the hydride transfer. Distal mutations can lead to non-local structural changes and significantly impact the probability of sampling configurations conducive to the hydride transfer, thereby altering the free-energy barrier and the rate of hydride transfer. E. coli and B. subtilis DHFR enzymes, which have similar tertiary structures and hydride transfer rates with 44% sequence identity, exhibit both similarities and differences in the equilibrium motions and conformational changes correlated to hydride transfer, suggesting a balance of conservation and flexibility across species.

Protective effects of Sesamum indicum extract against oxidative stress induced by vanadium on isolated rat hepatocytes.

PubMed

Hosseini, Mir-Jamal; Shahraki, Jafar; Tafreshian, Saman; Salimi, Ahmad; Kamalinejad, Mohammad; Pourahmad, Jalal

2016-08-01

Vanadium toxicity is a challenging problem to human and animal health with no entirely understanding cytotoxic mechanisms. Previous studies in vanadium toxicity showed involvement of oxidative stress in isolated liver hepatocytes and mitochondria via increasing of ROS formation, release of cytochrome c and ATP depletion after incubation with different concentrations (25-200 µM). Therefore, we aimed to investigate the protective effects of Sesamum indicum seed extract (100-300 μg/mL) against oxidative stress induced by vanadium on isolated rat hepatocytes. Our results showed that quite similar to Alpha-tocopherol (100 µM), different concentrations of extract (100-300 μg/mL) protected the isolated hepatocyte against all oxidative stress/cytotoxicity markers induced by vanadium in including cell lysis, ROS generation, mitochondrial membrane potential decrease and lysosomal membrane damage. Besides, vanadium induced mitochondrial/lysosomal toxic interaction and vanadium reductive activation mediated by glutathione in vanadium toxicity was significantly (P < 0.05) ameliorated by Sesamum indicum extracts. These findings suggested a hepato-protective role for extracts against liver injury resulted from vanadium toxicity. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 979-985, 2016. © 2015 Wiley Periodicals, Inc.

Why Antidiabetic Vanadium Complexes are Not in the Pipeline of “Big Pharma” Drug Research? A Critical Review

PubMed Central

Scior, Thomas; Guevara-Garcia, Jose Antonio; Do, Quoc-Tuan; Bernard, Philippe; Laufer, Stefan

2016-01-01

Public academic research sites, private institutions as well as small companies have made substantial contributions to the ongoing development of antidiabetic vanadium compounds. But why is this endeavor not echoed by the globally operating pharmaceutical companies, also known as “Big Pharma”? Intriguingly, today’s clinical practice is in great need to improve or replace insulin treatment against Diabetes Mellitus (DM). Insulin is the mainstay therapeutically and economically. So, why do those companies develop potential antidiabetic drug candidates without vanadium (vanadium-free)? We gathered information about physicochemical and pharmacological properties of known vanadium-containing antidiabetic compounds from the specialized literature, and converted the data into explanations (arguments, the “pros and cons”) about the underpinnings of antidiabetic vanadium. Some discoveries were embedded in chronological order while seminal reviews of the last decade about the Medicinal chemistry of vanadium and its history were also listed for further understanding. In particular, the concepts of so-called “noncomplexed or free” vanadium species (i.e. inorganic oxido-coordinated species) and “biogenic speciation” of antidiabetic vanadium complexes were found critical and subsequently documented in more details to answer the question. PMID:26997154

The role of phosphate additive in stabilization of sulphuric-acid-based vanadium(V) electrolyte for all-vanadium redox-flow batteries

NASA Astrophysics Data System (ADS)

Roznyatovskaya, Nataliya V.; Roznyatovsky, Vitaly A.; Höhne, Carl-Christoph; Fühl, Matthias; Gerber, Tobias; Küttinger, Michael; Noack, Jens; Fischer, Peter; Pinkwart, Karsten; Tübke, Jens

2017-09-01

Catholyte in all-vanadium redox-flow battery (VRFB) which consists of vanadium salts dissolved in sulphuric acid is known to be stabilized by phosphoric acid to slow down the thermal aging at temperatures higher than 40 °C. To reveal the role of phosphoric acid, the thermally-induced aggregation is investigated using variable-temperature 51V, 31P, 17O, 1H nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering (DLS). The results indicate that the thermal stabilization of vanadium(V) electrolyte is attained by the involvement of monomeric and dimeric vanadium(V) species in the reaction with phosphoric acid which is concurrent to the formation of neutral hydroxo-aqua vanadium(V) precipitation precursor. The dimers are stabilized by counter ions due to association reaction or if such stabilization is not possible, precipitation of vanadium pentoxide is favored. The evolution of particles size distributions at 50 °C in electrolyte samples containing 1.6 M vanadium and 4.0 M total sulphate and the pathways of precipitate formation are discussed. The optimal total phosphate concentration is found to be of 0.15 M. However, the induction time is assumed to be dependent not only on the total phosphate concentrations, but also on the ratio of total vanadium(V) to sulphate concentrations.

The effect of stress state on zirconium hydride reorientation

NASA Astrophysics Data System (ADS)

Cinbiz, Mahmut Nedim

Prior to storage in a dry-cask facility, spent nuclear fuel must undergo a vacuum drying cycle during which the spent fuel rods are heated up to elevated temperatures of ≤ 400°C to remove moisture the canisters within the cask. As temperature increases during heating, some of the hydride particles within the cladding dissolve while the internal gas pressure in fuel rods increases generating multi-axial hoop and axial stresses in the closed-end thin-walled cladding tubes. As cool-down starts, the hydrogen in solid solution precipitates as hydride platelets, and if the multiaxial stresses are sufficiently large, the precipitating hydrides reorient from their initial circumferential orientation to radial orientation. Radial hydrides can severely embrittle the spent nuclear fuel cladding at low temperature in response to hoop stress loading. Because the cladding can experience a range of stress states during the thermo-mechanical treatment induced during vacuum drying, this study has investigated the effect of stress state on the process of hydride reorientation during controlled thermo-mechanical treatments utilizing the combination of in situ X-ray diffraction and novel mechanical testing analyzed by the combination of metallography and finite element analysis. The study used cold worked and stress relieved Zircaloy-4 sheet containing approx. 180 wt. ppm hydrogen as its material basis. The failure behavior of this material containing radial hydrides was also studied over a range of temperatures. Finally, samples from reactor-irradiated cladding tubes were examined by X-ray diffraction using synchrotron radiation. To reveal the stress state effect on hydride reorientation, the critical threshold stress to reorient hydrides was determined by designing novel mechanical test samples which produce a range of stress states from uniaxial to "near-equibiaxial" tension when a load is applied. The threshold stress was determined after thermo-mechanical treatments by correlating the finite element stress-state results with the spatial distribution of hydride microstructures observed within the optical micrographs for each sample. Experiments showed that the hydride reorientation was enhanced as the stress biaxiality increased. The threshold stress decreased from 150 MPa to 80 MPa when stress biaxiality ratio increased from uniaxial tension to near-equibiaxial tension. This behavior was also predicted by classical nucleation theory based on the Gibbs free energy of transformation being assisted by the far-field stress. An analysis of in situ X-ray diffraction data obtained during a thermo-mechanical cycle typical of vacuum drying showed a complex lattice-spacing behavior of the hydride phase during the dissolution and precipitation. The in-plane hydrides showed bilinear lattice expansion during heating with the intrinsic thermal expansion rate of the hydrides being observed only at elevated temperatures as they dissolve. For radial hydrides that precipitate during cooling under stress, the spacing of the close-packed {111} planes oriented normal to the maximum applied stress was permanently higher than the corresponding {111} plane spacing in the other directions. This behavior is believed to be a result of a complex stress state within the precipitating plate-like hydrides that induces a strain component within the hydrides normal to its "plate" face (i.e., the applied stress direction) that exceeds the lattice spacing strains in the other directions. During heat-up, the lattice spacing of these same "plate" planes actually contract due to the reversion of the stress state within the plate-like hydrides as they dissolve. The presence of radial hydrides and their connectivity with in-plane hydrides was shown to increase the ductile-to-brittle transition temperature during tensile testing. This behavior can be understood in terms of the role of radial hydrides in promoting the initiation of a long crack that subsequently propagates under fracture mechanics conditions. Finally, the d-spacing of irradiated Zircaloy-4 and M5 cladding tubes was measured at room temperature and compared to that of unirradiated samples.

The Influence of Vanadium Microalloying on the Production of Thin Slab Casting and Direct Rolled Steel Strip

NASA Astrophysics Data System (ADS)

Li, Yu; Milbourn, David

Vanadium microalloying is highly effective in high strength strip steels produced by thin slab casting and direct rolled process. Because of the high solubility of V(C,N) in austenite, vanadium is likely to remain in solution during casting, equalisation and rolling. Vanadium microalloyed steels have better hot ductility and are less prone to transverse cracking than niobium containing steels. Despite a coarse as-cast austenite grain size before rolling, significant grain refinement can be achieved in vanadium microalloyed steels by repeated recrystallization during rolling, resulting in a fine uniform ferrite microstructure in final strip. Almost all vanadium present in microalloyed steels is available to precipitate in ferrite as very fine particles, contributing to precipitation strengthening. Vanadium microalloyed steels show less sensitivity to rolling process variables and exhibit excellent combination of strength and toughness.

Pharmacokinetics of vanadium in humans after intravenous administration of a vanadium containing albumin solution

PubMed Central

Heinemann, Günter; Fichtl, Burckhard; Vogt, Wolfgang

2003-01-01

Aims Vanadium is currently undergoing clinical trials as an oral drug in patients with noninsulin-dependent diabetes mellitus. Furthermore, vanadium occurs in elevated concentrations in the blood of patients receiving intravenous albumin solutions containing large amounts of the metal ion as an impurity. The present study was performed to examine the pharmacokinetics of vanadium in humans following a single intravenous (i.v.) dose of a commercial albumin solution containing a high amount of vanadium. Methods The study was conducted in five healthy volunteer subjects who received intravenously 90 ml of a commercial 20% albumin infusion solution containing 47.6 µg vanadium as an impurity. Vanadium concentrations in serum and urine were determined by electrothermal atomic absorption spectrometry. Results Vanadium serum concentrations after i.v. administration were measured for 31 days. The data could be fitted by a triexponential function corresponding formally to a three-compartment model. There was an initial rapid decrease in serum concentrations with half-lives of 1.2 and 26 h. This was followed by a long-terminal half-life time of 10 days. The terminal phase accounted for about 80% of the total area under the serum concentration-time curve (AUC). The mean apparent volume of distribution of the central compartment was found to be 10 l. The volume of distribution at steady state was 54 l, and total clearance was 0.15 l h−1. Vanadium was mainly excreted by the kidneys. About 52% of the dose was recovered in the urine after 12 days. Conclusions This study provides data on vanadium pharmacokinetics in healthy humans. PMID:12630973

Effect of vanadium contamination on the framework and micropore structure of ultra stable Y-zeolite.

PubMed

Etim, U J; Xu, B; Ullah, Rooh; Yan, Z

2016-02-01

Y-zeolites are the main component of fluid catalytic cracking (FCC) catalyst for conversion of crude petroleum to products of high demand including transportation fuel. We investigated effects of vanadium which is present as one of the impurities in FCC feedstock on the framework and micropore structure of ultra-stable (US) Y-zeolite. The zeolite samples were prepared and characterized using standard techniques including: (1) X-ray diffraction, (2) N2 adsorption employing non local density functional theory method, NLDFT, (3) Transmittance and Pyridine FTIR, (4) Transmittance electron microscopy (TEM), and (5) (27)Al and (29)Si MAS-NMR. Results revealed that in the presence of steam, vanadium caused excessive evolution of non inter-crystalline mesopores and structural damage. The evolved mesopore size averaged about 25.0nm at 0.5wt.% vanadium loading, far larger than mesopore size in zeolitic materials with improved hydrothermal stability and performance for FCC catalyst. A mechanism of mesopore formation based on accelerated dealumination has been proposed and discussed. Vanadium immobilization experiments conducted to mitigate vanadium migration into the framework clearly showed vanadium is mobile at reaction conditions. From the results, interaction of vanadium with the passivator limits and decreases mobility and activity of vanadium into inner cavities of the zeolite capable of causing huge structure breakdown and acid sites destruction. This study therefore deepens insight into the causes of alteration in activity and selectivity of vanadium contaminated catalyst and hints on a possible mechanism of passivation in vanadium passivated FCC catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

NREL, American Vanadium Demonstrate First-of-Its-Kind Battery Management

Science.gov Websites

System | Energy Systems Integration Facility | NREL American Vanadium NREL, American Vanadium Demonstrate First-of-Its-Kind Battery Management System NREL researchers are collaborating with American Vanadium, an integrated energy storage company, to evaluate and demonstrate the first North American

76 FR 78888 - Final Results of Expedited Sunset Review: Ferrovanadium and Nitrided Vanadium From Russia

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-20

... Sunset Review: Ferrovanadium and Nitrided Vanadium From Russia AGENCY: Import Administration... and nitrided vanadium from the Russian Federation (Russia), pursuant to section 751(c) of the Tariff... vanadium from Russia, pursuant to section 751(c) of the Act. See Initiation of Five-Year (``Sunset...

77 FR 51825 - Ferrovanadium and Nitrided Vanadium From Russia

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-27

... Nitrided Vanadium From Russia Determination On the basis of the record \\1\\ developed in the subject five... order on ferrovanadium and nitrided vanadium from Russia would not be likely to lead to continuation or... in USITC Publication 4345 (August 2012), entitled Ferrovanadium and Nitrided Vanadium from Russia...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the vanadium ore...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the vanadium ore...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... uranium, radium and vanadium ores subcategory. 440.30 Section 440.30 Protection of Environment... SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.30 Applicability; description of the uranium, radium and vanadium ores subcategory. The provisions of this subpart C are applicable to...

Consolidation and fabrication techniques for vanadium-20 w/o titanium /TV-20/

NASA Technical Reports Server (NTRS)

Burt, W. R.; Karasek, F. J.; Kramer, W. C.; Mayfield, R. M.; Mc Gowan, R. D.

1968-01-01

Tests of the mechanical properties, fuel compatibility, sodium corrosion and irradiation behavior were made for vanadium and vanadium alloy. Improved methods for consolidation and fabrication of bar, rod, sheet, and high-quality, small diameter, thin-wall tubing of vanadium-20 without titanium are reported.

METHOD AND APPARATUS FOR MAKING URANIUM-HYDRIDE COMPACTS

DOEpatents

Wellborn, W.; Armstrong, J.R.

1959-03-10

A method and apparatus are presented for making compacts of pyrophoric hydrides in a continuous operation out of contact with air. It is particularly useful for the preparation of a canned compact of uranium hydride possessing high density and purity. The metallic uranium is enclosed in a container, positioned in a die body evacuated and nvert the uranium to the hydride is admitted and the container sealed. Heat is applied to bring about the formation of the hydride, following which compression is used to form the compact sealed in a container ready for use.

Combined on-board hydride slurry storage and reactor system and process for hydrogen-powered vehicles and devices

DOEpatents

Brooks, Kriston P; Holladay, Jamelyn D; Simmons, Kevin L; Herling, Darrell R

2014-11-18

An on-board hydride storage system and process are described. The system includes a slurry storage system that includes a slurry reactor and a variable concentration slurry. In one preferred configuration, the storage system stores a slurry containing a hydride storage material in a carrier fluid at a first concentration of hydride solids. The slurry reactor receives the slurry containing a second concentration of the hydride storage material and releases hydrogen as a fuel to hydrogen-power devices and vehicles.

Mineralogy and geochemistry of vanadium in the Colorado Plateau

USGS Publications Warehouse

Weeks, A.D.

1961-01-01

The chief domestic source of vanadium is uraniferous sandstone in the Colorado Plateau. Vanadium is 3-, 4-, or 5-valent in nature and, as oxides or combined with other elements, it forms more than 40 minerals in the Plateau ores. These ores have been studied with regard to the relative amounts of vanadium silicates and oxide-vanadates, uranium-vanadium ratios, the progressive oxidation of black low-valent ores to high-valent carnotite-type ores, and theories of origin. ?? 1961.

CATALYTIC PROMOTION OF THE ADSORPTION OF VANADIUM ON AN ANIONIC EXCHANGE RESIN

DOEpatents

Bailes, R.H.; Ellis, D.A.

1958-08-26

An improvement in the process for the recovery of vanadium from acidic phosphatic solutions is presented. In this process the vanadium is first oxidized to the pentavaleat state, and is then separated by contacting such solutions with an anion exchange resin whereby adsorption of the complexed pentavalent vanadium is effected. The improvement lies in the fact that adsorp tion of the vanadium complex by the anion exchange resin is promoted and improved by providing fiuoride ions in solution to be contacted.

Exploring electrolyte preference of vanadium nitride supercapacitor electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bo; Chen, Zhaohui; Lu, Gang

Highlights: • Hierarchical VN nanostructures were prepared on graphite foam. • Electrolyte preference of VN supercapacitor electrodes was explored. • VN showed better capacitive property in organic and alkaline electrolytes than LiCl. - Abstract: Vanadium nitride hierarchical nanostructures were prepared through an ammonia annealing procedure utilizing vanadium pentoxide nanostructures grown on graphite foam. The electrochemical properties of hierarchical vanadium nitride was tested in aqueous and organic electrolytes. As a result, the vanadium nitride showed better capacitive energy storage property in organic and alkaline electrolytes. This work provides insight into the charge storage process of vanadium nitride and our findings canmore » shed light on other transition metal nitride-based electrochemical energy storage systems.« less

Chloride supporting electrolytes for all-vanadium redox flow batteries.

PubMed

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

Fabrication of VO2 thin film by rapid thermal annealing in oxygen atmosphere and its metal—insulator phase transition properties

NASA Astrophysics Data System (ADS)

Liang, Ji-Ran; Wu, Mai-Jun; Hu, Ming; Liu, Jian; Zhu, Nai-Wei; Xia, Xiao-Xu; Chen, Hong-Da

2014-07-01

Vanadium dioxide thin films have been fabricated through sputtering vanadium thin films and rapid thermal annealing in oxygen. The microstructure and the metal—insulator transition properties of the vanadium dioxide thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and a spectrometer. It is found that the preferred orientation of the vanadium dioxide changes from (1¯11) to (011) with increasing thickness of the vanadium thin film after rapid thermal annealing. The vanadium dioxide thin films exhibit an obvious metal—insulator transition with increasing temperature, and the phase transition temperature decreases as the film thickness increases. The transition shows hysteretic behaviors, and the hysteresis width decreases as the film thickness increases due to the higher concentration carriers resulted from the uncompleted lattice. The fabrication of vanadium dioxide thin films with higher concentration carriers will facilitate the nature study of the metal—insulator transition.

Cellular uptake of titanium and vanadium from addition of salts or fretting corrosion in vitro

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maurer, A.M.; Merritt, K.; Brown, S.A.

1994-02-01

The use of titanium and titanium-6% aluminum-4% vanadium alloy for dental and orthopedic implants has increased in the last decade. The implants are presumed to be compatible because oseointegration, bony apposition, and cell attachment are known. However, the cellular association of titanium and vanadium have remained unknown. This study examined the uptake of salts or fretting corrosion products. Titanium was not observed to be toxic to the cells. Vanadium was toxic at levels greater than 10[mu]g/mL. The percentage of cellular association of titanium was shown to be about 10 times that of vanadium. The percentage of cellular association of eithermore » element was greater from fretting corrosion than from the addition of salts. The presence of vanadium did not affect the cellular uptake of titanium. The presence of titanium decreased the cell association of vanadium.« less

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Lee, Hae-Min; Jeong, Gyoung Hwa; Kim, Sang-Wook; Kim, Chang-Koo

2017-04-01

Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2-5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

Vanadium in landscape components of western Transbaikalia

NASA Astrophysics Data System (ADS)

Kashin, V. K.

2017-10-01

Vanadium in soil-forming rocks, soils, and vegetation of forest-steppe, steppe, and dry-steppe landscapes of Transbaikalia has been studied. The mean element contents in rocks and soils are equal to its mean natural abundances (clarke values). The content of vanadium in soils is strictly determined by its content in parent materials; its dependence on the vanadium concentration in plants and on the soil pH and humus is less pronounced. With respect to the coefficient of biological uptake by plants, vanadium is assigned to the group of elements of slight accumulation (0.10-0.33) on mineral soils and of moderate accumulation (1.1-1.5) on peat bog soils. The mean vanadium concentration in steppe, meadow, and cultivated vegetation exceeds the norm for animals by 1.7-2.6 times but does not rich toxic levels. Vanadium uptake by plants is most intensive in meadow cenoses and is less intensive in dry-steppe cenoses.

Vanadium-uranium extraction from Wyoming vanadiferoud silicates. Report of investigations/1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayashi, M.; Nichols, I.L.; Huiatt, J.L.

1983-11-01

The Bureau of Mines conducted laboratory studies on low-grade vanadiferous silicates from the Pumpkin Buttes and Nine Mile Lake deposits of Wyoming to examine techniques for extracting vanadium and uranium. Recovery from low-grade sources such as these could contribute to future vanadium production and reduce reliance on vanadium imports.

77 FR 54897 - Ferrovanadium and Nitrided Vanadium from the Russian Federation: Revocation of Antidumping Duty...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-06

... nitrided vanadium from the Russian Federation (Russia) would not be likely to lead to continuation or... the antidumping duty order on ferrovanadium and nitrided vanadium from Russia. \\1\\ See Ferrovanadium and Nitrided Vanadium From Russia, 77 FR 51825 (August 27, 2012) (ITC Final). DATES: Effective Date...

76 FR 69736 - Draft Toxicological Review of Vanadium Pentoxide: In Support of Summary Information on the...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-09

... Toxicological Review of Vanadium Pentoxide: In Support of Summary Information on the Integrated Risk Information..., ``Toxicological Review of Vanadium Pentoxide: In Support of Summary Information on the Integrated Risk Information... Vanadium Pentoxide: In Support of Summary Information on the Integrated Risk Information System (IRIS)'' is...

Inhibited solid propellant composition containing beryllium hydride

NASA Technical Reports Server (NTRS)

Thompson, W. W. (Inventor)

1978-01-01

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

Hydrogen /Hydride/-air secondary battery

NASA Technical Reports Server (NTRS)

Sarradin, J.; Bronoel, G.; Percheron-Guegan, A.; Achard, J. C.

1979-01-01

The use of metal hydrides as negative electrodes in a hydrogen-air secondary battery seems promising. However, in an unpressurized cell, more stable hydrides that LaNi5H6 must be selected. Partial substitutions of nickel by aluminium or manganese increase the stability of hydrides. Combined with an air reversible electrode, a specific energy close to 100 Wh/kg can be expected.

Hydridable material for the negative electrode in a nickel-metal hydride storage battery

DOEpatents

Knosp, Bernard; Bouet, Jacques; Jordy, Christian; Mimoun, Michel; Gicquel, Daniel

1997-01-01

A monophase hydridable material for the negative electrode of a nickel-metal hydride storage battery with a "Lave's phase" structure of hexagonal C14 type (MgZn.sub.2) has the general formula: Zr.sub.1-x Ti.sub.x Ni.sub.a Mn.sub.b Al.sub.c Co.sub.d V.sub.e where ##EQU1##

Essentiality and toxicity of vanadium supplements in health and pathology.

PubMed

Gruzewska, K; Michno, A; Pawelczyk, T; Bielarczyk, H

2014-10-01

The biological properties of vanadium complexes have become an object of interest due to their therapeutic potential in several diseases. However, the mechanisms of action of vanadium salts are still poorly understood. Vanadium complexes are cofactors for several enzymes and also exhibit insulin-mimetic properties. Thus, they are involved in the regulation of glucose metabolism, including in patients with diabetes. In addition, vanadium salts may also normalize blood pressure and play a key role in the metabolism of the thyroid and of iron as well as in the regulation of total cholesterol, cholesterol HDL and triglyceride (TG) levels in blood. Moreover, in cases of hypoxia, vanadium compounds may improve cardiomyocytes function. They may also exhibit both carcinogenic and anti-cancer properties. These include dose- and exposure-time-dependent induction and inhibition of the proliferation and survival of cancer cells. On the other hand, the balance between vanadium's therapeutic properties and its side effects has not yet been determined. Therefore, any studies on the potential use of vanadium compounds as supplements to support the treatment of a number of diseases must be strictly monitored for adverse effects.

Electronic structure of lead telluride-based alloys, doped with vanadium

NASA Astrophysics Data System (ADS)

Skipetrov, E. P.; Golovanov, A. N.; Slynko, E. I.; Slynko, V. E.

2013-01-01

The crystal structure, composition, galvanomagnetic properties in low magnetic fields (4.2 K ≤ T ≤ 300 K, B ≤ 0.07 T), and the Shubnikov-de Haas effect (T = 4.2 K, B ≤ 7 T) are studied in Pb1-x-ySnxVyTe (x = 0, 0.05-0.18) alloys synthesized by the Bridgman technique with variable vanadium impurity concentrations. It is shown that increasing the vanadium content leads to the formation of regions enriched in vanadium and of microscopic inclusions of compounds with compositions close to V3Te4. In Pb1-yVyTe stabilization of the Fermi level by a deep vanadium level, an insulator-metal transition, and a rise in the free electron concentration are observed as the vanadium content is increased. The variation in the free charge carrier concentration with increasing vanadium concentration in Pb1-yVyTe and Pb1-x-ySnxVyTe (x = 0.05-0.18) alloys is compared. Possible models for rearrangement of the electronic structure in Pb1-x-ySnxVyTe alloys with vanadium doping are discussed.

Kinetic model of whole-body vanadium metabolism: studies in sheep

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, B.W.; Hansard, S.L. II; Ammerman, C.B.

1986-08-01

A compartmental model for vanadium metabolism in sheep has been proposed. The model is consistent with data obtained from sheep fed a control diet (2.6 ppm vanadium) containing 0 or 200 ppm supplemental vanadium. Sheep were administered UYV dioxovanadium either orally or intravenously. Blood feces, and urine radioactivity were monitored for 6 days postdosing. Several new insights regarding vanadium metabolism are suggested and tested against the data using the model. Some of these include 1) significant absorption of UYV occurs from the upper gastrointestinal tract; 2) an in vivo process is necessary in order for UYV dioxovanadium to be convertedmore » into a more biologically reactive species; 3) at steady state the upper and lower gastrointestinal tracts contain at least 10- and 100-fold more mass of vanadium, respectively, than does blood. No statistically significant differences in transport rate constants were found between animals receiving 0 and 200 ppm supplemental dietary vanadium. The availability of a model will enable the refinement of future studies regarding vanadium metabolism in the ruminant.« less

Cottonseed meal, dehydrated grass and ascorbic acid as dietary factors preventing toxicity of vanadium for the chick

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L.R.; Lawrence, W.W.

1971-01-01

Studies have been conducted which show that the replacement of 5% sucrose in a sucrose-fish meal diet for chicks with degossypolized cottonseed meal prevents the toxicity of 20 ppm added vanadium. The addition of 5% dehydrated grass to the same ration markedly reduced the toxicity symptoms. No such reduction in vanadium toxicity resulted when soybean meal, corn gluten meal, meat meal, fish meal, casein, isolated soybean protein, zein or wheat gluten were added to the ration. No evidence was found that the gossypol remaining in the cottonseed meal was the detoxifying agent. The addition of 0.25 to 0.50% ascorbic acidmore » to the sucrose-fish meal basal ration prevented the toxic symptoms resulting from the addition of 20 ppm vanadium derived from HN/sub 4/VO/sub 3/. The vanadium derived from VOSO/sub 4/ and VOCl/sub 2/ (vanadium valence 4) was as toxic as vanadium derived from HN/sub 4/VO/sub 3/ (V = valence 5). This leads one to question that the action of ascorbic acid in reducing vanadium toxicity is through its property of a reducing agent which might change the vanadium in VH/sub 4/VO/sub 3/ to a lower valence, presumably less toxic.« less

Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium.

PubMed

Pitman, Catherine L; Brereton, Kelsey R; Miller, Alexander J M

2016-02-24

Aqueous hydride transfer is a fundamental step in emerging alternative energy transformations such as H2 evolution and CO2 reduction. "Hydricity," the hydride donor ability of a species, is a key metric for understanding transition metal hydride reactivity, but comprehensive studies of aqueous hydricity are scarce. An extensive and self-consistent aqueous hydricity scale is constructed for a family of Ru and Ir hydrides that are key intermediates in aqueous catalysis. A reference hydricity is determined using redox potentiometry and spectrophotometric titration for a particularly water-soluble species. Then, relative hydricity values for a range of species are measured using hydride transfer equilibria, taking advantage of expedient new synthetic procedures for Ru and Ir hydrides. This large collection of hydricity values provides the most comprehensive picture so far of how ligands impact hydricity in water. Strikingly, we also find that hydricity can be viewed as a continuum in water: the free energy of hydride transfer changes with pH, buffer composition, and salts present in solution.

Hydride compositions

DOEpatents

Lee, Myung W.

1995-01-01

A composition for use in storing hydrogen, and a method for making the composition. The composition comprises a mixture of two or more hydrides, each hydride having a different series of hydrogen sorption isotherms that contribute to the overall isotherms of the mixture. The hydrides are chosen so that the isotherms of the mixture have regions wherein the hydrogen equilibrium pressure increases with increasing hydrogen, preferably linearly. The isotherms of the mixture can be adjusted by selecting hydrides with different isotherms and by varying the amounts of the individual hydrides, or both. Preferably, the mixture is made up of hydrides that have isotherms with substantially flat plateaus and in nearly equimolar amounts. The composition is activated by degassing, exposing to hydrogen and then heating at a temperature below the softening temperature of any of the. constituents so that their chemical and structural integrity is preserved. When the composition is used to store hydrogen, its hydrogen content can be found simply by measuring P.sub.H.sbsb.2 and determining H/M from the isothermic function of the composition.

On the Chemistry of Hydrides of N Atoms and O+ Ions

NASA Astrophysics Data System (ADS)

Awad, Zainab; Viti, Serena; Williams, David A.

2016-08-01

Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H2 formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O+ ions detected by Herschel/HIFI that are present along many sight lines in the Galaxy. The O+ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

Hydride compositions

DOEpatents

Lee, Myung, W.

1994-01-01

Disclosed are a composition for use in storing hydrogen and a method for making the composition. The composition comprises a mixture of two or more hydrides, each hydride having a different series of hydrogen sorption isotherms that contribute to the overall isotherms of the mixture. The hydrides are chosen so that the isotherms of the mixture have regions wherein the H equilibrium pressure increases with increasing hydrogen, preferably linearly. The isotherms of the mixture can be adjusted by selecting hydrides with different isotherms and by varying the amounts of the individual hydrides, or both. Preferably, the mixture is made up of hydrides that have isotherms with substantially flat plateaus and in nearly equimolar amounts. The composition is activated by degassing, exposing to H, and then heating below the softening temperature of any of the constituents. When the composition is used to store hydrogen, its hydrogen content can be found simply by measuring P{sub H}{sub 2} and determining H/M from the isothermic function of the composition.

Vanadium bioavailability and toxicity to soil microorganisms and plants.

PubMed

Larsson, Maja A; Baken, Stijn; Gustafsson, Jon Petter; Hadialhejazi, Golshid; Smolders, Erik

2013-10-01

Vanadium, V, is a redox-sensitive metal that in solution, under aerobic conditions, prevails as the oxyanion vanadate(V). There is little known regarding vanadium toxicity to soil biota, and the present study was set up to determine the toxicity of added vanadate to soil organisms and to investigate the relationship between toxicity and vanadium sorption in soils. Five soils with contrasting properties were spiked with 7 different doses (3.2-3200 mg V kg(-1)) of dissolved vanadate, and toxicity was measured with 2 microbial and 3 plant assays. The median effective concentration (EC50) thresholds of the microbial assays ranged from 28 mg added V kg(-1) to 690 mg added V kg(-1), and the EC50s in the plant assays ranged from 18 mg added V kg(-1) to 510 mg added V kg(-1). The lower thresholds were in the concentration range of the background vanadium in the untreated control soils (15-58 mg V kg(-1)). The vanadium toxicity to plants decreased with a stronger soil vanadium sorption strength. The EC50 values for plants expressed on a soil solution basis ranged from 0.8 mg V L(-1) to 15 mg V L(-1) and were less variable among soils than corresponding values based on total vanadium in soil. It is concluded that sorption decreases the toxicity of added vanadate and that soil solution vanadium is a more robust measure to determine critical vanadium concentrations across soils. © 2013 SETAC.

Vanadium exposure-induced striatal learning and memory alterations in rats

PubMed Central

Sun, Liping; Wang, Keyue; Li, Yan; Fan, Qiyuan; Zheng, Wei; Li, Hong

2017-01-01

Occupational and environmental exposure to vanadium has been associated with toxicities in reproductive, respiratory, and cardiovascular systems. The knowledge on whether and how vanadium exposure caused neurobehavioral changes remains incomplete. This study was designed to investigate the changes in learning and memory following drinking water exposure to vanadium, and to conduct the preliminary study on underlying mechanisms. Male Sprague-Dawley rats were exposed to vanadium dissolved in drinking water at the concentration of 0.0, 0.5, 1.0 and 2.0 g/L, as the control, low-, medium-, and high- dose groups, respectively, for 12 weeks. The results by the Morris water maze test showed that the time for the testing animal to find the platform in the high exposed group was increased by 82.9% and 49.7%, as compared to animals in control and low-dose groups (p <0.05). There were significantly fewer rats in the medium- and high- dose groups than in the control group who were capable of crossing the platform (p <0.05). Quantitation of vanadium by atomic absorption spectrophotometry revealed a significant dose-dependent accumulation of vanadium in striatum (r = 0.931, p <0.01). Histopathological examination further demonstrated a degenerative damage in vanadium-exposed striatum. Interestingly, with the increase of the dose of vanadium, the contents of neurotransmitter ACh, 5-HT and GABA in the striatum increased; however, the levels of Syn1 was significantly reduced in the exposed groups compared with controls (p <0.05). These data suggest that vanadium exposure apparently reduces the animals’ learning ability. This could be due partly to vanadium’s accumulation in striatum and the ensuing toxicity to striatal structure and synaptic plasticity. Further research is warranted for mechanistic understanding of vanadium-induced neurotoxicity. PMID:28625925

Direct synthesis of catalyzed hydride compounds

DOEpatents

Gross, Karl J.; Majzoub, Eric

2004-09-21

A method is disclosed for directly preparing alkali metal aluminum hydrides such as NaAlH.sub.4 and Na.sub.3 AlH.sub.6 from either the alkali metal or its hydride, and aluminum. The hydride thus prepared is doped with a small portion of a transition metal catalyst compound, such as TiCl.sub.3, TiF.sub.3, or a mixture of these materials, in order to render them reversibly hydridable. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen while heating the mixture to about 125.degree. C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.

Influence of vanadium on serum lipid and lipoprotein profiles: a population-based study among vanadium exposed workers

PubMed Central

2014-01-01

Background Some experimental animal studies reported that vanadium had beneficial effects on blood total cholesterol (TC) and triglyceride (TG). However, the relationship between vanadium exposure and lipid, lipoprotein profiles in human subjects remains uncertain. This study aimed to compare the serum lipid and lipoprotein profiles of occupational vanadium exposed and non-exposed workers, and to provide human evidence on serum lipid, lipoprotein profiles and atherogenic indexes changes in relation to vanadium exposure. Methods This cross-sectional study recruited 533 vanadium exposed workers and 241 non-exposed workers from a Steel and Iron Group in Sichuan, China. Demographic characteristics and occupational information were collected through questionnaires. Serum lipid and lipoprotein levels were measured for all participants. The ratios of total cholesterol to high-density lipoprotein cholesterol (HDL-C), low-density lipoprotein cholesterol (LDL-C) to HDL-C and apoB to apoA-I were used as atherogenic indexes. A general linear model was applied to compare outcomes of the two groups while controlling possible confounders and multivariate logistic regression was performed to evaluate the relationship between low HDL-C level, abnormal atherogenic index and vanadium exposure. Results Higher levels of HDL-C and apoA-I could be observed in the vanadium exposed group compared with the control group (P < 0.05). Furthermore, atherogenic indexes (TC/HDL-C, LDL-C/HDL-C, and apoB/apoA-I ratios) were found statistically lower in the vanadium exposed workers (P < 0.05). Changes in HDL-C, TC/HDL-C, and LDL-C/HDL-C were more pronounced in male workers than that in female workers. In male workers, after adjusting for potential confounding variables as age, habits of smoking and drinking, occupational vanadium exposure was still associated with lower HDL-C (OR 0.41; 95% CI, 0.27-0.62) and abnormal atherogenic index (OR 0.38; 95% CI, 0.20-0.70). Conclusion Occupational vanadium exposure appears to be associated with increased HDL-C and apoA-I levels and decreased atherogenic indexes. Among male workers, a significantly negative association existed between low HDL-C level, abnormal atherogenic index and occupational vanadium exposure. This suggests vanadium has beneficial effects on blood levels of HDL-C and apoA-I. PMID:24558984

Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.

PubMed

Yang, Xinzheng

2013-09-07

Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.

Hydride Microstructure at the Metal-Oxide Interface of Zircaloy-4 from H.B. Robinson Nuclear Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut N; Edmondson, Philip D; Terrani, Kurt A

2017-01-01

This study investigates the hydride rim microstructure at the metal-oxide interface of Zircaloy-4 cladding segment removed from H.B. Robinson Nuclear Reactor by utilizing high resolution electron microscopy techniques with energy dispersive x-ray spectroscopy at Oak Ridge National Laboratory under the NSUF Rapid Turnout Experiment program. A complex stacking and orientation of hydride platelets has been observed below the sub-oxide layer. Furthermore, radial hydride platelets have been observed. EDS signals of both Fe and Cr has been reduced within hydrides whereas EDS signal of Sn is unaffected.

Hydrides of intermetallic compounds with a H/M ratio greater than unity obtained at high hydrogen pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Semenenko, K.N.; Klyamkin, S.N.

1993-11-01

Novel hydride phases with H/M > 1 based on Zr{sub 2}Pd, Hf{sub 2}Pd, and Hf{sub 2}Cu (structures of the MoSi{sub 2} type) have been synthesized at high H{sub 2} pressures. The X-ray diffraction investigations of the resulting hydrides have been carried out. Some factors determining the maximum hydrogen content in the hydrides of intermetallic compounds are discussed. A model structure of the hydrides obtained is proposed, which assumes the possibility of direct H-H interactions when the interatomic distances are less than 1 {angstrom}.

Polyhydrido Copper Clusters: Synthetic Advances, Structural Diversity, and Nanocluster-to-Nanoparticle Conversion.

PubMed

Dhayal, Rajendra S; van Zyl, Werner E; Liu, C W

2016-01-19

Metal hydride clusters have historically been studied to unravel their aesthetically pleasing molecular structures and interesting properties, especially toward hydrogen related applications. Central to this work is the hydride ligand, H¯, the smallest closed-shell spherical anion known. Two new developments in polyhydrido nanocluster chemistry include the determination of heretofore unknown hydride coordination modes and novel structural constructs, and conversion from the molecular entities to rhombus-shaped copper nanoparticles (CuNPs). These advances, together with hydrogen evolution and catalysis, have provided both experimentalists and theorists with a rich scientific directive to further explore. The isolation of hexameric [{(Ph3P)CuH}6] (Stryker reagent) could be regarded as the springboard for the recent emergence of polyhydrido copper cluster chemistry due to its utilization in a variety of organic chemical transformations. The stability of clusters of various nuclearity was improved through phosphine, pyridine, and carbene type ligands. Our focus lies with the isolation of novel copper (poly)hydride clusters using mostly the phosphor-1,1-dithiolato type ligands. We found such chalcogen-stabilized clusters to be exceptionally air and moisture stable over a wide range of nuclearities (Cu7 to Cu32). In this Account, we (i) report on state-of-the-art copper hydride cluster chemistry, especially with regards to the diverse and novel structural types generally, and newly discovered hydride coordination modes in particular, (ii) demonstrate the indispensable power of neutron diffraction for the unambiguous assignment and location of hydride ligand(s) within a cluster, and (iii) prove unique transformations that can occur not only between well characterized high nuclearity clusters, but also how such clusters can transform to uniquely shaped nanoparticles of several nanometers in diameter through copper hydride reduction. The increase in the number of low- to high-nuclearity hydride clusters allows for different means by which they can be classified. We chose a classification based on the coordination mode of hydride ligand within the cluster. This includes copper clusters associated with bridging (μ2-H) and capping (μ3-H) hydride modes, followed by an interstitial (μ4-H) hydride mode that was introduced for the first time into octa- and hepta-nuclear copper clusters stabilized by dichalcogen-type ligands. This breakthrough provided a means to explore higher nuclearity polyhydrido nanoclusters, which contain both capping (μ3-H) and interstitial (μ(4-6)-H) hydrides. The presence of bidentate ligands having mixed S/P dative sites led to air- and moisture-stable copper hydride nanoclusters. The formation of rhombus-shaped nanoparticles (CuNPs) from copper polyhydrides in the presence of excess borohydrides suggests the presence of metal hydrides as intermediates during the formation of nanoparticles.

Structural Characterization of Metal Hydrides for Energy Applications

NASA Astrophysics Data System (ADS)

George, Lyci

Hydrogen can be an unlimited source of clean energy for future because of its very high energy density compared to the conventional fuels like gasoline. An efficient and safer way of storing hydrogen is in metals and alloys as hydrides. Light metal hydrides, alanates and borohydrides have very good hydrogen storage capacity, but high operation temperatures hinder their application. Improvement of thermodynamic properties of these hydrides is important for their commercial use as a source of energy. Application of pressure on materials can have influence on their properties favoring hydrogen storage. Hydrogen desorption in many complex hydrides occurs above the transition temperature. Therefore, it is important to study the physical properties of the hydride compounds at ambient and high pressure and/or high temperature conditions, which can assist in the design of suitable storage materials with desired thermodynamic properties. The high pressure-temperature phase diagram, thermal expansion and compressibility have only been evaluated for a limited number of hydrides so far. This situation serves as a main motivation for studying such properties of a number of technologically important hydrides. Focus of this dissertation was on X-ray diffraction and Raman spectroscopy studies of Mg2FeH6, Ca(BH4) 2, Mg(BH4)2, NaBH4, NaAlH4, LiAlH4, LiNH2BH3 and mixture of MgH 2 with AlH3 or Si, at different conditions of pressure and temperature, to obtain their bulk modulus and thermal expansion coefficient. These data are potential source of information regarding inter-atomic forces and also serve as a basis for developing theoretical models. Some high pressure phases were identified for the complex hydrides in this study which may have better hydrogen storage properties than the ambient phase. The results showed that the highly compressible B-H or Al-H bonds and the associated bond disordering under pressure is responsible for phase transitions observed in brorohydrides or alanates. Complex hydrides exhibited very high compressibility suggesting possibility to destabilize them with pressure. With high capacity and favorable thermodynamics, complex hydrides are suitable for reversible storage. Further studies are required to overcome the kinetic barriers in complex hydrides by catalytic addition. A comparative study of the hydride properties with that of the constituting metal, and their inter relationships were carried out with many interesting features.

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2017-08-08

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

ION EXCHANGE PROCESS FOR THE RECOVERY AND PURIFICATION OF MATERIALS

DOEpatents

Long, R.S.; Bailes, R.H.

1958-04-15

A process for the recovery of certain metallic ions from aqueous solutions by ion exchange techniques is described. It is applicable to elements such as vanadium, chromium, nnanganese, and the like, which are capable of forming lower valent cations soluble in aqueous solutions and which also form ldgher valent anions soluble in aqueous acidic solutions. For example, small amounts of vanadium occurring in phosphoric acid prepared from phosphate rock may be recovered by reducing the vanadium to a trivalent cation adsorbing; the vanadium in a cationic exchange resin, then treating the resin with a suitable oxidizing agent to convert the adsorbed vanadium to a higher valent state, and finally eluting; the vanadium as an anion from the resin by means of an aqueous acidic solution.

Results of NDE Technique Evaluation of Clad Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kunerth, Dennis C.

2014-09-01

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

Method for controlled hydrogen charging of metals

DOEpatents

Cheng, Bo-Ching; Adamson, Ronald B.

1984-05-29

A method for controlling hydrogen charging of hydride forming metals through a window of a superimposed layer of a non-hydriding metal overlying the portion of the hydride forming metals to be charged.

A well-defined terminal vanadium(III) oxo complex.

PubMed

King, Amanda E; Nippe, Michael; Atanasov, Mihail; Chantarojsiri, Teera; Wray, Curtis A; Bill, Eckhard; Neese, Frank; Long, Jeffrey R; Chang, Christopher J

2014-11-03

The ubiquity of vanadium oxo complexes in the V+ and IV+ oxidation states has contributed to a comprehensive understanding of their electronic structure and reactivity. However, despite being predicted to be stable by ligand-field theory, the isolation and characterization of a well-defined terminal mononuclear vanadium(III) oxo complex has remained elusive. We present the synthesis and characterization of a unique terminal mononuclear vanadium(III) oxo species supported by the pentadentate polypyridyl ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2). Exposure of [V(II)(NCCH3)(PY5Me2)](2+) (1) to either dioxygen or selected O-atom-transfer reagents yields [V(IV)(O)(PY5Me2)](2+) (2). The metal-centered one-electron reduction of this vanadium(IV) oxo complex furnishes a stable, diamagnetic [V(III)(O)(PY5Me2)](+) (3) species. The vanadium(III) oxo species is unreactive toward H- and O-atom transfer but readily reacts with protons to form a putative vanadium hydroxo complex. Computational results predict that further one-electron reduction of the vanadium(III) oxo species will result in ligand-based reduction, even though pyridine is generally considered to be a poor π-accepting ligand. These results have implications for future efforts toward low-valent vanadyl chemistry, particularly with regard to the isolation and study of formal vanadium(II) oxo species.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Liquid suspensions of reversible metal hydrides

DOEpatents

Reilly, J.J.; Grohse, E.W.; Winsche, W.E.

1983-12-08

The reversibility of the process M + x/2 H/sub 2/ ..-->.. MH/sub x/, where M is a metal hydride former that forms a hydride MH/sub x/ in the presence of H/sub 2/, generally used to store and recall H/sub 2/, is found to proceed under a liquid, thereby to reduce contamination, provide better temperature control and provide in situ mobility of the reactants. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen (at high pressures) and to release (at low pressures) previously stored hydrogen. The direction of the flow of the H/sub 2/ through the liquid is dependent upon the H/sub 2/ pressure in the gas phase at a given temperature. When the former is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particle. When the H/sub 2/ pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Enrichment, Distribution of Vanadium-Containing Protein in Vanadium-Enriched Sea Cucumber Apostichopus japonicus and the Ameliorative Effect on Insulin Resistance.

PubMed

Liu, Yanjun; Zhou, Qingxin; Zhao, Yanlei; Wang, Yiming; Wang, Yuming; Wang, Jingfeng; Xu, Jie; Xue, Changhu

2016-05-01

Sea cucumbers are a potential source of natural organic vanadium that may improve insulin resistance. In this work, vanadium was accumulated rapidly in blood, body wall, and intestine by sea cucumber Apostichopus japonicus. Furthermore, water-soluble vanadium-containing proteins, the main form of the organic vanadium, were tentatively accumulated and isolated by a bioaccumulation experiment. It was also designed to evaluate the beneficial effect of vanadium-containing proteins (VCPs) from sea cucumber rich in vanadium on the development of hyperglycemia and insulin resistance in C57BL/6J mice fed with a high-fat high-sucrose diet (HFSD). HFSD mice treated with VCPs significantly decreased fasting blood glucose, serum insulin, and HOMA-IR values as compared to HFSD mice, respectively. Serum adiponectin, resistin, TNF-α, and leptin levels in insulin-resistant mice were dramatically reduced by a VCP supplement. These results show an ameliorative effect on insulin resistance by treatment with VCPs. Such compound seems to be a valuable therapy to achieve and/or maintain glycemic control and therapeutic agents in the treatment arsenal for insulin resistance and type 2 diabetes.

Comparison of bioavailable vanadium in alfalfa rhizosphere soil extracted by an improved BCR procedure and EDTA, HCl, and NaNO₃ single extractions in a pot experiment with V-Cd treatments.

PubMed

Yang, Jie; Teng, Yanguo; Zuo, Rui; Song, Liuting

2015-06-01

The BCR sequential extraction procedure was compared with EDTA, HCl, and NaNO3 single extractions for evaluating vanadium bioavailability in alfalfa rhizosphere soil. The amounts of vanadium extracted by these methods were in the following order: BCR (bioavailable V) > EDTA ≈ HCl > NaNO3. Both correlation analysis and stepwise regression were adopted to illustrate the extractable vanadium between different reagents. The correlation coefficients between extracted vanadium and the vanadium contents in alfalfa roots were R NaNO3 = 0.948, R HCl = 0.902, R EDTA = 0.816, and R bioavailable V = 0.819. The stepwise multiple regression equation of the NaNO3 extraction was the most significant at a 95 % confidence interval. The influence of pH, total organic carbon, and cadmium content of soil to vanadium bioavailability were not definite. In summary, both the BCR sequential extraction and the single extraction methods were valid approaches for predicting vanadium bioavailability in alfalfa rhizosphere soil, especially the single extractions.

Extraction of Vanadium from Vanadium Slag Via Non-salt Roasting and Ammonium Oxalate Leaching

NASA Astrophysics Data System (ADS)

Li, Meng; Du, Hao; Zheng, Shili; Wang, Shaona; Zhang, Yang; Liu, Biao; Dreisinger, David Bruce; Zhang, Yi

2017-10-01

A clean method featuring non-salt roasting followed by (NH4)2C2O4 leaching to recover vanadium from vanadium slag was proposed. The carcinogenic Cr6+ compounds and exhaust gases were avoided, and the water generated from vanadate precipitation may be recycled and reused in this new leaching process. The leaching residues may be easily used by a blast furnace. Moreover, (NH4)2C2O4 solution was used as a leaching medium to avoid expensive and complicated ammonium controlling operations as a result of the stability of (NH4)2C2O4 at a high temperature. The transformation mechanisms of vanadium- and chromium-bearing phases were systematically investigated by x-ray diffraction analysis and scanning electron microscopy with energy-disperse x-ray spectrometry, respectively. In addition, the effects of oxygen concentration, roasting temperature, and holding time on vanadium recovery were investigated. Finally, the effects of leaching variables on the vanadium leaching rate were also examined.

Theoretical analysis and experiments for the carburization of vanadium-bearing hot metal

NASA Astrophysics Data System (ADS)

Ma, Deng; Wu, Wei; Dai, Shifan; Liu, Zhibin

2018-01-01

In this study, the feasibility of the carburization of vanadium-bearing hot metal was first investigated by thermodynamic analysis. Next, three carburizers, namely a low-nitrogen carburizer, anthracite, and coke, were used for carburization of 500 g of vanadium-bearing hot metal at 1450 °C, 1500 °C, and 1550 °C, respectively. The carbon increments for the low-nitrogen carburizer, anthracite and coke followed decreasing order in the temperature range from 1450 °C to 1550 °C. Anthracite was the most cost-effective carburizer. Hence, anthracite is used in pilot-scale experiments of the vanadium-bearing hot metal (100 kg and 200 kg). Finally, vanadium extraction experiments of the vanadium-bearing hot metal were carried out in a top-bottom-combined blowing induction furnace. It is proved that the average superheat degree of semi-steel increases from 100 °C to 198 °C by the carburization of vanadium-containing hot metal. Foundation Item: Item Sponsored by National Science Foundation of China (51674092)

Vanadium-Binding Ability of Nucleoside Diphosphate Kinase from the Vanadium-Rich Fan Worm, Pseudopotamilla occelata.

PubMed

Yamaguchi, Nobuo; Yoshinaga, Masafumi; Kamino, Kei; Ueki, Tatsuya

2016-06-01

Polychaete fan worms and ascidians accumulate high levels of vanadium ions. Several vanadiumbinding proteins, known as vanabins, have been found in ascidians. However, no vanadium-binding factors have been isolated from the fan worm. In the present study, we sought to identify vanadiumbinding proteins in the branchial crown of the fan worm using immobilized metal ion affinity chromatography. A nucleoside diphosphate kinase (NDK) homolog was isolated and determined to be a vanadium-binding protein. Kinase activity of the NDK homologue, PoNDK, was suppressed by the addition of V(IV), but was unaffected by V(V). The effect of V(IV) on PoNDK precedes its activation by Mg(II). This is the first report to describe the relationship between NDK and V(IV). PoNDK is located in the epidermis of the branchial crown, and its distribution is very similar to that of vanadium. These results suggest that PoNDK is associated with vanadium accumulation and metabolism in P. occelata.

Critical V2O5/TeO2 Ratio Inducing Abrupt Property Changes in Vanadium Tellurite Glasses.

PubMed

Kjeldsen, Jonas; Rodrigues, Ana C M; Mossin, Susanne; Yue, Yuanzheng

2014-12-26

Transition metal containing glasses have unique electrical properties and are therefore often used for electrochemical applications, such as in batteries. Among oxide glasses, vanadium tellurite glasses exhibit the highest electronic conductivity and thus the high potential for applications. In this work, we investigate how the dynamic and physical properties vary with composition in the vanadium tellurite system. The results show that there exists a critical V(2)O(5) concentration of 45 mol %, above which the local structure is subjected to a drastic change with increasing V(2)O(5), leading to abrupt changes in both hardness and liquid fragility. Electronic conductivity does not follow the expected correlation to the valence state of the vanadium as predicted by the Mott-Austin equation but shows a linear correlation to the mean distance between vanadium ions. These findings could contribute to designing optimum vanadium tellurite compositions for electrochemical devices. The work gives insight into the mechanism of electron conduction in the vanadium tellurite systems.

Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

NASA Astrophysics Data System (ADS)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

2018-03-01

In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V2O5; therefore, wastewater containing a high level of NH4 + is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH4 + concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH4 + was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.

Recent progress on gas tungsten arc welding of vanadium alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, J.F.; Grossbeck, M.L.; Goodwin, G.M.

1997-04-01

This is a progress report on a continuing research project to acquire a fundamental understanding of the metallurgical processes in the welding of vanadium alloys. It also has the goal of developing techniques for welding structural vanadium alloys. The alloy V-4Cr-4Ti is used as a representative alloy of the group; it is also the prime candidate vanadium alloy for the U.S. Fusion Program at the present time. However, other alloys of this class were used in the research as necessary. The present work focuses on recent findings of hydrogen embrittlement found in vanadium alloy welds. It was concluded that themore » atmosphere in the inert gas glove box was insufficient for welding 6mm thick vanadium alloy plates.« less

The Influence of Vanadium on Ferrite and Bainite Formation in a Medium Carbon Steel

NASA Astrophysics Data System (ADS)

Sourmail, T.; Garcia-Mateo, C.; Caballero, F. G.; Cazottes, S.; Epicier, T.; Danoix, F.; Milbourn, D.

2017-09-01

The influence of vanadium additions on transformation kinetics has been investigated in a medium carbon forging steel. Using dilatometry to track transformation during continuous cooling or isothermal transformation, the impact of vanadium on both ferrite-pearlite and bainite has been quantified. Transmission electron microscopy and atom probe tomography have been used to establish whether vanadium was present in solid solution, or as clusters and precipitates. The results show that vanadium in solid solution has a pronounced retarding influence on ferrite-pearlite formation and that, unlike in the case of niobium, this effect can be exploited even during relatively slow cooling. The influence on bainite transformation was found to depend on temperature; an explanation in terms of the effect of vanadium on heterogeneous nucleation is tentatively proposed.

Development of metal hydride composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Congdon, J.W.

1992-12-01

Most of current hydride technology at Savannah River Site is based on beds of metal hydride powders; the expansion upon hydridation and the cycling results in continued breakdown into finer particles. Goal is to develop a composite which will contain the fines in a dimensionally stable matrix, for use in processes which require a stable gas flow through a hydride bed. Metal hydride composites would benefit the advanced Thermal Cycling Absorption process (hydrogen isotope separation), and the Replacement Tritium Facility (storage, pumping, compression, purification of hydrogen isotopes). These composites were fabricated by cold compaction of a mixture of metal hydridemore » granules and coarse copper powder; the porosity in the granules was introduced by means of ammonium carbonate. The composite pellets were cycled 138 times in hydrogen with the loss of LANA0.75 (LaNi{sub 4.25}Al{sub 0.75}) limited to the surface. Vacuum sintering can provide additional strength at the edges. Without a coating, the metal hydride particles exposed at the pellet surface can be removed by cycling several times in hydrogen.« less

Effects of outgassing of loader chamber walls on hydriding of thin films for commercial applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Provo, James L., E-mail: jlprovo@verizon.net

2014-07-01

An important aspect of understanding industrial processing is to know the characteristics of the materials used in such processes. A study was performed to determine the effects of hydriding chamber material on the degree of hydriding for the commercial production of thin film hydride targets for various research universities, commercial companies, and government national laboratories. The goal was to increase the degree of hydriding of various thin film hydrides and to study the vacuum environment during air-exposure hydriding. For this purpose, dynamic residual gas analysis during deuterium gas hydride processing was utilized with erbium thin films, employing a special set-upmore » for direct dynamic hydride gas sampling during processing at elevated temperature and full loading gas pressure. Complete process data for (1) a copper–(1.83 wt. %)beryllium wet hydrogen fired passivated (600 °C–1 h) externally heated pipe hydriding chamber are reported. Dynamic residual gas analysis comparisons during hydriding are presented for hydriding chambers made from (2) alumina (99.8 wt. %), (3) copper (with an interior aluminum coating ∼10 k Å thick, and (4) for a stainless-steel air-fired passivated (900 °C–1 h) chamber. Dynamic data with deuterium gas in the chamber at the hydriding temperature (450 °C) showed the presence and growth of water vapor (D{sub 2}O) and related mixed ion species(H{sub 2}O{sup +}, HDO{sup +}, D{sub 2}O{sup +}, and OD{sup +}) from hydrogen isotope exchange reactions during the 1 h process time. Peaks at mass-to-charge ratios (i.e., m/e) of 12(C{sup +}), 16(CD{sub 2}{sup +}), 17(CHD{sub 2}{sup +}), and 18(CD{sub 3}{sup +}, OD{sup +}) increased for approximately the first half hour of a 1 h hydriding process and then approach steady state. Mass-to-charge peaks at 19(HDO{sup +}) and 20(D{sub 2}O{sup +}) continue to increase throughout the process cycle. Using the m/e = 20 (D{sub 2}O{sup +}) peak intensity from chamber (1)–Cu(1.83 wt. %)Be as a standard, the peak intensity from chamber (4)—stainless-steel (air-fired) was 7.1× higher, indicating that the surface of stainless-steel had a larger concentration of reactive oxygen and/or water than hydrogen. The (D{sub 2}O{sup +}) peak intensity from chamber (3)—Cu (interior Al coating) was 1.55× larger and chamber (2)—alumina(99.8%) was 1.33× higher than Cu(1.83 wt. %)Be. Thus copper–(1.83 wt. %)beryllium was the best hydriding chamber material studied followed closely by the alumina (99.8 wt. %) chamber. Gas take-up by Er occluder targets processed in Cu(1.83 wt. %)Be hydriding chambers (i.e., gas/metal atomic ratios) correlate with the dynamic RGA data.« less

The structural studies of vanadium substituted lithium-bismuth-boro-tellurite glass

NASA Astrophysics Data System (ADS)

Madhu, A.; Eraiah, B.

2018-05-01

The structural studies of vanadium substituted lithium-bismuth-boro-tellurite glass is successfully prepared and certain analysis like XRD,FTIR,DTA/TGA with density, molar volume are done. The amorphous phase has been identified based on X-ray diffraction analysis. The vanadium oxide plays the role as a glass-modifier and influences on BO3 ↔ BO4 conversion. The observed nonlinear variation in Tg with vanadium oxide increase, it reflects structural changes. The nonlinear variation of density and molar volume can be attributed to vanadium oxide incorporation have increased the number of Non-bridging oxygen (NBO'S).

Use of reversible hydrides for hydrogen storage

NASA Technical Reports Server (NTRS)

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

1980-01-01

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

High temperature metal hydrides as heat storage materials for solar and related applications.

PubMed

Felderhoff, Michael; Bogdanović, Borislav

2009-01-01

For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 degrees C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

PubMed Central

Felderhoff, Michael; Bogdanović, Borislav

2009-01-01

For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described. PMID:19333448

Quantitation and detection of vanadium in biologic and pollution materials

NASA Technical Reports Server (NTRS)

Gordon, W. A.

1974-01-01

A review is presented of special considerations and methodology for determining vanadium in biological and air pollution materials. In addition to descriptions of specific analysis procedures, general sections are included on quantitation of analysis procedures, sample preparation, blanks, and methods of detection of vanadium. Most of the information presented is applicable to the determination of other trace elements in addition to vanadium.

Sodium-based hydrides for thermal energy applications

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Dimensionally stable metallic hydride composition

DOEpatents

Heung, Leung K.

1994-01-01

A stable, metallic hydride composition and a process for making such a composition. The composition comprises a uniformly blended mixture of a metal hydride, kieselguhr, and a ballast metal, all in the form of particles. The composition is made by subjecting a metal hydride to one or more hydrogen absorption/desorption cycles to disintegrate the hydride particles to less than approximately 100 microns in size. The particles are partly oxidized, then blended with the ballast metal and the kieselguhr to form a uniform mixture. The mixture is compressed into pellets and calcined. Preferably, the mixture includes approximately 10 vol. % or more kieselguhr and approximately 50 vol. % or more ballast. Metal hydrides that can be used in the composition include Zr, Ti, V, Nb, Pd, as well as binary, tertiary, and more complex alloys of La, Al, Cu, Ti, Co, Ni, Fe, Zr, Mg, Ca, Mn, and mixtures and other combinations thereof. Ballast metals include Al, Cu and Ni.

ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jy-An John; Yan, Yong; Wang, Hong

A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydridesmore » in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation tests of hydrided Zircaloy-4 cladding, which served as a guideline to prepare in-cell hydride reorientation samples with high burnup HBR fuel segments. This report also provides the Phase II CIRFT test data for the hydride reorientation irradiated samples. The variations in fatigue life are provided in terms of moment, equivalent stress, curvature, and equivalent strain for the tested SNFs. The CIRFT results appear to indicate that hydride reoriented treatment (HRT) have a negative effect on fatigue life, in addition to hydride reorientation effect. For HR4 specimen that had no pressurization procedure applied, the thermal annealing treatment alone showed a negative impact on the fatigue life compared to the HBR rod.« less

Effect of vanadium on colonic aberrant crypt foci induced in rats by 1,2 Dimethyl hydrazine

PubMed Central

Kanna, P Suresh; Mahendrakumar, CB; Chakraborty, T; Hemalatha, P; Banerjee, Pratik; Chatterjee, M

2003-01-01

AIM: To investigate the chemo preventive effects of vanadium on rat colorectal carcinogenesis induced by 1,2-dimethylhydrazine (DMH). METHODS: Male Sprague-Dawley Rats were randomly divided into four groups. Rats in Group A received saline vehicle alone for 16 weeks. Rats in Group B were given DMH injection once a week intraperitoneally for 16 weeks; rats in Group C, with the same DMH treatment as in the Group B, but received 0.5-ppm vanadium in the form ammonium monovanadate ad libitum in drinking water. Rats in the Group D received vanadium alone as in the Group C without DMH injection. RESULTS: Aberrant crypt foci (ACF) were formed in animals in DMH-treated groups at the end of week 16. Compared to DMH group, vanadium treated group had less ACF (P < 0.001). At the end of week 32, all rats in DMH group developed large intestinal tumors. Rats treated with vanadium contained significantly few colonic adenomas and carcinomas (P < 0.05) compared to rats administered DMH only. In addition, a significant reduction (P < 0.05) in colon tumor burden (sum of tumor sizes per animal) was also evident in animals of Group C when compared to those in rats of carcinogen control Group B. The results also showed that vanadium significantly lowered PCNA index in ACF (P < 0.005). Furthermore, vanadium supplementation also elevated liver GST and Cyt P-450 activities (P < 0.001 and P < 0.02, respectively). CONCLUSION: Vanadium in the form of ammonium monovanadate supplemented in drinking water ad libitum has been found to be highly effective in reducing tumor incidence and preneoplastic foci on DMH-induced colorectal carcinogenesis. These findings suggest that vanadium administration can suppress colon carcinogenesis in rats. PMID:12717849

An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite.

PubMed

Chen, Desheng; Zhao, Hongxin; Hu, Guoping; Qi, Tao; Yu, Hongdong; Zhang, Guozhi; Wang, Lina; Wang, Weijing

2015-08-30

An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite was developed. In this study, a mixed solvent system of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) diluted with kerosene was used for the selective extraction of vanadium from a hydrochloric acid leaching solution that contained low vanadium concentration with high concentrations of iron and impurities of Ca, Mg, and Al. In the extraction process, the initial solution pH and the phase ratio had considerable functions in the extraction of vanadium from the hydrochloric acid leaching solution. Under optimal extraction conditions (i.e., 30-40°C for 10min, 1:3 phase ratio (O/A), 20% D2EHPA concentration (v/v), and 0-0.8 initial solution pH), 99.4% vanadium and only 4.2% iron were extracted by the three-stage counter-current extraction process. In the stripping process with H2SO4 as the stripping agent and under optimal stripping conditions (i.e., 20% H2SO4 concentration, 5:1 phase ratio (O/A), 20min stripping time, and 40°C stripping temperature), 99.6% vanadium and only 5.4% iron were stripped by the three-stage counter-current stripping process. The stripping solution contained 40.16g/LV2O5,0.691g/L Fe, 0.007g/L TiO2, 0.006g/L SiO2 and 0.247g/L CaO. A V2O5 product with a purity of 99.12% V2O5 and only 0.026% Fe was obtained after the oxidation, precipitation, and calcination processes. The total vanadium recovered from the hydrochloric acid leaching solution was 85.5%. Copyright © 2015 Elsevier B.V. All rights reserved.

A study on the reaction of Zircaloy-4 tube with hydrogen/steam mixture

NASA Astrophysics Data System (ADS)

Lee, Ji-Min; Kook, Dong-Hak; Cho, Il-Je; Kim, Yong-Soo

2017-08-01

In order to fundamentally understand the secondary hydriding mechanism of zirconium alloy cladding, the reaction of commercial Zircaloy-4 tubes with hydrogen and steam mixture was studied using a thermo-gravimetric analyser with two variables, H2/H2O ratio and temperature. Phenomenological analysis revealed that in the steam starvation condition, i.e., when the H2/H2O ratio is greater than 104, hydriding is the dominant reaction and the weight gain increases linearly after a short incubation time. On the other hand, when the gas ratio is 5 × 102 or 103, both hydriding and oxidation reactions take place simultaneously, leading to three distinct regimes: primary hydriding, enhanced oxidation, and massive hydriding. Microstructural changes of oxide demonstrate that when the weight gain exceeds a certain critical value, massive hydriding takes place due to the significant localized crack development within the oxide, which possibly simulates the secondary hydriding failure in a defective fuel operation. This study reveals that the steam starvation condition above the critical H2/H2O ratio is only a necessary condition for the secondary hydriding failure and, as a sufficient condition, oxide needs to grow sufficiently to reach the critical thickness that produces substantial crack development. In other words, in a real defective fuel operation incident, the secondary failure is initiated only when both steam starvation and oxide degradation conditions are simultaneously met. Therefore, it is concluded that the indispensable time for the critical oxide growth primarily determines the triggering time of massive hydriding failure.

Silica hydride intermediate for octadecylsilica and phenyl bonded phase preparation via heterogeneous hydrosilation in supercritical carbon dioxide.

PubMed

Scully, N M; Ashu-Arrah, B A; Nagle, A P; Omamogho, J O; O'Sullivan, G P; Friebolin, V; Dietrich, B; Albert, K; Glennon, J D

2011-04-15

Investigations into the preparation of silica hydride intermediate in supercritical carbon dioxide (sc-CO(2)) that avoids the use of organic solvents such as toluene or dioxane are described. The effects of reaction temperature, pressure and time on the surface coverage of the supercritical fluid generated silica hydride intermediate were studied. Under optimised supercritical conditions of 120°C, 483 bar and 3 h reaction time, silica hydride (Si-H) conversion efficiencies of ca. 40% were achieved for the hydride intermediate prepared from a monofunctional silane reagent (dimethylmethoxysilane). Si-H conversion efficiencies (as determined from (29)Si CP-MAS NMR spectral analysis) for the hydride intermediate prepared from triethoxysilane (TES) in sc-CO(2) were found to be comparable to those obtained using a TES silanisation approach in an organic solvent. (13)C and (29)Si CP-MAS-NMR spectroscopy was employed to provide a complete structural assignment of the silica hydride intermediates. Furthermore, supercritical CO(2) was subsequently employed as a reaction medium for the heterogenous hydrosilation of silica hydride with octadecene and with styrene, in the presence of a free radical initiator. These supercritical fluid generated reversed-phase materials were prepared in a substantially reduced reaction time (3 h) compared to organic solvent based methods (100 h reaction time). Silica functionalisation in sc-CO(2) presents an efficient and clean alternative to organic solvent based methods for the preparation of important silica hydride intermediate and silica bonded stationary phases via a hydrosilation approach. Copyright © 2010 Elsevier B.V. All rights reserved.

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

PubMed

Sepehr, Fatemeh; Paddison, Stephen J

2015-06-04

Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

Sealed aerospace metal-hydride batteries

NASA Technical Reports Server (NTRS)

Coates, Dwaine

1992-01-01

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

Precipitation of hydrides in high purity niobium after different treatments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkov, F.; Romanenko, A.; Trenikhina, Y.

Precipitation of lossy non-superconducting niobium hydrides represents a known problem for high purity niobium in superconducting applications. Using cryogenic optical and laser confocal scanning microscopy we have directly observed surface precipitation and evolution of niobium hydrides in samples after different treatments used for superconducting RF cavities for particle acceleration. Precipitation is shown to occur throughout the sample volume, and the growth of hydrides is well described by the fast diffusion-controlled process in which almost all hydrogen is precipitated atmore » $T=140$~K within $$\\sim30$$~min. 120$$^{\\circ}$$C baking and mechanical deformation are found to affect hydride precipitation through their influence on the number of nucleation and trapping centers.« less

Hydrolysis reactor for hydrogen production

DOEpatents

Davis, Thomas A.; Matthews, Michael A.

2012-12-04

In accordance with certain embodiments of the present disclosure, a method for hydrolysis of a chemical hydride is provided. The method includes adding a chemical hydride to a reaction chamber and exposing the chemical hydride in the reaction chamber to a temperature of at least about 100.degree. C. in the presence of water and in the absence of an acid or a heterogeneous catalyst, wherein the chemical hydride undergoes hydrolysis to form hydrogen gas and a byproduct material.

Modified lithium vanadium oxide electrode materials products and methods

DOEpatents

Thackeray, Michael M.; Kahaian, Arthur J.; Visser, Donald R.; Dees, Dennis W.; Benedek, Roy

1999-12-21

A method of improving certain vanadium oxide formulations is presented. The method concerns fluorine doping formulations having a nominal formula of LiV.sub.3 O.sub.8. Preferred average formulations are provided wherein the average oxidation state of the vanadium is at least 4.6. Herein preferred fluorine doped vanadium oxide materials, electrodes using such materials, and batteries including at least one electrode therein comprising such materials are provided.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Zhicheng; Rao, Linfeng; Abney, Carter W.

Adsorbents developed for the recovery of uranium from seawater display poor selectivity over other transition metals present in the ocean, with vanadium particularly problematic. To improve selectivity, an indispensable step is the positive identification of metal binding environments following actual seawater deployment. In this work we apply x-ray absorption fine structure (XAFS) spectroscopy to directly investigate the vanadium binding environment on seawater-deployed polyamidoxime adsorbents. Comparison of the x-ray absorption near edge spectra (XANES) reveal marked similarities to recently a reported non-oxido vanadium (V) structure formed upon binding with cyclic imidedioxime, a byproduct of generating amidoxime functionalities. Density functional theory (DFT)more » calculations provided a series of putative vanadium binding environments for both vanadium (IV) and vanadium (V) oxidation states, and with both amidoxime and cyclic imidedioxime. Fits of the extended XAFS (EXAFS) data confirmed vanadium (V) is bound exclusively by the cyclic imidedioxime moiety in a 1:2 metal:ligand fashion, though a modest structural distortion is also observed compared to crystal structure data and computationally optimized geometries which is attributed to morphology effects from the polymer graft chain and the absence of crystal packing interactions. These results demonstrate that improved selectivity for uranium over vanadium can be achieved by suppressing the formation of cyclic imidedioxime during preparation of polyamidoxime adsorbents for seawater uranium recovery.« less

Amorphous Mixed-Valence Vanadium Oxide/Exfoliated Carbon Cloth Structure Shows a Record High Cycling Stability.

PubMed

Song, Yu; Liu, Tian-Yu; Yao, Bin; Kou, Tian-Yi; Feng, Dong-Yang; Liu, Xiao-Xia; Li, Yat

2017-04-01

Previous studies show that vanadium oxides suffer from severe capacity loss during cycling in the liquid electrolyte, which has hindered their applications in electrochemical energy storage. The electrochemical instability is mainly due to chemical dissolution and structural pulverization of vanadium oxides during charge/discharge cyclings. In this study the authors demonstrate that amorphous mixed-valence vanadium oxide deposited on exfoliated carbon cloth (CC) can address these two limitations simultaneously. The results suggest that tuning the V 4+ /V 5+ ratio of vanadium oxide can efficiently suppress the dissolution of the active materials. The oxygen-functionalized carbon shell on exfoliated CC can bind strongly with VO x via the formation of COV bonding, which retains the electrode integrity and suppresses the structural degradation of the oxide during charging/discharging. The uptake of structural water during charging and discharging processes also plays an important role in activating the electrode material. The amorphous mixed-valence vanadium oxide without any protective coating exhibits record-high cycling stability in the aqueous electrolyte with no capacitive decay in 100 000 cycles. This work provides new insights on stabilizing vanadium oxide, which is critical for the development of vanadium oxide based energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physics of hydride fueled PWR

NASA Astrophysics Data System (ADS)

Ganda, Francesco

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

Hydrogen Production by Steam Reforming of Natural Gas Over Vanadium-Nickel-Alumina Catalysts.

PubMed

Yoo, Jaekyeong; Park, Seungwon; Song, Ji Hwan; Song, In Kyu

2018-09-01

A series of vanadium-nickel-alumina (xVNA) catalysts were prepared by a single-step sol-gel method with a variation of vanadium content (x, wt%) for use in the hydrogen production by steam reforming of natural gas. The effect of vanadium content on the physicochemical properties and catalytic activities of xVNA catalysts in the steam reforming of natural gas was investigated. It was found that natural gas conversion and hydrogen yield showed volcano-shaped trends with respect to vanadium content. It was also revealed that natural gas conversion and hydrogen yield increased with decreasing nickel crystallite size.

Effect of vanadium compounds on acid phosphatase activity.

PubMed

Vescina, C M; Sálice, V C; Cortizo, A M; Etcheverry, S B

1996-01-01

The direct effect of different vanadium compounds on acid phosphatase (ACP) activity was investigated. Vanadate and vanadyl but not pervanadate inhibited the wheat germ ACP activity. These vanadium derivatives did not alter the fibroblast Swiss 3T3 soluble fraction ACP activity. Using inhibitors of tyrosine phosphatases (PTPases), the wheat germ ACP was partially characterized as a PTPase. This study suggests that the inhibitory ability of different vanadium derivatives to modulate ACP activity seems to depend on the geometry around the vanadium atom more than on the oxidation state. Our results indicate a correlation between the PTPase activity and the sensitivity to vanadate and vanadyl cation.

Chemical Hydride Slurry for Hydrogen Production and Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClaine, Andrew W

2008-09-30

The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH 2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at amore » time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston University have demonstrated the technical viability of the process and have provided data for the cost analyses that have been performed. We also concluded that a carbothermic process could also produce magnesium at acceptable costs. The use of slurry as a medium to carry chemical hydrides has been shown during this project to offer significant advantages for storing, delivering, and distributing hydrogen: • Magnesium hydride slurry is stable for months and pumpable. • The oils of the slurry minimize the contact of oxygen and moisture in the air with the metal hydride in the slurry. Thus reactive chemicals, such as lithium hydride, can be handled safely in the air when encased in the oils of the slurry. • Though magnesium hydride offers an additional safety feature of not reacting readily with water at room temperatures, it does react readily with water at temperatures above the boiling point of water. Thus when hydrogen is needed, the slurry and water are heated until the reaction begins, then the reaction energy provides heat for more slurry and water to be heated. • The reaction system can be relatively small and light and the slurry can be stored in conventional liquid fuel tanks. When transported and stored, the conventional liquid fuel infrastructure can be used. • The particular metal hydride of interest in this project, magnesium hydride, forms benign byproducts, magnesium hydroxide (“Milk of Magnesia”) and magnesium oxide. • We have estimated that a magnesium hydride slurry system (including the mixer device and tanks) could meet the DOE 2010 energy density goals. During the investigation of hydriding techniques, we learned that magnesium hydride in a slurry can also be cycled in a rechargeable fashion. Thus, magnesium hydride slurry can act either as a chemical hydride storage medium or as a rechargeable hydride storage system. Hydrogen can be stored and delivered and then stored again thus significantly reducing the cost of storing and delivering hydrogen. Further evaluation and development of this concept will be performed as follow-on work under another project. However, since the cost of reducing magnesium from magnesium oxide makes up 85% of the cost of the slurry, if hydrogen can be stored many times in the slurry, then the cost of storing hydrogen can be spread over many units of hydrogen and can be significantly reduced from the costs of a chemical hydride system. This may be the most important finding of this project. If the slurry is used to carry a rechargeable hydride, the slurry can be stored in a conventional liquid fuel tank and delivered to a release system as hydrogen is needed. The release system will contain only the hydride needed to produce the hydrogen desired. This is in contrast to conventional designs proposed for other rechargeable hydride systems that store all the hydride in a large and heavy pressure and heat transfer vessel.« less

Carbon-Hydrogen Activation in Zerovalent Bis(1,5-cyclooctadiene) Complexes of the First Row Transition Metals: A Theoretical Study.

PubMed

Hu, Jia; Feng, Hao; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

2018-03-29

Stepwise interaction of first row transition metal atoms with 1,5-cyclooctadiene to give (C 8 H 12 ) 2 M complexes is studied using the M06-L/DZP density functional method. The experimentally known (C 8 H 12 ) 2 Ni is the thermodynamically most favorable complex, with a predicted geometry consistent with its experimental structure as determined by X-ray crystallography. The other transition metal atoms from scandium to zinc also interact exothermically with 1,5-cyclooctadiene to give (C 8 H 12 ) 2 M derivatives, but these exhibit lower symmetry than the S 4 symmetry exhibited by (C 8 H 12 ) 2 Ni. Carbon-hydrogen activation of CH 2 groups in a C 8 H 12 ligand is predicted for most systems. Thus, conversion of (η 2,2 -C 8 H 12 ) 2 M to (η 3,2 -C 8 H 11 )(η 2,1 -C 8 H 13 )M, through a hydride intermediate (η 3,2 -C 8 H 11 )(η 2,2 -C 8 H 12 )MH, is predicted for scandium, vanadium, chromium, manganese, and cobalt. For titanium with a low-lying empty orbital, further C-H activation through a hydride intermediate (η 6 -C 8 H 10 )(η 2,1 -C 8 H 13 )TiH is predicted, leading ultimately to (η 6 -C 8 H 10 )(η 1,1 -C 8 H 14 )Ti, in which the hexahapto η 6 -C 8 H 10 ligand is shown by NICS to be aromatic. These two C-H activation processes on a titanium center represent the dehydrogenation of 1,5-cyclooctadiene to 1,3,5-cyclooctatriene with the second 1,5-cyclooctadiene ligand as the hydrogen acceptor. For zinc C-H activation terminates at (η 1 -C 8 H 11 )(C 8 H 12 )ZnH, which has a C-Zn-H three-center bond. No energetically favorable C-H activation processes are predicted for the iron, nickel, and copper (η 2,2 -C 8 H 12 ) 2 M derivatives.

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

NASA Technical Reports Server (NTRS)

Zollars, G. F.

1980-01-01

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

Key hydride vibrational modes in [NiFe] hydrogenase model compounds studied by resonance Raman spectroscopy and density functional calculations.

PubMed

Shafaat, Hannah S; Weber, Katharina; Petrenko, Taras; Neese, Frank; Lubitz, Wolfgang

2012-11-05

Hydrogenase proteins catalyze the reversible conversion of molecular hydrogen to protons and electrons. While many enzymatic states of the [NiFe] hydrogenase have been studied extensively, there are multiple catalytically relevant EPR-silent states that remain poorly characterized. Analysis of model compounds using new spectroscopic techniques can provide a framework for the study of these elusive states within the protein. We obtained optical absorption and resonance Raman (RR) spectra of (dppe)Ni(μ-pdt)Fe(CO)(3) and [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)(3)][BF(4)], which are structural and functional model compounds for the EPR-silent Ni-SI and Ni-R states of the [NiFe] hydrogenase active site. The studies presented here use RR spectroscopy to probe vibrational modes of the active site, including metal-hydride stretching vibrations along with bridging ligand-metal and Fe-CO bending vibrations, with isotopic substitution used to identify key metal-hydride modes. The metal-hydride vibrations are essentially uncoupled and represent isolated, localized stretching modes; the iron-hydride vibration occurs at 1530 cm(-1), while the nickel-hydride vibration is observed at 945 cm(-1). The significant discrepancy between the metal-hydride vibrational frequencies reflects the slight asymmetry in the metal-hydride bond lengths. Additionally, time-dependent density functional theory (TD-DFT) calculations were carried out to obtain theoretical RR spectra of these compounds. On the basis of the detailed comparison of theory and experiment, the dominant electronic transitions and significant normal modes probed in the RR experiments were assigned; the primary transitions in the visible wavelengths represent metal-to-metal and metal-to-ligand charge transfer bands. Inherent properties of metal-hydride vibrational modes in resonance Raman spectra and DFT calculations are discussed together with the prospects of observing such vibrational modes in metal-hydride-containing proteins. Such a combined theoretical and experimental approach may be valuable for characterization of analogous redox states in the [NiFe] hydrogenases.

Metastable Metal Hydrides for Hydrogen Storage

DOE PAGES

Graetz, Jason

2012-01-01

The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However, a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however, many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. Onmore » the other hand, the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid, low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However, a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.« less

Investigation of the reaction of 5Al-2.5Sn titanium with hydrogen at subzero temperature

NASA Technical Reports Server (NTRS)

Williams, D. N.; Wood, R. A.

1972-01-01

An investigation of the effect of temperature on the surface hydriding reaction of 5Al-2.5Sn titanium exposed to hydrogen at 250 psig was made. The temperature range studied extended from 160 F to -160 F. Reaction conditions were controlled so as to expose a vacuum-cleaned, oxide-free alloy surface to an ultrapure hydrogen atmosphere. Reaction times up to 1458 hours were studied. The hydriding reaction was extremely sensitive to experimental variables and the reproducibility of reaction behavior was poor. However, it was demonstrated that the reaction proceeded quite rapidly at 160 F; as much as 1 mil surface hydriding being observed after exposure for 162 hours. The amount of hydriding appeared to decrease with decreasing temperature at 75 F, -36 F, and -76 F. No surface hydriding was detected either by vacuum fusion analysis or by metallographic examination after exposure for 1458 hours at -110 F or -160 F. Tensile properties were unaffected by surface hydriding of the severity developed in this program (up to 1 mil thick) as determined by slow strain rate testing of hydrided sheet tensile samples.

Method of making crack-free zirconium hydride

DOEpatents

Sullivan, Richard W.

1980-01-01

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

Apparatus for chemical synthesis

DOEpatents

Kong, Peter C [Idaho Falls, ID; Herring, J Stephen [Idaho Falls, ID; Grandy, Jon D [Idaho Falls, ID

2011-05-10

A method and apparatus for forming a chemical hydride is described and which includes a pseudo-plasma-electrolysis reactor which is operable to receive a solution capable of forming a chemical hydride and which further includes a cathode and a movable anode, and wherein the anode is moved into and out of fluidic, ohmic electrical contact with the solution capable of forming a chemical hydride and which further, when energized produces an oxygen plasma which facilitates the formation of a chemical hydride in the solution.

Method and apparatus for chemical synthesis

DOEpatents

Kong; Peter C. , Herring; J. Stephen , Grandy; Jon D.

2007-12-04

A method and apparatus for forming a chemical hydride is described and which includes a pseudo-plasma-electrolysis reactor which is operable to receive a solution capable of forming a chemical hydride and which further includes a cathode and a movable anode, and wherein the anode is moved into and out of fluidic, ohmic electrical contact with the solution capable of forming a chemical hydride and which further, when energized produces an oxygen plasma which facilitates the formation of a chemical hydride in the solution.

The Crystal Structure of Thorium and Zirconium Dihydrides by X-ray and Neutron Diffraction

DOE R&D Accomplishments Database

Rundle, R.E.; Shull, C.G.; Wollan, E.O.

1951-04-20

Thorium forms a tetragonal lower hydride of composition ThH{sub 2}. The hydrides ThH{sub 2}, ThD{sub 2}, and ZrD{sub 2} have been studied by neutron diffraction in order that hydrogen positions could be determined. The hydrides are isomorphous, and have a deformed fluorite structure. Metal-hydrogen distances in thorium hydride are unusually large, as in UH{sub 3}. Thorium and zirconium scattering amplitudes and a revised scattering amplitude for deuterium are reported.

SUPERCONDUCTING VANADIUM BASE ALLOY

DOEpatents

Cleary, H.J.

1958-10-21

A new vanadium-base alloy which possesses remarkable superconducting properties is presented. The alloy consists of approximately one atomic percent of palladium, the balance being vanadium. The alloy is stated to be useful in a cryotron in digital computer circuits.

Mineral resource of the month: vanadium

USGS Publications Warehouse

Magyar, Michael J.

2007-01-01

Vanadium, the name of which comes from Vanadis, a goddess in Scandinavian mythology, is one of the most important ferrous metals. Vanadium has many uses, but the metal’s metallurgical applications, such as an alloying element in iron and steel, account for more than 85 percent of U.S. consumption. The dominant nonmetallurgical use of the metal is as a catalyst for the production of maleic anhydride and sulfuric acid, ceramics, vanadium chemicals and electronics.

Hydrophilic Channel Alignment of Perfluoronated Sulfonic-Acid Ionomers for Vanadium Redox Flow Batteries.

PubMed

So, Soonyong; Cha, Min Suc; Jo, Sang-Woo; Kim, Tae-Ho; Lee, Jang Yong; Hong, Young Taik

2018-06-13

It is known that uniaxially drawn perfluoronated sulfonic-acid ionomers (PFSAs) show diffusion anisotropy because of the aligned water channels along the deformation direction. We apply the uniaxially stretched membranes to vanadium redox flow batteries (VRFBs) to suppress the permeation of active species, vanadium ions through the transverse directions. The aligned water channels render much lower vanadium permeability, resulting in higher Coulombic efficiency (>98%) and longer self-discharge time (>250 h). Similar to vanadium ions, proton conduction through the membranes also decreases as the stretching ratio increases, but the thinned membranes show the enhanced voltage and energy efficiencies over the range of current density, 50-100 mA/cm 2 . Hydrophilic channel alignment of PFSAs is also beneficial for long-term cycling of VRFBs in terms of capacity retention and cell performances. This simple pretreatment of membranes offers an effective and facile way to overcome high vanadium permeability of PFSAs for VRFBs.

Vanadium Extraction from Shale via Sulfuric Acid Baking and Leaching

NASA Astrophysics Data System (ADS)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

2018-01-01

Fluorides are widely used to improve vanadium extraction from shale in China. Sulfuric acid baking-leaching (SABL) was investigated as a means of recovering vanadium which does not require the use of fluorides and avoids the productions of harmful fluoride-containing wastewater. Various effective factors were systematically studied and the experimental results showed that 90.1% vanadium could be leached from the shale. On the basis of phase transformations and structural changes after baking the shale, a mechanism of vanadium extraction from shale via SABL was proposed. The mechanism can be described as: (1) sulfuric acid diffusion into particles; (2) the formation of concentrated sulfuric acid media in the particles after water evaporation; (3) hydroxyl groups in the muscovite were removed and transient state [SO4 2-] was generated; and (4) the metals in the muscovite were sulfated by active [SO4 2-] and the vanadium was released. Thermodynamics modeling confirmed this mechanism.

Plasma enhanced chemical vapor deposition (PECVD) method of forming vanadium oxide films and vanadium oxide thin-films prepared thereby

DOEpatents

Zhang, Ji-Guang; Tracy, C. Edwin; Benson, David K.; Turner, John A.; Liu, Ping

2000-01-01

A method is disclosed of forming a vanadium oxide film on a substrate utilizing plasma enhanced chemical vapor deposition. The method includes positioning a substrate within a plasma reaction chamber and then forming a precursor gas comprised of a vanadium-containing chloride gas in an inert carrier gas. This precursor gas is then mixed with selected amounts of hydrogen and oxygen and directed into the reaction chamber. The amounts of precursor gas, oxygen and hydrogen are selected to optimize the final properties of the vanadium oxide film An rf plasma is generated within the reaction chamber to chemically react the precursor gas with the hydrogen and the oxygen to cause deposition of a vanadium oxide film on the substrate while the chamber deposition pressure is maintained at about one torr or less. Finally, the byproduct gases are removed from the plasma reaction chamber.

Graphite furnace atomic absorption spectrometric determination of vanadium after cloud point extraction in the presence of graphene oxide

NASA Astrophysics Data System (ADS)

López-García, Ignacio; Marín-Hernández, Juan José; Hernández-Córdoba, Manuel

2018-05-01

Vanadium (V) and vanadium (IV) in the presence of a small concentration of graphene oxide (0.05 mg mL-1) are quantitatively transferred to the coacervate obtained with Triton X-114 in a cloud point microextraction process. The surfactant-rich phase is directly injected into the graphite atomizer of an atomic absorption spectrometer. Using a 10-mL aliquot sample and 150 μL of a 15% Triton X-114 solution, the enrichment factor for the analyte is 103, which results in a detection limit of 0.02 μg L-1 vanadium. The separation of V(V) and V(IV) using an ion-exchanger allows speciation of the element at low concentrations. Data for seven reference water samples with certified vanadium contents confirm the reliability of the procedure. Several beer samples are also analyzed, those supplied as canned drinks showing low levels of tetravalent vanadium.

A nested case-control study of prenatal vanadium exposure and low birthweight.

PubMed

Jiang, Minmin; Li, Yuanyuan; Zhang, Bin; Zhou, Aifen; Zheng, Tongzhang; Qian, Zhengmin; Du, Xiaofu; Zhou, Yanqiu; Pan, Xinyun; Hu, Jie; Wu, Chuansha; Peng, Yang; Liu, Wenyu; Zhang, Chuncao; Xia, Wei; Xu, Shunqing

2016-09-01

Is prenatal vanadium exposure associated with adverse birth outcomes? The odds of low birthweight (LBW) are increased 2.23-fold in mothers with a urinary vanadium of ≥2.91 μg/g creatinine compared with that in mothers with a urinary vanadium of ≤1.42 μg/g creatinine. Human exposure to vanadium occurs through intake of food, water and polluted air. Vanadium has been suggested to have fetotoxicity and developmental toxicity in animal studies, and epidemiological studies have reported an association between a decrease in birthweight and vanadium exposure estimated from particulate matter. A nested case-control study involving 816 study participants (204 LBW cases and 612 matched controls) was conducted with data from the prospective Healthy Baby Cohort between 2012 and 2014 in the province of Hubei, China. Vanadium concentrations in 816 maternal urine samples collected before delivery [the median gestational age was 39 weeks (range 27-42 weeks)] were measured by inductively coupled plasma mass spectrometry. Information on the infants' birth outcomes was obtained from medical records. Conditional logistic regression was used to calculate the odds ratios (ORs) and 95% confidence intervals (CIs). The median urinary vanadium concentration of the cases was much higher than that of the controls (3.04 μg/g creatinine versus 1.93 μg/g creatinine). The results revealed a significant positive trend between the odds of LBW and level of maternal urinary vanadium [relative to the lowest tertile; adjusted OR = 1.69 (95% CI: 0.92, 3.10) for the medium tertile; adjusted OR = 2.23 (95% CI: 1.23, 4.05) for the highest tertile; P-trend = 0.02]. Additionally, the association was not modified by maternal age (P for heterogeneity = 0.70) or infant gender (P for heterogeneity = 0.21). The maternal urine sample was collected before labor, and the maternal urinary vanadium levels measured at one point in time may not accurately reflect the vanadium burden during the entire pregnancy. The results of this study can enrich the biological monitoring data on urinary vanadium in pregnant women; and may be evidence that vanadium may affect fetal development. This work was supported by the National Natural Science Foundation of China (21437002, 81372959 and 81402649), the R&D Special Fund for Public Welfare Industry (Environment) (201309048) and the Fundamental Research Funds for the Central Universities, HUST (2016YXZD043). The authors have no conflicts of interest to declare. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Brain Metal Distribution and Neuro-Inflammatory Profiles after Chronic Vanadium Administration and Withdrawal in Mice

PubMed Central

Folarin, Oluwabusayo R.; Snyder, Amanda M.; Peters, Douglas G.; Olopade, Funmilayo; Connor, James R.; Olopade, James O.

2017-01-01

Vanadium is a potentially toxic environmental pollutant and induces oxidative damage in biological systems including the central nervous system (CNS). Its deposition in brain tissue may be involved in the pathogenesis of certain neurological disorders which after prolonged exposure can culminate into more severe pathology. Most studies on vanadium neurotoxicity have been done after acute exposure but in reality some populations are exposed for a lifetime. This work was designed to ascertain neurodegenerative consequences of chronic vanadium administration and to investigate the progressive changes in the brain after withdrawal from vanadium treatment. A total of 85 male BALB/c mice were used for the experiment and divided into three major groups of vanadium treated (intraperitoneally (i.p.) injected with 3 mg/kg body weight of sodium metavanadate and sacrificed every 3 months till 18 months); matched controls; and animals that were exposed to vanadium for 3 months and thereafter the metal was withdrawn. Brain tissues were obtained after animal sacrifice. Sagittal cut sections of paraffin embedded tissue (5 μm) were analyzed by the Laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS) to show the absorption and distribution of vanadium metal. Also, Haematoxylin and Eosin (H&E) staining of brain sections, and immunohistochemistry for Microglia (Iba-1), Astrocytes (GFAP), Neurons (Neu-N) and Neu-N + 4′,6-diamidine-2′-pheynylindole dihydrochloride (Dapi) Immunofluorescent labeling were observed for morphological and morphometric parameters. The LA–ICP–MS results showed progressive increase in vanadium uptake with time in different brain regions with prediction for regions like the olfactory bulb, brain stem and cerebellum. The withdrawal brains still show presence of vanadium metal in the brain slightly more than the controls. There were morphological alterations (of the layering profile, nuclear shrinkage) in the prefrontal cortex, cellular degeneration (loss of dendritic arborization) and cell death in the Hippocampal CA1 pyramidal cells and Purkinje cells of the cerebellum, including astrocytic and microglial activation in vanadium exposed brains which were all attenuated in the withdrawal group. With exposure into old age, the evident neuropathology was microgliosis, while progressive astrogliosis became more attenuated. We have shown that chronic administration of vanadium over a lifetime in mice resulted in metal accumulation which showed regional variabilities with time. The metal profile and pathological effects were not completely eliminated from the brain even after a long time withdrawal from vanadium metal. PMID:28790895

Iron hydrides formation in interstellar clouds

NASA Astrophysics Data System (ADS)

Bar-Nun, A.; Pasternak, M.; Barrett, P. H.

1980-07-01

A recent Moessbauer study with Fe-57 in a solid hydrogen or hydrogen-argon matrix demonstrated the formation of an iron hydride molecule (FeH2) at 2.5-5 K. Following this and other studies, the possible existence of iron hydride molecules in interstellar clouds is proposed. In clouds, the iron hydrides FeH and FeH2 would be formed only on grains, by encounters of H atoms or H2 molecules with Fe atoms which are adsorbed on the grains. The other transition metals, Sc, Ti, V, Cr, Mn, Co, N, Cd and also Cu and Ca form hydrides of the type M-H, which could be responsible, at least in part, for the depletion of these metals in clouds.

High-Frequency Fe-H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT.

PubMed

Pelmenschikov, Vladimir; Gee, Leland B; Wang, Hongxin; MacLeod, K Cory; McWilliams, Sean F; Skubi, Kazimer L; Cramer, Stephen P; Holland, Patrick L

2018-05-30

High-spin iron species with bridging hydrides have been detected in species trapped during nitrogenase catalysis, but there are few general methods of evaluating Fe-H bonds in high-spin multinuclear iron systems. An 57 Fe nuclear resonance vibrational spectroscopy (NRVS) study on an Fe(μ-H) 2 Fe model complex reveals Fe-H stretching vibrations for bridging hydrides at frequencies greater than 1200 cm -1 . These isotope-sensitive vibrational bands are not evident in infrared (IR) spectra, showing the power of NRVS for identifying hydrides in this high-spin iron system. Complementary density functional theory (DFT) calculations elucidate the normal modes of the rhomboidal iron hydride core. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vanadium release in whole blood, serum and urine of patients implanted with a titanium alloy hip prosthesis.

PubMed

Catalani, S; Stea, S; Beraudi, A; Gilberti, M E; Bordini, B; Toni, A; Apostoli, P

2013-08-01

Vanadium (V) is a minor constituent of the Titanium-Aluminum-Vanadium (TiAlV) alloy currently used in cementless hip prostheses. Present study aimed at verifying the correlation of vanadium levels among different matrices and assessing reference levels of the ion in a population of patients wearing a well-functioning hip prosthesis. Vanadium was measured using Inductive Coupled Plasma Mass Spectrometry (ICP-MS) in whole blood, serum and urine of 129 patients implanted with a TiAlV-alloy hip prosthesis. The values in the serum were above the upper limit of the reference values in 42% of patients (29% in urine and 13% in whole blood). A good correlation among matrices was observed (p < 0.001). The cohort of patients (N = 32) complaining of pain or in which a loosening or damage to the prosthesis was assessed showed a significantly higher excretion of vanadium in urine as compared with the remaining asymptomatic patients (p = 0.001). The 95th percentile distribution of vanadium in the cohort of patients with a well-functioning prosthesis was 0.3 μg/L in whole blood, 0.5 μg/L in serum and 2.8 μg/L in urine, higher that in the unexposed population, especially for urine. The presence of a prosthesis, even though well-functioning, may cause a possible release of vanadium into the blood and a significant urinary excretion. The reference values of vanadium of the asymptomatic patients with titanium alloy hip prostheses supplied information regarding the background exposure level of the ions and their lower and upper limits.

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

PubMed

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

2007-11-22

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

A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures.

PubMed

Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

2014-03-24

Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures

NASA Astrophysics Data System (ADS)

Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

2014-03-01

Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

Another Look at the Mechanisms of Hydride Transfer Enzymes with Quantum and Classical Transition Path Sampling.

PubMed

Dzierlenga, Michael W; Antoniou, Dimitri; Schwartz, Steven D

2015-04-02

The mechanisms involved in enzymatic hydride transfer have been studied for years, but questions remain due, in part, to the difficulty of probing the effects of protein motion and hydrogen tunneling. In this study, we use transition path sampling (TPS) with normal mode centroid molecular dynamics (CMD) to calculate the barrier to hydride transfer in yeast alcohol dehydrogenase (YADH) and human heart lactate dehydrogenase (LDH). Calculation of the work applied to the hydride allowed for observation of the change in barrier height upon inclusion of quantum dynamics. Similar calculations were performed using deuterium as the transferring particle in order to approximate kinetic isotope effects (KIEs). The change in barrier height in YADH is indicative of a zero-point energy (ZPE) contribution and is evidence that catalysis occurs via a protein compression that mediates a near-barrierless hydride transfer. Calculation of the KIE using the difference in barrier height between the hydride and deuteride agreed well with experimental results.

Thermal desorption of hydrogen from Mg2Ni hydrogen storage materials.

PubMed

Hur, Tae Hong; Han, Jeong Seb; Kim, Jin Ho; Kim, Byung Kwan

2011-07-01

In order to investigate the influence of HCS on the hydrogen occupation site of Mg2Ni alloy, the thermal desorption technique has been applied to Mg2Ni hydride made by hydriding combustion synthesis (HCS). Mg2Ni was made under low temperature in a short time by the HCS compared to conventional melting process. At various initial hydride wt% from 0.91 to 3.52, the sample was heated to 623 K at a rate of 1.0 K/min. The starting temperature of the evolution of hydrogen goes higher as the initial hydride wt% increases. Only one peak is shown in the case of the small initial hydride wt%. But two peaks appeared with increasing initial hydride wt%. The activation energies obtained by the first and second peaks are 113.0 and 99.5 kJ/mol respectively. The two site occupation model by Darriet et al. was proved. The influence of HCS on the hydrogen occupation site of Mg2Ni alloy is nonexistent.

Hydride-Meisenheimer Complex Formation and Protonation as Key Reactions of 2,4,6-Trinitrophenol Biodegradation by Rhodococcus erythropolis

PubMed Central

Rieger, Paul-Gerhard; Sinnwell, Volker; Preuß, Andrea; Francke, Wittko; Knackmuss, Hans-Joachim

1999-01-01

Biodegradation of 2,4,6-trinitrophenol (picric acid) by Rhodococcus erythropolis HLPM-1 proceeds via initial hydrogenation of the aromatic ring system. Here we present evidence for the formation of a hydride-Meisenheimer complex (anionic ς-complex) of picric acid and its protonated form under physiological conditions. These complexes are key intermediates of denitration and productive microbial degradation of picric acid. For comparative spectroscopic identification of the hydride complex, it was necessary to synthesize this complex for the first time. Spectroscopic data revealed the initial addition of a hydride ion at position 3 of picric acid. This hydride complex readily picks up a proton at position 2, thus forming a reactive species for the elimination of nitrite. Cell extracts of R. erythropolis HLPM-1 transform the chemically synthesized hydride complex into 2,4-dinitrophenol. Picric acid is used as the sole carbon, nitrogen, and energy source by R. erythropolis HLPM-1. PMID:9973345

Influence of hydride orientation on fracture toughness of CWSR Zr-2.5%Nb pressure tube material between RT and 300 °C

NASA Astrophysics Data System (ADS)

Sharma, Rishi K.; Sunil, Saurav; Kumawat, B. K.; Singh, R. N.; Tewari, Asim; Kashyap, B. P.

2017-05-01

An experimental setup was designed, fabricated and used to form radial hydrides in Zr-2.5%Nb alloy pressure tube spool. The design of setup was based on ensuring a hoop stress in the spool greater than threshold stress for reorientation of hydrides in this alloy, which was achieved by manipulating the thermal expansion coefficient of the plunger and pressure tube material and diametral interference between them. The experimental setup was loaded on a universal testing machine (UTM) fitted with an environmental chamber and subjected to a temperature cycle for the stress reorientation treatment. The metallographic examination of the hydrogen charged spools subjected to stress re-orientation treatment using this set up revealed formation of predominantly radial hydrides. The variation of fracture toughness of material containing radial hydride with test temperature showed typical 'S' curve behavior with transition temperatures more than that of the material containing circumferential hydride.

UV-vis-DR study of VO x/SiO 2 catalysts prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Moussa, N.; Ghorbel, A.

2008-12-01

Vanadia-silica catalysts with different vanadium loadings were prepared by sol-gel process. UV-vis diffuse-reflectance spectroscopy was used to elucidate the effect of drying mode (i.e., xerogel vs. aerogel), vanadium loading and calcination on the molecular structure of supported vanadium species. The results indicate that for vanadium loading ranging from 2.8 to 11.2 wt.%, the band-gap energies of all catalysts varying from 2.28 to 2.68 eV which demonstrate that vanadium oxides are predominantly in octahedral structure with the presence of tetrahedral species. The discrimination of different surface VO x species has been based on their characteristic Ligand to Metal Charge Transfer (LMCT) O → V(V) and d-d transition. It was found that the LMCT band position of V dbnd O bond is not affected by calcination either in xerogels or in aerogels but the position and the shape of bands relative to bridging V sbnd O sbnd V bonds are affected by vanadium loading, calcination and drying mode. For the same V/Si ratio, band-gap energy of xerogel is lower than that of aerogel which indicate that vanadium species are more dispersed in aerogels than in xerogels. Drying and calcination led to rearrangement, dehydration, cleavage and crystallization of vanadium species which explain the presence of some amount of crystalline V 2O 5 in calcined samples.

Inverse association of plasma vanadium levels with newly diagnosed type 2 diabetes in a Chinese population.

PubMed

Wang, Xia; Sun, Taoping; Liu, Jun; Shan, Zhilei; Jin, Yilin; Chen, Sijing; Bao, Wei; Hu, Frank B; Liu, Liegang

2014-08-15

Vanadium compounds have been proposed to have beneficial effects on the pathogenesis and complications of type 2 diabetes. Our objective was to evaluate the association between plasma vanadium levels and type 2 diabetes. We performed a case-control study involving 1,598 Chinese subjects with or without newly diagnosed type 2 diabetes (December 2004-December 2007). Cases and controls were frequency-matched by age and sex. Plasma vanadium concentrations were measured and compared between groups. Analyses showed that plasma vanadium concentrations were significantly lower in cases with newly diagnosed type 2 diabetes than in controls (P = 0.001). Mean plasma vanadium levels in participants with and without diabetes were 1.0 μg/L and 1.2 μg/L, respectively. Participants in the highest quartile of plasma vanadium concentration had a notably lower risk of newly diagnosed type 2 diabetes (odds ratio = 0.26, 95% confidence interval: 0.19, 0.35; P < 0.001), compared with persons in the lowest quartile. The trend remained significant after adjustment for known risk factors and in further stratification analyses. Our results suggested that plasma vanadium concentrations were inversely associated with newly diagnosed type 2 diabetes in this Chinese population. © The Author 2014. Published by Oxford University Press on behalf of the Johns Hopkins Bloomberg School of Public Health. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

NASA Astrophysics Data System (ADS)

Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

2015-05-01

The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V2O5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V2O5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V2O5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/VxOx composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V2O5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing aid, such as the two cysteine-constrained peptides on the phage surface, and has potential for use in nanotechnology applications.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Hydrogen storage in the form of metal hydrides

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

High energy density battery based on complex hydrides

DOEpatents

Zidan, Ragaiy

2016-04-26

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

Iron diminishes the in vitro biological effect of vanadium.

EPA Science Inventory

Mechanistic pathways underlying inflammatory injury following exposures to vanadium-containing compounds are not defined. We tested the postulate that the in vitro biological effect of vanadium results from its impact on iron homeostasis. Human bronchial epithelial (HBE) cells ex...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

Roasting and leaching behaviors of vanadium and chromium in calcification roasting-acid leaching of high-chromium vanadium slag

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Zhou, Mi; Gao, Hui-yang; Liu, Jia-yi; Xue, Xiang-xin

2018-05-01

Calcification roasting-acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V2O5 ( n(CaO)/ n(V2O5)), roasting temperature, holding time, and the heating rate used in the oxidation-calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry-differential scanning calorimetry (TG-DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe0.6Cr0.4)2O3. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/ n(V2O5) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630°C for n(CaO)/ n(V2O5) ratios of 0.5 and 5, respectively.

Facile synthesis of hierarchical porous VOx@carbon composites for supercapacitors.

PubMed

Zhao, Chunxia; Cao, Jinqiao; Yang, Yunxia; Chen, Wen; Li, Junshen

2014-08-01

Hierarchical or micro-nano structured porous VOx@carbon composites were synthesized by a one-step method using phenolic resin as the carbon precursor and ammonium metavanadate as the source of vanadium oxides. The effects of the vanadium source loading on the microstructure and electrochemical properties of the composites were investigated. X-ray diffraction results showed that as the vanadium oxides source loading increased, vanadium oxides in the composites changed oxidation states from V2O3 to mixed states of V2O3 and VO2. Electrochemical test results indicated that the micro-nano porous structure of the composites could facilitate the ion diffusion in the rich porous structure and then promote the electrochemical reaction. More importantly, we found that vanadium oxides greatly enhanced the electrochemical performance of the materials, due to the faradic capacitance generated from vanadium oxide nanoparticles. A maximum specific capacitance of 171 F/g was obtained from VOx@carbon composite with vanadium loading of ∼44 wt%. Further increasing the VOx loading over this fraction was not beneficial. Our results suggested that hierarchical porous VOx@carbon composites were promising candidates for supercapacitor applications. Copyright © 2013 Elsevier Inc. All rights reserved.

Allergic reaction to vanadium causes a diffuse eczematous eruption and titanium alloy orthopedic implant failure.

PubMed

Engelhart, Sally; Segal, Robert J

2017-04-01

Allergy as a cause of adverse outcomes in patients with implanted orthopedic hardware is controversial. Allergy to titanium-based implants has not been well researched, as titanium is traditionally thought to be inert. We highlight the case of a patient who developed systemic dermatitis and implant failure after surgical placement of a titanium alloy (Ti6Al4V) plate in the left foot. The hardware was removed and the eruption cleared in the following weeks. The plate and screws were submitted for metal analysis. The elemental composition of both the plate and screws included 3 major elements-titanium, aluminum, and vanadium-as well as trace elements. Metal analysis revealed that the plate and screws had different microstructures, and electrochemical studies demonstrated that galvanic corrosion could have occurred between the plate and screws due to their different microstructures, contributing to the release of vanadium in vivo. The patient was patch tested with several metals including components of the implant and had a positive patch test reaction only to vanadium trichloride. These findings support a diagnosis of vanadium allergy and suggests that clinicians should consider including vanadium when patch testing patients with a suspected allergic reaction to vanadium-containing implants.

Effect of Vanadyl Rosiglitazone, a New Insulin-Mimetic Vanadium Complexes, on Glucose Homeostasis of Diabetic Mice.

PubMed

Jiang, Pingzhe; Dong, Zhen; Ma, Baicheng; Ni, Zaizhong; Duan, Huikun; Li, Xiaodan; Wang, Bin; Ma, Xiaofeng; Wei, Qian; Ji, Xiangzhen; Li, Minggang

2016-11-01

Diabetes has been cited as the most challenging health problem in the twenty-first century. Accordingly, it is urgent to develop a new type of efficient and low-toxic antidiabetic medication. Since vanadium compounds have insulin-mimetic and potential hypoglycemic activities for type 1 and type 2 diabetes, a new trend has been developed using vanadium and organic ligands to form a new compound in order to increase the intestinal absorption and reduce the toxicity of vanadium compound. In the current investigation, a new organic vanadium compounds, vanadyl rosiglitazone, was synthesized and determined by infrared spectra. Vanadyl rosiglitazone and three other organic vanadium compounds were administered to the diabetic mice through oral administration for 5 weeks. The results of mouse model test indicated that vanadyl rosiglitazone could regulate the blood glucose level and relieve the symptoms of polydipsia, polyphagia, polyuria, and weight loss without side effects and was more effective than the other three organic vanadium compounds including vanadyl trehalose, vanadyl metformin, and vanadyl quercetin. The study indicated that vanadyl rosiglitazone presents insulin-mimetic activities, and it will be a good potential candidate for the development of a new type of oral drug for type 2 diabetes.

Effects of Vanadium-Containing Compounds on Membrane Lipids and on Microdomains Used in Receptor-Mediated Signaling

PubMed Central

Roess, Deborah A.; Smith, Steven M. L.; Winter, Peter; Zhou, Jun; Dou, Ping; Baruah, Bharat; Trujillo, Alejandro M.; Levinger, Nancy E.; Yang, Xioda; Barisas, B. George; Crans, Debbie C.

2011-01-01

There is increasing evidence for the involvement of plasma membrane microdomains in insulin receptor function. Moreover, disruption of these structures, which are typically enriched in sphingomyelin and cholesterol, results in insulin resistance. Treatment strategies for insulin resistance include the use of vanadium compounds which have been shown in animal models to enhance insulin responsiveness. One possible mechanism for insulin-enhancing effects might involve direct effects of vanadium compounds on membrane lipid organization. These changes in lipid organization promote the partitioning of insulin receptors and other receptors into membrane microdomains where receptors are optimally functional. To explore this possibility, we have used several strategies involving vanadium complexes such as [VO2dipic]− (pyridin-2,6-dicarboxylatodioxovanadium(V)), decavanadate (V10O286−, V10), BMOV (bis(maltolato)oxovanadium(IV)) and [VO(saltris)]2 (2-salicylideniminato-2-(hydroxymethyl)-1,3-dihydroxypropane-oxovanadium(V)). Our strategies include an evaluation of interactions between vanadium-containing compounds and model lipid systems, an evaluation of the effects of vanadium compounds on lipid fluidity in erythrocyte membranes, and studies of the effects of vanadium-containing compounds on signaling events initiated by receptors known to use membrane microdomains as signaling platforms. PMID:18729092

Tackling capacity fading in vanadium flow batteries with amphoteric membranes

NASA Astrophysics Data System (ADS)

Oldenburg, Fabio J.; Schmidt, Thomas J.; Gubler, Lorenz

2017-11-01

Capacity fading and poor electrolyte utilization caused by electrolyte imbalance effects are major drawbacks for the commercialization of vanadium flow batteries (VFB). The influence of membrane type (cationic, anionic, amphoteric) on these effects is studied by determining the excess and net flux of each vanadium ion in an operating VFB assembled with a cation exchange membrane (CEM), Nafion® NR212, an anion exchange membrane (AEM), Fumatech FAP-450, and an amphoteric ion exchange membrane (AIEM) synthesized in-house. It is shown that the net vanadium flux, accompanied by water transport, is directed towards the positive side for the CEM and towards the negative side for the AEM. The content of cation and anion exchange groups in the AIEM is adjusted via radiation grafting to balance the vanadium flux between the two electrolyte sides. With the AIEM the net vanadium flux is significantly reduced and capacity fading due to electrolyte imbalances can be largely eliminated. The membrane's influence on electrolyte imbalance effects is characterized and quantified in one single charge-discharge cycle by analyzing the content of the four different vanadium species in the two electrolytes. The experimental data recorded herewith conclusively explains the electrolyte composition after 80 cycles.

The Current Status of Hydrogen Storage Alloy Development for Electrochemical Applications.

PubMed

Young, Kwo-Hsiung; Nei, Jean

2013-10-17

In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB₅, AB₂, A₂B₇-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical application, the nickel metal hydride battery, is summarized. Other electrochemical applications, such as Ni-hydrogen, fuel cell, Li-ion battery, air-metal hydride, and hybrid battery systems, also have been mentioned.

Technical and economic aspects of hydrogen storage in metal hydrides

NASA Technical Reports Server (NTRS)

Schmitt, R.

1981-01-01

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

The storage of hydrogen in the form of metal hydrides: An application to thermal engines

NASA Technical Reports Server (NTRS)

Gales, C.; Perroud, P.

1981-01-01

The possibility of using LaNi56, FeTiH2, or MgH2 as metal hydride storage sytems for hydrogen fueled automobile engines is discussed. Magnesium copper and magnesium nickel hydrides studies indicate that they provide more stable storage systems than pure magnesium hydrides. Several test engines employing hydrogen fuel have been developed: a single cylinder motor originally designed for use with air gasoline mixture; a four-cylinder engine modified to run on an air hydrogen mixture; and a gas turbine.

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, James J.; Grohse, Edward W.; Johnson, John R.; Winsche, deceased, Warren E.

1988-01-01

The reversible reaction M+x/2 H.sub.2 .rarw..fwdarw.MH.sub.x, wherein M is a reversible metal hydride former that forms a hydride MH.sub.x in the presence of H.sub.2, generally used to store and recall H.sub.2, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H.sub.2, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H.sub.2 through the liquid is dependent upon the H.sub.2 pressure in the gas phase at a given temperature. When the actual H.sub.2 pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particles. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, J.J.; Grohse, E.W.; Johnson, J.R.; Winsche, W.E.

1985-02-22

The reversible reaction M + x/2 H/sub 2/ reversible MH/sub x/, wherein M is a reversible metal hydride former that forms a hydride MH/sub x/ in the presence of H/sub 2/, generally used to store and recall H/sub 2/, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H/sub 2/ through the liquid is dependent upon the H/sub 2/ pressure in the gas phase at a given temperature. When the actual H/sub 2/ pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particle. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

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

NASA Astrophysics Data System (ADS)

Zhou, Chengshang

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

Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries

PubMed Central

Oumellal, Yassine; Bonnet, Jean-Pierre

2015-01-01

Summary The state of the art of conversion reactions of metal hydrides (MH) with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g−1 at a suitable potential (0.5 V vs Li+/Li0) and the lowest electrode polarization (<0.2 V) for conversion materials. Conversion process reaction mechanisms with lithium are subsequently detailed for MgH2, TiH2, complex hydrides Mg2MHx and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MHx + xLi+ + xe− in equilibrium with M + xLiH. Other reaction paths—involving solid solutions, metastable distorted phases, and phases with low hydrogen content—were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to address these drawbacks. The development of high-capacity hydride anodes should be inspired by the emergent nano-research prospects which share the knowledge of both hydrogen-storage and lithium-anode communities. PMID:26425434

VANADIUM CHEMISTRY ESSENTIALS FOR TREATMENT STUDIES

EPA Science Inventory

The importance of vanadium occurrence and treatment in drinking water has been elevated by its inclusion in the Contaminant Candidate List. Though it is still too early to know the nature of new regulatory requirements for vanadium, if indeed it becomes regulated, a substantial u...

Spectrophotometric determination of vanadium and its application to gas-turbine fuel-oils.

PubMed

Banerjee, S; Sinha, B P; Dutta, R K

1975-08-01

A very sensitive spectrophotometric method for the determination of vanadium in furnace oils is described. The intense indigo-blue colour developed by the reaction of vanadium with tannin and thioglycollic acid is measured at a wavelength of 600 nm at pH 4 and obeys Beer's law between 0.5 and 5 ppm vanadium. The method is applicable to gas-turbine fuel-oil and special navy fuel-oils. The common mineral constituents usually present in such oils do not interfere.

ON THE SEPARATION OF VANADIUM, MOLYBDENUM AND TUNGSTEN BY MEANS OF PAPER CHROMATOGRAPHY. PART I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tzou, S.; Liang, S.

1959-02-01

Molybdenum, tangsten, and vanadium are separated by chromatography as per-acids, and then detected with tannin solution. Of the seven solvents tested, n-butanolhydrogen peroxide-nitric acid mixtures offer the best separations. With the addition of dioxane, the R/sub F/ values of these elements increase, while vanadium and tungsten spots overlap. The formation of per-acids avoids the retainment of tungsten on the original spot and the tailings of vanadium and molybdenum spots. (B.O.G.)

Method for preparing high purity vanadium

DOEpatents

Schmidt, Frederick; Carlson, O. Norman

1986-09-09

A method for preparing high purity vanadium having a low silicon content has been developed. Vanadium pentoxide is reduced with a stoichiometric, or slightly deficient amount of aluminum to produce a vanadium-aluminum alloy containing an excess of oxygen. Silicon is removed by electron-beam melting the alloy under oxidizing conditions to promote the formation of SiO which is volatile at elevated temperatures. Excess oxygen is removed by heating the alloy in the presence of calcium metal to form calcium oxide.

Method for preparing high purity vanadium

DOEpatents

Schmidt, F.; Carlson, O.N.

1984-05-16

A method for preparing high purity vanadium having a low silicon content has been developed. Vanadium pentoxide is reduced with a stoichiometric, or slightly deficient amount of aluminum to produce a vanadium-aluminum alloy containing an excess of oxygen. Silicon is removed by electron-beam melting the alloy under oxidizing conditions to promote the formation of SiO which is volatile at elevated temperatures. Excess oxygen is removed by heating the alloy in the presence of calcium metal to form calcium oxide.

Vanadium inhibits DNA-protein cross-links and ameliorates surface level changes of aberrant crypt foci during 1,2-dimethylhydrazine induced rat colon carcinogenesis.

PubMed

Kanna, P Suresh; Saralaya, M G; Samanta, K; Chatterjee, M

2005-01-01

The trace mineral vanadium inhibits cancer development in a variety of experimental animal models. The present study was to gain insight into a putative anticancer effect of vanadium in a rat model of colon carcinogenesis. The in vivo study was intended to clarify the effect of vanadium on DNA-protein cross-links (DPC), surface level changes of aberrant crypt foci (ACF) and biotransformation status during 1,2-dimethylhydrazine (1,2-DMH) induced preneoplastic rat colon carcinogenesis. The comet assay showed statistically higher mean base values of DNA-protein mass (p<0.01) and mean frequencies of tailed cells (p<0.001) in the carcinogen-induced group after treatment with proteinase K. Treatment with vanadium in the form of ammonium monovanadate supplemented ad libitum in drinking water for the entire experimental period caused a significant (p<0.02) reduction (40%) in DNA-protein cross-links in colon cells. Further, the biotransformation status of vanadium was ascertained measuring the drug metabolising enzymes, glutathione S-transferase (GST) and cytochrome P-450 (Cyt P-450). Significantly, there was an increase in glutathione S-transferase and cytochrome P-450 levels (p<0.01 and p<0.02, respectively) in rats supplemented with vanadium as compared to their carcinogen controls. As an endpoint marker, we also evaluated the effect of vanadium on surface level changes of aberrant crypt foci induced by 1,2-DMH by scanning electron microscopy. Animals induced with 1,2-DMH and supplemented with vanadium showed a marked improvement in colonic architecture with less number of aberrant crypt foci in contrast to the animals induced with 1,2-DMH alone, thereby exhibiting its anti-carcinogenicity by modulating the markers studied herein.

Vanadium Induces Dopaminergic Neurotoxicity Via Protein Kinase C-Delta Dependent Oxidative Signaling Mechanisms: Relevance to Etiopathogenesis of Parkinson's Disease

PubMed Central

Afeseh Ngwa, Hilary; Kanthasamy, Arthi; Anantharam, Vellareddy; Song, Chunjuan; Witte, Travis; Houk, R. S.; Kanthasamy, Anumantha G.

2009-01-01

Environmental exposure to neurotoxic metals through various sources including exposure to welding fumes has been linked to an increased incidence of Parkinson's disease (PD). Welding fumes contain many different metals including vanadium typically present as particulates containing vanadium pentoxide (V2O5). However, possible neurotoxic effects of this metal oxide on dopaminergic neuronal cells are not well studied. In the present study, we characterized vanadium-induced oxidative stress-dependent cellular events in cell culture models of PD. V2O5 was neurotoxic to dopaminergic neuronal cells including primary nigral dopaminergic neurons and the EC50 was determined to be 37 μM in N27 dopaminergic neuronal cell model. The neurotoxic effect was accompanied by a time-dependent uptake of vanadium and upregulation of metal transporter proteins Tf and DMT1 in N27 cells. Additionally, vanadium resulted in a threefold increase in reactive oxygen species generation, followed by release of mitochondrial cytochrome c into cytoplasm and subsequent activation of caspase-9 (>fourfold) and caspase-3 (>ninefold). Interestingly, vanadium exposure induced proteolytic cleavage of native protein kinase Cdelta (PKCδ, 72-74 kDa) to yield a 41 kDa catalytically active fragment resulting in a persistent increase in PKCδ kinase activity. Co-treatment with pan-caspase inhibitor ZVAD-FMK significantly blocked vanadium-induced PKCδ proteolytic activation, indicating that caspases mediate PKCδ cleavage. Also, co-treatment with Z-VAD-FMK almost completely inhibited V2O5-induced DNA fragmentation. Furthermore, PKCδ knockdown using siRNA protected N27 cells from V2O5-induced apoptotic cell death. Collectively, these results demonstrate vanadium can exert neurotoxic effects in dopaminergic neuronal cells via caspase-3-dependent PKCδ cleavage, suggesting that metal exposure may promote nigral dopaminergic degeneration. PMID:19646462

The role of vanadium in biology.

PubMed

Rehder, Dieter

2015-05-01

Vanadium is special in at least two respects: on the one hand, the tetrahedral anion vanadate(v) is similar to the phosphate anion; vanadate can thus interact with various physiological substrates that are otherwise functionalized by phosphate. On the other hand, the transition metal vanadium can easily expand its sphere beyond tetrahedral coordination, and switch between the oxidation states +v, +iv and +iii in a physiological environment. The similarity between vanadate and phosphate may account for the antidiabetic potential of vanadium compounds with carrier ligands such as maltolate and picolinate, and also for vanadium's mediation in cardiovascular and neuronal defects. Other potential medicinal applications of more complex vanadium coordination compounds, for example in the treatment of parasitic tropical diseases, may also be rooted in the specific properties of the ligand sphere. The ease of the change in the oxidation state of vanadium is employed by prokarya (bacteria and cyanobacteria) as well as by eukarya (algae and fungi) in respiratory and enzymatic functions. Macroalgae (seaweeds), fungi, lichens and Streptomyces bacteria have available haloperoxidases, and hence enzymes that enable the 2-electron oxidation of halide X(-) with peroxide, catalyzed by a Lewis-acidic V(V) center. The X(+) species thus formed can be employed to oxidatively halogenate organic substrates, a fact with implications also for the chemical processes in the atmosphere. Vanadium-dependent nitrogenases in bacteria (Azotobacter) and cyanobacteria (Anabaena) convert N2 + H(+) to NH4(+) + H2, but are also receptive for alternative substrates such as CO and C2H2. Among the enigmas to be solved with respect to the utilization of vanadium in nature is the accumulation of V(III) by some sea squirts and fan worms, as well as the purport of the nonoxido V(IV) compound amavadin in the fly agaric.

DEVELOPMENT OF A FABRICATION PROCESS FOR SOL-GEL/METAL HYDRIDE COMPOSITE GRANULES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansen, E; Eric Frickey, E; Leung Heung, L

An external gelation process was developed to produce spherical granules that contain metal hydride particles in a sol-gel matrix. Dimensionally stable granules containing metal hydrides are needed for applications such as hydrogen separation and hydrogen purification that require columns containing metal hydrides. Gases must readily flow through the metal hydride beds in the columns. Metal hydrides reversibly absorb and desorb hydrogen and hydrogen isotopes. This is accompanied by significant volume changes that cause the metal hydride to break apart or decrepitate. Repeated cycling results in very fine metal hydride particles that are difficult to handle and contain. Fine particles tendmore » to settle and pack making it more difficult to flow gases through a metal hydride bed. Furthermore, the metal hydrides can exert a significant force on the containment vessel as they expand. These problems associated with metal hydrides can be eliminated with the granulation process described in this report. Small agglomerates of metal hydride particles and abietic acid (a pore former) were produced and dispersed in a colloidal silica/water suspension to form the feed slurry. Fumed silica was added to increase the viscosity of the feed slurry which helped to keep the agglomerates in suspension. Drops of the feed slurry were injected into a 27-foot tall column of hot ({approx}70 C), medium viscosity ({approx}3000 centistokes) silicone oil. Water was slowly evaporated from the drops as they settled. The drops gelled and eventually solidified to form spherical granules. This process is referred to as external gelation. Testing was completed to optimize the design of the column, the feed system, the feed slurry composition, and the operating parameters of the column. The critical process parameters can be controlled resulting in a reproducible fabrication technique. The residual silicone oil on the surface of the granules was removed by washing in mineral spirits. The granules were dried in air at 40 C. The granules were heated to 230 C for 30 minutes in argon to remove the remaining water and organic materials. The resulting product was spherical composite granules (100 to 2000 micron diameter) with a porous silica matrix containing small agglomerates of metal hydride particles. Open porosity in the silica matrix allows hydrogen to permeate rapidly through the matrix but the pores are small enough to contain the metal hydride particles. Additional porosity around the metal hydride particles, induced using abietic acid as a pore former, allows the particles to freely expand and contract without fracturing the brittle sol-gel matrix. It was demonstrated that the granules readily absorb and desorb hydrogen while remaining integral and dimensionally stable. Microcracking was observed after the granules were cycled in hydrogen five times. The strength of the granules was improved by coating them with a thin layer of a micro-porous polymer sol-gel that would allow hydrogen to freely pass through the coating but would filter out metal hydride poisons such as water and carbon monoxide. It was demonstrated that if a thin sol-gel coating was applied after the granules were cycled, the coating not only improved the strength of the granules but the coated granules retained their strength after additional hydrogen cycling tests. This additional strength is needed to extend the lifetime of the granules and to survive the compressive load in a large column of granules. Additional hydrogen adsorption tests are planned to evaluate the performance of coated granules after one hundred cycles. Tests will also be performed to determine the effects of metal hydride poisons on the granules. The results of these tests will be documented in a separate report. The process that was developed to form these granules could be scaled to a production process. The process to form granules from a mixture of metal hydride particles and pore former such as abietic acid can be scaled up using commercial granulators. The current laboratory-scale external gelation column produces approximately one gram of granules per hour. To increase the production output from a single column, multiple feed injection systems in a larger diameter column could be used.« less

Geochemical controls on vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Geochemical controls of vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Synthesis and characterization of polymeric V2O5/AlO(OH) with nanopores on alumina support.

PubMed

Ahmad, A L; Abd Shukor, S R; Leo, C P

2006-12-01

Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.

Microbial vanadium (V) reduction in groundwater with different soils from vanadium ore mining areas.

PubMed

Hao, Liting; Zhang, Baogang; Feng, Chuanping; Zhang, Zhenya; Lei, Zhongfang; Shimizu, Kazuya; Cao, Xuelong; Liu, Hui; Liu, Huipeng

2018-07-01

This work investigated the potential of vanadium (V) (V(V)) bioreduction by using soils sampled from four main kinds of vanadium ore mining areas, i.e. vanadium titanomagnetite, stone coal, petroleum associated minerals and uvanite as inocula. During a typical operation cycle of 60 h, the soils from vanadium titanomagnetite area and petroleum associated minerals area exhibited higher V(V) removal efficiencies, about 92.0 ± 2.0% and 91.0 ± 1.9% in comparison to 87.1 ± 1.9% and 69.0 ± 1.1% for the soils from uvanite and stone coal areas, respectively. Results from high-throughput 16 S rRNA gene pyrosequencing analysis reflect the accumulation of Bryobacter and Acidobacteriaceae with capabilities of V(V) reduction, accompanied with other functional species. This study is helpful to search new functional species for V(V) reduction and to develop in situ bioremediations of V(V) polluted groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane.

PubMed

Khadka, Nimesh; Dean, Dennis R; Smith, Dayle; Hoffman, Brian M; Raugei, Simone; Seefeldt, Lance C

2016-09-06

The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO(-)) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ("direct hydride transfer" reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ("associative" reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70(Val→Ala), α-195(His→Gln)) are found to significantly alter the distribution of products between formate and CO/CH4.

Photocatalytic Activity of Vanadium-Substituted ETS-10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash,M.; Rykov, S.; Lobo, R.

2007-01-01

Various amounts of vanadium have been isomorphously substituted for titanium in ETS-10, creating samples with V/(V+Ti) ratios of 0.13, 0.33, 0.43, and 1.00 and characterized experimentally using Raman, near-edge X-ray absorption fine structure (NEXAFS), X-ray powder diffraction, N{sub 2} adsorption, scanning electron microscopy (SEM), UV/vis spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Raman spectra reveal a disordered chain structure that contains different V-O bonds along with the presence of a V-O-Ti peak. The UV/vis spectra of the vanadium samples have three new absorption features in the visible region at 450, 594, and 850 nm, suggesting both V{sup 4+}more » and V{sup 5+} are present in the samples. NEXAFS results confirm the presence of both V{sup 5+} and V{sup 4+} in the vanadium samples, with a fraction of V{sup 4+} within the range of 0.2-0.4. The addition of vanadium lowers the band gap energy of ETS-10 from 4.32 eV to a minimum of 3.58 eV for the 0.43ETVS-10 sample. Studies of the photocatalytic polymerization of ethylene show that the 594 nm transition has no photocatalytic activity. The visible transition around 450 nm in the vanadium-incorporated samples is photocatalytically active, and the lower-concentration vanadium samples have higher photocatalytic activity than that of ETS-10 and AM-6, the all-vanadium analogue of ETS-10.« less

Catalytic destruction of PCDD/Fs over vanadium oxide-based catalysts.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Li, Xiao-Dong; Yan, Mi; Prabowo, Bayu; Li, Wen-Wei; Chen, Tong; Yan, Jian-Hua

2016-08-01

Vanadium oxide-based catalysts were developed for the destruction of vapour phase PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans). A vapour phase PCDD/Fs generating system was designed to supply stable PCDD/Fs steam with initial concentration of 3.2 ng I-TEQ Nm(-3). Two kinds of titania (nano-TiO2 and conventional TiO2) and alumina were used as catalyst supports. For vanadium-based catalysts supported on nano-TiO2, catalyst activity is enhanced with operating temperature increasing from 160 to 300 °C and then reduces with temperature rising further to 350 °C. It is mainly due to the fact that high volatility of organic compounds at 350 °C suppresses adsorption of PCDD/Fs on catalysts surface and then further inhibits the reaction between catalyst and PCDD/Fs. The optimum loading of vanadium on nano-TiO2 support is 5 wt.% where vanadium oxide presents highly dispersed amorphous state according to the Raman spectra and XRD patterns. Excessive vanadium will block the pore space and form microcrystalline V2O5 on the support surface. At the vanadium loading of 5 wt.%, nano-TiO2-supported catalyst performs best on PCDD/Fs destruction compared to Al2O3 and conventional TiO2. Chemical states of vanadium in the fresh, used and reoxidized VOx(5 %)/TiO2 catalysts at different operating temperature are also analysed by XPS.

Protective effect of alpha glucosyl hesperidin (G-hesperidin) on chronic vanadium induced testicular toxicity and sperm nuclear DNA damage in male Sprague Dawley rats.

PubMed

Vijaya Bharathi, B; Jaya Prakash, G; Krishna, K M; Ravi Krishna, C H; Sivanarayana, T; Madan, K; Rama Raju, G A; Annapurna, A

2015-06-01

The study was conducted to evaluate the vanadium-induced testicular toxicity and its effect on sperm parameters, sperm nuclear DNA damage and histological alterations in Sprague Dawley rats and to assess the protective effect of G-hesperidin against this damage. Treatment of rats with vanadium at a dose of 1 mg kg bw(-1) for 90 days resulted in significant reduction in serum testosterone levels, sperm count and motility. Further, a parallel increase in abnormal sperm morphology and adverse histopathological changes in testis was also associated with vanadium administration when compared to normal control. Moreover, sperm chromatin dispersion assay revealed that vanadium induces sperm nuclear DNA fragmentation. A marked increase in testicular malondialdehyde levels and decreased activity of antioxidant enzymes such as superoxide dismutase and catalase indicates vanadium-induced oxidative stress. Co-administration of G-hesperidin at a dose of 25 and 50 mg kg bw(-1) significantly attenuated the sperm parameters and histological changes by restoring the antioxidant levels in rat testis. These results suggested that vanadium exposure caused reduced bioavailability of androgens to the tissue and increased free radical formation, thereby causing structural and functional changes in spermatozoa. G-hesperidin exhibited antioxidant effect by protecting the rat testis against vanadium-induced oxidative damage, further ensures antioxidant potential of bioflavonoids. © 2014 Blackwell Verlag GmbH.

Oxidative Stress as a Mechanism Involved in Kidney Damage After Subchronic Exposure to Vanadium Inhalation and Oral Sweetened Beverages in a Mouse Model.

PubMed

Espinosa-Zurutuza, Maribel; González-Villalva, Adriana; Albarrán-Alonso, Juan Carlos; Colín-Barenque, Laura; Bizarro-Nevares, Patricia; Rojas-Lemus, Marcela; López-Valdéz, Nelly; Fortoul, Teresa I

Kidney diseases have notably increased in the last few years. This is partially explained by the increase in metabolic syndrome, diabetes, and systemic blood hypertension. However, there is a segment of the population that has neither of the previous risk factors, yet suffers kidney damage. Exposure to atmospheric pollutants has been suggested as a possible risk factor. Air-suspended particles carry on their surface a variety of fuel combustion-related residues such as metals, and vanadium is one of these. Vanadium might produce oxidative stress resulting in the damage of some organs such as the kidney. Additionally, in countries like Mexico, the ingestion of sweetened beverages is a major issue; whether these beverages alone are responsible for direct kidney damage or whether their ingestion promotes the progression of an existing renal damage generates controversy. In this study, we report the combined effect of vanadium inhalation and sweetened beverages ingestion in a mouse model. Forty CD-1 male mice were distributed in 4 groups: control, vanadium inhalation, 30% sucrose in drinking water, and vanadium inhalation plus sucrose 30% in drinking water. Our results support that vanadium inhalation and the ingestion of 30% sucrose induce functional and histological kidney damage and an increase in oxidative stress biomarkers, which were higher in the combined effect of vanadium plus 30% sucrose. The results also support that the ingestion of 30% sucrose alone without hyperglycemia also produces kidney damage.

Quantitative LIBS analysis of vanadium in samples of hexagonal mesoporous silica catalysts.

PubMed

Pouzar, Miloslav; Kratochvíl, Tomás; Capek, Libor; Smoláková, Lucie; Cernohorský, Tomás; Krejcová, Anna; Hromádko, Ludek

2011-02-15

The method for the analysis of vanadium in hexagonal mesoporous silica (V-HMS) catalysts using Laser Induced Breakdown Spectrometry (LIBS) was suggested. Commercially available LIBS spectrometer was calibrated with the aid of authentic V-HMS samples previously analyzed by ICP OES after microwave digestion. Deposition of the sample on the surface of adhesive tape was adopted as a sample preparation method. Strong matrix effect connected with the catalyst preparation technique (1st vanadium added in the process of HMS synthesis, 2nd already synthesised silica matrix was impregnated by vanadium) was observed. The concentration range of V in the set of nine calibration standards was 1.3-4.5% (w/w). Limit of detection was 0.13% (w/w) and it was calculated as a triple standard deviation from five replicated determinations of vanadium in the real sample with a very low vanadium concentration. Comparable results of LIBS and ED XRF were obtained if the same set of standards was used for calibration of both methods and vanadium was measured in the same type of real samples. LIBS calibration constructed using V-HMS-impregnated samples failed for measuring of V-HMS-synthesized samples. LIBS measurements seem to be strongly influenced with different chemical forms of vanadium in impregnated and synthesised samples. The combination of LIBS and ED XRF is able to provide new information about measured samples (in our case for example about procedure of catalyst preparation). Copyright © 2010 Elsevier B.V. All rights reserved.

Exploring hydride-π interactions and their tuning by σ-hole bonds: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Asadollahi, Soheila; Mousavian, Parisasadat

2018-01-01

In the present work, ab initio calculations are performed to investigate the geometry, interaction energy and bonding properties of binary complexes formed between metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CH3) and a series of π-acidic heteroaromatic rings. In all the resulting complexes, the heteroaromatic ring acts as a Lewis acid (electron acceptor), while the H atom of the HMX molecule acts as a Lewis base (electron donor). The nature of this interaction, called 'hydride-π' interaction, is explored in terms of molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. The results show that the interaction energies of these hydride-π interactions are between -1.24 and -2.72 kcal/mol. Furthermore, mutual influence between the hydride-π and halogen- or pnicogen-bonding interactions is studied in complexes in which these interactions coexist. For a given π-acidic ring, the formation of the pnicogen-bonding induces a larger enhancing effect on the strength of hydride-π bond than the halogen-bonding.

Vanadium-pumped titanium x-ray laser

DOEpatents

Nilsen, J.

1992-05-26

A resonantly photo-pumped x-ray laser is formed of a vanadium and titanium foil combination that is driven by two beams of intense line focused optical laser radiation. Ground state neon-like titanium ions are resonantly photo-pumped by line emission from fluorine-like vanadium ions. 4 figs.

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the...

Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

Hydrogen absorption properties of Mg-Ni alloys prepared by bulk mechanical alloying

NASA Astrophysics Data System (ADS)

Kuji, Toshiro

2001-04-01

The thermodynamic properties of the hydrides of Mg2-xNi (x=0-0.5) alloys produced by bulk mechanical alloying (BMA) were determined from pressure-composition (PC) isotherms for absorption over temperatures from 623 to 423 K. The vant Hoff plot for the plateau pressures of isotherms clearly indicated the existence of high and low temperature hydrides with different entropy and enthalpy for hydride formation. It was found that both the entropy and enthalpy values for the high temperature hydride were more negative than for the low temperature hydride. The phase transition temperature was 525 K for Mg2.0Ni and decreased while increasing the value of x. This allotropic transformation was well confirmed by in-situ XRD observations from RT to 673 K under hydrogen atmosphere or in vacuum.

Effect of delivery condition on desorption rate of ZrCo metal hydride bed for fusion fuel cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, H.G.; Yun, S.H.; Chung, D.

2015-03-15

For the safety of fusion fuel cycle, hydrogen isotope gases including tritium are stored as metal hydride form. To satisfy fueling requirement of fusion machine, rapid delivery from metal hydride bed is one of major factors for the development of tritium storage and delivery system. Desorption from metal hydride depends on the operation scenario by pressure and temperature control of the bed. The effect of operation scenario and pump performance on desorption rate of metal hydride bed was experimentally investigated using ZrCo bed. The results showed that the condition of pre-heating scenario before actual delivery of gas affected the deliverymore » performance. Different pumps were connected to desorption line from bed and the effect of pump capacity on desorption rate were also found to be significant. (authors)« less

Low-valent group 14 element hydride chemistry: towards catalysis.

PubMed

Hadlington, Terrance J; Driess, Matthias; Jones, Cameron

2018-06-05

The chemistry of group 14 element(ii) hydride complexes has rapidly expanded since the first stable example of such a compound was reported in 2000. Since that time it has become apparent that these systems display remarkable reactivity patterns, in some cases mimicking those of late transition-metal (TM) hydride compounds. This is especially so for the hydroelementation of unsaturated organic substrates. Recently, this aspect of their reactivity has been extended to the use of group 14 element(ii) hydrides as efficient, "TM-like" catalysts in organic synthesis. This review will detail how the chemistry of these hydride compounds has advanced since their early development. Throughout, there is a focus on the importance of ligand effects in these systems, and how ligand design can greatly modify a coordinated complex's electronic structure, reactivity, and catalytic efficiency.

Simultaneous plate forming and hydriding of La(Fe, Si)13 magnetocaloric powders

NASA Astrophysics Data System (ADS)

Yang, Nannan; You, Caiyin; Tian, Na; Zhang, Yue; Leng, Haiyan; He, Jun

2018-04-01

In this work, we propose a way to simultaneously realize the plate forming and hydriding of La(Fe, Si)13 powders by mixing hydride MgNiYHx and solder powders Sn3.0Ag0.5Cu. Under the annealing of the green compact, the hydriding of La(Fe, Si)13 was realized through absorbing the released hydrogen from the metallic hydride MgNiYHx. The Curie temperature of La(Fe, Si)13 alloy increased from 213 K to 333 K and hysteresis reduced from 3.3 J/kg·K to 1.33 J/kg·K. Due to the bonding of Sn3.0Ag0.5Cu powders, the mechanical strength of the composite compact was highly improved in comparison to the compact of La(Fe, Si)13 powders alone.

Bipolar Nickel-Metal Hydride Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

1998-01-01

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

Microstructural studies of hydrogen damage in metastable stainless steels. Ph.D. Thesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, S.

1994-12-31

The primary objective of this dissertation is to determine the role of microstructure in hydrogen-induced damage in austenitic stainless steels. Specific attention was focused on the interactions between hydrogen and the austenitic grain, twin boundaries and the matrix, and the associated phase transformations. An experimental program of research was conducted to determine the phase transformation and cracking path in hydrogen charged stainless steels. Normal-purity AISI 304 (Fe18CrYNi) and high-purity 305 (Fe18Cr12Ni) solution-annealet stainless steels were examined. The steels were cathodically charged with hydrogen at 1, 10 and 100 mA/sq cm at room temperature for 5 min. to 32 hours, inmore » an 1N H2SO4 solution with 0.25 g/l of NaAsO2 added as a hydrogen recombination poison. Resultant changes in microstructure and hydrogen damage due to charging and subsequent room temperature aging were studied by x-ray diffraction, optical microscope (in the Nomarski mode), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A new phase in 305 stainless steel was observed, and was identified as an epsilon(*) (hcp) hydride due to hydrogen charging. Two new phases in 304 stainless steel were found as gamma(*) (fcc) and epsilon(*) hydrides from hydrogen charging. The hydride formation mechanisms during charging were: (1) gamma yields gamma(*) hydride and (2) gamma yields epsilon yields epsilon(*) hydride. These hydrides are unstable and decomposed during room temperature aging in air. The decomposition mechanisms were: (1) epsilon(*) hydride (hcp) yields expanded epsilon (hcp) phase yields a (bcc) phase; (2) gamma(*) hydride yields gamma phase. The grain and twin boundary cracks were the results of charging and identified as the preferred cracking sites. Transgranular crack initiation and growth accompanied the decomposition of hydrides and were controlled by hydrogen outgassing during room temperature aging.« less

The Current Status of Hydrogen Storage Alloy Development for Electrochemical Applications

PubMed Central

Young, Kwo-hsiung; Nei, Jean

2013-01-01

In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB5, AB2, A2B7-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical application, the nickel metal hydride battery, is summarized. Other electrochemical applications, such as Ni-hydrogen, fuel cell, Li-ion battery, air-metal hydride, and hybrid battery systems, also have been mentioned. PMID:28788349

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... uranium, radium and vanadium ores subcategory. 440.30 Section 440.30 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.30 Applicability; description of the...

The Electronic Structure and Field Effects of an Organic-Based Room Temperature Magnetic Semiconductor

DTIC Science & Technology

2007-01-01

used. Other materials used in this study include: microscope slide glass for transistor substrates (Gold Seal), silicon nitride, Si3N4, sputtering...with the top in place. At LBNL the glass tubes were placed in a nitrogen filled glove bag attached to the XAS sample chamber where they were...valences such as vanadium(II) oxide (VO), vanadium(III) oxide (V2O3), vanadium(IV) oxide (VO2), and vanadium(IV) oxide ( V2O5 ). V2O3 in particular is an

One-step hydrothermal synthesis of hexangular starfruit-like vanadium oxide for high power aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Shao, Jie; Li, Xinyong; Qu, Qunting; Zheng, Honghe

2012-12-01

Homogenous hexangular starfruit-like vanadium oxide was prepared for the first time by a one-step hydrothermal method. The assembly process of hexangular starfruit-like structure was observed from TEM images. The electrochemical performance of starfruit-like vanadium oxide was examined by cyclic voltammetry and galvanostatic charge/discharge. The obtained starfruit-like vanadium oxide exhibits a high power capability (19 Wh kg-1 at the specific power of 3.4 kW kg-1) and good cycling stability for supercapacitors application.

Nuclear reactor fuel element with vanadium getter on cladding

DOEpatents

Johnson, Carl E.; Carroll, Kenneth G.

1977-01-01

A nuclear reactor fuel element is described which has an outer cladding, a central core of fissionable or mixed fissionable and fertile fuel material and a layer of vanadium as an oxygen getter on the inner surface of the cladding. The vanadium reacts with oxygen released by the fissionable material during irradiation of the core to prevent the oxygen from reacting with and corroding the cladding. Also described is a method for coating the inner surface of small diameter tubes of cladding with a layer of vanadium.

Investigation of crossover processes in a unitized bidirectional vanadium/air redox flow battery

NASA Astrophysics Data System (ADS)

grosse Austing, Jan; Nunes Kirchner, Carolina; Komsiyska, Lidiya; Wittstock, Gunther

2016-02-01

In this paper the losses in coulombic efficiency are investigated for a vanadium/air redox flow battery (VARFB) comprising a two-layered positive electrode. Ultraviolet/visible (UV/Vis) spectroscopy is used to monitor the concentrations cV2+ and cV3+ during operation. The most likely cause for the largest part of the coulombic losses is the permeation of oxygen from the positive to the negative electrode followed by an oxidation of V2+ to V3+. The total vanadium crossover is followed by inductively coupled plasma mass spectroscopy (ICP-MS) analysis of the positive electrolyte after one VARFB cycle. During one cycle 6% of the vanadium species initially present in the negative electrolyte are transferred to the positive electrolyte, which can account at most for 20% of the coulombic losses. The diffusion coefficients of V2+ and V3+ through Nafion® 117 are determined as DV2+ ,N 117 = 9.05 ·10-6 cm2 min-1 and DV3+ ,N 117 = 4.35 ·10-6 cm2 min-1 and are used to calculate vanadium crossover due to diffusion which allows differentiation between vanadium crossover due to diffusion and migration/electroosmotic convection. In order to optimize coulombic efficiency of VARFB, membranes need to be designed with reduced oxygen permeation and vanadium crossover.

Vanadium As a Potential Membrane Material for Carbon Capture: Effects of Minor Flue Gas Species.

PubMed

Yuan, Mengyao; Liguori, Simona; Lee, Kyoungjin; Van Campen, Douglas G; Toney, Michael F; Wilcox, Jennifer

2017-10-03

Vanadium and its surface oxides were studied as a potential nitrogen-selective membrane material for indirect carbon capture from coal or natural gas power plants. The effects of minor flue gas components (SO 2 , NO, NO 2 , H 2 O, and O 2 ) on vanadium at 500-600 °C were investigated by thermochemical exposure in combination with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and in situ X-ray diffraction (XRD). The results showed that SO 2 , NO, and NO 2 are unlikely to have adsorbed on the surface vanadium oxides at 600 °C after exposure for up to 10 h, although NO and NO 2 may have exhibited oxidizing effects (e.g., exposure to 250 ppmv NO/N 2 resulted in an 2.4 times increase in surface V 2 O 5 compared to exposure to just N 2 ). We hypothesize that decomposition of surface vanadium oxides and diffusion of surface oxygen into the metal bulk are both important mechanisms affecting the composition and morphology of the vanadium membrane. The results and hypothesis suggest that the carbon capture performance of the vanadium membrane can potentially be strengthened by material and process improvements such as alloying, operating temperature reduction, and flue gas treatment.

Current status and associated human health risk of vanadium in soil in China.

PubMed

Yang, Jie; Teng, Yanguo; Wu, Jin; Chen, Haiyang; Wang, Guoqiang; Song, Liuting; Yue, Weifeng; Zuo, Rui; Zhai, Yuanzheng

2017-03-01

A detailed assessment of vanadium contamination characteristics in China was conducted based on the first national soil pollution survey. The map overlay analysis was used to evaluate the contamination level of vanadium and the non-carcinogenic risk assessment model was calculated to quantify the vanadium exposure risks to human health. The results showed that, due to the drastically increased mining and smelting activities, 26.49% of soils were contaminated by vanadium scattered in southwest of China. According to Canadian soil quality guidelines, about 8.6% of the national soil pollution survey samples were polluted, and pose high non-carcinogenic risks to the public, especially to children living in the vicinity of heavily polluted mining areas. We propose the area near the boundary of Yunnan, Guizhou, Guangxi, and Sichuan provinces as priority control areas due to their higher geochemical background or higher health risks posed to the public. Finally, recommendations for management are proposed, including minimization of contaminant inputs, establishing stringent monitoring program, using phytoremediation, and strengthening the enforcement of relevant laws. Therefore, this study provides a comprehensive assessment of soil vanadium contamination in China, and the results will provide valuable information for China's soil vanadium management and risk avoidance. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

AIR PASSIVATION OF METAL HYDRIDE BEDS FOR WASTE DISPOSAL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J; R. H. Hsu, R

2007-07-02

Metal hydride beds offer compact, safe storage of tritium. After metal hydride beds have reached the end of their useful life, the beds will replaced with new beds and the old beds prepared for disposal. One acceptance criteria for hydride bed waste disposal is that the material inside the bed not be pyrophoric. To determine the pyrophoric nature of spent metal hydride beds, controlled air ingress tests were performed. A simple gas handling manifold fitted with pressure transducers and a calibrated volume were used to introduce controlled quantities of air into a metal hydride bed and the bed temperature risemore » monitored for reactivity with the air. A desorbed, 4.4 kg titanium prototype hydride storage vessel (HSV) produced a 4.4 C internal temperature rise upon the first air exposure cycle and a 0.1 C temperature rise upon a second air exposure. A total of 346 scc air was consumed by the bed (0.08 scc per gram Ti). A desorbed, 9.66 kg LaNi{sub 4.25}Al{sub 0.75} prototype storage bed experienced larger temperature rises over successive cycles of air ingress and evacuation. The cycles were performed over a period of days with the bed effectively passivated after the 12th cycle. Nine to ten STP-L of air reacted with the bed producing both oxidized metal and water.« less

Fast, quantitative, and nondestructive evaluation of hydrided LWR fuel cladding by small angle incoherent neutron scattering of hydrogen

DOE PAGES

Yan, Y.; Qian, S.; Littrell, K.; ...

2015-02-13

A non-destructive neutron scattering method to precisely measure the uptake of hydrogen and the distribution of hydride precipitates in light water reactor (LWR) fuel cladding was developed. Zircaloy-4 cladding used in commercial LWRs was used to produce hydrided specimens. The hydriding apparatus consists of a closed stainless steel vessel that contains Zr alloy specimens and hydrogen gas. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentration were selected for the neutron study. Optical microscopy shows that our hydriding procedure results in uniform distributionmore » of circumferential hydrides across the wall. Small angle neutron incoherent scattering was performed in the High Flux Isotope Reactor at Oak Ridge National Laboratory. This study demonstrates that the hydrogen in commercial Zircaloy-4 cladding can be measured very accurately in minutes by this nondestructive method over a wide range of hydrogen concentrations from a very small amount ( 20 ppm) to over 1000 ppm. The hydrogen distribution in a tube sample was obtained by scaling the neutron scattering rate with a factor determined by a calibration process using standard, destructive direct chemical analysis methods on the specimens. This scale factor will be used in future tests with unknown hydrogen concentrations, thus providing a nondestructive method for absolute hydrogen concentration determination.« less

The unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

PubMed

Wang, Jiandi; Wang, Wenmin; Huang, Liangfang; Yang, Xiaodi; Wei, Haiyan

2015-04-07

In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

PubMed

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

2015-06-30

For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

The increase in fatigue crack growth rates observed for Zircaloy-4 in a PWR environment

NASA Astrophysics Data System (ADS)

Cockeram, B. V.; Kammenzind, B. F.

2018-02-01

Cyclic stresses produced during the operation of nuclear reactors can result in the extension of cracks by processes of fatigue. Although fatigue crack growth rate (FCGR) data for Zircaloy-4 in air are available, little testing has been performed in a PWR primary water environment. Test programs have been performed by Gee et al., in 1989 and Picker and Pickles in 1984 by the UK Atomic Energy Authority, and by Wisner et al., in 1994, that have shown an enhancement in FCGR for Zircaloy-2 and Zircaloy-4 in high-temperature water. In this work, FCGR testing is performed on Zircaloy-4 in a PWR environment in the hydrided and non-hydrided condition over a range of stress-intensity. Measurements of crack extension are performed using a direct current potential drop (DCPD) method. The cyclic rate in the PWR primary water environment is varied between 1 cycle per minute to 0.1 cycle per minute. Faster FCGR rates are observed in water in comparison to FCGR testing performed in air for the hydrided material. Hydrided and non-hydrided materials had similar FCGR values in air, but the non-hydrided material exhibited much lower rates of FCGR in a PWR primary water environment than for hydrided material. Hydrides are shown to exhibit an increased tendency for cracking or decohesion in a PWR primary water environment that results in an enhancement in FCGR values. The FCGR in the PWR primary water only increased slightly with decreasing cycle frequency in the range of 1 cycle per minute to 0.1 cycle per minute. Comparisons between the FCGR in water and air show the enhancement from the PWR environment is affected by the applied stress intensity.

Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2] (+) (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimlos, Mark R.; Chang, Christopher H.; Curtis, Calvin J.

2008-07-07

Density functional theory (BLYP and B3LYP) and the polarized continuum model (PCM-UA0) for solvation have been used to investigate the effect of bite angle (P-M-P) of diphosphine ligands and the dihedral or twist angle between diphosphine ligands on the hydride donor abilities of Ni, Pd, and Pt [HM(diphosphine)2]+ complexes. It is found that an increased bite angle for a given transition metal atom results in poorer hydride donor abilities. However, hydride donor abilities for these complexes also decrease as the size of the alkyl side groups on the phosphorus atom increase (Et > Me > H) and with the lengthmore » of the metal phosphorus bond (Ni > Pd = Pt). These trends correlate with an increase in the twist angle between the two diphosphine ligands, which increases from 0° for a square-planar configuration to 90° for a tetrahedral geometry. Shorter M-P bonds, larger substituents on the diphosphine ligands, and larger bite angles all result in increased steric interactions between diphosphine ligands and larger dihedral or twist angles between the diphosphine ligands. The twist angle correlates much more strongly with hydride donor abilities than do bite angles alone. As the twist angle increases, the hydride donor ability decreases in a linear fashion. A frontier orbital analysis has been carried out, and it is shown that the hydride donor ability of [HM(diphosphine)2]+ complexes is largely determined by the energy of the lowest unoccupied molecular orbital of the corresponding [M(diphosphine)2]2+ complex. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2]+ (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimlos, Mark; Chang, Christopher H.; Curtis, Calvin J.

2008-06-23

Density functional theory (BLYP and B3LYP) and the polarized continuum model (PCM-UA0) for solvation have been used to investigate the effect of bite angle (P-M-P) of diphosphine ligands and the dihedral or twist angle between diphosphine ligands on the hydride donor abilities of Ni, Pd, and Pt [HM(diphosphine)2]+ complexes. It is found that an increased bite angle for a given transition metal atom results in poorer hydride donor abilities. However, hydride donor abilities for these complexes also decrease as the size of the alkyl side groups on the phosphorus atom increase (Et > Me > H) and with the lengthmore » of the metal phosphorus bond (Ni > Pd = Pt). These trends correlate with an increase in the twist angle between the two diphosphine ligands, which increases from 0° for a square-planar configuration to 90° for a tetrahedral geometry. Shorter M-P bonds, larger substituents on the diphosphine ligands, and larger bite angles all result in increased steric interactions between diphosphine ligands and larger dihedral or twist angles between the diphosphine ligands. The twist angle correlates much more strongly with hydride donor abilities than do bite angles alone. As the twist angle increases, the hydride donor ability decreases in a linear fashion. A frontier orbital analysis has been carried out, and it is shown that the hydride donor ability of [HM(diphosphine)2]+ complexes is largely determined by the energy of the lowest unoccupied molecular orbital of the corresponding [M(diphosphine)2]2+ complex. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Synthesis and hydriding properties of Li 2Mg(NH) 2

NASA Astrophysics Data System (ADS)

Markmaitree, Tippawan; Shaw, Leon L.

The phase pure Li 2Mg(NH) 2 has been synthesized via a dehydriding treatment of a ball milled 2LiNH 2 + MgH 2 mixture. This phase pure Li 2Mg(NH) 2 has been utilized to investigate its hydriding kinetics at the temperature range 180-220 °C. It is found that the hydriding process of Li 2Mg(NH) 2 is very sluggish even though it has favorable thermodynamic properties for near the ambient temperature operation. Holding at 200 °C for 10 h only results in 3.75 wt.% H 2 uptake. The detailed kinetic analysis reveals that the hydriding process of Li 2Mg(NH) 2 is diffusion-controlled. Thus, this study unambiguously indicates that the future direction to enhance the hydriding kinetics of this promising hydrogen storage material system should be to minimize the diffusion distance and increase the diffusion rate.

Hydride Transfer in DHFR by Transition Path Sampling, Kinetic Isotope Effects, and Heavy Enzyme Studies

PubMed Central

Wang, Zhen; Antoniou, Dimitri; Schwartz, Steven D.; Schramm, Vern L.

2016-01-01

Escherichia coli dihydrofolate reductase (ecDHFR) is used to study fundamental principles of enzyme catalysis. It remains controversial whether fast protein motions are coupled to the hydride transfer catalyzed by ecDHFR. Previous studies with heavy ecDHFR proteins labeled with 13C, 15N, and nonexchangeable 2H reported enzyme mass-dependent hydride transfer kinetics for ecDHFR. Here, we report refined experimental and computational studies to establish that hydride transfer is independent of protein mass. Instead, we found the rate constant for substrate dissociation to be faster for heavy DHFR. Previously reported kinetic differences between light and heavy DHFRs likely arise from kinetic steps other than the chemical step. This study confirms that fast (femtosecond to picosecond) protein motions in ecDHFR are not coupled to hydride transfer and provides an integrative computational and experimental approach to resolve fast dynamics coupled to chemical steps in enzyme catalysis. PMID:26652185

Transformation and precipitation in vanadium treated steels

NASA Astrophysics Data System (ADS)

Vassiliou, Andreas D.

A series of carbon manganese steels containing varying amounts of carbon, vanadium and nitrogen was investigated in relation to the solubility of VC and VN in austenite, the grain coarsening characteristics of austenite, the tempering of martensite and other structures, the transformation during continuous cooling, the effect of vanadium addition and increasing nitrogen content on the thermo-mechanical processing of austenite, and the transformation of various morphologies of austenite to ferrite.The sites for preferential nucleation and growth of ferrite were identified and the effect of ferrite grain size inhomogeneity was investigated with a view to minimising it.The C/N ratio in the V(CN) precipitates was largely controlled by C/N ratio in the steel and it was also influenced by the austenitising treatment. As expected, the solubility of VN was less than that of VC.A systematic investigation of austenitising time and temperature on the grain coarsening characteristics was carried out showing the effects of vanadium, carbon and nitrogen. It was tentatively suggested that C-C and N-N clustering in the vanadium free steels controlled the grain growth whereas in the presence of vanadium, it was shown that VN and VC pinned the austenite grain boundaries and restricted grain growth. However coarsening or solution of VC and VN allowed the grain bondaries to migrate and grain coarsening occurred. The grain coarsening temperature was controlled predominantly by VN, whilst the VC dissolved frequently below the grain coarsening temperature.In the as quenched martensite, increasing nitrogen progressively increased the as quenched hardness, and the hardness also greatly increased with increasing carbon and vanadium added together. Examining the precipitation strengthening in tempered martensite showed that in the absence of vanadium, martensite softened progressively with increasing temperature and time. Vanadium additions increased the hardness level during low temperature tempering and at higher tempering temperature introduced secondary hardening. The intensity of secondary hardening increased with increasing vanadium, whereas austenitising temperature had little or no effect. The softening after the secondary hardening was faster after austenitising at the higher temperature and when recrystallisation occurred at the highest tempering temperatures, the hardness was lower due to coarse recrystallised ferrite.Isothermal transformation studies showed that vanadium additions raised the Ar3 temperature and accelerated ferrite nucleation, whilst the growth of ferrite was delayed due to the formation of V(CN) interphase and general precipitation pinning, of the transformation front. Increasing nitrogen content in the V-steel increased the incubation period for ferrite nucleation and increasingly reduced the ferrite growth by increasing V(CN) precipitation pinning of the transformation front.Transformation during continuous cooling was examined in relation to the effect of vanadium, carbon and nitrogen together with the effect of austenitising temperature. Increasing austenitising temperature increased the austenite grain size, and it then became apparent that increasing vanadium, carbon and nitrogen increased the hardenability and raised the hardness level of the jominy curve for the non-martensitic products. (Abstract shortened by ProQuest.).

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

Vanadium-pumped titanium x-ray laser

DOEpatents

Nilsen, Joseph

1992-01-01

A resonantly photo-pumped x-ray laser (10) is formed of a vanadium (12) and titanium (14) foil combination (16) that is driven by two beams (18, 20) of intense line focused (22, 24) optical laser radiation. Ground state neon-like titanium ions (34) are resonantly photo-pumped by line emission from fluorine-like vanadium ions (32).

Modeling of ion transport through a porous separator in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

2016-09-01

In this work, we develop a two-dimensional, transient model to investigate the mechanisms of ion-transport through a porous separator in VRFBs and their effects on battery performance. Commercial-available separators with pore sizes of around 45 nm are particularly investigated and effects of key separator design parameters and operation modes are explored. We reveal that: i) the transport mechanism of vanadium-ion crossover through available separators is predominated by convection; ii) reducing the pore size below 15 nm effectively minimizes the convection-driven vanadium-ion crossover, while further reduction in migration- and diffusion-driven vanadium-ion crossover can be achieved only when the pore size is reduced to the level close to the sizes of vanadium ions; and iii) operation modes that can affect the pressure at the separator/electrode interface, such as the electrolyte flow rate, exert a significant influence on the vanadium-ion crossover rate through the available separators, indicating that it is critically important to equalize the pressure on each half-cell of a power pack in practical applications.

Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.

PubMed

Zhan, Guowu; Ng, Wei Cheng; Lin, Wenlin Yvonne; Koh, Shin Nuo; Wang, Chi-Hwa

2018-03-06

Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 μm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

In situ self-sacrificed template synthesis of vanadium nitride/nitrogen-doped graphene nanocomposites for electrochemical capacitors.

PubMed

Liu, Hong-Hui; Zhang, Hong-Ling; Xu, Hong-Bin; Lou, Tai-Ping; Sui, Zhi-Tong; Zhang, Yi

2018-03-15

Vanadium nitride and graphene have been widely used as pseudo-capacitive and electric double-layer capacitor electrode materials for electrochemical capacitors, respectively. However, the poor cycling stability of vanadium nitride and the low capacitance of graphene impeded their practical applications. Herein, we demonstrated an in situ self-sacrificed template method for the synthesis of vanadium nitride/nitrogen-doped graphene (VN/NGr) nanocomposites by the pyrolysis of a mixture of dicyandiamide, glucose, and NH 4 VO 3 . Vanadium nitride nanoparticles of the size in the range of 2 to 7 nm were uniformly embedded into the nitrogen-doped graphene skeleton. Furthermore, the VN/NGr nanocomposites with a high specific surface area and pore volume showed a high specific capacitance of 255 F g -1 at 10 mV s -1 , and an excellent cycling stability (94% capacitance retention after 2000 cycles). The excellent capacitive properties were ascribed to the excellent conductivity of nitrogen-doped graphene, high surface area, high pore volume, and the synergistic effect between vanadium nitride and nitrogen-doped graphene.

Reduction of Vanadium Oxide (VOx) under High Vacuum Conditions as Investigated by X-Ray Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Chourasia, A.

2015-03-01

Vanadium oxide thin films were formed by depositing thin films of vanadium on quartz substrates and oxidizing them in an atmosphere of oxygen. The deposition was done by the e-beam technique. The oxide films were annealed at different temperatures for different times under high vacuum conditions. The technique of x-ray photoelectron spectroscopy has been employed to study the changes in the oxidation states of vanadium and oxygen in such films. The spectral features in the vanadium 2p, oxygen 1s, and the x-ray excited Auger regions were investigated. The Auger parameter has been utilized to study the changes. The complete oxidation of elemental vanadium to V2O5 was observed to occur at 700°C. At any other temperature, a mixture of oxides consisting of V2O5 and VO2 was observed in the films. Annealing of the films resulted in the gradual loss of oxygen followed by reduction in the oxidation state from +5 to 0. The reduction was observed to depend upon the annealing temperature and the annealing time. Organized Research, TAMU-Commerce.

Effect of substrate temperature on thermochromic vanadium dioxide thin films sputtered from vanadium target

NASA Astrophysics Data System (ADS)

Madiba, I. G.; Kotsedi, L.; Ngom, B. D.; Khanyile, B. S.; Maaza, M.

2018-05-01

Vanadium dioxide films have been known as the most promising thermochromic thin films for smart windows which self-control the solar radiation and heat transfer for energy saving, comfort in houses and automotives. Such an attractive technological application is due to the fact that vanadium dioxide crystals exhibit a fast semiconductor-to-metal phase transition at a transition temperature Tc of about 68 °C, together with sharp optical changes from high transmitive to high reflective coatings in the IR spectral region. The phase transition has been associated with the nature of the microstructure, stoichiometry and stresses related to the oxide. This study reports on the effect of the crystallographic quality controlled by the substrate temperature on the thermochromic properties of vanadium dioxide thin films synthesized by reactive radio frequency inverted cylindrical magnetron sputtering from vanadium target. The reports results are based on X-ray diffraction, Atomic force microscopy, and UV-Visible spectrophotometer. The average crystalline grain size of VO2 increases with the substrate temperature, inducing stress related phenomena within the films.

Nuclear microscope analysis of blood cells from the tropical ascidian Phallusia philippinensis

NASA Astrophysics Data System (ADS)

Hogarth, A. N.; Thong, P. S. P.; Lane, D. J. W.; Watt, F.

1997-07-01

The present study examines the concentrations of vanadium, bromine and sulphur contained within cryofixed/freeze dried blood cells of the ascidian Phallusia philippinensis (Millar, 1975). Elemental profiles of seven cell types were obtained using the National University of Singapore nuclear microscope. Morula cells were found to contain the following mean values; 0.8% vanadium, 3.5% bromine and 6.1% sulphur. Signet ring cells contained 0.5% vanadium, 2.4% bromine and 1.5% sulphur. Compartment cells had 0.1% vanadium, 2.1% bromine and 2.4% sulphur. Other less abundant cell types such as lymphocytes, macrogranular amoebocytes, carotenoid pigment cells and granular amoebocytes were also analysed and found to contain 0.4%, 0.7%, 0.2% and 1.0% vanadium, 2.0%, 1.6%, 0.6% and 1.2% bromine and 1.3%, 1.5%, 0.3% and 4.3% sulphur respectively. Sulphur occurred in high levels in all cell types, which could indicate its involvement in the vanadium concentration process, while bromine, incorporated into complexes, may be utilised for anti-fouling rather than as a deterrent to predators.

Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Wang, Wei; Nie, Zimin

2013-11-01

The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approachmore » reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

A Disposable Alkaline Phosphatase-Based Biosensor for Vanadium Chronoamperometric Determination

PubMed Central

Alvarado-Gámez, Ana Lorena; Alonso-Lomillo, María Asunción; Domínguez-Renedo, Olga; Arcos-Martínez, María Julia

2014-01-01

A chronoamperometric method for vanadium ion determination, based on the inhibition of the enzyme alkaline phosphatase, is reported. Screen-printed carbon electrodes modified with gold nanoparticles were used as transducers for the immobilization of the enzyme. The enzymatic activity over 4-nitrophenyl phosphate sodium salt is affected by vanadium ions, which results in a decrease in the chronoamperometric current registered. The developed method has a detection limit of 0.39 ± 0.06 μM, a repeatability of 7.7% (n = 4) and a reproducibility of 8% (n = 3). A study of the possible interferences shows that the presence of Mo(VI), Cr(III), Ca(II) and W(VI), may affect vanadium determination at concentration higher than 1.0 mM. The method was successfully applied to the determination of vanadium in spiked tap water. PMID:24569772

A-15 Superconducting composite wires and a method for making

DOEpatents

Suenaga, Masaki; Klamut, Carl J.; Luhman, Thomas S.

1984-01-01

A method for fabricating superconducting wires wherein a billet of copper containing filaments of niobium or vanadium is rolled to form a strip which is wrapped about a tin-alloy core to form a composite. The alloy is a tin-copper alloy for niobium filaments and a gallium-copper alloy for vanadium filaments. The composite is then drawn down to a desired wire size and heat treated. During the heat treatment process, the tin in the bronze reacts with the niobium to form the superconductor niobium tin. In the case where vanadium is used, the gallium in the gallium bronze reacts with the vanadium to form the superconductor vanadium gallium. This new process eliminates the costly annealing steps, external tin plating and drilling of bronze ingots required in a number of prior art processes.

Wrapping process for fabrication of A-15 superconducting composite wires

DOEpatents

Suenaga, M.; Klamut, C.J.; Luhman, T.S.

1980-08-15

A method for fabricating superconducting wires wherein a billet of copper containing filaments of niobium or vanadium is rolled to form a strip which is wrapped about a tin-alloy core to form a composite. The alloy is a tin-copper alloy for niobium filaments and a gallium-copper alloy for vanadium filaments. The composite is then drawn down to a desired wire size and heat treated. During the heat treatment process, the tin in the bronze reacts with the niobium to form the superconductor niobium tin. In the case where vanadium is used, the gallium in the gallium bronze reacts with the vanadium to form the superconductor vanadium gallium. This new process eliminates the costly annealing steps, external tin plating and drilling of bronze ingots required in a number of prior art processes.

Fusion materials: Technical evaluation of the technology of vandium alloys for use as blanket structural materials in fusion power systems

NASA Astrophysics Data System (ADS)

1993-08-01

The Committee's evaluation of vanadium alloys as a structural material for fusion reactors was constrained by limited data and time. The design of the International Thermonuclear Experimental Reactor is still in the concept stage, so meaningful design requirements were not available. The data on the effect of environment and irradiation on vanadium alloys were sparse, and interpolation of these data were made to select the V-5Cr-5Ti alloy. With an aggressive, fully funded program it is possible to qualify a vanadium alloy as the principal structural material for the ITER blanket in the available 5 to 8-year window. However, the data base for V-5Cr-5Ti is limited and will require an extensive development and test program. Because of the chemical reactivity of vanadium the alloy will be less tolerant of system failures, accidents, and off-normal events than most other candidate blanket structural materials and will require more careful handling during fabrication of hardware. Because of the cost of the material more stringent requirements on processes, and minimal historical working experience, it will cost an order of magnitude to qualify a vanadium alloy for ITER blanket structures than other candidate materials. The use of vanadium is difficult and uncertain; therefore, other options should be explored more thoroughly before a final selection of vanadium is confirmed. The Committee views the risk as being too high to rely solely on vanadium alloys. In viewing the state and nature of the design of the ITER blanket as presented to the Committee, it is obvious that there is a need to move toward integrating fabrication, welding, and materials engineers into the ITER design team. If the vanadium alloy option is to be pursued, a large program needs to be started immediately. The commitment of funding and other resources needs to be firm and consistent with a realistic program plan.

[Interaction Between Occupational Vanadium Exposure and hsp70-hom on Neurobehavioral Function].

PubMed

Zhang, Qin; Liu, Yun-xing; Cui, Li; Li, Shun-pin; Gao, Wei; Hu, Gao-lin; Zhang, Zu-hui; Lan, Ya-jia

2016-01-01

In determine the effect of heat shock protein 70-hom gene (hsp70-hom) polymorphism on the neurobehavioral function of workers exposed to vanadium. Workers from the vanadium products and chemical industry were recruited by cluster sampling. Demographic data and exposure information were collected using a questionnaire. Neurobehavioral function was assessed by Neurobehavioral Core Test Battery. The hsp70-hom genotype was detected by restricted fragment length polymorphism-polymerase chain reaction (RFLP-PCR). A neurobehavioral index (NBI) was formulated through principal component analysis. Workers with a T/C genotype had worse performance in average reaction time, visual retention, digital span (backward), Santa Ana aiming (non-habitual hand), pursuit aiming (right points, total points), digit symbol and NBI score than others (P < 0.05). The relative risk of abnormal NBI score of the workers with a T/C genotype was 1.748 fold of those with a T/T genotype. The relative risk of abnormal.NBI score of the workers exposed to vanadium was 3.048 fold of controls (P < 0.05). But after adjustment with age and education, only vanadium exposure appeared with a significant effect on NBI score. When gene polymorphism and vanadium exposure coexisted, the effect of vanadium on neurobehavioral function was attenuated, but the influence of T/C genotype increased Codds ratio (OR = 4.577, P < 0.05). After adjustment with age and education, the OR of T/C genotype further increased to 7.777 (P < 0.05). Vanadium exposure and T/C genotype had.a bio-interaction effect on NBI score Crelative excess risk due to interaction (RERI) = 4.12, attributable proportion (AP) = 0.7, synergy index (S) = 6.45]. After adjustment with age and education, the RERI became 2.49 and the AP became 0.75, but no coefficient of interaction was produced. Priorities of occupational protection should be given to vanadium-exposed workers with a hsp70-hom T/C genotype and low education level.

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

PubMed

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

Destabilisation of complex hydrides through size effects.

PubMed

Christian, Meganne; Aguey-Zinsou, Kondo-Francois

2010-12-01

Nanoparticles of NaAlH4, LiAlH4 and LiBH4 were prepared by encapsulating their respective hydrides within carbon nanotubes by a wet chemical approach. The resulting confinement had a profound effect on the overall hydrogen storage properties of these hydrides, with NaAlH4 and LiAlH4 releasing hydrogen from room temperature, for example.

Wafer-Fused Orientation-Patterned GaAs

DTIC Science & Technology

2008-02-13

frequencies utilizing existing industrial foundries. 15. SUBJECT TERMS Orientation-patterned Gallium Arsenide, hydride vapor phase epitaxy, quasi-phase... Gallium Arsenide, hydride vapor phase epitaxy, quasi-phase-matching, nonlinear frequency conversion 1. INTRODUCTION Quasi-phase-matching (QPM)1...and E. Lallier, “Second harmonic generation of CO2 laser using thick quasi-phase-matched GaAs layer grown by hydride vapour phase epitaxy

Method of selective reduction of halodisilanes with alkyltin hydrides

DOEpatents

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

1989-01-01

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

Determination of hydride affinities of various aldehydes and ketones in acetonitrile.

PubMed

Zhu, Xiao-Qing; Chen, Xi; Mei, Lian-Rui

2011-05-06

The hydride affinities of 21 typical aldehydes and ketones in acetonitrile were determined by using an experimental method, which is valuable for chemists choosing suitable reducing agents to reduce them. The focus of this paper is to introduce a very facile experimental method, which can be used to determine the hydride affinities of various carbonyl compounds in solution.

Hydride heat pump with heat regenerator

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor)

1991-01-01

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

High H⁻ ionic conductivity in barium hydride.

PubMed

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

2015-01-01

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

Creation of Y2Ti2O7 nanoprecipitates to strengthen the Fe-14Cr-3Al-2W steels by adding Ti hydride and Y2O3 nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Linbo; Bai, Zhonglian; Shen, Hailong; Wang, Chenxi; Liu, Tong

2017-05-01

In order to prohibit the formation of large Y-Al-O precipitates, Ti hydride nanoparticles (NPs) were prepared and used to replace Ti as raw particles to fabricate the oxide dispersion strengthened (ODS) Fe-14Cr-3Al-2W-0.35Y2O3 steels by mechanical alloying (MA) and hot isostatic pressing (HIP). As the content of Ti hydride increases from 0.1 to 0.5 and 1.0 wt%, the oxide nanoprecipitates in the ODS steels changes from Y3Al5O12 phase to Y2Ti2O7 phase (semicoherent with the matrix), and the particle size is successfully reduced. The tensile strength of the ODS steel increases remarkably with increasing Ti hydride content. The sample with 1.0 wt% Ti hydride exhibits a high strength of 1049 MPa at 25 °C and 278 MPa at 700 °C. The creation of Y2Ti2O7 nanoprecipitates by adding Ti hydride NPs opens a new way to control the structure and size of the oxide precipitates in the ODS steels.

Reactivity of yttrium carboxylates toward alkylaluminum hydrides.

PubMed

Schädle, Christoph; Fischbach, Andreas; Herdtweck, Eberhardt; Törnroos, Karl W; Anwander, Reiner

2013-11-25

Yttrocene-carboxylate complex [Cp*2Y(OOCAr(Me))] (Cp*=C5Me5, Ar(Me) =C6H2Me3-2,4,6) was synthesized as a spectroscopically versatile model system for investigating the reactivity of alkylaluminum hydrides towards rare-earth-metal carboxylates. Equimolar reactions with bis-neosilylaluminum hydride and dimethylaluminum hydride gave adduct complexes of the general formula [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] (R=CH2SiMe3, Me). The use of an excess of the respective aluminum hydride led to the formation of product mixtures, from which the yttrium-aluminum-hydride complex [{Cp*2Y(μ-H)AlMe2(μ-H)AlMe2(μ-CH3)}2] could be isolated, which features a 12-membered-ring structure. The adduct complexes [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] display identical (1)J(Y,H) coupling constants of 24.5 Hz for the bridging hydrido ligands and similar (89)Y NMR shifts of δ=-88.1 ppm (R=CH2SiMe3) and δ=-86.3 ppm (R=Me) in the (89)Y DEPT45 NMR experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Homology of vanadium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasyutinskii, N.A.

1987-05-01

The authors examine the homology of vanadium oxide and note that data on the existence of phases and homogeneity limits in the V-O system are very contradictory. A graphical illustration shows the homologous series of vanadium oxides. The predominant part of the discrete formations in the system V-O is characterized by integral stoichiometry and forms six homologous series. It is found that homologous series of vanadium oxides are not only a basis for systematization of such oxides, but also may serve as a means for predicting the composition of new phases, limits of homogeneity, their structure, and properties.

Lithium vanadium oxides (Li1+xV3O8) as cathode materials in lithium-ion batteries for soldier portable power systems

NASA Astrophysics Data System (ADS)

Wang, Gaojun; Chen, Linfeng; Mathur, Gyanesh N.; Varadan, Vijay K.

2011-04-01

Improving soldier portable power systems is very important for saving soldiers' lives and having a strategic advantage in a war. This paper reports our work on synthesizing lithium vanadium oxides (Li1+xV3O8) and developing their applications as the cathode (positive) materials in lithium-ion batteries for soldier portable power systems. Two synthesizing methods, solid-state reaction method and sol-gel method, are used in synthesizing lithium vanadium oxides, and the chemical reaction conditions are determined mainly based on thermogravimetric and differential thermogravimetric (TG-DTG) analysis. The synthesized lithium vanadium oxides are used as the active positive materials in the cathodes of prototype lithium-ion batteries. By using the new solid-state reaction technique proposed in this paper, lithium vanadium oxides can be synthesized at a lower temperature and in a shorter time, and the synthesized lithium vanadium oxide powders exhibit good crystal structures and good electrochemical properties. In the sol-gel method, different lithium source materials are used, and it is found that lithium nitrate (LiNO3) is better than lithium carbonate (Li2CO3) and lithium hydroxide (LiOH). The lithium vanadium oxides synthesized in this work have high specific charge and discharge capacities, which are helpful for reducing the sizes and weights, or increasing the power capacities, of soldier portable power systems.

Cytotoxic effect of vanadium and oil-fired fly ash on hamster tracheal epithelium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schiff, L.J.; Graham, J.A.

1984-08-01

Hamster tracheal organ cultures were used to study the in vitro effects of vanadium and oil-fired fly ash on mucociliary respiratory epithelium. Two vanadium compounds, VOSO/sub 4/ and V/sub 2/O/sub 5/, and fly ash from an oil-fueled power plant were dissolved or suspended in culture medium over a range of concentrations and epithelia were exposed for 1 hr/day, for 9 consecutive days. At intervals during this period, alterations in cilia-beating frequency, cytology, and histology were documented by light microscopy. Explants treated with VOSO/sub 4/ either decreased ciliary activity or produced ciliostasis depending upon the concentration and length of exposure. Earlymore » morphological alterations consisted of vacuolization of both nuclei and cytoplasm. After multiple exposures, cytology of VOSO/sub 4/-treated respiratory mucosa was markedly affected. Similar changes were observed in cultures exposed to V/sub 2/O/sub 5/; however, the cytotoxicity appeared earlier and was more pronounced. Fly ash-treated explants produced similar biological effects when compared to both vanadium compounds. Thus, the data indicate that the extent of vanadium toxicity depends, at least in part, on the vanadium content of the compound tested, and that exposure to this metal and vanadium-rich fly ash can inhibit normal mucociliary function, a vital clearance mechanism in the respiratory tract.« less

[Determination of Fe, Ti and V in vanadium and titanium magnetite by ICP-OES and microwave-assisted digestion].

PubMed

Zhu, Xia-ping; Yin, Ji-xian; Chen, Wei-dong; Hu, Zi-Wen; Liang, Qing-xun; Chen, Tie-yao

2010-08-01

The method of determination of iron, titanium and vanadium in indissolvable vanadium and titanium magnetite has been established by inductively coupled plasma atomic emission spectroscopy through adding the complexant A and using microwave-assisted digestion. The optimal conditions are confirmed by orthogonal experiment: 0.1 g vanadium and titanium magnetite, 0.04 g complexant A, 12 mL concentrated HC1, 10 min digestion time, and 385 W microwave power. The newly-established method has been applied to digest vanadium and titanium magnetite of Panzhihua Iron and Steel Institute (GBW07226). The iron, titanium and vanadium were detected by ICP-OES, and both comparative error (Er%) and comparative standard deviation (RSD%) met the demand of analytical chemistry, and the complexant A can significantly accelerate the dissolution of vanadium and titanium magnetite through the complexation with the dissolved metal ions, and making the surface of sample and hydrochloric acid medium to update constantly. The determination of the main and trace elements of digestion solution at the same time was achieved by ICP-OES. The method has the advantages of less use of reagents, economy, rapidness, and being friendly to environment, and it meets the requirement for rapid and volume determination. So the method has the value of practical application for the entry-exit inspection and quarantine department of the state and other relevant inspection units.

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, G.N.; Coyle, C.L.; Hales, B.J.

Evidence for the existence of a vanadium-containing nitrogenase has existed for more than half a century, but progress in understanding this enzyme has only come recently. In 1980, Bishop and co-workers proposed that an alternative nitrogen-fixing enzyme exists in Azotobacter vinelandii and subsequently proposed that vanadium was involved. In 1986, Robson et al. demonstrated clearly that the alternate nitrogenase from Azotobacter chroococcum, Acl*, contained vanadium instead of molybdenum. Hales et al. have shown the vanadium is also found in the Azotobacter vinelandii alternative component I, Avl'. The molybdenum and vanadium nitrogenase proteins are similar in many respects. Like the molybdenummore » enzyme, both Acl* and Avl' exhibit an EPR spectrum characteristic of a species with an S = 3/2 ground state; Avl' also contains the so-called P-clusters. Additionally Acl* has recently been shown to possess an N-methylformamide soluble cofactor, FeVco, analogous to the well-known iron-molybdenum cofactor FeMoco. Arber et al. have reported X-ray absorption spectra for the Acl* enzyme and interpreted the EXAFS as evidence for a V-Fe-S cluster. The local vanadium structure is proposed to resemble a recently synthesized cubane-like VFe/sub 3/S/sub 4/ cluster, and analogies are drawn with the EXAFS-derived structure reported for the molybdenum nitrogenases. The authors report herein an X-ray absorption spectroscopic study of A. vinelandii vanadium nitrogenase, Avl', which supports and extends the work of Arber et al.« less

Preliminary investigation of the elemental variation and diagenesis of a tabular uranium deposit, La Sal Mine, San Juan County, Utah

USGS Publications Warehouse

Brooks, Robert A.; Campbell, John A.

1976-01-01

Ore in the La Sal mine, San Juan County, Utah, occurs as a typical tabular-type uranium deposit of the-Colorado Plateau. Uranium-vanadium occurs in the Salt Wash Member of the Jurassic Morrison Formation. Chemical and petrographic analyses were used to determine elemental variation and diagenetic aspects across the orebody. Vanadium is concentrated in the dark clay matrix, which constitutes visible ore. Uranium content is greater above the vanadium zone. Calcium, carbonate carbon, and lead show greater than fifty-fold increase across the ore zone, whereas copper and organic carbon show only a several-fold increase. Large molybdenum concentrations are present in and above the tabular layer, and large selenium concentrations occur below the uranium zone within the richest vanadium zone. Iron is enriched in the vanadium horizon. Chromium is depleted from above the ore and strongly enriched below. Elements that vary directly with the vanadium content include magnesium, iron, selenium, zirconium, strontium, titanium, lead, boron, yttrium, and scandium. The diagenetic sequence is as follows: (1) formation of secondary quartz overgrowths as cement; (2) infilling and lining of remaining pores with amber opaline material; (3) formation of vanadium-rich clay matrix, which has replaced overgrowths as well as quartz grains; (4) replacement of overgrowths and detrital grains by calcite; (5) infilling of pores with barite and the introduction of pyrite and marcasite.

Investigation of Lithium Metal Hydride Materials for Mitigation of Deep Space Radiation

NASA Technical Reports Server (NTRS)

Rojdev, Kristina; Atwell, William

2016-01-01

Radiation exposure to crew, electronics, and non-metallic materials is one of many concerns with long-term, deep space travel. Mitigating this exposure is approached via a multi-faceted methodology focusing on multi-functional materials, vehicle configuration, and operational or mission constraints. In this set of research, we are focusing on new multi-functional materials that may have advantages over traditional shielding materials, such as polyethylene. Metal hydride materials are of particular interest for deep space radiation shielding due to their ability to store hydrogen, a low-Z material known to be an excellent radiation mitigator and a potential fuel source. We have previously investigated 41 different metal hydrides for their radiation mitigation potential. Of these metal hydrides, we found a set of lithium hydrides to be of particular interest due to their excellent shielding of galactic cosmic radiation. Given these results, we will continue our investigation of lithium hydrides by expanding our data set to include dose equivalent and to further understand why these materials outperformed polyethylene in a heavy ion environment. For this study, we used HZETRN 2010, a one-dimensional transport code developed by NASA Langley Research Center, to simulate radiation transport through the lithium hydrides. We focused on the 1977 solar minimum Galactic Cosmic Radiation environment and thicknesses of 1, 5, 10, 20, 30, 50, and 100 g/cm2 to stay consistent with our previous studies. The details of this work and the subsequent results will be discussed in this paper.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries.

PubMed

Kim, Ki Jae; Park, Min-Sik; Kim, Jae-Hun; Hwang, Uk; Lee, Nam Jin; Jeong, Goojin; Kim, Young-Jun

2012-06-04

A new approach for enhancing the electrochemical performance of carbon felt electrodes by employing non-precious metal oxides is designed. The outstanding electro-catalytic activity and mechanical stability of Mn(3)O(4) are advantageous in facilitating the redox reaction of vanadium ions, leading to efficient operation of a vanadium redox flow battery.

40 CFR 421.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... technical grade molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 40.778 18.145 Chromium... vanadium plus pure grade molybdenum produced Arsenic 121.720 54.162 Chromium 25.625 10.483 Lead 24.460 11... times. (c) Vanadium decomposition wet air pollution control. BPT Limitations for the Secondary...

77 FR 46712 - Ferrovanadium and Nitrided Vanadium From the Russian Federation: Negative Final Determination of...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-06

... Determination We determine that the importation of vanadium pentoxide from the Russian Federation (Russia) by...) from Russia, within the meaning of section 781(a) of the Tariff Act of 1930, as amended (the Act). \\1... its negative preliminary determination that Evraz's imports of vanadium pentoxide from Russia that are...

Vanadium(III)-l-cysteine enhances the sensitivity of murine breast adenocarcinoma cells to cyclophosphamide by promoting apoptosis and blocking angiogenesis.

PubMed

Basu, Abhishek; Bhattacharjee, Arin; Baral, Rathindranath; Biswas, Jaydip; Samanta, Amalesh; Bhattacharya, Sudin

2017-05-01

Various epidemiological and preclinical studies have already established the cancer chemopreventive potential of vanadium-based compounds. In addition to its preventive efficacy, studies have also indicated the abilities of vanadium-based compounds to induce cell death selectively toward malignant cells. Therefore, the objective of the present investigation is to improve the therapeutic efficacy and toxicity profile of an alkylating agent, cyclophosphamide, by the concurrent use of an organovanadium complex, vanadium(III)-l-cysteine. In this study, vanadium(III)-l-cysteine (1 mg/kg body weight, per os) was administered alone as well as in combination with cyclophosphamide (25 mg/kg body weight, intraperitoneal) in concomitant and pretreatment schedule in mice bearing breast adenocarcinoma cells. The results showed that the combination treatment significantly decreased the tumor burden and enhanced survivability of tumor-bearing mice through generation of reactive oxygen species in tumor cells. These ultimately led to DNA damage, depolarization of mitochondrial membrane potential, and apoptosis in tumor cells. Further insight into the molecular pathway disclosed that the combination treatment caused upregulation of p53 and Bax and suppression of Bcl-2 followed by the activation of caspase cascade and poly (ADP-ribose) polymerase cleavage. Administration of vanadium(III)-l-cysteine also resulted in significant attenuation of peritoneal vasculature and sprouting of the blood vessels by decreasing the levels of vascular endothelial growth factor A and matrix metalloproteinase 9 in the ascites fluid of tumor-bearing mice. Furthermore, vanadium(III)-l-cysteine significantly attenuated cyclophosphamide-induced hematopoietic, hepatic, and genetic damages and provided additional survival advantages. Hence, this study suggested that vanadium(III)-l-cysteine may offer potential therapeutic benefit in combination with cyclophosphamide by augmenting anticancer efficacy and diminishing toxicity to the host.

Adsorption of Vanadium (V) from SCR Catalyst Leaching Solution and Application in Methyl Orange.

PubMed

Sha, Xuelong; Ma, Wei; Meng, Fanqing; Wang, Ren; Fuping, Tian; Wei, Linsen

2016-12-01

  In this study, we explored an effective and low-cost catalyst and its adsorption capacity and catalytic capacity for Methyl Orange Fenton oxidation degradation were investigated. The catalyst was directly prepared by reuse of magnetic iron oxide (Fe3O4) after saturated adsorption of vanadium (V) from waste SCR (Selective Catalytic Reduction) catalyst. The obtained catalyst was characterized by FTIR, XPS and the results showed that vanadium (V) adsorption process of Fe3O4 nanoparticles was non-redox reaction. The effects of pH, adsorption kinetics and equilibrium isotherms of adsorption were assessed. Adsorption of vanadium (V) ions by Fe3O4 nanoparticles could be well described by the Sips isotherm model which controlled by the mixed surface reaction and diffusion (MSRDC) adsorption kinetic model. The results show that vanadium (V) was mainly adsorbed on external surface of the Fe3O4 nanoparticles. The separation-recovering tungsten (VI) and vanadium (V) from waste SCR catalyst alkaline solution through pH adjustment was also investigated in this study. The results obtained from the experiments indicated that tungsten (VI) was selectively adsorbed from vanadium (V)/tungsten (VI) mixed solution in certain acidic condition by Fe3O4 nanoparticle to realize their recovery. Tungsten (V) with some impurity can be obtained by releasing from adsorbent, which can be confirmed by ICP-AES. The Methyl Orange degradation catalytic performance illustrated that the catalyst could improve Fenton reaction effectively at pH = 3.0 compare to Fe3O4 nanoparticles alone. Therefore, Fe3O4 nanoparticle adsorbed vanadium (V) has a potential to be employed as a heterogeneous Fenton-like catalyst in the present contribution, and its catalytic activity was mainly evaluated in terms of the decoloration efficiency of Methyl Orange.

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

PubMed

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural study of VO {sub x} doped aluminium fluoride and aluminium oxide catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheurell, Kerstin; Scholz, Gudrun; Kemnitz, Erhard

The structural properties of vanadium doped aluminium oxyfluorides and aluminium oxides, prepared by a modified sol-gel synthesis route, were thoroughly investigated. The influence of the preparation technique and the calcination temperature on the coordination of vanadium, aluminium and fluorine was analysed by different spectroscopic methods such as Raman, MAS NMR and ESR spectroscopy. In all samples calcined at low temperatures (350 deg. C), vanadium coexists in two oxidation states V{sup IV} and V{sup V}, with V{sup IV} as dominating species in the vanadium doped aluminium oxyfluorides. In the fluoride containing solids aluminium as well as vanadium are coordinated by fluorinemore » and oxygen. Thermal annealing of 800 deg. C leads to an extensive reorganisation of the original matrices and to the oxidation of V{sup IV} to V{sup V} in both systems. - Graphical abstract: Structure model for VO {sub x} doped aluminium oxide.« less

TEM investigation of ductile iron alloyed with vanadium.

PubMed

Dymek, S; Blicharski, M; Morgiel, J; Fraś, E

2010-03-01

This article presents results of the processing and microstructure evolution of ductile cast iron, modified by an addition of vanadium. The ductile iron was austenitized closed to the solidus (1095 degrees C) for 100 h, cooled down to 640 degrees C and held on at this temperature for 16 h. The heat treatment led to the dissolution of primary vanadium-rich carbides and their subsequent re-precipitation in a more dispersed form. The result of mechanical tests indicated that addition of vanadium and an appropriate heat treatment makes age hardening of ductile iron feasible. The precipitation processes as well as the effect of Si content on the alloy microstructure were examined by scanning and transmission electron microscopy. It was shown that adjacent to uniformly spread out vanadium-rich carbides with an average size of 50 nm, a dispersoid composed of extremely small approximately 1 nm precipitates was also revealed.

Insight into the adsorption mechanisms of vanadium(V) on a high-efficiency biosorbent (Ti-doped chitosan bead).

PubMed

Liu, Xin; Zhang, Lingfan

2015-08-01

In this present study, a new chitosan bead modified with titanium ions (TiCB) was prepared and employed for the adsorption of vanadium ions from aqueous solutions. Batch adsorption experiments were performed to research the effect of various factors, including pH, temperature, contact time and initial concentration of vanadium(V) ions. The adsorption of vanadium was followed by the pseudo second-order kinetic and the Langmuir isotherm model, with a remarkable maximum adsorption capacity of 210 mg/g. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the nature of adsorption was feasible, spontaneous (ΔG°<0) and endothermic (ΔH°>0) process. FTIR, EDS, EMI and XPS studies suggested that the mechanisms of adsorption were possibly attributed to electrostatic attraction, ligand-exchange and redox reaction between TiCB and vanadium ions. Copyright © 2015 Elsevier B.V. All rights reserved.

Vanadium removal from LD converter slag using bacteria and fungi.

PubMed

Mirazimi, S M J; Abbasalipour, Z; Rashchi, F

2015-04-15

Removal of vanadium from Linz-Donawits (LD) converter slag was investigated by means of three different species of microbial systems: Acidithiobacillus thiooxidans (autotrophic bacteria), Pseudomonas putida (heterotrophic bacteria) and Aspergillus niger (fungi). The bioleaching process was carried out in both one-step and two-step process and the leaching efficiencies in both cases were compared. Formation of inorganic and organic acids during the leaching process caused mobilization of vanadium. In order to reduce toxic effects of the metal species on the above mentioned microorganisms, a prolonged adaptation process was performed. Both bacteria, A. thiooxidans and P. putida were able to remove more than 90% of vanadium at slag concentrations of 1-5 g L(-1) after 15 days. Also, the maximum achievable vanadium removal in the fungal system was approximately 92% at a slag concentration of 1 g L(-1) after 22 days. Copyright © 2015 Elsevier Ltd. All rights reserved.

Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arber, J.M.; de Boer, E.; Garner, C.D.

Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure datamore » confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.« less

Hydride heat pump

DOEpatents

Cottingham, James G.

1977-01-01

Method and apparatus for the use of hydrides to exhaust heat from one temperature source and deliver the thermal energy extracted for use at a higher temperature, thereby acting as a heat pump. For this purpose there are employed a pair of hydridable metal compounds having different characteristics working together in a closed pressure system employing a high temperature source to upgrade the heat supplied from a low temperature source.

Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

DOEpatents

Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

2008-06-10

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

Hydride reorientation and its impact on ambient temperature mechanical properties of high burn-up irradiated and unirradiated recrystallized Zircaloy-2 nuclear fuel cladding with an inner liner

NASA Astrophysics Data System (ADS)

Auzoux, Q.; Bouffioux, P.; Machiels, A.; Yagnik, S.; Bourdiliau, B.; Mallet, C.; Mozzani, N.; Colas, K.

2017-10-01

Precipitation of radial hydrides in zirconium-based alloy cladding concomitant with the cooling of spent nuclear fuel during dry storage can potentially compromise cladding integrity during its subsequent handling and transportation. This paper investigates hydride reorientation and its impact on ductility in unirradiated and irradiated recrystallized Zircaloy-2 cladding with an inner liner (cladding for boiling water reactors) subjected to hydride reorientation treatments. Cooling from 400 °C, hydride reorientation occurs in recrystallized Zircaloy-2 with liner at a lower effective stress in irradiated samples (below 40 MPa) than in unirradiated specimens (between 40 and 80 MPa). Despite significant hydride reorientation, unirradiated recrystallized Zircaloy-2 with liner cladding containing ∼200 wppm hydrogen shows a high diametral strain at fracture (>15%) during burst tests at ambient temperature. This ductile behavior is due to (1) the lower yield stress of the recrystallized cladding materials in comparison to hydride fracture strength (corrected by the compression stress arising from the precipitation) and (2) the hydride or hydrogen-depleted zone as a result of segregation of hydrogen into the liner layer. In irradiated Zircaloy-2 with liner cladding containing ∼340 wppm hydrogen, the conservation of some ductility during ring tensile tests at ambient temperature after reorientation treatment at 400 °C with cooling rates of ∼60 °C/h is also attributed to the existence of a hydride-depleted zone. Treatments at lower cooling rates (∼6 °C/h and 0.6 °C/h) promote greater levels of hydrogen segregation into the liner and allow for increased irradiation defect annealing, both of which result in a significant increase in ductility. Based on this investigation, given the very low cooling rates typical of dry storage systems, it can be concluded that the thermal transients associated with dry storage should not degrade, and more likely should actually improve, ductility of recrystallized Zircaloy-2 cladding with inner liner with such hydrogen content.

Role of coordination geometry in dictating the barrier to hydride migration in d6 square-pyramidal iridium and rhodium pincer complexes.

PubMed

Findlater, Michael; Cartwright-Sykes, Alison; White, Peter S; Schauer, Cynthia K; Brookhart, Maurice

2011-08-10

Syntheses of the olefin hydride complexes [(POCOP)M(H)(olefin)][BAr(f)(4)] (6a-M, M = Ir or Rh, olefin = C(2)H(4); 6b-M, M = Ir or Rh, olefin = C(3)H(6); POCOP = 2,6-bis(di-tert-butylphosphinito)benzene; BAr(f) = tetrakis(3,5-trifluoromethylphenyl)borate) are reported. A single-crystal X-ray structure determination of 6b-Ir shows a square-pyramidal coordination geometry for Ir, with the hydride ligand occupying the apical position. Dynamic NMR techniques were used to characterize these complexes. The rates of site exchange between the hydride and the olefinic hydrogens yielded ΔG(++) = 15.6 (6a-Ir), 16.8 (6b-Ir), 12.0 (6a-Rh), and 13.7 (6b-Rh) kcal/mol. The NMR exchange data also established that hydride migration in the propylene complexes yields exclusively the primary alkyl intermediate arising from 1,2-insertion. Unexpectedly, no averaging of the top and bottom faces of the square-pyramidal complexes is observed in the NMR spectra at high temperatures, indicating that the barrier for facial equilibration is >20 kcal/mol for both the Ir and Rh complexes. A DFT computational study was used to characterize the free energy surface for the hydride migration reactions. The classical terminal hydride complexes, [M(POCOP)(olefin)H](+), are calculated to be the global minima for both Rh and Ir, in accord with experimental results. In both the Rh ethylene and propylene complexes, the transition state for hydride migration (TS1) to form the agostic species is higher on the energy surface than the transition state for in-place rotation of the coordinated C-H bond (TS2), while for Ir, TS2 is the high point on the energy surface. Therefore, only for the case of the Rh complexes is the NMR exchange rate a direct measure of the hydride migration barrier. The trends in the experimental barriers as a function of M and olefin are in good agreement with the trends in the calculated exchange barriers. The calculated barriers for the hydride migration reaction in the Rh complexes are ∼2 kcal/mol higher than for the Ir complexes, despite the fact that the energy difference between the olefin hydride ground state and the agostic alkyl structure is ∼4 kcal/mol larger for Ir than for Rh. This feature, together with the high barrier for interchange of the top and bottom faces of the complexes, is proposed to arise from the unique coordination geometry of the agostic complexes and the strong preference for a cis-divacant octahedral geometry in four-coordinate intermediates. © 2011 American Chemical Society

A nickel metal hydride battery for electric vehicles

NASA Astrophysics Data System (ADS)

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

1993-04-01

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

Vanadium Microalloyed High Strength Martensitic Steel Sheet for Hot-Dip Coating

NASA Astrophysics Data System (ADS)

Hutchinson, Bevis; Komenda, Jacek; Martin, David

Cold rolled steels with various vanadium and nitrogen levels have been treated to simulate the application of galvanizing and galvannealing to hardened martensitic microstructures. Strength levels were raised 100-150MPa by alloying with vanadium, which mitigates the effect of tempering. This opens the way for new ultra-high strength steels with corrosion resistant coatings produced by hot dip galvanising.

Synthesis of nanostructured vanadium powder by high-energy ball milling: X-ray diffraction and high-resolution electron microscopy characterization

NASA Astrophysics Data System (ADS)

Krishnan, Vinoadh Kumar; Sinnaeruvadi, Kumaran

2016-10-01

Vanadium metal powders, ball milled with different surfactants viz., stearic acid, KCl and NaCl, have been studied by X-ray diffraction and transmission electron microscopy. The surfactants alter the microstructural and morphological characteristics of the powders. Ball milling with stearic acid results in solid-state amorphization, while powders milled with KCl yield vanadium-tungsten carbide nanocomposite mixtures. NaCl proved to be an excellent surfactant for obtaining nanostructured fusion-grade vanadium powders. In order to understand the reaction mechanism behind any interstitial addition in the ball-milled powders, CHNOS analysis was performed.

Vanadium doped tin dioxide as a novel sulfur dioxide sensor.

PubMed

Das, S; Chakraborty, S; Parkash, O; Kumar, D; Bandyopadhyay, S; Samudrala, S K; Sen, A; Maiti, H S

2008-04-15

Considering the short-term exposure limit of SO2 to be 5 ppm, we first time report that semiconductor sensors based on vanadium doped SnO2 can be used for SO2 leak detection because of their good sensitivity towards SO2 at concentrations down to 5 ppm. Such sensors are quite selective in presence of other gases like carbon monoxide, methane and butane. The high sensitivity of vanadium doped tin dioxide towards SO2 may be understood by considering the oxidation of sulfur dioxide to sulfur trioxide on SnO2 surface through redox cycles of vanadium-sulfur-oxygen adsorbed species.

Balancing Osmotic Pressure of Electrolytes for Nanoporous Membrane Vanadium Redox Flow Battery with a Draw Solute.

PubMed

Yan, Ligen; Li, Dan; Li, Shuaiqiang; Xu, Zhi; Dong, Junhang; Jing, Wenheng; Xing, Weihong

2016-12-28

Vanadium redox flow batteries with nanoporous membranes (VRFBNM) have been demonstrated to be good energy storage devices. Yet the capacity decay due to permeation of vanadium and water makes their commercialization very difficult. Inspired by the forward osmosis (FO) mechanism, the VRFBNM battery capacity decrease was alleviated by adding a soluble draw solute (e.g., 2-methylimidazole) into the catholyte, which can counterbalance the osmotic pressure between the positive and negative half-cell. No change of the electrolyte volume has been observed after VRFBNM being operated for 55 h, revealing that the permeation of water and vanadium ions was effectively limited. Consequently, the Coulombic efficiency (CE) of nanoporous TiO 2 vanadium redox flow battery (VRFB) was enhanced from 93.5% to 95.3%, meanwhile, its capacity decay was significantly suppressed from 60.7% to 27.5% upon the addition of soluble draw solute. Moreover, the energy capacity of the VRFBNM was noticeably improved from 297.0 to 406.4 mAh remarkably. These results indicate balancing the osmotic pressure via the addition of draw solute can restrict pressure-dependent vanadium permeation and it can be established as a promising method for up-scaling VRFBNM application.

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Amorphous and Crystalline Vanadium Oxides as High-Energy and High-Power Cathodes for Three-Dimensional Thin-Film Lithium Ion Batteries.

PubMed

Mattelaer, Felix; Geryl, Kobe; Rampelberg, Geert; Dendooven, Jolien; Detavernier, Christophe

2017-04-19

Flexible wearable electronics and on-chip energy storage for wireless sensors drive rechargeable batteries toward thin-film lithium ion batteries. To enable more charge storage on a given surface, higher energy density materials are required, while faster energy storage and release can be obtained by going to thinner films. Vanadium oxides have been examined as cathodes in classical and thin-film lithium ion batteries for decades, but amorphous vanadium oxide thin films have been mostly discarded. Here, we investigate the use of atomic layer deposition, which enables electrode deposition on complex three-dimensional (3D) battery architectures, to obtain both amorphous and crystalline VO 2 and V 2 O 5 , and we evaluate their thin-film cathode performance. Very high volumetric capacities are found, alongside excellent kinetics and good cycling stability. Better kinetics and higher volumetric capacities were observed for the amorphous vanadium oxides compared to their crystalline counterparts. The conformal deposition of these vanadium oxides on silicon micropillar structures is demonstrated. This study shows the promising potential of these atomic layer deposited vanadium oxides as cathodes for 3D all-solid-state thin-film lithium ion batteries.

Vanadium oxide thin films produced by magnetron sputtering from a V2O5 target at room temperature

NASA Astrophysics Data System (ADS)

de Castro, Marcelo S. B.; Ferreira, Carlos L.; de Avillez, Roberto R.

2013-09-01

Vanadium oxide thin films were grown by RF magnetron sputtering from a V2O5 target at room temperature, an alternative route of production of vanadium oxide thin films for infrared detector applications. The films were deposited on glass substrates, in an argon-oxygen atmosphere with an oxygen partial pressure from nominal 0% to 20% of the total pressure. X-ray diffraction (XRD) and X-ray photon spectroscopy (XPS) analyses showed that the films were a mixture of several vanadium oxides (V2O5, VO2, V5O9 and V2O3), which resulted in different colors, from yellow to black, depending on composition. The electrical resistivity varied from 1 mΩ cm to more than 500 Ω cm and the thermal coefficient of resistance (TCR), varied from -0.02 to -2.51% K-1. Computational thermodynamics was used to simulate the phase diagram of the vanadium-oxygen system. Even if plasma processes are far from equilibrium, this diagram provides the range of oxygen pressures that lead to the growth of different vanadium oxide phases. These conditions were used in the present work.

Effect of vanadium doping on structural and magnetic properties of defective nano-nickel ferrite

NASA Astrophysics Data System (ADS)

Heiba, Zein K.; Mohamed, Mohamed Bakr; Wahba, Adel Maher; Almalowi, M. I.

2018-04-01

Nano-nickel ferrites defected by vanadium doping (NiV x Fe2-1.67 x O4, 0 ≤ x ≤ 0.25) were prepared using a simple sol gel method. Rietveld analysis revealed a nonmonotonic change in lattice parameter, oxygen parameter and magnetization upon doping with vanadium. Cation distributions suggested from either Rietveld analysis or from experimental magnetic moments were in a good agreement. For low doping values ( x = 0.05), vanadium was residing mainly in octahedral sites, while for samples with vanadium content ( x ≥ 0.1) a significant part of vanadium ions resided at tetrahedral sites; a result which has been confirmed by the analysis of Fourier-transform infrared (FTIR) spectrums obtained for the samples. The transmission electron microscope (TEM) image showed fine spherical particles with size of ˜ 11 nm. All samples showed a superparamagnetic nature with a nonmonotonic change of either magnetization ( M S) or coercivity (H C) with the content of nonmagnetic V5+. The cation occupancies indicated presence of an enormous number of vacancies through doping with high valence cation V5+, making present samples potential electrodes for Li- or Na-ion batteries.

Visible light driven photocatalyst of vanadium (V3+) doped TiO2 synthesized using sonochemical method

NASA Astrophysics Data System (ADS)

Aini, N.; Ningsih, R.; Maulina, D.; Lami’, F. F.; Chasanah, S. N.

2018-03-01

TiO2 has been widely investigated due to its superior photocatalytic activity under ultraviolet irradiation among the photocatalyst materials. In this research, vanadium (V3+) was doped into TiO2 to enhance its light response under visible irradiation for wider application. Vanadium was introduced into TiO2 lattice at various concentration respectively 0.3, 0.5, 0.7 and 0.9% using simple and fast sonochemical method. X-Ray Diffraction data show that vanadium doped TiO2 crystallized in anatase phase with I41amd space group. X-Ray Diffraction pattern shifted to lower value of 2θ due to vanadium dopant. It indicated that V3+ was incorporated into anatase lattice. UV-Vis Diffuse Reflectance Spectra was revealed that the doped TiO2 has lowered reflectance and enhanced absorption coefficient in visible region than undoped TiO2 and commercial anatase TiO2. Band gap energy for undoped and doped TiO2 were respectively 3.22, 3.05, 2.93, 3.03 and 2.40 eV. Therefore vanadium doped TiO2 had potential to be applied under visible light.

Comparative erythropoietic effects of three vanadium compounds.

PubMed

Hogan, G R

2000-07-10

The biotoxic effects of vanadium are variable depending upon a number of factors including the oxidation state of the test compound. This study reports the effects of three vanadium compounds on peripheral erythrocytes. On day 0 female ICR mice received a single injection of vanadium chloride (V-III), vanadyl sulfate (V-IV), or sodium orthovandate (V-V). At scheduled intervals post-injection, the number of circulating erythrocytes [red blood cells per millimeter cubed (RBC/mm3)], reticulocyte percentages, and radioiron uptake percentages were determined and compared to mice receiving saline only. Data show that all three test substances promoted a significant lowering of RBC/mm3 beginning on day 1 for V-IV and V-V and on day 2 for V-III through day 4. The reticulocyte percentages increase followed the same time course as that of the peripheral RBC decrease. Peak reticulocytosis was noted on days 2 and 4 for all three vanadium-treated groups; for V-IV and V-V the increase continued to day 6. Radioiron data showed an erythropoietic stimulation by a significant increase in uptake percentages on days 4-6 after vanadium injections compared to saline-treated controls.

Vanadium(IV/V) complexes of Triapine and related thiosemicarbazones: Synthesis, solution equilibrium and bioactivity.

PubMed

Kowol, Christian R; Nagy, Nóra V; Jakusch, Tamás; Roller, Alexander; Heffeter, Petra; Keppler, Bernhard K; Enyedy, Éva A

2015-11-01

The stoichiometry and thermodynamic stability of vanadium(IV/V) complexes of Triapine and two related α(N)-heterocyclic thiosemicarbazones (TSCs) with potential antitumor activity have been determined by pH-potentiometry, EPR and (51)V NMR spectroscopy in 30% (w/w) dimethyl sulfoxide/water solvent mixtures. In all cases, mono-ligand complexes in different protonation states were identified. Dimethylation of the terminal amino group resulted in the formation of vanadium(IV/V) complexes with considerably higher stability. Three of the most stable complexes were also synthesized in solid state and comprehensively characterized. The biological evaluation of the synthesized vanadium complexes in comparison to the metal-free ligands in different human cancer cell lines revealed only minimal influence of the metal ion. Thus, in addition the coordination ability of salicylaldehyde thiosemicarbazone (STSC) to vanadium(IV/V) ions was investigated. The exchange of the pyridine nitrogen of the α(N)-heterocyclic TSCs to a phenolate oxygen in STSC significantly increased the stability of the complexes in solution. Finally, this also resulted in increased cytotoxicity activity of a vanadium(V) complex of STSC compared to the metal-free ligand. Copyright © 2015 Elsevier Inc. All rights reserved.

Determination of mercury and vanadium concentration in Johnius belangerii (C) fish in Musa estuary in Persian Gulf.

PubMed

Fard, Neamat Jaafarzadeh Haghighi; Ravanbakhsh, Maryam; Ramezani, Zahra; Ahmadi, Mehdi; Angali, Kambiz Ahmadi; Javid, Ahmad Zare

2015-08-15

The main aim of this study was to determine the concentrations of mercury and vanadium in Johnius belangerii (C) fish in the Musa estuary. A total of 67 fishes were caught from the Musa estuary during five intervals of 15days in the summer of 2013. After biometric measurements were conducted, the concentrations of mercury and vanadium were measured in the muscle tissue of fish using a direct method analyzer (DMA) and a graphite furnace atomic absorption spectrophotometer, respectively. The mean concentration of mercury and vanadium in the muscle tissue of fish was 3.154±1.981 and 2.921±0.873mg/kg w.w, respectively. The generalized linear model (GLM) analysis showed a significantly positive relationship among mercury concentration, length, and weight (P=0.000). In addition, there was a significantly negative relationship between vanadium concentration and fish length (P=0.000). A reverse association was found between concentrations of mercury and vanadium. Mercury concentration exceeded the allowable standards of the Environmental Protection Agency (EPA), the World Health Organization (WHO), and the Food and Drug Administration (FDA) in J. belangerii (C). Copyright © 2015 Elsevier Ltd. All rights reserved.

Nickel and vanadium in air particulates at Dhahran (Saudi Arabia) during and after the Kuwait oil fires

NASA Astrophysics Data System (ADS)

Sadiq, M.; Mian, A. A.

Air particulates, both the total suspended (TSP) and inhalable (PM 10, smaller than 10 microns in size), were collected during and after the Kuwait oil fires (from March 1991 to July 1992) using Hi-Vol samplers. These samples were wet-digested at 120°C in an aqua regia and perchloric acids mixture for 3 h. Air particulate samples collected in 1982 at the same location were prepared similarly. Concentrations of nickel and vanadium were determined in the aliquot samples using an inductively coupled argon plasma analyser (ICAP). The monthly mean concentrations of nickel and vanadium, on volume basis, increased rapidly from March to June and decreased sharply during July-August in 1991. The minimum mean concentrations of these elements were found in the particulate samples collected in December 1991 which gradually increased through May 1992. Like 1991, nickel and vanadium concentrations in the air particulates spiked in June and decreased again in July 1992. This distribution pattern of nickel and vanadium concentrations was similar to that of the predominant wind from the north (Kuwait). In general, concentrations of these elements were higher in the air particulates collected during April-July 1991 as compared with those collected in 1992 during the same period. The TSPs contained higher concentrations of nickel and vanadium than those found in the PM 10 samples. However, this trend was reversed when concentrations of nickel and vanadium, on were expressed on particulate weight basis. The monthly mean concentrations of nickel and vanadium, on weight basis, decreased gradually through 1991 and increased slightly from March to July 1992. Concentrations of these elements were significantly higher in the air particulate samples collected in 1991 than those samples collected during 1982 at the same location. The data of this study suggest a contribution of the Kuwait oil fires in elevating nickel and vanadium concentrations in the air particulates at Dhahran during April-July 1991. Concentrations of these elements were largely below their proposed limits in the ambient air (for nickel-50 μg m -3, air; for vanadium—1 μg m -3 air). It is, therefore, anticipated that concentrations of nickel and vanadium in the air particulate samples were not a health concern during Kuwait oil fires at Dhahran, Saudi Arabia.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwarz, R.B.; Bach, H.T.; Harms, U.

We used a resonant-ultrasound-spectroscopy technique to measure the three independent elastic constants of PdH{sub x}, PdD{sub x}, and PdT{sub x} single crystals at 300 K. For 0.1x0.62 our PdH{sub x} crystals are two-phase mixtures of coherent {alpha} and {beta} hydride phases. For increasing x in this range, C{sub 44} decreases monotonically whereas C'=12(C11-C12) has a concave parabolic dependence. This difference is because C' is softened by an anelastic relaxation resulting from acoustic-stress-induced changes in the shape of the coherent lenticular-shape precipitates ({beta}-hydride precipitates in {alpha}-hydride matrix and {alpha}-hydride precipitates in {beta}-hydride matrix). In the {beta}-phase C' and C{sub 44} decreasemore » with increasing hydrogen (or deuterium or tritium) content. Furthermore, C' exhibits a strong isotope effect whereas C{sub 44} does not. This effect is attributed to differences in the excitation of optical phonons in Pd-H, Pd-D and Pd-T.« less

Titanium compacts produced by the pulvimetallurgical hydride-dehydride method for biomedical applications.

PubMed

Barreiro, M M; Grana, D R; Kokubu, G A; Luppo, M I; Mintzer, S; Vigna, G

2010-04-01

Titanium powder production by the hydride-dehydride method has been developed as a non-expensive process. In this work, commercially pure grade two Ti specimens were hydrogenated. The hydrided material was milled in a planetary mill. The hydrided titanium powder was dehydrided and then sieved to obtain a particle size between 37 and 125 microm in order to compare it with a commercial powder produced by chemical reduction with a particle size lower than 150 microm. Cylindrical green compacts were obtained by uniaxial pressing of the powders at 343 MPa and sintering in vacuum. The powders and the density of sintered compacts were characterized, the oxygen content was measured and in vivo tests were performed in the tibia bones of Wistar rats in order to evaluate their biocompatibility. No differences were observed between the materials which were produced either with powders obtained by the hydride-dehydride method or with commercial powders produced by chemical reduction regarding modifications in compactation, sintering and biological behaviour.

Hydrogen interactions with metals

NASA Technical Reports Server (NTRS)

Mclellan, R. B.; Harkins, C. G.

1975-01-01

Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

Advanced nickel-metal hydride cell development at Hughes: A joint work with US government

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Pickett, D.F.; Stockel, J.F.

1995-07-01

Hughes is currently engaged in the development of an advanced nickel-metal hydride (Ni/MHx) cell for spacecraft application with performance goals of 15 years of operation in a geosynchronous earth orbit at 805 depth of discharge and over 30,000 cycles of life at 30% depth of discharge in a typical low earth orbit. The authors have developed the basic fabrication technique for a lightweight and potentially long life nickel electrode which is usable in space Ni/MHx cells. The authors have developed several attractive hydride alloys which are usable in hydride electrodes and basic fabrication techniques for lightweight, inexpensive, and potentially longmore » life hydride electrodes for a Ni/MHx cell. Utilizing Hughes extensive experiences in development of advanced Ni/Cd and Ni/H{sub 2} cells, the authors plan to develop a first generation space Ni/MHx cell design by 1995 and have the cell flight ready by 1997.« less

Impact of distal mutations on the network of coupled motions correlated to hydride transfer in dihydrofolate reductase.

PubMed

Wong, Kim F; Selzer, Tzvia; Benkovic, Stephen J; Hammes-Schiffer, Sharon

2005-05-10

A comprehensive analysis of the network of coupled motions correlated to hydride transfer in dihydrofolate reductase is presented. Hybrid quantum/classical molecular dynamics simulations are combined with a rank correlation analysis method to extract thermally averaged properties that vary along the collective reaction coordinate according to a prescribed target model. Coupled motions correlated to hydride transfer are identified throughout the enzyme. Calculations for wild-type dihydrofolate reductase and a triple mutant, along with the associated single and double mutants, indicate that each enzyme system samples a unique distribution of coupled motions correlated to hydride transfer. These coupled motions provide an explanation for the experimentally measured nonadditivity effects in the hydride transfer rates for these mutants. This analysis illustrates that mutations distal to the active site can introduce nonlocal structural perturbations and significantly impact the catalytic rate by altering the conformational motions of the entire enzyme and the probability of sampling conformations conducive to the catalyzed reaction.

The development of nickel-metal hydride technology for use in aerospace applications

NASA Technical Reports Server (NTRS)

Rampel, Guy; Johnson, Herschel; Dell, Dan; Wu, Tony; Puglisi, Vince

1992-01-01

The nickel metal hydride technology for battery application is relatively immature even though this technology was made widely known by Philips' scientists as long ago as 1970. Recently, because of the international environmental regulatory pressures being placed on cadmium in the workplace and in disposal practices, battery companies have initiated extensive development programs to make this technology a viable commercial operation. These hydrides do not pose a toxilogical threat as does cadmium. Also, they provide a higher energy density and specific energy when compared to the other nickel based battery technologies. For these reasons, the nickel metal hydride electrochemisty is being evaluated as the next power source for varied applications such as laptop computers, cellular telephones, electric vehicles, and satellites. A parallel development effort is under way to look at aerospace applications for nickel metal hydride cells. This effort is focused on life testing of small wound cells of the commercial type to validate design options and development of prismatic design cells for aerospace applications.

Hydrogen and dihydrogen bonding of transition metal hydrides

NASA Astrophysics Data System (ADS)

Jacobsen, Heiko

2008-04-01

Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

Neutron diffraction studies of a four-coordinated hydride in near square-planar geometry

DOE PAGES

Liao, Jian -Hong; Dhayal, Rajendra Singh; Wang, Xiaoping; ...

2014-10-07

The structure of a nanospheric polyhydrido copper cluster, [Cu 20(H) 11{S 2P(O iPr) 2} 9], was determined by single-crystal neutron diffraction. Cu 20 cluster consists of an elongated triangular orthobicupola constructed from 18 Cu atoms that encapsulate a [Cu 2H 5} 3- ion in the center with an exceptionally short Cu-Cu distance. The eleven hydrides in the cluster display three different coordination modes to the Cu atoms: Six μ 3-hydrides in pyramidal geometry, two μ 4-hydrides in tetrahedral cavity, and three μ 4-hydrides in an unprecedented near square-planar geometry. The neutron data set was collected on a small crystal ofmore » the size 0.20 mm x 0.50 mm x 0.65 mm for seven days using the Spallation Neutron Source TOPAZ single-crystal time-of-flight Laue diffractometer at the Oak Ridge National Laboratory. Furthermore, the final R-factor is 8.64% for 16014 reflections.« less

Electrochemical hydride generation for the simultaneous determination of hydride forming elements by inductively coupled plasma-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Castillo, J. R.; Sturgeon, R. E.

2004-04-01

Simultaneous measurements of As, Sb, Se, Sn and Ge were performed by inductively coupled plasma atomic emission spectrometry following their electrochemical hydride generation. An electrochemical hydride generator based on a concentric arrangement with a porous cathode, working in a continuous flow mode was used. The effects of sample flow rate, applied current and electrolytic solution concentration on response were studied and their influence on the mechanisms of hydride generation discussed. Four materials, particulate lead, reticulated vitreous carbon (RVC), silver and amalgamated silver were tested as cathode materials. The best results were achieved with particulate lead and RVC cathodes, wherein generation efficiencies higher than 80% were estimated for most of the analytes. In general, limits of detection between 0.1 and 3.6 ng ml -1 and a precision better than 5% were achieved using a lead cathode. The analysis of a marine sediment reference material (PACS-2, NRC) showed good agreement with the certified values for As and Se.

A review of catalyst-enhanced magnesium hydride as a hydrogen storage material

NASA Astrophysics Data System (ADS)

Webb, C. J.

2015-09-01

Magnesium hydride remains an attractive hydrogen storage material due to the high hydrogen capacity and low cost of production. A high activation energy and poor kinetics at practical temperatures for the pure material have driven research into different additives to improve the sorption properties. This review details the development of catalytic additives and their effect on the activation energy, kinetics and thermodynamic properties of magnesium hydride.

Neutron diffraction investigation of γ manganese hydride

NASA Astrophysics Data System (ADS)

Fedotov, V. K.; Antonov, V. E.; Kolesnikov, A. I.; Beskrovnyi, A. I.; Grosse, G.; Wagner, F. E.

1998-08-01

A profile analysis of the neutron diffraction spectrum of the fcc high pressure hydride λ-MnH 0.41 measured under ambient conditions showed that hydrogen is randomly distributed over the octahedral interstices of the fcc metal lattice and that the hydride is an antiferromagnet with the same collinear spin structure as pure λ-Mn, but with a smaller magnetic moment of about 1.9 Bohr magnetons per Mn atom.

Cryo-Milling and the Hydrogen Storage Properties of NaAlH4

NASA Astrophysics Data System (ADS)

Feller, Kevin; Dobbins, Tabbetha

2013-03-01

High energy ball milling of metal hydrides is a common way to both introduce catalysts (e.g. TiCl3) and to simultaneously increase the surface area. Both catalysis and increased surface area improve hydrogen storage capacity of the material. Nanostructuring of hydrides by depositing them into mesoporous templates (such as anodized alumina, MOFs, and SBA-15) has become a common way to increase surface area. However, the mesoporous template does not add hydrogen storage capacity--and thus, tends to decreased overall storage weight percent for the nanostructured hydride material. As with most materials, hydrides become brittle at low temperatures and will tend to fracture more readily. We will process Sodium Aluminum Hydride (NaAlH4) using cryogenic high energy ball milling using an in-house modified chamber SPEX Certiprep M8000 mixer/mill in order to gain a nanostructured hydride without mesoporous template material. Details of the modified mixer mill design will be presented. Ultimately, our planned future work is to study the resultant material using x-ray diffraction (Scherrer method for crystallite size), absorption/desorption temperature programmed desorption (TPD), and ultrasmall-angle x-ray scattering (USAXS) microstructural quantification to understand the role of cryomilling on enhancing the material's ability to store (and release) hydrogen.

Atomic site preferences and structural evolution in vanadium-doped ZrSiO4 from multinuclear solid-state NMR

NASA Astrophysics Data System (ADS)

Dajda, N.; Dixon, J. M.; Smith, M. E.; Carthey, N.; Bishop, P. T.

2003-01-01

Solid state NMR spectra of 29Si are reported from pure and vanadium-doped zircon (V-ZrSiO4) samples. The vanadium concentration is varied up to ˜1-mol % V4+ by using both conventional-firing and sol-gel routes, and 51V NMR data are also recorded. 17O NMR of 17O isotopically enriched samples shows that the initial gel is completely amorphous with the whole range of possible M-O-M' linkages detected, and that this structure evolves into a fully ordered ZrSiO4 structure with calcination. Static 91Zr NMR data is reported from a pure zircon sample. The NMR data are used to quantify the amount of vanadium entering the zircon structure, and to elucidate its site preference within the lattice. Two contact shifted peaks with very different T1 relaxation from the main zircon peak but attributable to the zircon lattice are observed in the 29Si NMR spectra for all samples. These spectra are consistent with vanadium substitution on both the tetrahedral and dodecahedral sites, with a slight preference for the silicon site. The data show that the relative occupation of these two sites is almost independent of the preparation method and vanadium concentration. At a higher vanadium concentration a third additional peak is observed which may indicate another substitution site. Variable temperature NMR and susceptibility measurements indicate the hyperfine nature of the interactions influencing silicon from V4+ ions in the different sites.

Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

PubMed

Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

2012-04-01

Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries. Copyright © 2011 Elsevier Inc. All rights reserved.

Molybdenum and vanadium do not replace tungsten in the catalytically active forms of the three tungstoenzymes in the hyperthermophilic archaeon Pyrococcus furiosus.

PubMed Central

Mukund, S; Adams, M W

1996-01-01

Three different types of tungsten-containing enzyme have been previously purified from Pyrococcus furiosus (optimum growth temperature, 100 degrees C): aldehyde ferredoxin oxidoreductase (AOR), formaldehyde ferredoxin oxidoreductase (FOR), and glyceraldehyde-3-phosphate oxidoreductase (GAPOR). In this study, the organism was grown in media containing added molybdenum (but not tungsten or vanadium) or added vanadium (but not molybdenum or tungsten). In both cell types, there were no dramatic changes compared with cells grown with tungsten, in the specific activities of hydrogenase, ferredoxin:NADP oxidoreductase, or the 2-keto acid ferredoxin oxidoreductases specific for pyruvate, indolepyruvate, 2-ketoglutarate, and 2-ketoisovalerate. Compared with tungsten-grown cells, the specific activities of AOR, FOR, and GAPOR were 40, 74, and 1%, respectively, in molybdenum-grown cells, and 7, 0, and 0%, respectively, in vanadium-grown cells. AOR purified from vanadium-grown cells lacked detectable vanadium, and its tungsten content and specific activity were both ca. 10% of the values for AOR purified from tungsten-grown cells. AOR and FOR purified from molybdenum-grown cells contained no detectable molybdenum, and their tungsten contents and specific activities were > 70% of the values for the enzymes purified from tungsten-grown cells. These results indicate that P. furiosus uses exclusively tungsten to synthesize the catalytically active forms of AOR, FOR, and GAPOR, and active molybdenum- or vanadium-containing isoenzymes are not expressed when the cells are grown in the presence of these other metals. PMID:8550411

In vitro and ex vivo vanadium antitumor activity in (TGF-β)-induced EMT. Synergistic activity with carboplatin and correlation with tumor metastasis in cancer patients.

PubMed

Petanidis, Savvas; Kioseoglou, Efrosini; Domvri, Kalliopi; Zarogoulidis, Paul; Carthy, Jon M; Anestakis, Doxakis; Moustakas, Aristidis; Salifoglou, Athanasios

2016-05-01

Epithelial to mesenchymal transition (EMT) plays a key role in tumor progression and metastasis as a crucial event for cancer cells to trigger the metastatic niche. Transforming growth factor-β (TGF-β) has been shown to play an important role as an EMT inducer in various stages of carcinogenesis. Previous reports had shown that antitumor vanadium inhibits the metastatic potential of tumor cells by reducing MMP-2 expression and inducing ROS-dependent apoptosis. However, the role of vanadium in (TGF-β)-induced EMT remains unclear. In the present study, we report for the first time on the inhibitory effects of vanadium on (TGF-β)-mediated EMT followed by down-regulation of ex vivo cancer stem cell markers. The results demonstrate blockage of (TGF-β)-mediated EMT by vanadium and reduction in the mitochondrial potential of tumor cells linked to EMT and cancer metabolism. Furthermore, combination of vanadium and carboplatin (a) resulted in synergistic antitumor activity in ex vivo cell cultures, and (b) prompted G0/G1 cell cycle arrest and sensitization of tumor cells to carboplatin-induced apoptosis. Overall, the findings highlight the multifaceted antitumor action of vanadium and its synergistic antitumor efficacy with current chemotherapy drugs, knowledge that could be valuable for targeting cancer cell metabolism and cancer stem cell-mediated metastasis in aggressive chemoresistant tumors. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Deterioration Seen in Myelin Related Morphophysiology in Vanadium Exposed Rats is Partially Protected by Concurrent Iron Deficiency.

PubMed

Usende, Ifukibot Levi; Leitner, Dominque F; Neely, Elizabeth; Connor, James R; Olopade, James O

2016-08-30

Oligodendrocyte development and myelination occurs vigorously during the early post natal period which coincides with the period of peak mobilization of iron. Oligodendrocyte progenitor cells (OPCs) are easily disturbed by any agent that affects iron homeostasis and its assimilation into these cells. Environmental exposure to vanadium, a transition metal can disrupt this iron homeostasis. We investigated the interaction of iron deficiency and vanadium exposure on the myelination infrastructure and its related neurobehavioural phenotypes, and neurocellular profiles in developing rat brains. Control group (C) dams were fed normal diet while Group 2 (V) dams were fed normal diet and pups were injected with 3mg/kg body weight of sodium metavanadate daily from postnatal day (PND) 1-21. Group 3 (I+V) dams were fed iron deficient diet after delivery and pups injected with 3mg/kg body weight sodium metavanadate from PND1-21. Body and brain weights deteriorated in I+V relative to C and V while neurobehavioral deficit occurred more in V. Whereas immunohistochemical staining shows more astrogliosis and microgliosis indicative of neuroinflammation in I+V, more intense OPCs depletion and hypomyelination were seen in the V, and this was partially protected in I+V. In in vitro studies, vanadium induced glial cells toxicity was partially protected only at the LD 50 dose with the iron chelator, desferroxamine. The data indicate that vanadium promotes myelin damage and iron deficiency in combination with vanadium partially protects this neurotoxicological effects of vanadium.

[Effect of vanadium exposure on neurobehavioral function in workers].

PubMed

Zhu, C W; Liu, Y X; Huang, C J; Gao, W; Hu, G L; Li, J; Zhang, Q; Lan, Y J

2016-02-20

To establish the comprehensive indicators for neurobehavioral function test, and to investigate the possible adverse effect of long-time vanadium exposure on neurobehavioral function and its features in workers. From July to November, 2012, The Neurobehavioral Core Test Battery(NCTB) recommended by WHO was used to conduct tests for 128 workers in vanadium exposure group and 128 workers in control group. The t-test and analysis of covariance were used to compare the differences in each indicator in NCTB between different populations, and the principal component analysis was used to establish the comprehensive neurobehavioral index(NBI) and investigate the effect of vanadium on workers' neurobehavioral function. The vanadium exposure group had significantly lower visual retention score(6.9±1.9), digit span(order) score(8.9±2.9), lifting and turning dexterity(the non-handed hand) score (14.1±3.6), pursuit aiming test(the number of correct dots) score(65.7±24.8), and digit symbol score (31.1±15.0) than the control group (8.2±1.3, 9.4±2.7, 15.5±3.0, 76.5±23.8, and 33.7±9.5)(all P<0.05). The vanadium exposure group also had a significantly lower NBI than the control group(-0.167±0.602 vs 0.168±0.564, P<0.05). Long-term vanadium exposure can influence the workers' neurobehavioral function, with the manifestations of decreased hearing and visual memory, movement velocity, accuracy, and coordination.

Lactational Vitamin E Protects Against the Histotoxic Effects of Systemically Administered Vanadium in Neonatal Rats.

PubMed

Olaolorun, F A; Obasa, A A; Balogun, H A; Aina, O O; Olopade, J O

2014-12-29

The work investigated the protective role of lactational vitamin E administration on vanadium-induced histotoxicity. Three groups of Wistar rats, with each group comprising of two dams and their pups, were used in this study. Group I pups were administered intraperitoneal injection of sterile water at volumes corresponding to the dose rate of the vanadium (sodium metavanadate) treated group from postnatal day (PND) 1-14 while those in Group II were administered intraperitoneal injection of 3mg/kg vanadium from PND 1-14. Group III pups were administered intraperitoneal injection of 3mg/kg vanadium while the dam received oral vitamin E (500 mg) concurrently every 72 hours. The results showed that group II pups exhibited histopathological changes which included seminiferous tubule disruption of the testes characterised by vacuolar degeneration and coagulative necrosis of spermatogonia and Sertoli cells with reduction in mitosis, and areas of interstitial thickening with fibroblast proliferation. In addition, the lungs showed disruption of the bronchiolar wall and denudation of the bronchiolar respiratory epithelium while the liver showed hydropic degeneration and coagulative necrosis of the centrilobular hepatocytes. These histotoxic changes were ameliorated in the vanadium + vitamin E group. We conclude that lactational vitamin E protects against the histotoxic effects of vanadium and could be a consideration for supplementation in the occupationally and environmentally exposed neonates. However, caution should be taken in vitamin E supplementation because there is still equivocal evidence surrounding its benefits as a supplement at the moment.

Investigation of Local Environments in Nafion-SiO2 Composite Membranes used in Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Schwenzer, Birgit; Kim, Soowhan

2012-04-01

The proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, the polymer composite membranes such as SiO2 incorporated Nafion membranes are recently reported as highly promising for the redox flow batteries. However, there is conflicting reports regarding the performance of this Nafion-SiO2 composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO2 composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transformed Infra Red (FTIR) spectroscopy, and ultravioletmore » visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the 19F and 29Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The 29Si NMR shows that the silica particles interaction via hydrogen bonds to the sulfonic groups of Nafion and diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO2 composite membrane materials in vanadium redox flow batteries.« less

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE PAGES

d'Entremont, A.; Corgnale, C.; Sulic, M.; ...

2017-08-31

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

d'Entremont, A.; Corgnale, C.; Sulic, M.

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Importance of a serine proximal to the C(4a) and N(5) flavin atoms for hydride transfer in choline oxidase.

PubMed

Yuan, Hongling; Gadda, Giovanni

2011-02-08

Choline oxidase catalyzes the flavin-dependent, two-step oxidation of choline to glycine betaine with the formation of an aldehyde intermediate. In the first oxidation reaction, the alcohol substrate is initially activated to its alkoxide via proton abstraction. The substrate is oxidized via transfer of a hydride from the alkoxide α-carbon to the N(5) atom of the enzyme-bound flavin. In the wild-type enzyme, proton and hydride transfers are mechanistically and kinetically uncoupled. In this study, we have mutagenized an active site serine proximal to the C(4a) and N(5) atoms of the flavin and investigated the reactions of proton and hydride transfers by using substrate and solvent kinetic isotope effects. Replacement of Ser101 with threonine, alanine, cysteine, or valine resulted in biphasic traces in anaerobic reductions of the flavin with choline investigated in a stopped-flow spectrophotometer. Kinetic isotope effects established that the kinetic phases correspond to the proton and hydride transfer reactions catalyzed by the enzyme. Upon removal of Ser101, there is an at least 15-fold decrease in the rate constants for proton abstraction, irrespective of whether threonine, alanine, valine, or cysteine is present in the mutant enzyme. A logarithmic decrease spanning 4 orders of magnitude is seen in the rate constants for hydride transfer with increasing hydrophobicity of the side chain at position 101. This study shows that the hydrophilic character of a serine residue proximal to the C(4a) and N(5) flavin atoms is important for efficient hydride transfer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu Tangkui, E-mail: zhutangkui@sohu.com; Li, Miaoquan, E-mail: honeymli@nwpu.edu.cn

Effect of hydrogen content on the lattice parameter of Ti-6Al-4V alloy has been investigated by X-ray diffraction. The experimental results show that the solution of hydrogen in the Ti-6Al-4V alloy affects significantly on the lattice parameters of {alpha}, {beta} and {delta} phases, especially the {beta} phase. Furthermore, the critical hydrogen content of {delta} hydride formation for Ti-6Al-4V alloy is 0.385 wt.%. When the hydrogen content is lower than the critical hydrogen content, the {delta} hydride cannot precipitate and the lattice parameter ({alpha}) of {beta} phase linearly increases with the increasing of hydrogen content. When the hydrogen content is higher thanmore » the critical hydrogen content, the {delta} hydride precipitates and the lattice parameter ({alpha}) of {beta} phase varies inconspicuously with hydrogen content. In addition, the effects of lattice variations and {delta} hydride formation on microstructure are discussed. The {alpha}/{beta} interfaces of lamellar transformed {beta} phase become fuzzy with the increasing of hydrogen content because of the lattice expansion of {beta} phase. Compared with that of the Ti-6Al-4V alloy at low hydrogen content ({<=} 0.385 wt.%), the contrasts of primary {alpha} phase and transformed {beta} phase of Ti-6Al-4V alloy at high hydrogen content ({>=} 0.385 wt.%) were completely reversed due to the formation of {delta} hydride. - Research Highlights: {yields} A novel method for determining {delta} hydride in Ti-6Al-4V alloy is presented. {yields} The critical hydrogen content of {delta} hydride formation is 0.385 wt.%. {yields} The lattice parameter of {beta} phase can be expressed as follows: a=0.323(1+9.9x10{sup -2}C{sub H}) . {yields} Precipitation of {delta} hydride has a significant influence on the microstructure. {yields} The {alpha}/{beta} interfaces of transformed {beta} phase became fuzzy in the hydrogenated alloy.« less

Influence of uranium hydride oxidation on uranium metal behaviour

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, N.; Hambley, D.; Clarke, S.A.

2013-07-01

This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, ifmore » sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)« less

VANADIUM ALLOYS

DOEpatents

Smith, K.F.; Van Thyne, R.J.

1959-05-12

This patent deals with vanadium based ternary alloys useful as fuel element jackets. According to the invention the ternary vanadium alloys, prepared in an arc furnace, contain from 2.5 to 15% by weight titanium and from 0.5 to 10% by weight niobium. Characteristics of these alloys are good thermal conductivity, low neutron capture cross section, good corrosion resistance, good welding and fabricating properties, low expansion coefficient, and high strength.

Insulin and vanadium protect against osteoarthritis development secondary to diabetes mellitus in rats.

PubMed

El Karib, Abbas O; Al-Ani, Bahjat; Al-Hashem, Fahaid; Dallak, Mohammad; Bin-Jaliah, Ismaeel; El-Gamal, Basiouny; Bashir, Salah O; Eid, Refaat A; Haidara, Mohamed A

2016-07-01

Diabetic complications such as cardiovascular disease and osteoarthritis (OA) are among the common public health problems. The effect of insulin on OA secondary to diabetes has not been investigated before in animal models. Therefore, we sought to determine whether insulin and the insulin-mimicking agent, vanadium can protect from developing OA in diabetic rats. Type 1 diabetes mellitus (T1DM) was induced in Sprague-Dawley rats and treated with insulin and/or vanadium. Tissues harvested from the articular cartilage of the knee joint were examined by scanning electron microscopy, and blood samples were assayed for oxidative stress and inflammatory biomarkers. Eight weeks following the induction of diabetes, a profound damage to the knee joint compared to the control non-diabetic group was observed. Treatment of diabetic rats with insulin and/or vanadium differentially protected from diabetes-induced cartilage damage and deteriorated fibrils of collagen fibers. The relative biological potencies were insulin + vanadium > insulin > vanadium. Furthermore, there was about 2- to 5-fold increase in TNF-α (from 31.02 ± 1.92 to 60.5 ± 1.18 pg/ml, p < 0.0001) and IL-6 (from 64.67 ± 8.16 to 338.0 ± 38.9 pg/ml, p < 0.0001) cytokines and free radicals measured as TBARS (from 3.21 ± 0.37 to 11.48 ± 1.5 µM, p < 0.0001) in the diabetic group, which was significantly reduced with insulin and or vanadium. Meanwhile, SOD decreased (from 17.79 ± 8.9 to 8.250.29, p < 0.0001) and was increased with insulin and vanadium. The relative potencies of the treating agents on inflammatory and oxidative stress biomarkers were insulin + vanadium > insulin > vanadium. The present study demonstrates that co-administration of insulin and vanadium to T1DM rats protect against diabetes-induced OA possibly by lowering biomarkers of inflammation and oxidative stress.

Carbon quantum dots and a method of making the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zidan, Ragaiy; Teprovich, Joseph A.; Washington, Aaron L.

The present invention is directed to a method of preparing a carbon quantum dot. The carbon quantum dot can be prepared from a carbon precursor, such as a fullerene, and a complex metal hydride. The present invention also discloses a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride and a polymer containing a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride.

Method of selective reduction of polyhalosilanes with alkyltin hydrides

DOEpatents

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

1989-01-01

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

Method of producing hydrogen

DOEpatents

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

2006-12-26

A method of producing hydrogen is disclosed and which includes providing a first composition; providing a second composition; reacting the first and second compositions together to produce a chemical hydride; providing a liquid and reacting the chemical hydride with the liquid in a manner to produce a high pressure hydrogen gas and a byproduct which includes the first composition; and reusing the first composition formed as a byproduct in a subsequent chemical reaction to form additional chemical hydride.

Low density metal hydride foams

DOEpatents

Maienschein, Jon L.; Barry, Patrick E.

1991-01-01

Disclosed is a low density foam having a porosity of from 0 to 98% and a density less than about 0.67 gm/cc, prepared by heating a mixture of powered lithium hydride and beryllium hydride in an inert atmosphere at a temperature ranging from about 455 to about 490 K for a period of time sufficient to cause foaming of said mixture, and cooling the foam thus produced. Also disclosed is the process of making the foam.

Pulsed laser deposition of air-sensitive hydride epitaxial thin films: LiH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oguchi, Hiroyuki, E-mail: oguchi@nanosys.mech.tohoku.ac.jp; Micro System Integration Center; Isobe, Shigehito

2015-09-01

We report on the epitaxial thin film growth of an air-sensitive hydride, lithium hydride (LiH), using pulsed laser deposition (PLD). We first synthesized a dense LiH target, which is key for PLD growth of high-quality hydride films. Then, we obtained epitaxial thin films of [100]-oriented LiH on a MgO(100) substrate at 250 °C under a hydrogen pressure of 1.3 × 10{sup −2} Pa. Atomic force microscopy revealed that the film demonstrates a Stranski-Krastanov growth mode and that the film with a thickness of ∼10 nm has a good surface flatness, with root-mean-square roughness R{sub RMS} of ∼0.4 nm.

A study of H+ production using metal hydride and other compounds by means of laser ion source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sekine M.; Kondo K.; Okamura, M.

2012-02-22

A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH2 and ZrH2) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be usedmore » as a target for proton laser ion source.« less

Reduction of Carbon Monoxide. Past Research Summary

DOE R&D Accomplishments Database

Schrock, R. R.

1982-01-01

Research programs for the year on the preparation, characterization, and reactions of binuclear tantalum complexes are described. All evidence to date suggest the following of these dimeric molecules: (1) the dimer does not break into monomers under mild conditions; (2) intermolecular hydride exchange is not negligible, but it is slow; (3) intermolecular non-ionic halide exchange is fast; (4) the ends of the dimers can rotate partially with respect to one another. The binuclear tantalum hydride complexes were found to react with carbon monoxide to give a molecule which is the only example of reduction of CO by a transition metal hydride to give a complex containing a CHO ligand. Isonitrides also reacted in a similar manner with dimeric tantalum hydride. (ATT)

Effects of H sub 2 S addition on the performance of fresh vs. used CoMo catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rankel, L.A.

1991-01-01

When a Co/Mo catalyst is used for processing vanadium-containing heavy oils, vanadium deposits on the catalyst. As the amount of vanadium on the CoMo catalyst increases, the catalytic effects of CoMo decline and the presence of vanadium starts to influence the hydroprocessing products. Model feeds have been used to explore the changes in the catalytic activity of CoMo, aged CoMo, and VS{sub x} on alumina. Desulfurization, denitrogenation, deoxygenation, aromatics hydrogenation, and metals removal were monitored. This paper reports that, upon the addition of hydrogen sulfide to hydrogen, improvements in the catalysts for aromatics hydrogenation, denitrogenation and metals removal were observed.

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries

DOE PAGES

Liu, Qi; Li, Zhe-Fei; Liu, Yadong; ...

2015-01-20

The long-standing issues of low intrinsic electronic conductivity, slow lithium-ion diffusion and irreversible phase transitions on deep discharge prevent the high specific capacity/energy (443 mAh g -1 and 1,550 Wh kg -1) vanadium pentoxide from being used as the cathode material in practical battery applications. Here we develop a method to incorporate graphene sheets into vanadium pentoxide nanoribbons via the sol–gel process. The resulting graphene-modified nanostructured vanadium pentoxide hybrids contain only 2 wt. % graphene, yet exhibits extraordinary electrochemical performance: a specific capacity of 438 mAh g -1, approaching the theoretical value (443 mAh g -1), a long cyclability andmore » significantly enhanced rate capability. Such performance is the result of the combined effects of the graphene on structural stability, electronic conduction, vanadium redox reaction and lithium-ion diffusion supported by various experimental studies. Finally, this method provides a new avenue to create nanostructured metal oxide/graphene materials for advanced battery applications.« less

Recovery of Vanadium from Magnetite Ore Using Direct Acid Leaching: Optimization of Parameters by Plackett-Burman and Response Surface Methodologies

NASA Astrophysics Data System (ADS)

Nejad, Davood Ghoddocy; Khanchi, Ali Reza; Taghizadeh, Majid

2018-06-01

Recovery of vanadium from magnetite ore by direct acid leaching is discussed. The proposed process, which employs a mixture of nitric and sulfuric acids, avoids pyrometallurgical treatments since such treatment consumes a high amount of energy. To determine the optimum conditions of vanadium recovery, the leaching process is optimized through Plackett-Burman (P-B) design and response surface methodology (RSM). In this respect, temperature (80-95°C), liquid to solid ratio (L/S) (3-10 mL g-1), sulfuric acid concentration (3-6 M), nitric acid concentration (5-10 vol.%) and time (4-8 h) are considered as the independent variables. According to the P-B approach, temperature and acid concentrations are, respectively, the most effective parameters in the leaching process. These parameters are optimized using RSM to maximize recovery of vanadium by direct acid leaching. In this way, 86.7% of vanadium can be extracted from magnetic ore.

A Contemporary Treatment Approach to Both Diabetes and Depression by Cordyceps sinensis, Rich in Vanadium

PubMed Central

Guo, Jian-You; Han, Chun-Chao

2010-01-01

Diabetes mellitus is accompanied by hormonal and neurochemical changes that can be associated with anxiety and depression. Both diabetes and depression negatively interact, in that depression leads to poor metabolic control and hyperglycemia exacerbates depression. We hypothesize one novel vanadium complex of vanadium-enriched Cordyceps sinensis (VECS), which is beneficial in preventing depression in diabetes, and influences the long-term course of glycemic control. Vanadium compounds have the ability to imitate the action of insulin, and this mimicry may have further favorable effects on the level of treatment satisfaction and mood. C. sinensis has an antidepressant-like activity, and attenuates the diabetes-induced increase in blood glucose concentrations. We suggest that the VECS may be a potential strategy for contemporary treatment of depression and diabetes through the co-effect of C. sinensis and vanadium. The validity of the hypothesis can most simply be tested by examining blood glucose levels, and swimming and climbing behavior in streptozotocin-induced hyperglycemic rats. PMID:19948751

Effect of diet composition on vanadium toxicity for the chick

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L.R.

1966-01-01

Studies to determine the effect of diet composition on the toxicity of 20 ppm added vanadium for the young chick have shown: growth depression of 25-30% with a corn-soybean meal ration but only 3-7% with a corn-herring fish meal diet. Growth depression of 35-40% with a semi-purified sucrose-soybean meal diet and approximately 50% with a diet of sucrose and herring fish meal. Adding graded levels of corn to the sucrose-fish meal ration and fish meal to the corn-soybean meal ration reduced vanadium toxicity. The corn fractions, ash, oil, starch, zein and gluten did not reduce vanadium toxicity. Removing the addedmore » magnesium (300 ppm) and potassium (2000 ppm) from the sucrose-fish meal ration did not affect growth rate or mortality. However removal of these materials from the basal ration increased growth depression due to added vanadium from 43-56% and increased mortality from 10-80%. 4 references, 9 tables.« less

Bipolar resistive switching in room temperature grown disordered vanadium oxide thin-film devices

NASA Astrophysics Data System (ADS)

Wong, Franklin J.; Sriram, Tirunelveli S.; Smith, Brian R.; Ramanathan, Shriram

2013-09-01

We demonstrate bipolar switching with high OFF/ON resistance ratios (>104) in Pt/vanadium oxide/Cu structures deposited entirely at room temperature. The SET (RESET) process occurs when negative (positive) bias is applied to the top Cu electrode. The vanadium oxide (VOx) films are amorphous and close to the vanadium pentoxide stoichiometry. We also investigated Cu/VOx/W structures, reversing the position of the Cu electrode, and found the same polarity dependence with respect to the top and bottom electrodes, which suggests that the bipolar nature is linked to the VOx layer itself. Bipolar switching can be observed at 100 °C, indicating that it not due to a temperature-induced metal-insulator transition of a vanadium dioxide second phase. We discuss how ionic drift can lead to the bipolar electrical behavior of our junctions, similar to those observed in devices based on several other defective oxides. Such low-temperature processed oxide switches could be of relevance to back-end or package integration processing schemes.

Fabrication of vanadium dioxide polycrystalline films with higher temperature coefficient of resistance

NASA Astrophysics Data System (ADS)

Li, Jinhua; Yuan, Ningyi; Jiang, Meiping; Kun, Li

2011-08-01

Vanadium Dioxide Polycrystalline Films with High Temperature Coefficient of Resistance(TCR) were fabricated by modified Ion Beam Enhanced Deposition(IBED) method. The TCR of the Un-doping VO2 was about -4%/K at room temperature after appropriate thermal annealing. The XRD results clearly showed that IBED polycrystalline VO2 films had a single [002] orientation of VO2(M). The TCR of 5at.%W and 7at.% Ta doped Vanadium Dioxide Polycrystalline Films were high up to -18%/K and -12%/K at room temperature, respectively. Using 7at.% Ta and 2at.% Ti co-doping, the TCR of the co-doped vanadium oxide film was -7%/K and without hysteresis during temperature increasing and decresing from 0-80°C. It should indicate that the W-doped vanadium dioxide films colud be used for high sensing IR detect and the Ta/Ti co-doped film without hysteresis is suitable for infrarid imaging application.

Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

PubMed Central

Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-01-01

In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states—a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal–insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids. PMID:28613281

Thymic cytoarchitecture changes in mice exposed to vanadium.

PubMed

Ustarroz-Cano, Martha; Garcia-Pelaez, Isabel; Cervantes-Yepez, Silvana; Lopez-Valdez, Nelly; Fortoul, Teresa I

2017-12-01

The thymus is a vital immune system organ wherein selection of T-lymphocytes occurs in a process regulated by dendritic and epithelial thymic cells. Previously, we have reported that in a mouse model of vanadium inhalation, a decrease in CD11c dendritic cells was observed. In the present study, we report on a thymic cortex-medulla distribution distortion in these hosts due to apparent effects of the inhaled vanadium on cytokeratin-5 (K5 + ) epithelial cells in the same mouse model - after 1, 2, and 4 weeks of exposure - by immunohistochemistry. These cells - together with dendritic cells - eliminate autoreactive T-cell clones and regulate the production of regulatory T-cells in situ. Because both cell types are involved in the negative selection of autoreactive clones, a potential for an increase in development of autoimmune conditions could be a possible consequence among individuals who might be exposed often to vanadium in air pollution, including dwellers of highly polluted cities with elevated levels of particulate matter onto which vanadium is often adsorbed.

Properties of vanadium-loaded iron sorbent after alkali regeneration.

PubMed

Khalid, Muhammad Kamran; Leiviskä, Tiina; Tanskanen, Juha

2017-11-01

The aim of this research was to investigate the regeneration and reuse of a commercial granular iron sorbent (mainly goethite) when used in vanadium removal. A regeneration rate of 3 M NaOH was the highest (85%) achieved, followed by 2 M NaOH (79%) and 1 M NaOH (68%). The breakthrough curves show that the regenerated material can be reused. The BET (Brunauer-Emmett-Teller) surface area increased by 35-38% and the total pore volume increased by 123-130% as a consequence of NaOH treatment. The results indicated that sodium hydroxide could be used for the regeneration of iron sorbent although the regeneration was incomplete. This may be explained by the fact that vanadium diffusion into pores is a significant sorption mechanism in addition to complex formation with surface functional groups. As a consequence, vanadium desorbability from pores is not as effective as the regeneration of surface sites. X-ray photoelectron spectroscopy analyses confirmed a very low vanadium content on the surface of the NaOH-treated iron sorbent.

Recovery of Vanadium from Magnetite Ore Using Direct Acid Leaching: Optimization of Parameters by Plackett-Burman and Response Surface Methodologies

NASA Astrophysics Data System (ADS)

Nejad, Davood Ghoddocy; Khanchi, Ali Reza; Taghizadeh, Majid

2018-03-01

Recovery of vanadium from magnetite ore by direct acid leaching is discussed. The proposed process, which employs a mixture of nitric and sulfuric acids, avoids pyrometallurgical treatments since such treatment consumes a high amount of energy. To determine the optimum conditions of vanadium recovery, the leaching process is optimized through Plackett-Burman (P-B) design and response surface methodology (RSM). In this respect, temperature (80-95°C), liquid to solid ratio (L/S) (3-10 mL g-1), sulfuric acid concentration (3-6 M), nitric acid concentration (5-10 vol.%) and time (4-8 h) are considered as the independent variables. According to the P-B approach, temperature and acid concentrations are, respectively, the most effective parameters in the leaching process. These parameters are optimized using RSM to maximize recovery of vanadium by direct acid leaching. In this way, 86.7% of vanadium can be extracted from magnetic ore.

Effect of Mechanical Activation Treatment on the Recovery of Vanadium from Converter Slag

NASA Astrophysics Data System (ADS)

Xiang, Junyi; Huang, Qingyun; Lv, Xuewei; Bai, Chenguang

2017-10-01

The high roasting temperature and low leaching efficiency of vanadium from vanadium-bearing converter slag are regarded as the main factors significantly influencing the application of calcification roasting-acid leaching processes in the cleaner production of vanadium. In this study, a mechanical activation treatment was performed to enhance the extraction of vanadium from converter slag. The enhancement effects obtained from mechanical activation were comprehensively evaluated through indices such as the roasting temperature and leaching efficiency. The effects of mechanical activation time, roasting temperature, leaching temperature, solid to liquid ratio, particle size, and acid concentration on the leaching efficiency were investigated. Microstructure morphology and elemental analyses of the raw materials and leaching residue were also investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results demonstrated that the mechanical activation significantly decreased the optimum roasting temperature from 1173 K to 1073 K (900 °C to 800 °C) and increased the leaching efficiency from 86.0 to 90.9 pct.

Nanocrystalline ordered vanadium carbide: Superlattice and nanostructure

NASA Astrophysics Data System (ADS)

Kurlov, A. S.; Gusev, A. I.; Gerasimov, E. Yu.; Bobrikov, I. A.; Balagurov, A. M.; Rempel, A. A.

2016-02-01

The crystal structure, micro- and nanostructure of coarse- and nanocrystalline powders of ordered vanadium carbide V8C7 have been examined by X-ray and neutron diffraction and electron microscopy methods. The synthesized coarse-crystalline powder of ordered vanadium carbide has flower-like morphology. It was established that the real ordered phase has the composition V8C7-δ (δ ≅ 0.03) deviating from perfect stoichiometric composition V8C7. The vanadium atoms forming the octahedral environment □V6 of vacant sites in V8C7-δ are displaced towards the vacancy □. The presence of carbon onion-like structures was found in the vanadium carbide powders with a small content of free (uncombined) carbon. The nanopowders of V8C7-δ carbide with average particle size of 20-30 nm produced by high-energy milling of coarse-crystalline powder retain the crystal structure of the initial powder, but differ in the lattice deformation distortion anisotropy.

Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation

NASA Astrophysics Data System (ADS)

Natalio, Filipe; André, Rute; Hartog, Aloysius F.; Stoll, Brigitte; Jochum, Klaus Peter; Wever, Ron; Tremel, Wolfgang

2012-08-01

Marine biofouling--the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls--is an expensive problem that is currently without an environmentally compatible solution. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage the environment through metal leaching (for example, of copper and zinc) and bacteria resistance. Here, we show that vanadium pentoxide nanowires act like naturally occurring vanadium haloperoxidases to prevent marine biofouling. In the presence of bromide ions and hydrogen peroxide, the nanowires catalyse the oxidation of bromide ions to hypobromous acid (HOBr). Singlet molecular oxygen (1O2) is formed and this exerts strong antibacterial activity, which prevents marine biofouling without being toxic to marine biota. Vanadium pentoxide nanowires have the potential to be an alternative approach to conventional anti-biofouling agents.

Correlation between molten vanadium salts and the structural degradation of HK-type steel superheater tubes

NASA Astrophysics Data System (ADS)

de Carvalho Nunes, Frederico; de Almeida, Luiz Henrique; Ribeiro, André Freitas

2006-12-01

HK steels are among the most used heat-resistant cast stainless steels, being corrosion-resistant and showing good mechanical properties at high service temperatures. These steels are widely used in reformer furnaces and as superheater tubes. During service, combustion gases leaving the burners come in contact with these tubes, resulting in corrosive attack and a large weight loss occurs due to the presence of vanadium, which forms low melting point salts, removing the protective oxide layer. In this work the external surface of a tube with dramatic wall thickness reduction was analyzed using light microscopy, scanning electron microscopy, and transmission electron microscopy. The identification of the phases was achieved by energy dispersive spectroscopy (EDS) analyses. The results showed oxides arising from the external surface. In this oxidized region vanadium compounds inside chromium carbide particles were also observed, due to inward vanadium diffusion during corrosion attack. A chemical reaction was proposed to explain the presence of vanadium in the metal microstructure.

Crack growth through the thickness of thin-sheet Hydrided Zircaloy-4

NASA Astrophysics Data System (ADS)

Raynaud, Patrick A. C.

In recent years, the limits on fuel burnup have been increased to allow an increase in the amount of energy produced by a nuclear fuel assembly thus reducing waste volume and allowing greater capacity factors. As a result, it is paramount to ensure safety after longer reactor exposure times in the case of design-basis accidents, such as reactivity-initiated accidents (RIA). Previously proposed failure criteria do not directly address the particular cladding failure mechanism during a RIA, in which crack initiation in brittle outer-layers is immediately followed by crack growth through the thickness of the thin-wall tubing. In such a case, the fracture toughness of hydrided thin-wall cladding material must be known for the conditions of through-thickness crack growth in order to predict the failure of high-burnup cladding. The fracture toughness of hydrided Zircaloy-4 in the form of thin-sheet has been examined for the condition of through-thickness crack growth as a function of hydride content and distribution at 25°C, 300°C, and 375°C. To achieve this goal, an experimental procedure was developed in which a linear hydride blister formed across the width of a four-point bend specimen was used to inject a sharp crack that was subsequently extended by fatigue pre-cracking. The electrical potential drop method was used to monitor the crack length during fracture toughness testing, thus allowing for correlation of the load-displacement record with the crack length. Elastic-plastic fracture mechanics were used to interpret the experimental test results in terms of fracture toughness, and J-R crack growth resistance curves were generated. Finite element modeling was performed to adapt the classic theories of fracture mechanics applicable to thick-plate specimens to the case of through-thickness crack growth in thin-sheet materials, and to account for non-uniform crack fronts. Finally, the hydride microstructure was characterized in the vicinity of the crack tip by means of digital image processing, so as to understand the influence of the hydride microstructure on fracture toughness, at the various test temperatures. Crack growth occurred through a microstructure which varied within the thickness of the thin-sheet Zircaloy-4 such that the hydrogen concentration and the radial hydride content decreased with increasing distance from the hydride blister. At 25°C, the fracture toughness was sensitive to the changes in hydride microstructure, such that the toughness KJi decreased from 39 MPa√m to 24 MPa√m with increasing hydrogen content and increasing the fraction of radial hydrides. The hydride particles present in the Zircaloy-4 substrate fractured ahead of the crack tip, and crack growth occurred by linking the crack-tip with the next hydride-induced primary void ahead of it. Unstable crack growth was observed at 25°C prior to any stable crack growth in the specimens where the hydrogen content was the highest. At 375°C as well as in most cases at 300°C, the hydride particles were resistant to cracking and the resistance to crack-growth initiation was very high. As a result, for this bend test procedure, crack extension was solely due to crack-tip blunting instead of crack growth in all tests at 375°C and in most cases at 300°C. The lower bound for fracture toughness at these temperatures, the parameter KJPmax, had values of K JPmax˜54MPa√m at both 300°C and 375°C. For cases where stable crack growth occurred at 300°C, the fracture toughness was K Ji˜58MPa√m and the tearing modulus was twice as high as that at 25°C. It is believed that the failure of hydrided Zircaloy-4 thin-wall cladding can be predicted using fracture mechanics analyses when failure occurs by crack growth. This failure mechanism was observed to occur in all cases at 25°C and in some cases at 300°C. However, at more elevated temperatures, such as 375°C, failure will likely occur by a mechanism other than crack growth, possibly by an imperfection-induced shear instability.

Density functional theory mechanistic study of the reduction of CO2 to CH4 catalyzed by an ammonium hydridoborate ion pair: CO2 activation via formation of a formic acid entity.

PubMed

Wen, Mingwei; Huang, Fang; Lu, Gang; Wang, Zhi-Xiang

2013-10-21

Density functional theory computations have been applied to gain insight into the CO2 reduction to CH4 with Et3SiH, catalyzed by ammonium hydridoborate 1 ([TMPH](+)[HB(C6F5)3](-), where TMP = 2,2,6,6-tetramethylpiperidine) and B(C6F5)3. The study shows that CO2 is activated through the concerted transfer of H(δ+) and H(δ-) of 1 to CO2, giving a complex (IM2) with a well-formed HCOOH entity, followed by breaking of the O-H bond of the HCOOH entity to return H(δ+) to TMP, resulting in an intermediate 2 ([TMPH](+)[HC(═O)OB(C6F5)3)](-)), with CO2 being inserted into the B-H bond of 1. However, unlike CO2 insertion into transition-metal hydrides, the direct insertion of CO2 into the B-H bond of 1 is inoperative. The computed CO2 activation mechanism agrees with the experimental synthesis of 2 via reacting HCOOH with TMP/B(C6F5)3. Subsequent to the CO2 activation and B(C6F5)3-mediated hydrosilylation of 2 to regenerate the catalyst (1), giving HC(═O)OSiEt3 (5), three hydride-transfer steps take place, sequentially transferring H(δ-) of Et3SiH to 5 to (Et3SiO)2CH2 (6, the product of the first hydride-transfer step) to Et3SiOCH3 (7, the product of the second hydride-transfer step) and finally resulting in CH4. These hydride transfers are mediated by B(C6F5)3 via two SN2 processes without involving 1. B(C6F5)3 acts as a hydride carrier that, with the assistance of a nucleophilic attack of 5-7, first grabs H(δ-) from Et3SiH (the first SN2 process), giving HB(C6F5)3(-), and then leave H(δ-) of HB(C6F5)3(-) to the electrophilic C center of 5-7 (the second SN2 process). The SN2 processes utilize the electrophilic and nucleophilic characteristics possessed by the hydride acceptors (5-7). The hydride-transfer mechanism is different from that in the CO2 reduction to methanol catalyzed by N-heterocyclic carbene (NHC) and PCP-pincer nickel hydride ([Ni]H), where the characteristic of possessing a C═O double bond of the hydride acceptors is utilized for hydride transfer. The mechanistic differences elucidate why the present system can completely reduce CO2 to CH4, whereas NHC and [Ni]H catalysts can only mediate the reduction of CO2 to [Si]OCH3 and catBOCH3, respectively. Understanding this could help in the development of catalysts for selective CO2 reduction to CH4 or methanol.

Plasmonic Structures for CMOS Photonics and Control of Spontaneous Emission

DTIC Science & Technology

2013-04-01

structures; v) developed CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vi) also engaged in a partnership with...CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vii. exploring approaches to enhance spontaneous emission in...size and bandwidth, we are exploring phase-change materials and, in particular, vanadium dioxide. VO2 undergoes an insulator-to-metal phase transition

Imaging of Vanadium in Microfossils: A New Potential Biosignature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.

Being able to distinguish unambiguously the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from non-biological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This too, is important for the search for life on Mars; either by in situ analyses via rovers, or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biologicalmore » origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature, that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagensis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. Here, we propose that taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenecity of putative microfossil-like structures.« less

A mixed acid based vanadium-cerium redox flow battery with a zero-gap serpentine architecture

NASA Astrophysics Data System (ADS)

Leung, P. K.; Mohamed, M. R.; Shah, A. A.; Xu, Q.; Conde-Duran, M. B.

2015-01-01

This paper presents the performance of a vanadium-cerium redox flow battery using conventional and zero-gap serpentine architectures. Mixed-acid solutions based on methanesulfonate-sulfate anions (molar ratio 3:1) are used to enhance the solubilities of the vanadium (>2.0 mol dm-3) and cerium species (>0.8 mol dm-3), thus achieving an energy density (c.a. 28 Wh dm-3) comparable to that of conventional all-vanadium redox flow batteries (20-30 Wh dm-3). Electrochemical studies, including cyclic voltammetry and galvanostatic cycling, show that both vanadium and cerium active species are suitable for energy storage applications in these electrolytes. To take advantage of the high open-circuit voltage (1.78 V), improved mass transport and reduced internal resistance are facilitated by the use of zero-gap flow field architecture, which yields a power density output of the battery of up to 370 mW cm-2 at a state-of-charge of 50%. In a charge-discharge cycle at 200 mA cm-2, the vanadium-cerium redox flow battery with the zero-gap architecture is observed to discharge at a cell voltage of c.a. 1.35 V with a coulombic efficiency of up to 78%.

Measuring the state of charge of the electrolyte solution in a vanadium redox flow battery using a four-pole cell device

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-12-01

The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.

Effectively suppressing vanadium permeation in vanadium redox flow battery application with modified Nafion membrane with nacre-like nanoarchitectures

NASA Astrophysics Data System (ADS)

Zhang, Lesi; Ling, Ling; Xiao, Min; Han, Dongmei; Wang, Shuanjin; Meng, Yuezhong

2017-06-01

A novel self-assembled composite membrane, Nafion-[PDDA/ZrP]n with nacre-like nanostructures was successfully fabricated by a layer-by-layer (LbL) method and used as proton exchange membrane for vanadium redox flow battery applications. Poly(diallyldimethylammonium chloride) (PDDA) with positive charges and zirconium phosphate (ZrP) nanosheets with negative charges can form ultra-thin nacre-like nanostructure on the surface of Nafion membrane via the ionic crosslinking of tightly folded macromolecules. The lamellar structure of ZrP nanosheets and Donnan exclusion effect of PDDA can greatly decrease the vanadium ion permeability and improve the selectivity of proton conductivity. The fabricated Nafion-[PDDA/ZrP]4 membrane shows two orders of magnitude lower vanadium ion permeability (1.05 × 10-6 cm2 min-1) and 12 times higher ion selectivity than those of pristine Nafion membrane at room temperature. Consequently, the performance of vanadium redox flow batteries (VRFBs) assembled with Nafion-[PDDA/ZrP]3 membrane achieved a highly coulombic efficiency (CE) and energy efficiency (EE) together with a very slow self-discharge rate. When comparing with pristine Nafion VRFB, the CE and EE values of Nafion-[PDDA/ZrP]3 VRFB are 10% and 7% higher at 30 mA cm-2, respectively.

Pore-Size-Tuned Graphene Oxide Frameworks as Ion-Selective and Protective Layers on Hydrocarbon Membranes for Vanadium Redox-Flow Batteries.

PubMed

Kim, Soohyun; Choi, Junghoon; Choi, Chanyong; Heo, Jiyun; Kim, Dae Woo; Lee, Jang Yong; Hong, Young Taik; Jung, Hee-Tae; Kim, Hee-Tak

2018-05-07

The laminated structure of graphene oxide (GO) membranes provides exceptional ion-separation properties due to the regular interlayer spacing ( d) between laminate layers. However, a larger effective pore size of the laminate immersed in water (∼11.1 Å) than the hydrated diameter of vanadium ions (>6.0 Å) prevents its use in vanadium redox-flow batteries (VRFB). In this work, we report an ion-selective graphene oxide framework (GOF) with a d tuned by cross-linking the GO nanosheets. Its effective pore size (∼5.9 Å) excludes vanadium ions by size but allows proton conduction. The GOF membrane is employed as a protective layer to address the poor chemical stability of sulfonated poly(arylene ether sulfone) (SPAES) membranes against VO 2 + in VRFB. By effectively blocking vanadium ions, the GOF/SPAES membrane exhibits vanadium-ion permeability 4.2 times lower and a durability 5 times longer than that of the pristine SPAES membrane. Moreover, the VRFB with the GOF/SPAES membrane achieves an energy efficiency of 89% at 80 mA cm -2 and a capacity retention of 88% even after 400 cycles, far exceeding results for Nafion 115 and demonstrating its practical applicability for VRFB.

Improved capacitance characteristics of electrospun ACFs by pore size control and vanadium catalyst.

PubMed

Im, Ji Sun; Woo, Sang-Wook; Jung, Min-Jung; Lee, Young-Seak

2008-11-01

Nano-sized carbon fibers were prepared by using electrospinning, and their electrochemical properties were investigated as a possible electrode material for use as an electric double-layer capacitor (EDLC). To improve the electrode capacitance of EDLC, we implemented a three-step optimization. First, metal catalyst was introduced into the carbon fibers due to the excellent conductivity of metal. Vanadium pentoxide was used because it could be converted to vanadium for improved conductivity as the pore structure develops during the carbonization step. Vanadium catalyst was well dispersed in the carbon fibers, improving the capacitance of the electrode. Second, pore-size development was manipulated to obtain small mesopore sizes ranging from 2 to 5 nm. Through chemical activation, carbon fibers with controlled pore sizes were prepared with a high specific surface and pore volume, and their pore structure was investigated by using a BET apparatus. Finally, polyacrylonitrile was used as a carbon precursor to enrich for nitrogen content in the final product because nitrogen is known to improve electrode capacitance. Ultimately, the electrospun activated carbon fibers containing vanadium show improved functionality in charge/discharge, cyclic voltammetry, and specific capacitance compared with other samples because of an optimal combination of vanadium, nitrogen, and fixed pore structures.

Imaging of Vanadium in Microfossils: A New Potential Biosignature

DOE PAGES

Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.; ...

2017-11-01

Being able to distinguish unambiguously the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from non-biological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This too, is important for the search for life on Mars; either by in situ analyses via rovers, or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biologicalmore » origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature, that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagensis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. Here, we propose that taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenecity of putative microfossil-like structures.« less

Molecular geometry of vanadium dichloride and vanadium trichloride: a gas-phase electron diffraction and computational study.

PubMed

Varga, Zoltán; Vest, Brian; Schwerdtfeger, Peter; Hargittai, Magdolna

2010-03-15

The molecular geometries of VCl2 and VCl3 have been determined by computations and gas-phase electron diffraction (ED). The ED study is a reinvestigation of the previously published analysis for VCl2. The structure of the vanadium dichloride dimer has also been calculated. According to our joint ED and computational study, the evaporation of a solid sample of VCl2 resulted in about 66% vanadium trichloride and 34% vanadium dichloride in the vapor. Vanadium dichloride is unambiguously linear in its 4Sigma(g)+ ground electronic state. For VCl3, all computations yielded a Jahn-Teller-distorted ground-state structure of C(2v) symmetry. However, it lies merely less than 3 kJ/mol lower than the 3E'' state (D(3h) symmetry). Due to the dynamic nature of the Jahn-Teller effect in this case, rigorous distinction cannot be made between the planar models of either D(3h) symmetry or C(2v) symmetry for the equilibrium structure of VCl3. Furthermore, the presence of several low-lying excited electronic states of VCl3 is expected in the high-temperature vapor. To our knowledge, this is the first experimental and computational study of the VCl3 molecule.

Imaging of Vanadium in Microfossils: A New Potential Biosignature

NASA Astrophysics Data System (ADS)

Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.; Lai, Barry; Vogt, Stefan; Breuer, Pierre; Steemans, Philippe; Lay, Peter A.

2017-11-01

The inability to unambiguously distinguish the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from nonbiological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This, too, is important for the search for life on Mars by in situ analyses via rovers or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biological origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagenesis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. We propose that, taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenicity of putative microfossil-like structures.

Understanding the Reduction Kinetics of Aqueous Vanadium(V) and Transformation Products Using Rotating Ring-Disk Electrodes.

PubMed

Chen, Gongde; Liu, Haizhou

2017-10-17

Vanadium(V) is an emerging contaminant in the most recent Environmental Protection Agency's candidate contaminant list (CCL4). The redox chemistry of vanadium controls its occurrence in the aquatic environment, but the impact of vanadium(V) speciation on the redox properties remains largely unknown. This study utilized the rotating ring-disk electrode technique to examine the reduction kinetics of four pH- and concentration-dependent vanadium(V) species in the presence and the absence of phosphate. Results showed that the reduction of VO 2 + , H x V 4 O 12+x (4+x)- (V 4 ), and HVO 4 2- proceeded via a one-electron transfer, while that of Na x H y V 10 O 28 (6-x-y)- (V 10 ) underwent a two-electron transfer. Koutecky-Levich and Tafel analyses showed that the intrinsic reduction rate constants followed the order of V 10 > VO 2 + > V 4 > HVO 4 2- . Ring-electrode collection efficiency indicated that the reduction product of V 10 was stable, while those of VO 2 + , HVO 4 2- , and V 4 had short half-lives that ranged from milliseconds to seconds. With molar ratios of phosphate to vanadium(V) varying from 0 to 1, phosphate accelerated the reduction kinetics of V 10 and V 4 and enhanced the stability of the reduction products of VO 2 + , V 4 , and HVO 4 2- . This study suggests that phosphate complexation could enhance the reductive removal of vanadium(V) and inhibit the reoxidation of its reduction product in water treatment.

Removal and recovery of vanadium from alkaline steel slag leachates with anion exchange resins.

PubMed

Gomes, Helena I; Jones, Ashley; Rogerson, Mike; Greenway, Gillian M; Lisbona, Diego Fernandez; Burke, Ian T; Mayes, William M

2017-02-01

Leachable vanadium (V) from steel production residues poses a potential environmental hazard due to its mobility and toxicity under the highly alkaline pH conditions that characterise these leachates. This work aims to test the efficiency of anion exchange resins for vanadium removal and recovery from steel slag leachates at a representative average pH of 11.5. Kinetic studies were performed to understand the vanadium sorption process. The sorption kinetics were consistent with a pseudo-first order kinetic model. The isotherm data cannot differentiate between the Langmuir and Freundlich models. The maximum adsorption capacity (Langmuir value q max ) was 27 mg V g -1 resin. In column anion exchange, breakthrough was only 14% of the influent concentration after passing 90 L of steel slag leachate with 2 mg L -1 V through the column. When eluting the column 57-72% of vanadium was recovered from the resin with 2 M NaOH. Trials on the reuse of the anion exchange resin showed it could be reused 20 times without loss of efficacy, and on average 69% of V was recovered during regeneration. The results document for the first time the use of anion exchange resins to remove vanadium from steel slag leachate. As an environmental contaminant, removal of V from leachates may be an obligation for long-term management requirements of steel slag repositories. Vanadium removal coupled with the recovery can potentially be used to offset long-term legacy treatment costs. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.

A comparative assessment of the acute inhalation toxicity of vanadium compounds.

PubMed

Rajendran, N; Seagrave, J C; Plunkett, L M; MacGregor, J A

2016-11-01

Vanadium compounds have become important in industrial processes, resulting in workplace exposure potential and are present in ambient air as a result of fossil fuel combustion. A series of acute nose-only inhalation toxicity studies was conducted in both rats and mice in order to obtain comparative data on the acute toxicity potential of compounds used commercially. V 2 O 3 , V 2 O 4 , and V 2 O 5 , which have different oxidation states (+3, +4, +5, respectively), were delivered as micronized powders; the highly water-soluble and hygroscopic VOSO 4 (+4) could not be micronized and was instead delivered as a liquid aerosol from an aqueous solution. V 2 O 5 was the most acutely toxic micronized powder in both species. Despite its lower overall percentage vanadium content, a liquid aerosol of VOSO 4 was more toxic than the V 2 O 5 particles in mice, but not in rats. These data suggest that an interaction of characteristics, i.e., bioavailability, solubility and oxidation state, as well as species sensitivity, likely affect the toxicity potential of vanadium compounds. Based on clinical observations and gross necropsy findings, the lung appeared to be the target organ for all compounds. The level of hazard posed will depend on the specific chemical form of the vanadium. Future work to define the inhalation toxicity potential of vanadium compounds of various oxidation states after repeated exposures will be important in understanding how the physico-chemical and biological characteristics of specific vanadium compounds interact to affect toxicity potential and the potential risks posed to human health.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

Quantitative Assessment of Proliferative Effects of Oral Vanadium on Pancreatic Islet Volumes and Beta Cell Numbers of Diabetic Rats

PubMed Central

Pirmoradi, Leila; Noorafshan, Ali; Safaee, Akbar; Dehghani, Gholam Abbas

2016-01-01

Background: Oral vanadyl sulfate (vanadium) induces normoglycemia, proliferates beta cells and prevents pancreatic islet atrophy in streptozotocin-induced diabetic rats. Soteriological method is used to quantitate the proliferative effects of vanadium on beta-cell numbers and islet volumes of normal and diabetic rats. Methods: Adult male Sprague-Dawley rats were made diabetic with intravenous streptozotocin injection (40 mg/kg). Normal and diabetic rats were divided into four groups. While control normal and diabetic (CD) groups used water, vanadium-treated normal (VTN) and diabetic (VTD) groups used solutions containing vanadyl sulfate (0.5-1 mg/mL, VOSO4+5H2O). Tail blood samples were used to measure blood glucose (BG) and plasma insulin. Two months after treatment, rats were sacrificed, pancreata prepared, and stereology method was used to quantitatively evaluate total beta cell numbers (TBCN) and total islet volumes (TISVOL). Results: Normoglycemia persisted in VTN with significantly decreased plasma insulin (0.190.08 vs. 0.970.27 ng/dL, P<0.002). The respective high BG (53249 vs. 14446 mg/dL, P<0.0001) and reduced plasma insulin (0.260.15 vs. 0.540.19 ng/dL, P<0.002) seen in CD were reversed in VTD during vanadium treatment or withdrawal. While the induction of diabetes, compared to their control, significantly decreased TISVOL (1.90.2 vs. 3.030.6 mm3, P<0.003) and TBCN (0.990.1 vs. 3.20.2 x 106, P<0.003), vanadium treatment significantly increased TISVOL (2.90.8 and 4.071.0 mm3, P<0.003) and TBCN (1.50.3 and 3.80.6 x 106, P<0.03). Conclusion: Two-month oral vanadium therapy in STZ-diabetic rats ameliorated hyperglycemia by partially restoring plasma insulin. This action was through proliferative actions of vanadium in preventing islet atrophy by increasing beta-cell numbers. PMID:26459400

Tryptophan 80 and leucine 143 are critical for the hydride transfer step of thymidylate synthase by controlling active site access.

PubMed

Fritz, Timothy A; Liu, Lu; Finer-Moore, Janet S; Stroud, Robert M

2002-06-04

Mutant forms of thymidylate synthase (TS) with substitutions at the conserved active site residue, Trp 80, are deficient in the hydride transfer step of the TS reaction. These mutants produce a beta-mercaptoethanol (beta-ME) adduct of the 2'-deoxyuridine-5'-monophosphate (dUMP) exocyclic methylene intermediate. Trp 80 has been proposed to assist hydride transfer by stabilizing a 5,6,7,8-tetrahydrofolate (THF) radical cation intermediate [Barrett, J. E., Lucero, C. M., and Schultz, P. G. (1999) J. Am. Chem. Soc. 121, 7965-7966.] formed after THF changes its binding from the cofactor pocket to a putative alternate site. To understand the molecular basis of hydride transfer deficiency in a mutant in which Trp 80 was changed to Gly, we determined the X-ray structures of this mutant Escherichia coli TS complexed with dUMP and the folate analogue 10-propargyl-5,8-dideazafolate (CB3717) and of the wild-type enzyme complexed with dUMP and THF. The mutant enzyme has a cavity in the active site continuous with bulk solvent. This cavity, sealed from bulk solvent in wild-type TS by Leu 143, would allow nucleophilic attack of beta-ME on the dUMP C5 exocyclic methylene. The structure of the wild-type enzyme/dUMP/THF complex shows that THF is bound in the cofactor binding pocket and is well positioned to transfer hydride to the dUMP exocyclic methylene. Together, these results suggest that THF does not reorient during hydride transfer and indicate that the role of Trp 80 may be to orient Leu 143 to shield the active site from bulk solvent and to optimally position the cofactor for hydride transfer.

Agile Thermal Management STT-RX. Catalytic Influence of Ni-based Additives on the Dehydrogentation Properties of Ball Milled MgH2 (PREPRINT)

DTIC Science & Technology

2011-12-01

Wronski: Particle size, grain size and gamma-MgH2 effects on the desorption properties of nanocrystal- line commercial magnesium hydride processed...Catalytic effects of various forms of nickel on the synthesis rate and hydrogen desorption properties of nanocrystalline magnesium hydride (MgH2...dehydrogenation reaction. 15. SUBJECT TERMS magnesium hydride , MgH, thermal energy storage materials, endothermic reaction 16. SECURITY CLASSIFICATION

Lih thermal energy storage device

DOEpatents

Olszewski, Mitchell; Morris, David G.

1994-01-01

A thermal energy storage device for use in a pulsed power supply to store waste heat produced in a high-power burst operation utilizes lithium hydride as the phase change thermal energy storage material. The device includes an outer container encapsulating the lithium hydride and an inner container supporting a hydrogen sorbing sponge material such as activated carbon. The inner container is in communication with the interior of the outer container to receive hydrogen dissociated from the lithium hydride at elevated temperatures.

Hydrogen transmission/storage with a metal hydride/organic slurry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breault, R.W.; Rolfe, J.; McClaine, A.

1998-08-01

Thermo Power Corporation has developed a new approach for the production, transmission, and storage of hydrogen. In this approach, a chemical hydride slurry is used as the hydrogen carrier and storage media. The slurry protects the hydride from unanticipated contact with moisture in the air and makes the hydride pumpable. At the point of storage and use, a chemical hydride/water reaction is used to produce high-purity hydrogen. An essential feature of this approach is the recovery and recycle of the spent hydride at centralized processing plants, resulting in an overall low cost for hydrogen. This approach has two clear benefits:more » it greatly improves energy transmission and storage characteristics of hydrogen as a fuel, and it produces the hydrogen carrier efficiently and economically from a low cost carbon source. The preliminary economic analysis of the process indicates that hydrogen can be produced for $3.85 per million Btu based on a carbon cost of $1.42 per million Btu and a plant sized to serve a million cars per day. This compares to current costs of approximately $9.00 per million Btu to produce hydrogen from $3.00 per million Btu natural gas, and $25 per million Btu to produce hydrogen by electrolysis from $0.05 per Kwh electricity. The present standard for production of hydrogen from renewable energy is photovoltaic-electrolysis at $100 to $150 per million Btu.« less

Materials considerations in the design of a metal-hydride heat pump for an advanced extravehicular mobility unit

NASA Technical Reports Server (NTRS)

Liebert, B. E.

1986-01-01

A metal-hydride heat pump (HHP) has been proposed to provide an advanced regenerable nonventing thermal sink for the liquid-cooled garment worn during an extravehicular activity (EVA). The conceptual design indicates that there is a potential for significant advantages over the one presently being used by shuttle crew personnel as well as those that have been proposed for future use with the space station. Compared to other heat pump designs, a HHP offers the potential for extended use with no electrical power requirements during the EVA. In addition, a reliable, compact design is possible due to the absence of moving parts other than high-reliability check valves. Because there are many subtleties in the properties of metal hydrides for heat pump applications, it is essential that a prototype hydride heat pump be constructed with the selected materials before a committment is made for the final design. Particular care must be given to the evaporator heat exchanger worn by the astronaut since the performance of hydride heat pumps is generally heat transfer limited.

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

PubMed

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

2012-08-21

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

Storing energy in metal hydrides - A review of the physical metallurgy

NASA Astrophysics Data System (ADS)

Ivey, D. G.; Northwood, D. O.

1983-02-01

The properties of metal hydrides, which are significant in terms of their potential as a hydrogen storage medium, are discussed. Attention is given to bonding and electronic factors of metal hydrides, which, when combined with hydrogen, form saline, ionic, metallic, and covalent bonds, with the resultant materials being either solid, liquid, or gaseous. Metallic bonds are the most promising for hydrogen storage, and involve most of the elements of groups IIIA-VIIIA in the periodic table. An analysis of the thermodynamics and kinetics of metal hydrides is presented, noting the effects of alloy composition, crystal structure, and contaminants on the effectiveness of the materials as hydrides. Hysteresis has been found to occur when the transition pressure in a pressure-composition-temperature curve is higher for absorption than for desorption, although the actual causes for hysteresis are not understood. The AB group of intermetallics has been determined to store hydrogen at the lowest cost. Examples from tests using the AB compounds are outlined, and attempts to rectify storage requirement deficiencies by adjusting the alloy compositions are described.

Making a Splash in Homogeneous CO₂ Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms.

PubMed

Wiedner, Eric; Linehan, John

2018-06-06

Molecular catalysts for hydrogenation of CO₂ are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO₂ hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO₂. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO₂. Additionally, the solvent can impact catalysis by converting CO₂ into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C 5 Me 5) 2U(μ-H)] 2

DOE PAGES

Pagano, Justin K.; Dorhout, Jacquelyn M.; Czerwinski, Kenneth R.; ...

2016-03-18

Here, this work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C 5Me 5) 2U–H] x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C 5Me5)2UMe2 (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C 5Me 5) 2U(H)(μ-H)] 2 (2), which was harnessed to prepare a varietymore » of organometallic complexes, including (C 5Me 5) 2U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C 5Me 5) 2U(C 4Me 4) (11).« less

SSH2S: Hydrogen storage in complex hydrides for an auxiliary power unit based on high temperature proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Baricco, Marcello; Bang, Mads; Fichtner, Maximilian; Hauback, Bjorn; Linder, Marc; Luetto, Carlo; Moretto, Pietro; Sgroi, Mauro

2017-02-01

The main objective of the SSH2S (Fuel Cell Coupled Solid State Hydrogen Storage Tank) project was to develop a solid state hydrogen storage tank based on complex hydrides and to fully integrate it with a High Temperature Proton Exchange Membrane (HT-PEM) fuel cell stack. A mixed lithium amide/magnesium hydride system was used as the main storage material for the tank, due to its high gravimetric storage capacity and relatively low hydrogen desorption temperature. The mixed lithium amide/magnesium hydride system was coupled with a standard intermetallic compound to take advantage of its capability to release hydrogen at ambient temperature and to ensure a fast start-up of the system. The hydrogen storage tank was designed to feed a 1 kW HT-PEM stack for 2 h to be used for an Auxiliary Power Unit (APU). A full thermal integration was possible thanks to the high operation temperature of the fuel cell and to the relative low temperature (170 °C) for hydrogen release from the mixed lithium amide/magnesium hydride system.

Texture and hydride orientation relationship of Zircaloy-4 fuel clad tube during its fabrication for pressurized heavy water reactors

NASA Astrophysics Data System (ADS)

Vaibhaw, Kumar; Rao, S. V. R.; Jha, S. K.; Saibaba, N.; Jayaraj, R. N.

2008-12-01

Zircaloy-4 material is used for cladding tube in pressurized heavy water reactors (PHWRs) of 220 MWe and 540 MWe capacity in India. These tubes are fabricated by using various combinations of thermo-mechanical processes to achieve desired mechanical and corrosion properties. Cladding tube develops crystallographic texture during its fabrication, which has significant influence on its in-reactor performance. Due to radiolytic decomposition of water Zircaloy-4 picks-up hydrogen. This hydrogen in excess of its maximum solubility in reactor operating condition (˜300 °C), precipitates as zirconium hydrides causing embrittlement of cladding tube. Hydride orientation in the radial direction of the tube limits the service life and lowers the fuel burn-up in reactor. The orientation of the hydride primarily depends on texture developed during fabrication. A correlation between hydride orientation ( F n) with the texture in the tube during its fabrication has been developed using a second order polynomial. The present work is aimed at quantification and correlation of texture evolved in Zircaloy-4 cladding tube using Kearn's f-parameter during its fabrication process.

Regenerative Hydride Heat Pump

NASA Technical Reports Server (NTRS)

Jones, Jack A.

1992-01-01

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

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages.

PubMed

Stitt, C A; Harker, N J; Hallam, K R; Paraskevoulakos, C; Banos, A; Rennie, S; Jowsey, J; Scott, T B

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed.

Selective Reduction of CO2 to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes.

PubMed

Hicken, Alexandra; White, Andrew J P; Crimmin, Mark R

2017-11-20

A series of heterobimetallic complexes containing three-center, two-electron Au-H-Cu bonds have been prepared from addition of a parent gold hydride to a bent d 10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu-H-Cu and M-H-M + moieties (M=Cu, Ag). The well-defined heterobimetallic hydride complexes act as precatalysts for the conversion of CO 2 into HCO 2 Bpin with HBpin as the reductant. The selectivity of the heterobimetallic complexes for the catalytic production of a formate equivalent surpasses that of the parent monomeric Group 11 complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 hydrogenation on a metal hydride surface.

PubMed

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

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages

PubMed Central

Harker, N. J.; Hallam, K. R.; Paraskevoulakos, C.; Banos, A.; Rennie, S.; Jowsey, J.

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed. PMID:26176551

Performance Characterization and Optimization of Microgrid-Based Energy Generation and Storage Technologies

DTIC Science & Technology

2012-01-01

A. Rufer, “Multiphysics and energetic modeling of a vanadium redox flow battery ,” in Proc. 2008 IEEE International Conference on Sustainable...p. 81. [11] K.W. Knehr and E.C. Kumbur, "Open circuit voltage of vanadium redox flow batteries : Discrepancy between models and experiments...Blanc and A. Rufer, “Multiphysics and energetic modeling of a vanadium redox flow battery ,” in Proc. 2008 IEEE International Conference on Sustainable

Exploratory Phase Transition-Based Switches Using Functional Oxides

DTIC Science & Technology

2011-02-02

TECHNICAL REPORT Abstract Vanadium dioxide ( VO2 ) undergoes a sharp metal-insulator transition (MIT) in the vicinity of room temperature and there is...18 The mechanisms governing metal-insulator transition (MIT) in vanadium dioxide ( VO2 ) is an intensively explored subject in condensed matter...textured vanadium dioxide films were grown on single crystal Al2O3 (0001) substrates by RF-sputtering from a VO2 target (99.5%, AJA International Inc

Temperature Dependence of Uranium and Vanadium Adsorption on Amidoxime-Based Adsorbents in Natural Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Gill, Gary A.; Tsouris, Costas

The apparent enthalpy and entropy of the complexation of uranium (VI) and vanadium (V) with amidoxime ligands grafted onto polyethylene fiber was determined using time series measurements of adsorption capacities in natural seawater at three different temperatures. The complexation of uranium was highly endothermic, while the complexation of vanadium showed minimal temperature sensitivity. Amidoxime-based polymeric adsorbents exhibit significantly increased uranium adsorption capacities and selectivity in warmer waters.

Amorphous vanadium oxide coating on graphene by atomic layer deposition for stable high energy lithium ion anodes.

PubMed

Sun, Xiang; Zhou, Changgong; Xie, Ming; Hu, Tao; Sun, Hongtao; Xin, Guoqing; Wang, Gongkai; George, Steven M; Lian, Jie

2014-09-21

Uniform amorphous vanadium oxide films were coated on graphene via atomic layer deposition and the nano-composite displays an exceptional capacity of ~900 mA h g(-1) at 200 mAg(-1) with an excellent capacity retention at 1 A g(-1) after 200 cycles. The capacity contribution (1161 mA h g(-1)) from vanadium oxide only almost reaches its theoretical value.

Geochemistry of environmentally sensitive trace elements in Permian coals from the Huainan coalfield, Anhui, China

USGS Publications Warehouse

Chen, J.; Liu, Gaisheng; Jiang, M.; Chou, C.-L.; Li, H.; Wu, B.; Zheng, Lingyun; Jiang, D.

2011-01-01

To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals. ?? 2011 Elsevier B.V.

Method of forming a chemical composition

DOEpatents

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

2007-10-09

A method of forming a chemical composition such as a chemical hydride is described and which includes the steps of selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of hydrogen; and exposing the selected composition to an amount of ionizing radiation to encourage the changing of the chemical bonds of the selected composition, and chemically reacting the selected composition with the source of hydrogen to facilitate the formation of a chemical hydride.

An all-solid-state metal hydride - Sulfur lithium-ion battery

NASA Astrophysics Data System (ADS)

López-Aranguren, Pedro; Berti, Nicola; Dao, Anh Ha; Zhang, Junxian; Cuevas, Fermín; Latroche, Michel; Jordy, Christian

2017-07-01

A metal hydride is used for the first time as anode in a complete all-solid-state battery with sulfur as cathode and LiBH4 as solid electrolyte. The hydride is a nanocomposite made of MgH2 and TiH2 counterparts. The battery exhibits a high reversible capacity of 910 mAh g-1 with discharge plateaus at 1.8 V and 1.4 V. Moreover, the capacity remains to 85% of the initial value over the 25 first charge/discharge cycles.

Method of production of pure hydrogen near room temperature from aluminum-based hydride materials

DOEpatents

Pecharsky, Vitalij K.; Balema, Viktor P.

2004-08-10

The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel.

LiH thermal energy storage device

DOEpatents

Olszewski, M.; Morris, D.G.

1994-06-28

A thermal energy storage device for use in a pulsed power supply to store waste heat produced in a high-power burst operation utilizes lithium hydride as the phase change thermal energy storage material. The device includes an outer container encapsulating the lithium hydride and an inner container supporting a hydrogen sorbing sponge material such as activated carbon. The inner container is in communication with the interior of the outer container to receive hydrogen dissociated from the lithium hydride at elevated temperatures. 5 figures.

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, G.L.

1984-05-18

A method for preparing reactive metal surfaces, particularly uranium surfaces is disclosed, whereby the metal is immediately reactive to hydrogen gas at room temperature and low pressure. The metal surfaces are first pretreated by exposure to an acid which forms an adherent hydride-bearing composition on the metal surface. Subsequent heating of the pretreated metal at a temperature sufficient to decompose the hydride coating in vacuum or inert gas renders the metal surface instantaneously reactive to hydrogen gas at room temperature and low pressure.

Phase I. Lanthanum-based Start Materials for Hydride Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gschneidner, K. A.; Schmidt, F. A.; Frerichs, A. E.

The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La 1-xR x)(Ni 1-yM y)(Si z), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

METHOD OF PREPARING URANIUM, THORIUM, OR PLUTONIUM OXIDES IN LIQUID BISMUTH

DOEpatents

Davidson, J.K.; Robb, W.L.; Salmon, O.N.

1960-11-22

A method is given for forming compositions, as well as the compositions themselves, employing uranium hydride in a liquid bismuth composition to increase the solubility of uranium, plutonium and thorium oxides in the liquid bismuth. The finely divided oxide of uranium, plutonium. or thorium is mixed with the liquid bismuth and uranium hydride, the hydride being present in an amount equal to about 3 at. %, heated to about 5OO deg C, agitated and thereafter cooled and excess resultant hydrogen removed therefrom.

A study of hydriding kinetics of metal hydrides using a physically based model

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the effects of multidimensional phase growth and transitions between rate-limiting processes on the experimentally determined reaction rates. Unlike conventional solid state reaction analysis methods, this model relies fully on rate parameters based on the physical mechanisms occurring in the hydride reaction and can be extended to reactions in any dimension.

Growth control of the oxidation state in vanadium oxide thin films

DOE PAGES

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; ...

2014-12-05

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metalinsulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V₂⁺²O₃, V⁺⁴O₂, and V₂⁺⁵O₅. A well pronounced MIT was only observed in VO₂ films grown in a very narrow range of oxygen partial pressure P(O₂). The films grown either in lower (< 10 mTorr) or higher P(O₂) (> 25 mTorr) result in V₂O₃ and V₂O₅ phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO₂ thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an 3 improved MIT behavior.« less

Evaluating electrically insulating films deposited on V-4% Cr-4% Ti by reactive CVD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, J.H.; Cho, W.D.

1997-04-01

Previous CaO coatings on V-4%Cr-4%Ti exhibited high-ohmic insulator behavior even though a small amount of vanadium from the alloy was incorporated in the coating. However, when the vanadium concentration in the coatings is > 15 wt%, the coating becomes conductive. When the vanadium concentration is high in localized areas, a calcium vanadate phase that exhibits semiconductor behavior can form. To explore this situation, CaO and Ca-V-O coatings were produced on vanadium alloys by chemical vapor deposition (CVD) and by a metallic-vapor process to investigate the electrical resistance of the coatings. Initially, the vanadium alloy specimens were either charged with oxygenmore » in argon that contained trace levels of oxygen, or oxidized for 1.5-3 h in a 1% CO-CO{sub 2} gas mixture or in air to form vanadium oxide at 625-650{degrees}C. Most of the specimens were exposed to calcium vapor at 800-850{degrees}C. Initial and final weights were obtained to monitor each step, and surveillance samples were removed for examination by optical and scanning electron microscopy and electron-energy-dispersive and X-ray diffraction analysis; the electrical resistivity was also measured. The authors found that Ca-V-O films exhibited insulator behavior when the ratio of calcium concentration to vanadium concentration R in the film was > 0.9, and semiconductor or conductor behavior for R < 0.8. However, in some cases, semiconductor behavior was observed when CaO-coated samples with R > 0.98 were exposed in liquid lithium. Based on these studies, the authors conclude that semiconductor behavior occurs if a conductive calcium vanadate phase is present in localized regions in the CaO coating.« less

Growth control of the oxidation state in vanadium oxide thin films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V2 + 3 O 3 , V + 4 O 2 , and V2 + 5 O 5 . A well pronounced MIT was only observed in VO2 films grown in a very narrow range of oxygen partial pressure P(O2). The films grown either in lower (<10 mTorr) or higher P(O2) (>25 mTorr) result in V2O3 and V2O5 phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO2 thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions.

PubMed

Ayala Quezada, Alejandro; Ohara, Keisuke; Ratanawimarnwong, Nuanlaor; Nacapricha, Duangjai; Murakami, Hiroya; Teshima, Norio; Sakai, Tadao

2015-11-01

An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures. Copyright © 2015 Elsevier B.V. All rights reserved.

High-Fat Diet Increased Renal and Hepatic Oxidative Stress Induced by Vanadium of Wistar Rat.

PubMed

Wang, J P; Cui, R Y; Zhang, K Y; Ding, X M; Luo, Y H; Bai, S P; Zeng, Q F; Xuan, Y; Su, Z W

2016-04-01

The study was conducted to assess the effect of vanadium (V) in high-fat diet on the liver and kidney of rats in a 5-week trial. Seventy-two female Wistar rats (BW = 95 ± 5 g) were randomly allotted into eight groups. Groups I, II, III, and IV obtained low-fat diet containing 0, 3, 15, and 30 mg/kg V, and V, VI, VII, and VIII groups received the respective vanadium doses with high-fat diet, respectively. There were lesions in the liver and kidney of V, VI, VII, and VIII groups, granular degeneration and vacuolar degeneration were observed in the renal tubular and glomerulus epithelial cells, and hepatocytes showed granular degeneration and vacuolar degeneration. Supplemented high-fat diet with vanadium was shown to decrease (P < 0.05) activities of superoxide dismutase, total antioxidant capacity, glutathione-S transferase, and NAD(P)H/quinone oxidoreductase 1 (NQO1) and increase malondialdehyde content in the liver and kidney. The relative expression of hepatic nuclear factor erythroid 2-related factor 2 (Nrf-2) and NQO1 mRNA was downregulated by V addition and high-fat diet, and the effect of V was more pronounced in high-fat diet (interaction, P < 0.05), with VIII group having the lowest mRNA expression of Nrf-2 and NQO1 in the liver and kidney. In conclusion, it suggested that dietary vanadium ranging from 15 to 30 mg/kg could lead to oxidative damage and vanadium accumulation in the liver and kidney, which caused renal and hepatic toxicity. The high-fat diet enhanced vanadium-induced hepatic and renal damage, and the mechanism was related to the modulation of the hepatic and renal mRNA expression of Nrf-2 and NQO1.

Does the relief of glucose toxicity act as a mediator in proliferative actions of vanadium on pancreatic islet beta cells in streptozocin diabetic rats?

PubMed

Pirmoradi, Leila; Mohammadi, Mohammad Taghi; Safaei, Akbar; Mesbah, Fakhardin; Dehghani, Gholam Abbas

2014-07-01

Data shows vanadium protects pancreatic beta cells (BC) from diabetic animals. Whether this effect is direct or through the relief of glucose toxicity is not clear. This study evaluated the potential effect of oral vanadyl sulfate (vanadium) on glycemic status and pancreatic BC of normal and diabetic rats. Rats were divided into five groups of normal and diabetic. Diabetes was induced with streptozocin (40 mg/kg, i.v.). Normal rats used water (CN) or vanadium (1 mg/ml VOSO4, VTN). Diabetic rats used water (CD), water plus daily neutral protamine Hagedorn insulin injection (80 U/kg, ITD) or vanadium (VTD). Blood samples were taken for blood glucose (BG, mg/dL) and insulin (ng/dL) measurements. After two months, the pancreata of sacrificed rats were prepared for islet staining. Pre-treated normal BG was 88 ± 2, and diabetic BG was 395 ± 9. The final BG in CD, VTD, and ITD was 509 ± 22, 138 ± 14, and 141 ± 14, respectively. Insulin in VTN (0.75 ± 0.01) and VTD (0.78 ± 0.01) was similar, higher than CD (0.51 ± 0.07) but lower than CN (2.51 ± 0.02). VTN islets compared to CN had larger size and denser central core insulin immunoreactivity with plentiful BC. CD and ITD islets were atrophied and had scattered insulin immunoreactivity spots and low BC mass. VTD islets were almost similar to CN. Besides insulin-like activity, vanadium protected pancreatic islet BC, and the relief of glucose toxicity happening with vanadium had a little role in this action.

Effect of Vanadium and Tea Polyphenols on Intestinal Morphology, Microflora and Short-Chain Fatty Acid Profile of Laying Hens.

PubMed

Yuan, Z H; Wang, J P; Zhang, K Y; Ding, X M; Bai, S P; Zeng, Q F; Xuan, Y; Su, Z W

2016-12-01

Vanadium (V) is a trace element which can induce dysfunction of gastro-intestine and egg quality deterioration of laying hens. This study was conducted to determine the effect of tea polyphenols (TP) on intestinal morphology, microflora, and short-chain fatty acid (SCFA) profile of laying hens fed vanadium containing diets. A total of 120 Lohman laying hens (67-week-old) were randomly divided into 4 groups with 6 replicates and 5 birds each for a 35-day feeding trial. The dietary treatments were as follows: (1) control (CON), fed a basal diet; (2) vanadium treatment (V10), CON +10 mg V/kg; (3) TP treatment 1 (TP1): V10 + 600 mg TP/kg; (4) TP treatment 2 (TP2): V10 + 1000 mg TP/kg. Fed 10 mg V/kg diets to laying hens did not affect the cecum flora diversity index (H), degree of homogeneity (EH), and richness (S), but hens fed TP2 diet decreased the H, EH, and S (P < 0.05). The cecum butyrate acid concentration was lower in V10 treatment and higher in TP2 treatment (P < 0.05). Addition of 10 mg/kg V resulted in an increased (P < 0.01) duodenal cell apoptosis rate, and 1000 mg/kg TP supplementation overcame (P < 0.01) this reduction effect induced by vanadium. The results indicated that supplementation of 10 mg/kg vanadium increased duodenal cell apoptosis and reduced cecum butyrate acid content. Addition of 1000 mg/kg TP increased the SCFA production to affect cecum flora ecology and protected the duodenal cell from excess apoptosis caused by vanadium.

Removal of vanadium from industrial wastewater using iron sorbents in batch and continuous flow pilot systems.

PubMed

Leiviskä, Tiina; Khalid, Muhammad Kamran; Sarpola, Arja; Tanskanen, Juha

2017-04-01

This study investigated the removal of vanadium from real industrial wastewater by using six iron materials: commercial iron sorbent (CFH-12), commercial mineral sorbent (AQM), blast furnace sludge (BFS), steel converter sludge (SCS), ferrochrome slag (FeCr) and slag from a steel foundry (OKTO). Batch tests revealed that CFH-12 (ferric oxyhydroxide) removed vanadium most efficiently, which was explained by its high iron content and the amorphous form of the iron, and that the sorption followed the Langmuir isotherm. With a dosage of 10 g/l and an initial vanadium concentration of 58.2 mg/l, 91-94% removal rates for vanadium were achieved in the studied pH range (3-9). Other sorbents showed significantly lower efficiency than CFH-12, with the exception of BFS at acidic pH (93%). Based on the batch test results, CFH-12 was selected for a pilot study made on site. The pilot study demonstrated the feasibility of CFH-12 to remove vanadium at high temperature (80 °C) from concentrated industrial wastewater with fluctuating water quality (vanadium concentration varied from 51 to 83 mg/l, pH about 9 (at 25 °C)). Leaching of impurities (mainly S, Ca, Mg and K) into the effluent occurred during the first day, but subsequently good quality effluent was produced (e.g. <0.1 mg/l V). During the pilot study, the amorphous iron material of CFH-12 was crystallized into a hematite-like phase (Fe 1.67 H 0.99 O 3 ), and goethite (FeO(OH)) with a higher average pore diameter, probably due to the hot process conditions to which CFH-12 was exposed for over five days. Copyright © 2016 Elsevier Ltd. All rights reserved.

Does the Relief of Glucose Toxicity Act As a Mediator in Proliferative Actions of Vanadium on Pancreatic Islet Beta Cells in Streptozocin Diabetic Rats?

PubMed Central

Pirmoradi, Leila; Mohammadi, Mohammad Taghi; Safaei, Akbar; Mesbah, Fakhardin; Dehghani, Gholam Abbas

2014-01-01

Background: Data shows vanadium protects pancreatic beta cells (BC) from diabetic animals. Whether this effect is direct or through the relief of glucose toxicity is not clear. This study evaluated the potential effect of oral vanadyl sulfate (vanadium) on glycemic status and pancreatic BC of normal and diabetic rats. Methods: Rats were divided into five groups of normal and diabetic. Diabetes was induced with streptozocin (40 mg/kg, i.v.). Normal rats used water (CN) or vanadium (1 mg/ml VOSO4, VTN). Diabetic rats used water (CD), water plus daily neutral protamine Hagedorn insulin injection (80 U/kg, ITD) or vanadium (VTD). Blood samples were taken for blood glucose (BG, mg/dL) and insulin (ng/dL) measurements. After two months, the pancreata of sacrificed rats were prepared for islet staining. Results: Pre-treated normal BG was 88 ± 2, and diabetic BG was 395 ± 9. The final BG in CD, VTD, and ITD was 509 ± 22, 138 ± 14, and 141 ± 14, respectively. Insulin in VTN (0.75 ± 0.01) and VTD (0.78 ± 0.01) was similar, higher than CD (0.51 ± 0.07) but lower than CN (2.51 ± 0.02). VTN islets compared to CN had larger size and denser central core insulin immunoreactivity with plentiful BC. CD and ITD islets were atrophied and had scattered insulin immunoreactivity spots and low BC mass. VTD islets were almost similar to CN. Conclusion: Besides insulin-like activity, vanadium protected pancreatic islet BC, and the relief of glucose toxicity happening with vanadium had a little role in this action. PMID:24842144

Growth control of the oxidation state in vanadium oxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Shinbuhm; Meyer, Tricia L.; Lee, Ho Nyung, E-mail: hnlee@ornl.gov

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V{sub 2}{sup +3}O{sub 3}, V{sup +4}O{sub 2}, and V{sub 2}{sup +5}O{sub 5}. A well pronounced MIT was only observed in VO{sub 2} films grown in a very narrow range of oxygen partial pressure P(O{sub 2}). The films grown either in lower (<10 mTorr) or higher P(O{sub 2}) (>25 mTorr) result in V{sub 2}O{sub 3} and V{sub 2}O{sub 5} phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO{sub 2} thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.« less

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

Positron lifetime in vanadium oxide bronzes

NASA Astrophysics Data System (ADS)

Dryzek, J.; Dryzek, E.

2003-09-01

The positron lifetime (PL) and Doppler broadening (DB) of annihilation line measurements have been performed in vanadium oxide bronzes MxV2O5. The dependence of these annihilation characteristics on the kind and concentration of the metal M donor has been observed. In the PL spectrum only one lifetime component has been detected in all studied bronzes. The results indicate the positron localization in the structural tunnels present in the crystalline lattice of the vanadium oxide bronzes. (

Molecular based magnets comprising vanadium tetracyanoethylene complexes for shielding electromagnetic fields

DOEpatents

Epstein, A.J.; Morin, B.G.

1998-10-13

The invention presents a vanadium tetracyanoethylene solvent complex for electromagnetic field shielding, and a method for blocking low frequency and magnetic fields using these vanadium tetracyanoethylene compositions. The compositions of the invention can be produced at ambient temperature and are light weight, low density and flexible. The materials of the present invention are useful as magnetic shields to block low frequency fields and static fields, and for use in cores in transformers and motors. 21 figs.

Molecular based magnets comprising vanadium tetracyanoethylene complexes for shielding electromagnetic fields

DOEpatents

Epstein, Arthur J.; Morin, Brian G.

1998-01-01

The invention presents a vanadium tetracyanoethylene solvent complex for electromagnetic field shielding, and a method for blocking low frequency and magnetic fields using these vanadium tetracyanoethylene compositions. The compositions of the invention can be produced at ambient temperature and are light weight, low density and flexible. The materials of the present invention are useful as magnetic shields to block low frequency fields and static fields, and for use in cores in transformers and motors.

Anion-conductive membranes with ultralow vanadium permeability and excellent performance in vanadium flow batteries.

PubMed

Mai, Zhensheng; Zhang, Huamin; Zhang, Hongzhang; Xu, Wanxing; Wei, Wenping; Na, Hui; Li, Xianfeng

2013-02-01

Anion exchange membranes prepared from quaternized poly(tetramethyl diphenyl ether sulfone) (QAPES) were first investigated in the context of vanadium flow battery (VFB) applications. The membranes showed an impressive suppression effect on vanadium ions. The recorded vanadium permeability was 0.02×10(-7)-0.09×10(-7) cm(2) min(-1), which was two orders of magnitude lower than that of Nafion 115. The self-discharge duration of a VFB single cell with a QAPES membrane is four times longer than that of Nafion 115. The morphological difference in hydrophilic domains between QAPES and Nafion was confirmed by TEM. After soaking the membranes in VO(2)(+) solution, adsorbed vanadium ions can barely be found in QAPES, whereas the hydrophilic domains of Nafion were stained. In the ex situ chemical stability test, QAPES showed a high tolerance to VO(2)(+) and remained intact after immersion in VO(2)(+) solution for over 250 h. The performance of a VFB single cell assembled with QAPES membranes is equal to or even better than that of Nafion 115 and remains stable in a long-term cycle test. These results indicate that QAPES membranes can be an ideal option in the fabrication of high-performance VFBs with low electric capacity loss. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

PubMed

Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

2013-04-29

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

PubMed

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Effect of Variable Oxidation States of Vanadium on the Structural, Optical, and Dielectric Properties of B2O3-Li2O-ZnO-V2O5 Glasses.

PubMed

Arya, S K; Danewalia, S S; Arora, Manju; Singh, K

2016-12-01

In the present study, the effect of variable vanadium oxidation states on the structural, optical, and dielectric properties of vanadium oxide containing lithium borate glasses has been investigated. Electron paramagnetic resonance studies indicate that vanadium in these glasses is mostly in the V 4+ state, having a tetragonal symmetry. As the glass composition of V 2 O 5 increases, tetragonality also increases at the cost of octahedral symmetry. The photoluminescence (PL) spectra of these glasses are dominated by zinc oxide transition, whereas the peaks pertaining to the vanadyl group are not visible in the PL spectra. The optical absorption spectra show a single wide absorption band, which is attributed to V 4+ ions in these glasses. The ac conductivity of the glasses increases with an increase in vanadium content. The highest electrical conductivity observed is ∼10 -5 S cm -1 at 250 °C for the glass with 2.5 mol % V 2 O 5 . Electrical conductivity is dominated by electron conduction, as indicated by the activation energy calculation.

Thermally Stable Solution Processed Vanadium Oxide as a Hole Extraction Layer in Organic Solar Cells

PubMed Central

Alsulami, Abdullah; Griffin, Jonathan; Alqurashi, Rania; Yi, Hunan; Iraqi, Ahmed; Lidzey, David; Buckley, Alastair

2016-01-01

Low-temperature solution-processable vanadium oxide (V2Ox) thin films have been employed as hole extraction layers (HELs) in polymer bulk heterojunction solar cells. V2Ox films were fabricated in air by spin-coating vanadium(V) oxytriisopropoxide (s-V2Ox) at room temperature without the need for further thermal annealing. The deposited vanadium(V) oxytriisopropoxide film undergoes hydrolysis in air, converting to V2Ox with optical and electronic properties comparable to vacuum-deposited V2O5. When s-V2Ox thin films were annealed in air at temperatures of 100 °C and 200 °C, OPV devices showed similar results with good thermal stability and better light transparency. Annealing at 300 °C and 400 °C resulted in a power conversion efficiency (PCE) of 5% with a decrement approximately 15% lower than that of unannealed films; this is due to the relative decrease in the shunt resistance (Rsh) and an increase in the series resistance (Rs) related to changes in the oxidation state of vanadium. PMID:28773356

Concentration Dependence of VO2+ Crossover of Nafion for Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawton, Jamie; Jones, Amanda; Zawodzinski, Thomas A

2013-01-01

The VO2+ crossover, or permeability, through Nafion in a vanadium redox flow battery (VRFB) was monitored as a function of sulfuric acid concentration and VO2+ concentration. A vanadium rich solution was flowed on one side of the membrane through a flow field while symmetrically on the other side a blank or vanadium deficit solution was flowed. The blank solution was flowed through an electron paramagnetic resonance (EPR) cavity and the VO2+ concentration was determined from the intensity of the EPR signal. Concentration values were fit using a solution of Fick s law that allows for the effect of concentration changemore » on the vanadium rich side. The fits resulted in permeability values of VO2+ ions across the membrane. Viscosity measurements of many VO2+ and H2SO4 solutions were made at 30 60 C. These viscosity values were then used to determine the effect of the viscosity of the flowing solution on the permeability of the ion. 2013 The Electrochemical Society. [DOI: 10.1149/2.004306jes] All rights reserved.« less

Switching adhesion forces by crossing the metal–insulator transition in Magnéli-type vanadium oxide crystals

PubMed Central

Klemm, Matthias; Horn, Siegfried; Woydt, Mathias

2011-01-01

Summary Magnéli-type vanadium oxides form the homologous series VnO2 n -1 and exhibit a temperature-induced, reversible metal–insulator first order phase transition (MIT). We studied the change of the adhesion force across the transition temperature between the cleavage planes of various vanadium oxide Magnéli phases (n = 3 … 7) and spherical titanium atomic force microscope (AFM) tips by systematic force–distance measurements with a variable-temperature AFM under ultrahigh vacuum conditions (UHV). The results show, for all investigated samples, that crossing the transition temperatures leads to a distinct change of the adhesion force. Low adhesion corresponds consistently to the metallic state. Accordingly, the ability to modify the electronic structure of the vanadium Magnéli phases while maintaining composition, stoichiometry and crystallographic integrity, allows for relating frictional and electronic material properties at the nano scale. This behavior makes the vanadium Magnéli phases interesting candidates for technology, e.g., as intelligent devices or coatings where switching of adhesion or friction is desired. PMID:21977416

Doping of vanadium to nanocrystalline diamond films by hot filament chemical vapor deposition

PubMed Central

2012-01-01

Doping an impure element with a larger atomic volume into crystalline structure of buck crystals is normally blocked because the rigid crystalline structure could not tolerate a larger distortion. However, this difficulty may be weakened for nanocrystalline structures. Diamonds, as well as many semiconductors, have a difficulty in effective doping. Theoretical calculations carried out by DFT indicate that vanadium (V) is a dopant element for the n-type diamond semiconductor, and their several donor state levels are distributed between the conduction band and middle bandgap position in the V-doped band structure of diamond. Experimental investigation of doping vanadium into nanocrystalline diamond films (NDFs) was first attempted by hot filament chemical vapor deposition technique. Acetone/H2 gas mixtures and vanadium oxytripropoxide (VO(OCH2CH2CH3)3) solutions of acetone with V and C elemental ratios of 1:5,000, 1:2,000, and 1:1,000 were used as carbon and vanadium sources, respectively. The resistivity of the V-doped NDFs decreased two orders with the increasing V/C ratios. PMID:22873631

Amphoteric Ion-Exchange Membranes with Significantly Improved Vanadium Barrier Properties for All-Vanadium Redox Flow Batteries.

PubMed

Nibel, Olga; Rojek, Tomasz; Schmidt, Thomas J; Gubler, Lorenz

2017-07-10

All-vanadium redox flow batteries (VRBs) have attracted considerable interest as promising energy-storage devices that can allow the efficient utilization of renewable energy sources. The membrane, which separates the porous electrodes in a redox flow cell, is one of the key components in VRBs. High rates of crossover of vanadium ions and water through the membrane impair the efficiency and capacity of a VRB. Thus, membranes with low permeation rate of vanadium species and water are required, also characterized by low resistance and stability in the VRB environment. Here, we present a new design concept for amphoteric ion-exchange membranes, based on radiation-induced grafting of vinylpyridine into an ethylene tetrafluoroethylene base film and a two-step functionalization to introduce cationic and anionic exchange sites, respectively. During long-term cycling, redox flow cells containing these membranes showed higher efficiency, less pronounced electrolyte imbalance, and significantly reduced capacity decay compared to the cells with the benchmark material Nafion 117. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

IRIS Toxicological Review of Vanadium Pentoxide ...

EPA Pesticide Factsheets

On September 30, 2011, the draft Toxicological Review of Vanadium Pentoxide and the charge to external peer reviewers were released for external peer review and public comment. The Toxicological Review and charge were reviewed internally by EPA and by other federal agencies and White House Offices before public release. In the new IRIS process (May 2009), introduced by the EPA Administrator, all written comments on IRIS assessments submitted by other federal agencies and White House Offices will be made publicly available. Accordingly, interagency comments and the interagency science consultation draft of the IRIS Toxicological Review of Vanadium Pentoxide and the charge to external peer reviewers are posted on this site. EPA is reassessing its IRIS toxicological review of vanadium pentoxide (CASRN 1314-62-1). This vanadium pentoxide reassessment consists of an oral reference dose (RfD), an inhalation reference concentration (RfC), an inhalation unit risk (IUR) and a cancer weight of evidence descriptor. This is the first assessment developing an RfC or IUR for this compound. This assessment is intended to provide human health data to support agency regulatory decisions.

Catalytic determination of vanadium in water

USGS Publications Warehouse

Fishman, M. J.; Skougstad, M.W.

1964-01-01

A rapid, accurate, and sensitive spectrophotometric method for the quantitative determination of trace amounts of vanadium in water is based on the catalytic effect of vanadium on the rate of oxidation of gallic acid by persulfate in acid solution. Under given conditions of concentrations of reactants, temperature, and reaction time, the extent of oxidation of gallic acid is proportional to the concentration of vanadium present. Vanadium is determined by measuring the absorbance of the sample at 415 m?? and comparison with standard solutions treated in an identical manner. Concentrations in the range of from 0.1 to 8.0 ??g. per liter may be determined with a standard deviation of 0.2 or less. By reducing the reaction time, the method may be extended to cover the range from 1 to 100 ??g. with a standard deviation of 0.8 or less. Several substances interfere, including chloride above 100 p.p.m., and bromide and iodide in much lower concentrations. Interference from the halides is eliminated or minimized by the addition of mercuric nitrate solution. Most other substances do not interfere at the concentration levels at which they commonly occur in natural waters.

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

[Determination of vanadium concentration in foods produced on the Eastern Coast of Lake Maracaibo].

PubMed

Tudares, C M; Villalobos, H D

1998-04-01

In the northeastern coast of Lake Maracaibo it has been reported some years ago a high incidence of congenital malformations of the Central Nervous Systems (Neural Tube Defects Type). This epidemiological problem is present in other countries too (Ireland and New Zealand) and has been associated with oil activities. In fact, some experimental works inform about the vanadium compounds cellular toxic effects mainly in the Central Nervous System of mammals. The main goal of this work is to measure the vanadium content in foods produced in the northeastern coast of Lake Maracaibo. Lagunillas, Valmore Rodriguez, and Baralt were the districts selected for the work. The digestion of the samples achieved by the methodology reported by Myron et al., with Graphite Furnace Atomic Absorption. The amounts of vanadium in the different foods analized were higher than the controls in the bibliographic reports. At this moment, there is not definitive proofs that vanadium compounds are the etiological agents of the Neural Tube Defects, but, these compounds are presents in foods produced in the northeastern coast of Lake Maracaibo.

Electrical and Infrared Optical Properties of Vanadium Oxide Semiconducting Thin-Film Thermometers

NASA Astrophysics Data System (ADS)

Zia, Muhammad Fakhar; Abdel-Rahman, Mohamed; Alduraibi, Mohammad; Ilahi, Bouraoui; Awad, Ehab; Majzoub, Sohaib

2017-10-01

A synthesis method has been developed for preparation of vanadium oxide thermometer thin film for microbolometer application. The structure presented is a 95-nm thin film prepared by sputter-depositing nine alternating multilayer thin films of vanadium pentoxide (V2O5) with thickness of 15 nm and vanadium with thickness of 5 nm followed by postdeposition annealing at 300°C in nitrogen (N2) and oxygen (O2) atmospheres. The resulting vanadium oxide (V x O y ) thermometer thin films exhibited temperature coefficient of resistance (TCR) of -3.55%/°C with room-temperature resistivity of 2.68 Ω cm for structures annealed in N2 atmosphere, and TCR of -3.06%/°C with room-temperature resistivity of 0.84 Ω cm for structures annealed in O2 atmosphere. Furthermore, optical measurements of N2- and O2-annealed samples were performed by Fourier-transform infrared ellipsometry to determine their dispersion curves, refractive index ( n), and extinction coefficient ( k) at wavelength from 7000 nm to 14,000 nm. The results indicate the possibility of applying the developed materials in thermometers for microbolometers.

Nonaqueous actinide hydride dissolution and production of actinide $beta$- diketonates

DOEpatents

Crisler, L.R.

1975-11-11

Actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a hydride of the actinide material in a mixture of carbon tetrachloride and methanol. (auth)