The Physiological Functions and Structural Determinants of Catalytic Bias in the [FeFe]-Hydrogenases CpI and CpII of Clostridium pasteurianum Strain W5

Science.gov (United States)

Therien, Jesse B.; Artz, Jacob H.; Poudel, Saroj; Hamilton, Trinity L.; Liu, Zhenfeng; Noone, Seth M.; Adams, Michael W. W.; King, Paul W.; Bryant, Donald A.; Boyd, Eric S.; Peters, John W.

2017-01-01

The first generation of biochemical studies of complex, iron-sulfur-cluster-containing [FeFe]-hydrogenases and Mo-nitrogenase were carried out on enzymes purified from Clostridium pasteurianum (strain W5). Previous studies suggested that two distinct [FeFe]-hydrogenases are expressed differentially under nitrogen-fixing and non-nitrogen-fixing conditions. As a result, the first characterized [FeFe]-hydrogenase (CpI) is presumed to have a primary role in central metabolism, recycling reduced electron carriers that accumulate during fermentation via proton reduction. A role for capturing reducing equivalents released as hydrogen during nitrogen fixation has been proposed for the second hydrogenase, CpII. Biochemical characterization of CpI and CpII indicated CpI has extremely high hydrogen production activity in comparison to CpII, while CpII has elevated hydrogen oxidation activity in comparison to CpI when assayed under the same conditions. This suggests that these enzymes have evolved a catalytic bias to support their respective physiological functions. Using the published genome of C. pasteurianum (strain W5) hydrogenase sequences were identified, including the already known [NiFe]-hydrogenase, CpI, and CpII sequences, and a third hydrogenase, CpIII was identified in the genome as well. Quantitative real-time PCR experiments were performed in order to analyze transcript abundance of the hydrogenases under diazotrophic and non-diazotrophic growth conditions. There is a markedly reduced level of CpI gene expression together with concomitant increases in CpII gene expression under nitrogen-fixing conditions. Structure-based analyses of the CpI and CpII sequences reveal variations in their catalytic sites that may contribute to their alternative physiological roles. This work demonstrates that the physiological roles of CpI and CpII are to evolve and to consume hydrogen, respectively, in concurrence with their catalytic activities in vitro, with CpII capturing excess

How Formaldehyde Inhibits Hydrogen Evolution by [FeFe]-Hydrogenases: Determination by ¹³C ENDOR of Direct Fe-C Coordination and Order of Electron and Proton Transfers.

Science.gov (United States)

Bachmeier, Andreas; Esselborn, Julian; Hexter, Suzannah V; Krämer, Tobias; Klein, Kathrin; Happe, Thomas; McGrady, John E; Myers, William K; Armstrong, Fraser A

2015-04-29

Formaldehyde (HCHO), a strong electrophile and a rapid and reversible inhibitor of hydrogen production by [FeFe]-hydrogenases, is used to identify the point in the catalytic cycle at which a highly reactive metal-hydrido species is formed. Investigations of the reaction of Chlamydomonas reinhardtii [FeFe]-hydrogenase with formaldehyde using pulsed-EPR techniques including electron-nuclear double resonance spectroscopy establish that formaldehyde binds close to the active site. Density functional theory calculations support an inhibited super-reduced state having a short Fe-(13)C bond in the 2Fe subsite. The adduct forms when HCHO is available to compete with H(+) transfer to a vacant, nucleophilic Fe site: had H(+) transfer already occurred, the reaction of HCHO with the Fe-hydrido species would lead to methanol, release of which is not detected. Instead, Fe-bound formaldehyde is a metal-hydrido mimic, a locked, inhibited form analogous to that in which two electrons and only one proton have transferred to the H-cluster. The results provide strong support for a mechanism in which the fastest pathway for H2 evolution involves two consecutive proton transfer steps to the H-cluster following transfer of a second electron to the active site.

[Fe]-hydrogenases in green algae: photo-fermentation and hydrogen evolution under sulfur deprivation

Energy Technology Data Exchange (ETDEWEB)

Winkler, M.; Hemschemeier, A.; Happe, T. [Botanisches Institut der Universitat Bonn (Germany); Gotor, C. [CSIC y Universidad de Sevilla (Spain). Instituto de Bioquimica Vegetal y Fotosintesis; Melis, A. [University of California, Berkeley, CA (United States). Department of Plant and Microbial Biology

2002-12-01

Recent studies indicate that [Fe]-hydrogenases and H{sub 2} metabolism are widely distributed among green algae. The enzymes are simple structured and catalyze H{sub 2} evolution with similar rates than the more complex [Fe]-hydrogenases from bacteria. Different green algal species developed diverse strategies to survive under sulfur deprivation. Chlamydomonas reinhardtii evolves large quantities of hydrogen gas in the absence of sulfur. In a sealed culture of C. reinhardtii, the photosynthetic O{sub 2} evolution rate drops below the rate of respiratory O{sub 2} consumption due to a reversible inhibition of photosystem II, thus leading to an intracellular anaerobiosis. The algal cells survive under these anaerobic conditions by switching their metabolism to a kind of photo-fermentation. Although possessing a functional [Fe]-hydrogenase gene, the cells of Scenedesmus obliquus produce no significant amounts of H{sub 2} under S-depleted conditions. Biochemical analyses indicate that S. obliquus decreases almost the complete metabolic activities while maintaining a low level of respiratory activity. (author)

Ab Initio Electronic Structure Calculation of [4Fe-3S] Cluster of Hydrogenase as Dihydrogen Dissociation/Production Catalyst

Science.gov (United States)

Kim, Jaehyun; Kang, Jiyoung; Nishigami, Hiroshi; Kino, Hiori; Tateno, Masaru

2018-03-01

Hydrogenases catalyze both the dissociation and production of dihydrogen (H2). Most hydrogenases are inactivated rapidly and reactivated slowly (in vitro), in the presence of dioxygen (O2) and H2, respectively. However, membrane-bound [NiFe] hydrogenases (MBHs) sustain their activity even together with O2, which is termed "O2 tolerance". In previous experimental analyses, an MBH was shown to include a hydroxyl ion (OH-) bound to an Fe of the super-oxidized [4Fe-3S]5+ cluster in the proximity of the [NiFe] catalytic cluster. In this study, the functional role of the OH- in the O2 tolerance was investigated by ab initio electronic structure calculation of the [4Fe-3S] proximal cluster. The analysis revealed that the OH- significantly altered the electronic structure, thereby inducing the delocalization of the lowest unoccupied molecular orbital (LUMO) toward the [NiFe] catalytic cluster, which may intermediate the electron transfer between the catalytic and proximal clusters. This can promote the O2-tolerant catalytic cycle in the hydrogenase reaction.

Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase

Science.gov (United States)

Brazzolotto, Deborah; Gennari, Marcello; Queyriaux, Nicolas; Simmons, Trevor R.; Pécaut, Jacques; Demeshko, Serhiy; Meyer, Franc; Orio, Maylis; Artero, Vincent; Duboc, Carole

2016-11-01

Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centred reactivity found at the active site of [NiFe] hydrogenases. Here, we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2 evolution (second-order rate constant of 2.5 × 104 M-1 s-1 turnover frequency of 250 s-1 at 10 mM H+ concentration) from mildly acidic solutions.

Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

Energy Technology Data Exchange (ETDEWEB)

Sode, Olaseni; Voth, Gregory A., E-mail: gavoth@uchicago.edu [Department of Chemistry, James Franck Institute, Institute for Biophysical Dynamics, Computation Institute, The University of Chicago, Chicago, Illinois 60637, USA and Computing, Environment and Life Sciences, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2014-12-14

Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A{sup 2−}, a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A{sup 2-} by closing a cavity that could otherwise fill with water near the proximal Fe of the active site.

Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

International Nuclear Information System (INIS)

Sode, Olaseni; Voth, Gregory A.

2014-01-01

Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A 2− , a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A 2- by closing a cavity that could otherwise fill with water near the proximal Fe of the active site

Redox reactions of [FeFe]-hydrogenase models containing an internal amine and a pendant phosphine.

Science.gov (United States)

Zheng, Dehua; Wang, Mei; Chen, Lin; Wang, Ning; Sun, Licheng

2014-02-03

A diiron dithiolate complex with a pendant phosphine coordinated to one of the iron centers, [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe2(CO)5}] (1), was prepared and structurally characterized. The pendant phosphine is dissociated together with a CO ligand in the presence of excess PMe3, to afford [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe(CO)2(PMe3)}2] (2). Redox reactions of 2 and related complexes were studied in detail by in situ IR spectroscopy. A series of new Fe(II)Fe(I) ([3](+) and [6](+)), Fe(II)Fe(II) ([4](2+)), and Fe(I)Fe(I) (5) complexes relevant to Hox, Hox(CO), and Hred states of the [FeFe]-hydrogenase active site were detected. Among these complexes, the molecular structures of the diferrous complex [4](2+) with the internal amine and the pendant phosphine co-coordinated to the same iron center and the triphosphine diiron complex 5 were determined by X-ray crystallography. To make a comparison, the redox reactions of an analogous complex, [(μ-SCH2)2N(CH2C6H5){Fe(CO)2(PMe3)}2] (7), were also investigated by in situ IR spectroscopy in the absence or presence of extrinsic PPh3, which has no influence on the oxidation reaction of 7. The pendant phosphine in the second coordination sphere makes the redox reaction of 2 different from that of its analogue 7.

CO-Bridged H-Cluster Intermediates in the Catalytic Mechanism of [FeFe]-Hydrogenase CaI.

Science.gov (United States)

Ratzloff, Michael W; Artz, Jacob H; Mulder, David W; Collins, Reuben T; Furtak, Thomas E; King, Paul W

2018-06-20

The [FeFe]-hydrogenases ([FeFe] H 2 ases) catalyze reversible H 2 activation at the H-cluster, which is composed of a [4Fe-4S] H subsite linked by a cysteine thiolate to a bridged, organometallic [2Fe-2S] ([2Fe] H ) subsite. Profoundly different geometric models of the H-cluster redox states that orchestrate the electron/proton transfer steps of H 2 bond activation have been proposed. We have examined this question in the [FeFe] H 2 ase I from Clostridium acetobutylicum (CaI) by Fourier-transform infrared (FTIR) spectroscopy with temperature annealing and H/D isotope exchange to identify the relevant redox states and define catalytic transitions. One-electron reduction of H ox led to formation of H red H + ([4Fe-4S] H 2+ -Fe I -Fe I ) and H red ' ([4Fe-4S] H 1+ -Fe II -Fe I ), with both states characterized by low frequency μ-CO IR modes consistent with a fully bridged [2Fe] H . Similar μ-CO IR modes were also identified for H red H + of the [FeFe] H 2 ase from Chlamydomonas reinhardtii (CrHydA1). The CaI proton-transfer variant C298S showed enrichment of an H/D isotope-sensitive μ-CO mode, a component of the hydride bound H-cluster IR signal, H hyd . Equilibrating CaI with increasing amounts of NaDT, and probed at cryogenic temperatures, showed H red H + was converted to H hyd . Over an increasing temperature range from 10 to 260 K catalytic turnover led to loss of H hyd and appearance of H ox , consistent with enzymatic turnover and H 2 formation. The results show for CaI that the μ-CO of [2Fe] H remains bridging for all of the "H red " states and that H red H + is on pathway to H hyd and H 2 evolution in the catalytic mechanism. These results provide a blueprint for designing small molecule catalytic analogs.

Krypton Derivatization of an O2 -Tolerant Membrane-Bound [NiFe] Hydrogenase Reveals a Hydrophobic Tunnel Network for Gas Transport.

Science.gov (United States)

Kalms, Jacqueline; Schmidt, Andrea; Frielingsdorf, Stefan; van der Linden, Peter; von Stetten, David; Lenz, Oliver; Carpentier, Philippe; Scheerer, Patrick

2016-04-25

[NiFe] hydrogenases are metalloenzymes catalyzing the reversible heterolytic cleavage of hydrogen into protons and electrons. Gas tunnels make the deeply buried active site accessible to substrates and inhibitors. Understanding the architecture and function of the tunnels is pivotal to modulating the feature of O2 tolerance in a subgroup of these [NiFe] hydrogenases, as they are interesting for developments in renewable energy technologies. Here we describe the crystal structure of the O2 -tolerant membrane-bound [NiFe] hydrogenase of Ralstonia eutropha (ReMBH), using krypton-pressurized crystals. The positions of the krypton atoms allow a comprehensive description of the tunnel network within the enzyme. A detailed overview of tunnel sizes, lengths, and routes is presented from tunnel calculations. A comparison of the ReMBH tunnel characteristics with crystal structures of other O2 -tolerant and O2 -sensitive [NiFe] hydrogenases revealed considerable differences in tunnel size and quantity between the two groups, which might be related to the striking feature of O2 tolerance. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Purification and characterization of [Fe]-hydrogenase from high yielding hydrogen-producing strain, Enterobacter cloacae IIT-BT08 (MTCC 5373)

Energy Technology Data Exchange (ETDEWEB)

Dutta, Tumpa; Das, Amit Kumar; Das, Debabrata [Department of Biotechnology, Indian Institute of Technology, Kharagpur, WB 721302 (India)

2009-09-15

Fe-hydrogenase from Enterobacter cloacae IIT-BT08 was purified 1284 fold with specific activity of 335 {mu}mol H{sub 2}/min/mg protein for hydrogen evolution using reduced methyl viologen as an electron-donor at 25 C. The molecular weight of the monomeric enzyme was determined to be 51 kDa by MALDI-ToF mass spectrometry. The PI of the enzyme was {proportional_to}5.6 displaying its acidic nature. The optimal temperature and pH for hydrogen evolution was 37 C and 7-7.2 respectively. The affinity constant, K{sub m} for reduced methyl viologen was 0.57 {+-} 0.03 mM and that of reduced ferredoxin was 0.72 {+-} 0.04 {mu}M. The enzyme contained {proportional_to}11.47 gm-atom Fe/mol of Fe-hydrogenase. Electron paramagnetic resonance analysis ascertained the existence of iron molecules as [4Fe-4S] clusters. The internal amino acid sequences of trypsin digested peptides of hydrogenase as determined by ESI MS/MS Q-ToF showed 80-87% identities with the respective sequences of Clostridium sp. and Trichomonas sp. hydrogenase. (author)

Designed Surface Residue Substitutions in [NiFe] Hydrogenase that Improve Electron Transfer Characteristics

Directory of Open Access Journals (Sweden)

Isaac T. Yonemoto

2015-01-01

Full Text Available Photobiological hydrogen production is an attractive, carbon-neutral means to convert solar energy to hydrogen. We build on previous research improving the Alteromonas macleodii “Deep Ecotype” [NiFe] hydrogenase, and report progress towards creating an artificial electron transfer pathway to supply the hydrogenase with electrons necessary for hydrogen production. Ferredoxin is the first soluble electron transfer mediator to receive high-energy electrons from photosystem I, and bears an electron with sufficient potential to efficiently reduce protons. Thus, we engineered a hydrogenase-ferredoxin fusion that also contained several other modifications. In addition to the C-terminal ferredoxin fusion, we truncated the C-terminus of the hydrogenase small subunit, identified as the available terminus closer to the electron transfer region. We also neutralized an anionic patch surrounding the interface Fe-S cluster to improve transfer kinetics with the negatively charged ferredoxin. Initial screening showed the enzyme tolerated both truncation and charge neutralization on the small subunit ferredoxin-binding face. While the enzyme activity was relatively unchanged using the substrate methyl viologen, we observed a marked improvement from both the ferredoxin fusion and surface modification using only dithionite as an electron donor. Combining ferredoxin fusion and surface charge modification showed progressively improved activity in an in vitro assay with purified enzyme.

[NiFe] hydrogenase structural and functional models: new bio-inspired catalysts for hydrogen evolution

International Nuclear Information System (INIS)

Oudart, Y.

2006-09-01

Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)

Heterologous expression of an algal hydrogenase in a heterocystous cyanobacterium

Energy Technology Data Exchange (ETDEWEB)

Thorsten Heidorn; Peter Lindblad [Dept. of Physiological Botany, Uppsala University, Villavogen 6, SE-752 36 Uppsala, (Sweden)

2006-07-01

For the expression of an active algal [FeFe] hydrogenase in the heterocystous cyanobacterium Nostoc punctiforme A TCC 29133 the Chlamydomonas reinhardtii hydrogenase gene hydA1 and the accessory genes hydEF and hydG are to be introduced into the cyanobacteria cells. The genes were amplified by PCR from EST clones, cloned into the cloning vector pBluescript SK+ and sequenced. An expression vector for multi-cistronic cloning, based on pSCR202, was constructed and for a functional test GFP was inserted as a reporter gene. The GFP construct was transformed into Nostoc punctiforme A TCC 29133 by electroporation and expression of GFP was visualized by fluorescence microscopy. (authors)

Heterologous expression of an algal hydrogenase in a heterocystous cyanobacterium

International Nuclear Information System (INIS)

Thorsten Heidorn; Peter Lindblad

2006-01-01

For the expression of an active algal [FeFe] hydrogenase in the heterocystous cyanobacterium Nostoc punctiforme A TCC 29133 the Chlamydomonas reinhardtii hydrogenase gene hydA1 and the accessory genes hydEF and hydG are to be introduced into the cyanobacteria cells. The genes were amplified by PCR from EST clones, cloned into the cloning vector pBluescript SK+ and sequenced. An expression vector for multi-cistronic cloning, based on pSCR202, was constructed and for a functional test GFP was inserted as a reporter gene. The GFP construct was transformed into Nostoc punctiforme A TCC 29133 by electroporation and expression of GFP was visualized by fluorescence microscopy. (authors)

Hydrogen-producing microflora and Fe-Fe hydrogenase diversities in seaweed bed associated with marine hot springs of Kalianda, Indonesia.

Science.gov (United States)

Xu, Shou-Ying; He, Pei-Qing; Dewi, Seswita-Zilda; Zhang, Xue-Lei; Ekowati, Chasanah; Liu, Tong-Jun; Huang, Xiao-Hang

2013-05-01

Microbial fermentation is a promising technology for hydrogen (H(2)) production. H(2) producers in marine geothermal environments are thermophilic and halotolerant. However, no one has surveyed an environment specifically for thermophilic bacteria that produce H(2) through Fe-Fe hydrogenases (H(2)ase). Using heterotrophic medium, several microflora from a seaweed bed associated with marine hot springs were enriched and analyzed for H(2) production. A H(2)-producing microflora was obtained from Sargassum sp., 16S rRNA genes and Fe-Fe H(2)ase diversities of this enrichment were also analyzed. Based on 16S rRNA genes analysis, 10 phylotypes were found in the H(2)-producing microflora showing 90.0-99.5 % identities to known species, and belonged to Clostridia, Gammaproteobacteria, and Bacillales. Clostridia were the most abundant group, and three Clostridia phylotypes were most related to known H(2) producers such as Anaerovorax odorimutans (94.0 % identity), Clostridium papyrosolvens (98.4 % identity), and Clostridium tepidiprofundi (93.1 % identity). For Fe-Fe H(2)ases, seven phylotypes were obtained, showing 63-97 % identities to known Fe-Fe H(2)ases, and fell into four distinct clusters. Phylotypes HW55-3 and HM55-1 belonged to thermophilic and salt-tolerant H(2)-producing Clostridia, Halothermothrix orenii-like Fe-Fe H(2)ases (80 % identity), and cellulolytic H(2)-producing Clostridia, C. papyrosolvens-like Fe-Fe H(2)ases (97 % identity), respectively. The results of both 16S rRNA genes and Fe-Fe H(2)ases surveys suggested that the thermophilic and halotolerant H(2)-producing microflora in seaweed bed of hot spring area represented previously unknown H(2) producers, and have potential application for H(2) production.

[NiFe] hydrogenase structural and functional models: new bio-inspired catalysts for hydrogen evolution; Modeles structuraux et fonctionnels du site actif des hydrogenases [NiFe]: de nouveaux catalyseurs bio-inspires pour la production d'hydrogene

Energy Technology Data Exchange (ETDEWEB)

Oudart, Y

2006-09-15

Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)

Heterologous expression of an algal hydrogenase in a hetero-cystous cyanobacterium

Energy Technology Data Exchange (ETDEWEB)

Thorsten Heidorn; Peter Lindblad [Dept. of Physiological Botany, Uppsala University, V illavagen 6, SE-752 36 Uppsala, (Sweden)

2006-07-01

For the expression of an active algal [FeFe] hydrogenase in the hetero-cystous cyanobacterium Nostoc punctiforme A TCC 29133 the Chlamydomonas reinhardtii hydrogenase gene hydA1 and the accessory genes hydEF and hydG are to be introduced into the cyano-bacterial cells. The genes were amplified by PCR from EST clones, cloned into the cloning vector pBluescript SK+ and sequenced. An expression vector for multi-cistronic cloning, based on pSCR202, was constructed and for a functional test GFP was inserted as a reporter gene. The GFP construct was transformed into Nostoc punctiforme A TCC 29133 by electroporation and expression of GFP was visualized by fluorescence microscopy. (authors)

Heterologous expression of an algal hydrogenase in a hetero-cystous cyanobacterium

International Nuclear Information System (INIS)

Thorsten Heidorn; Peter Lindblad

2006-01-01

For the expression of an active algal [FeFe] hydrogenase in the hetero-cystous cyanobacterium Nostoc punctiforme A TCC 29133 the Chlamydomonas reinhardtii hydrogenase gene hydA1 and the accessory genes hydEF and hydG are to be introduced into the cyano-bacterial cells. The genes were amplified by PCR from EST clones, cloned into the cloning vector pBluescript SK+ and sequenced. An expression vector for multi-cistronic cloning, based on pSCR202, was constructed and for a functional test GFP was inserted as a reporter gene. The GFP construct was transformed into Nostoc punctiforme A TCC 29133 by electroporation and expression of GFP was visualized by fluorescence microscopy. (authors)

[NiFe] hydrogenase structural and functional models: new bio-inspired catalysts for hydrogen evolution; Modeles structuraux et fonctionnels du site actif des hydrogenases [NiFe]: de nouveaux catalyseurs bio-inspires pour la production d'hydrogene

Energy Technology Data Exchange (ETDEWEB)

Oudart, Y

2006-09-15

Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)

Disclosure of key stereoelectronic factors for efficient H2 binding and cleavage in the active site of [NiFe]-hydrogenases.

Science.gov (United States)

Bruschi, Maurizio; Tiberti, Matteo; Guerra, Alessandro; De Gioia, Luca

2014-02-05

A comparative analysis of a series of DFT models of [NiFe]-hydrogenases, ranging from minimal NiFe clusters to very large systems including both the first and second coordination sphere of the bimetallic cofactor, was carried out with the aim of unraveling which stereoelectronic properties of the active site of [NiFe]-hydrogenases are crucial for efficient H2 binding and cleavage. H2 binding to the Ni-SIa redox state is energetically favored (by 4.0 kcal mol(-1)) only when H2 binds to Ni, the NiFe metal cluster is in a low spin state, and the Ni cysteine ligands have a peculiar seesaw coordination geometry, which in the enzyme is stabilized by the protein environment. The influence of the Ni coordination geometry on the H2 binding affinity was then quantitatively evaluated and rationalized analyzing frontier molecular orbitals and populations. Several plausible reaction pathways leading to H2 cleavage were also studied. It turned out that a two-step pathway, where H2 cleavage takes place on the Ni-SIa redox state of the enzyme, is characterized by very low reaction barriers and favorable reaction energies. More importantly, the seesaw coordination geometry of Ni was found to be a key feature for facile H2 cleavage. The discovery of the crucial influence of the Ni coordination geometry on H2 binding and activation in the active site of [NiFe]-hydrogenases could be exploited in the design of novel biomimetic synthetic catalysts.

Hydrogen Activation by Biomimetic [NiFe]-Hydrogenase Model Containing Protected Cyanide Cofactors

Science.gov (United States)

Manor, Brian C.; Rauchfuss, Thomas B.

2013-01-01

Described are experiments that allow incorporation of cyanide cofactors and hydride substrate into active site models [NiFe]-hydrogenases (H2ases). Complexes of the type (CO)2(CN)2Fe(pdt)Ni(dxpe), (dxpe = dppe, 1; dxpe = dcpe, 2) bind the Lewis acid B(C6F5)3 (BArF3) to give the adducts (CO)2(CNBArF3)2Fe(pdt)Ni(dxpe), (1(BArF3)2, 2(BArF3)2). Upon decarbonylation using amine oxides, these adducts react with H2 to give hydrido derivatives Et4N[(CO)(CNBArF3)2Fe(H)(pdt)Ni(dxpe)], (dxpe = dppe, Et4N[H3(BArF3)2]; dxpe = dcpe, Et4N[H4(BArF3)2]). Crystallographic analysis shows that Et4N[H3(BArF3)2] generally resembles the active site of the enzyme in the reduced, hydride-containing states (Ni-C/R). The Fe-H…Ni center is unsymmetrical with rFe-H = 1.51(3) and rNi-H = 1.71(3) Å. Both crystallographic and 19F NMR analysis show that the CNBArF3− ligands occupy basal and apical sites. Unlike cationic Ni-Fe hydrides, [H3(BArF3)2]− and [H4(BArF3)2]− oxidize at mild potentials, near the Fc+/0 couple. Electrochemical measurements indicate that in the presence of base, [H3(BArF3)2]− catalyzes the oxidation of H2. NMR evidence indicates dihydrogen bonding between these anionic hydrides and ammonium salts, which is relevant to the mechanism of hydrogenogenesis. In the case of Et4N[H3(BArF3)2], strong acids such as HCl induce H2 release to give the chloride Et4N[(CO)(CNBArF3)2Fe(pdt)(Cl)Ni(dppe)]. PMID:23899049

Enzymatic and spectroscopic properties of a thermostable [NiFe]‑hydrogenase performing H2-driven NAD+-reduction in the presence of O2.

Science.gov (United States)

Preissler, Janina; Wahlefeld, Stefan; Lorent, Christian; Teutloff, Christian; Horch, Marius; Lauterbach, Lars; Cramer, Stephen P; Zebger, Ingo; Lenz, Oliver

2018-01-01

Biocatalysts that mediate the H 2 -dependent reduction of NAD + to NADH are attractive from both a fundamental and applied perspective. Here we present the first biochemical and spectroscopic characterization of an NAD + -reducing [NiFe]‑hydrogenase that sustains catalytic activity at high temperatures and in the presence of O 2 , which usually acts as an inhibitor. We isolated and sequenced the four structural genes, hoxFUYH, encoding the soluble NAD + -reducing [NiFe]‑hydrogenase (SH) from the thermophilic betaproteobacterium, Hydrogenophilus thermoluteolus TH-1 T (Ht). The HtSH was recombinantly overproduced in a hydrogenase-free mutant of the well-studied, H 2 -oxidizing betaproteobacterium Ralstonia eutropha H16 (Re). The enzyme was purified and characterized with various biochemical and spectroscopic techniques. Highest H 2 -mediated NAD + reduction activity was observed at 80°C and pH6.5, and catalytic activity was found to be sustained at low O 2 concentrations. Infrared spectroscopic analyses revealed a spectral pattern for as-isolated HtSH that is remarkably different from those of the closely related ReSH and other [NiFe]‑hydrogenases. This indicates an unusual configuration of the oxidized catalytic center in HtSH. Complementary electron paramagnetic resonance spectroscopic analyses revealed spectral signatures similar to related NAD + -reducing [NiFe]‑hydrogenases. This study lays the groundwork for structural and functional analyses of the HtSH as well as application of this enzyme for H 2 -driven cofactor recycling under oxic conditions at elevated temperatures. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural Mimics of the [Fe]-Hydrogenase: A Complete Set for Group VIII Metals.

Science.gov (United States)

Barik, Chandan Kr; Ganguly, Rakesh; Li, Yongxin; Leong, Weng Kee

2018-06-18

A set of structural mimics of the [Fe]-hydrogenase active site comprising all the group VIII metals, viz., [M(2-NHC(O)C 5 H 4 N)(CO) 2 (2-S-C 5 H 4 N)], has been synthesized. They exist as a mixture of isomers in solution, and the relative stability of the isomers depends on the nature of the metal and the substituent at the 6-position of the pyridine ligand.

Metagenomic and PCR-based diversity surveys of [FeFe]-hydrogenases combined with isolation of alkaliphilic hydrogen-producing bacteria from the serpentinite-hosted Prony hydrothermal field, New Caledonia

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Nan Mei

2016-08-01

Full Text Available High amounts of hydrogen are emitted in the serpentinite-hosted hydrothermal field of the Prony Bay (PHF, New Caledonia, where high-pH (~11, low-temperature (<40°C and low-salinity fluids are discharged in both intertidal and shallow submarine environments. In this study, we investigated the diversity and distribution of potentially hydrogen-producing bacteria in Prony hyperalkaline springs by using metagenomic analyses and different PCR-amplified DNA sequencing methods. The retrieved sequences of hydA genes, encoding the catalytic subunit of [FeFe]-hydrogenases and, used as a molecular marker of hydrogen-producing bacteria, were mainly related to those of Firmicutes and clustered into two distinct groups depending on sampling locations. Intertidal samples were dominated by new hydA sequences related to uncultured Firmicutes retrieved from paddy soils, while submarine samples were dominated by diverse hydA sequences affiliated with anaerobic and/or thermophilic submarine Firmicutes pertaining to the orders Thermoanaerobacterales or Clostridiales. The novelty and diversity of these [FeFe]-hydrogenases may reflect the unique environmental conditions prevailing in the PHF (i.e. high-pH, low-salt, mesothermic fluids. In addition, novel alkaliphilic hydrogen-producing Firmicutes (Clostridiales and Bacillales were successfully isolated from both intertidal and submarine PHF chimney samples. Both molecular and cultivation-based data demonstrated the ability of Firmicutes originating from serpentinite-hosted environments to produce hydrogen by fermentation, potentially contributing to the molecular hydrogen balance in situ.

Metagenomic and PCR-Based Diversity Surveys of [FeFe]-Hydrogenases Combined with Isolation of Alkaliphilic Hydrogen-Producing Bacteria from the Serpentinite-Hosted Prony Hydrothermal Field, New Caledonia.

Science.gov (United States)

Mei, Nan; Postec, Anne; Monnin, Christophe; Pelletier, Bernard; Payri, Claude E; Ménez, Bénédicte; Frouin, Eléonore; Ollivier, Bernard; Erauso, Gaël; Quéméneur, Marianne

2016-01-01

High amounts of hydrogen are emitted in the serpentinite-hosted hydrothermal field of the Prony Bay (PHF, New Caledonia), where high-pH (~11), low-temperature (< 40°C), and low-salinity fluids are discharged in both intertidal and shallow submarine environments. In this study, we investigated the diversity and distribution of potentially hydrogen-producing bacteria in Prony hyperalkaline springs by using metagenomic analyses and different PCR-amplified DNA sequencing methods. The retrieved sequences of hydA genes, encoding the catalytic subunit of [FeFe]-hydrogenases and, used as a molecular marker of hydrogen-producing bacteria, were mainly related to those of Firmicutes and clustered into two distinct groups depending on sampling locations. Intertidal samples were dominated by new hydA sequences related to uncultured Firmicutes retrieved from paddy soils, while submarine samples were dominated by diverse hydA sequences affiliated with anaerobic and/or thermophilic submarine Firmicutes pertaining to the orders Thermoanaerobacterales or Clostridiales. The novelty and diversity of these [FeFe]-hydrogenases may reflect the unique environmental conditions prevailing in the PHF (i.e., high-pH, low-salt, mesothermic fluids). In addition, novel alkaliphilic hydrogen-producing Firmicutes (Clostridiales and Bacillales) were successfully isolated from both intertidal and submarine PHF chimney samples. Both molecular and cultivation-based data demonstrated the ability of Firmicutes originating from serpentinite-hosted environments to produce hydrogen by fermentation, potentially contributing to the molecular hydrogen balance in situ.

Modelling the active site of NiFe hydrogenases: new catalysts for the electro-production of H2 and mechanistic studies

International Nuclear Information System (INIS)

Canaguier, S.

2009-01-01

NiFe hydrogenases are unique metalloenzymes that catalyze H + /H 2 interconversion with remarkable efficiency close to the thermodynamic potential. Their active site consists of a hetero-bimetallic complex containing a nickel ion in a sulphur-rich environment connected by two thiolate bridges to an organometallic cyano-carbonyl iron moiety. In order to improve the understanding of the enzymatic mechanism and to obtain new base-metal electrocatalysts for H 2 production, we synthesized a series of bio-inspired low molecular weight model complexes with the butterfly structure Ni(μ-S 2 )M (M= Ru, Mn and Fe). All these compounds displayed a catalytic activity of hydrogen production. Modulating the electronic and steric properties of the ruthenium center allowed optimizing the catalytic performances of these compounds in terms of stability, catalytic rate and overpotential. Mechanistic studies of the catalytic cycle of the Ni-Ru complexes have also been carried out. They allowed us to suggest a bio-relevant bridging hydride as the catalytic intermediate. Finally, we synthesized one of the first Ni-Fe complexes that is both a structural and a functional model of NiFe hydrogenase. (author) [fr

Carbon monoxide and cyanide as intrinsic ligands to iron in the active site of [NiFe]-hydrogenases. NiFe(CN)2CO, biology's way to activate H2

NARCIS (Netherlands)

Pierik, A.J.; Roseboom, W.; Happe, R.P.; Bagley, K.A.; Albracht, S.P.J.

1999-01-01

Infrared-spectroscopic studies on the [NiFe]-hydrogenase of Chromatium vinosum-enriched in 15N or 13C, as well as chemical analyses, show that this enzyme contains three non-exchangeable, intrinsic, diatomic molecules as ligands to the active site, one carbon monoxide molecule and two cyanide

A density functional theory study on the active center of Fe-only hydrogenase: characterization and electronic structure of the redox states.

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Liu, Zhi-Pan; Hu, P

2002-05-08

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z)() (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fe(d) at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(I) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(I)-Fe(I) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride. Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(I) species, but cannot bond with the Fe(I)-Fe(I) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2 pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (i) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2 pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(I)-Fe(I) complexes; and (iii) in the e(g)-2 pi orbital

Multiscale Modeling of the Active Site of [Fe] Hydrogenase: The H2 Binding Site in Open and Closed Protein Conformations

DEFF Research Database (Denmark)

Hedegård, Erik D.; Kongsted, Jacob; Ryde, Ulf

2015-01-01

A series of QM/MM optimizations of the full protein of [Fe] hydrogenase were performed. The FeGP cofactor has been optimized in the water-bound resting state (1), with a side-on bound dihydrogen (2), or as a hydride intermediate (3). For inclusion of H4MPT in the closed structure, advanced multis...... that hydride transfer from 3 has a significantly higher barrier than found in previous studies neglecting the full protein environment....

Identification of an Isothiocyanate on the HypEF Complex Suggests a Route for Efficient Cyanyl-Group Channeling during [NiFe]-Hydrogenase Cofactor Generation.

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Sven T Stripp

Full Text Available [NiFe]-hydrogenases catalyze uptake and evolution of H2 in a wide range of microorganisms. The enzyme is characterized by an inorganic nickel/ iron cofactor, the latter of which carries carbon monoxide and cyanide ligands. In vivo generation of these ligands requires a number of auxiliary proteins, the so-called Hyp family. Initially, HypF binds and activates the precursor metabolite carbamoyl phosphate. HypF catalyzes removal of phosphate and transfers the carbamate group to HypE. In an ATP-dependent condensation reaction, the C-terminal cysteinyl residue of HypE is modified to what has been interpreted as thiocyanate. This group is the direct precursor of the cyanide ligands of the [NiFe]-hydrogenase active site cofactor. We present a FT-IR analysis of HypE and HypF as isolated from E. coli. We follow the HypF-catalyzed cyanation of HypE in vitro and screen for the influence of carbamoyl phosphate and ATP. To elucidate on the differences between HypE and the HypEF complex, spectro-electrochemistry was used to map the vibrational Stark effect of naturally cyanated HypE. The IR signature of HypE could ultimately be assigned to isothiocyanate (-N=C=S rather than thiocyanate (-S-C≡N. This has important implications for cyanyl-group channeling during [NiFe]-hydrogenase cofactor generation.

Molecular cloning, characterization, and overexpression of a novel [Fe]-hydrogenase isolated from a high rate of hydrogen producing Enterobacter cloacae IIT-BT 08

International Nuclear Information System (INIS)

Mishra, Jayshree; Khurana, Seema; Kumar, Narendra; Ghosh, Ananta K.; Das, Debabrata

2004-01-01

Degenerate primers were designed from the conserved zone of hydA structural gene encoding for catalytic subunit of [Fe]-hydrogenase of different hydrogen producing bacteria. A 750 bp of PCR product was amplified by using the above-mentioned degenerate primers and genomic DNA of Enterobacter cloacae IIT-BT 08 as template. The amplified PCR product was cloned and sequenced. The sequence showed the presence of an ORF of 450 bp with significant similarity (40%) with C-terminal end of the conserved zone (H-cluster) of [Fe]- hydrogenase. hydA ORF was then amplified and cloned in-frame with GST in pGEX4T-1 and overexpressed in a non-hydrogen producing Escherichia coli BL-21 to produce a GST-fusion protein of a calculated molecular mass of about 42.1 kDa. Recombinant protein was purified and specifically recognized by anti-GST monoclonal antibody through Western blot. Southern hybridization confirmed the presence of this gene in E. cloacae IIT-BT 08 genome. In vitro hydrogenase assay with the overexpressed hydrogenase enzyme showed that it is catalytically active upon anaerobic adaptation. In vivo hydrogenase assay confirmed the presence of H 2 gas in the gas mixture obtained from the batch culture of recombinant E. coli BL-21. A tentative molecular mechanism has been proposed about the transfer of electron from electron donor to H-cluster without the mediation of the F-cluster

Second coordination sphere effects in [FeFe]-Hydrogenase mimics

NARCIS (Netherlands)

Zaffaroni, R.

2017-01-01

Iron–iron hydrogenase are fascinating metallo‐enzymes able to reversibly perform interconversion between protons and dihydrogen with high rates at low overpotentials. Nevertheless, activity and stability of synthetic analogues without the protein matrix are rarely comparable to the enzyme. This

Presence and expression of hydrogenase specific C-terminal endopeptidases in cyanobacteria

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Lindblad Peter

2003-05-01

Full Text Available Abstract Background Hydrogenases catalyze the simplest of all chemical reactions: the reduction of protons to molecular hydrogen or vice versa. Cyanobacteria can express an uptake, a bidirectional or both NiFe-hydrogenases. Maturation of those depends on accessory proteins encoded by hyp-genes. The last maturation step involves the cleavage of a ca. 30 amino acid long peptide from the large subunit by a C-terminal endopeptidase. Until know, nothing is known about the maturation of cyanobacterial NiFe-hydrogenases. The availability of three complete cyanobacterial genome sequences from strains with either only the uptake (Nostoc punctiforme ATCC 29133/PCC 73102, only the bidirectional (Synechocystis PCC 6803 or both NiFe-hydrogenases (Anabaena PCC 7120 prompted us to mine these genomes for hydrogenase maturation related genes. In this communication we focus on the presence and the expression of the NiFe-hydrogenases and the corresponding C-terminal endopeptidases, in the three strains mentioned above. Results We identified genes encoding putative cyanobacterial hydrogenase specific C-terminal endopeptidases in all analyzed cyanobacterial genomes. The genes are not part of any known hydrogenase related gene cluster. The derived amino acid sequences show only low similarity (28–41% to the well-analyzed hydrogenase specific C-terminal endopeptidase HybD from Escherichia coli, the crystal structure of which is known. However, computational secondary and tertiary structure modeling revealed the presence of conserved structural patterns around the highly conserved active site. Gene expression analysis shows that the endopeptidase encoding genes are expressed under both nitrogen-fixing and non-nitrogen-fixing conditions. Conclusion Anabaena PCC 7120 possesses two NiFe-hydrogenases and two hydrogenase specific C-terminal endopeptidases but only one set of hyp-genes. Thus, in contrast to the Hyp-proteins, the C-terminal endopeptidases are the only known

Chemistry and the iron - only hydrogenase

International Nuclear Information System (INIS)

Tard, C.; Razavet, M.; Liu, X.; Ibrahim, S.; Pickett, Ch.

2005-01-01

Complete text of publication follows: Chemistry related to the hydrogenases is developing very rapidly and providing some informative insights into how the biological systems might function. Although still very much at a blue skies stage, there is some prospect for the design of artificial assemblies, materials and devices with technological application for hydrogen production/uptake provided robust system can be designed with low over potentials for hydrogen/proton interconversion (1). The iron-only hydrogenase possesses a peculiar di-iron unit coordinated by CO and CN, ligands which are normally associated with poisoning biological function. This sub-site unit is attached to a [4Fe4S] cubane center to form the catalytic site of the hydrogenase which is known as the 'H-cluster'. The synthesis of artificial sub-sites will first be described together with how their structures, spectroscopy and reactivity provides some key insights into the natural system viz. unprecedented bridging carbonyl and Fe(I) motifs in biology (2-4). How we have approached putting together the entire iron-sulfur framework of the H-cluster will then be described together with its electron-transfer and electrocatalytic properties (4). Finally, I will describe some early work on how we are beginning to incorporate structural motifs of the active-site into conducting polymer matrices, how they function as (albeit poor) electrocatalysts for hydrogen evolution, and where we see the way ahead. (1)The Chemistry and the Hydrogenases. D.J. Evans and C.J. Pickett, Chem. Soc. Rev., 32, 268-275, 2003; (2)Electron-Transfer at a Di-thiolate-Bridged Di-Iron Assembly; Electrocatalytic Hydrogen Evolution. S.J. Borg, T. Behrsing and S.P. Best, M. Ravazet, X. Liu and C.J. Pickett, J Amer. Chem. Soc., 2004, 126, 509-533; (3) Dissecting the intimate mechanism of cyanation of [Fe2S3] complexes related to the active site of all-iron hydrogenases by DFT analysis of energetics, transition states, intermediates and

Single-Amino Acid Modifications Reveal Additional Controls on the Proton Pathway of [FeFe]-Hydrogenase

Energy Technology Data Exchange (ETDEWEB)

Cornish, Adam J.; Ginovska, Bojana; Thelen, Adam; da Silva, Julio C. S.; Soares, Thereza A.; Raugei, Simone; Dupuis, Michel; Shaw, Wendy J.; Hegg, Eric L.

2016-06-07

The proton pathway of [FeFe]-hydrogenase is essential for enzymatic H2 production and oxidation and is composed of four residues and a modeled water molecule. Recently, a computational analysis of this pathway revealed that the solvent-exposed residue of the pathway (Glu282) could form hydrogen bonds to two residues outside of the pathway (Arg286 and Ser320), implicating that these residues could function in regulating proton transfer. Substituting Arg286 with leucine eliminates hydrogen bonding with Glu282 and results in a 2.5-fold enhancement in H2 production activity, suggesting that Arg286 serves an important role in controlling the rate of proton delivery. In contrast, substitution of Ser320 with alanine reduces the rate approximately 5-fold, implying that it either acts as a member of the pathway or influences Glu282 to enable proton transfer. Interestingly, QM/MM and molecular dynamics calculations indicate that Ser320 does not play an electronic or structural role. QM calculations also estimate that including Ser320 in the pathway does not significantly change the barrier to proton movement, providing further support for its role as a member of the proton pathway. While further studies are needed to quantify the role of Ser320, collectively, these data provide evidence that the enzyme scaffold plays a significant role in modulating the activity of the enzyme, demonstrating that the rate of intraprotein proton transfer can be accelerated, particularly in a non-biological context. This work was supported by the DOE Great Lakes Bioenergy Research Center (DOE BER Office of Science, DE-FC02-07ER64494). In addition, support from the DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences (WJS, BGP, SR) is gratefully acknowledged. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of

Improved production of biohydrogen in light-powered Escherichia coli by co-expression of proteorhodopsin and heterologous hydrogenase

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Kim Jaoon YH

2012-01-01

Full Text Available Abstract Background Solar energy is the ultimate energy source on the Earth. The conversion of solar energy into fuels and energy sources can be an ideal solution to address energy problems. The recent discovery of proteorhodopsin in uncultured marine γ-proteobacteria has made it possible to construct recombinant Escherichia coli with the function of light-driven proton pumps. Protons that translocate across membranes by proteorhodopsin generate a proton motive force for ATP synthesis by ATPase. Excess protons can also be substrates for hydrogen (H2 production by hydrogenase in the periplasmic space. In the present work, we investigated the effect of the co-expression of proteorhodopsin and hydrogenase on H2 production yield under light conditions. Results Recombinant E. coli BL21(DE3 co-expressing proteorhodopsin and [NiFe]-hydrogenase from Hydrogenovibrio marinus produced ~1.3-fold more H2 in the presence of exogenous retinal than in the absence of retinal under light conditions (70 μmole photon/(m2·s. We also observed the synergistic effect of proteorhodopsin with endogenous retinal on H2 production (~1.3-fold more with a dual plasmid system compared to the strain with a single plasmid for the sole expression of hydrogenase. The increase of light intensity from 70 to 130 μmole photon/(m2·s led to an increase (~1.8-fold in H2 production from 287.3 to 525.7 mL H2/L-culture in the culture of recombinant E. coli co-expressing hydrogenase and proteorhodopsin in conjunction with endogenous retinal. The conversion efficiency of light energy to H2 achieved in this study was ~3.4%. Conclusion Here, we report for the first time the potential application of proteorhodopsin for the production of biohydrogen, a promising alternative fuel. We showed that H2 production was enhanced by the co-expression of proteorhodopsin and [NiFe]-hydrogenase in recombinant E. coli BL21(DE3 in a light intensity-dependent manner. These results demonstrate that E. coli

Molecular biology of microbial hydrogenases.

Science.gov (United States)

Vignais, P M; Colbeau, A

2004-07-01

Hydrogenases (H2ases) are metalloproteins. The great majority of them contain iron-sulfur clusters and two metal atoms at their active center, either a Ni and an Fe atom, the [NiFe]-H2ases, or two Fe atoms, the [FeFe]-H2ases. Enzymes of these two classes catalyze the reversible oxidation of hydrogen gas (H2 2 H+ + 2 e-) and play a central role in microbial energy metabolism; in addition to their role in fermentation and H2 respiration, H2ases may interact with membrane-bound electron transport systems in order to maintain redox poise, particularly in some photosynthetic microorganisms such as cyanobacteria. Recent work has revealed that some H2ases, by acting as H2-sensors, participate in the regulation of gene expression and that H2-evolving H2ases, thought to be involved in purely fermentative processes, play a role in membrane-linked energy conservation through the generation of a protonmotive force. The Hmd hydrogenases of some methanogenic archaea constitute a third class of H2ases, characterized by the absence of Fe-S cluster and the presence of an iron-containing cofactor with catalytic properties different from those of [NiFe]- and [FeFe]-H2ases. In this review, we emphasise recent advances that have greatly increased our knowledge of microbial H2ases, their diversity, the structure of their active site, how the metallocenters are synthesized and assembled, how they function, how the synthesis of these enzymes is controlled by external signals, and their potential use in biological H2 production.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases

OpenAIRE

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-01-01

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the c...

Isolation and characterization of the small subunit of the uptake hydrogenase from the cyanobacterium Nostoc punctiforme.

Science.gov (United States)

Raleiras, Patrícia; Kellers, Petra; Lindblad, Peter; Styring, Stenbjörn; Magnuson, Ann

2013-06-21

In nitrogen-fixing cyanobacteria, hydrogen evolution is associated with hydrogenases and nitrogenase, making these enzymes interesting targets for genetic engineering aimed at increased hydrogen production. Nostoc punctiforme ATCC 29133 is a filamentous cyanobacterium that expresses the uptake hydrogenase HupSL in heterocysts under nitrogen-fixing conditions. Little is known about the structural and biophysical properties of HupSL. The small subunit, HupS, has been postulated to contain three iron-sulfur clusters, but the details regarding their nature have been unclear due to unusual cluster binding motifs in the amino acid sequence. We now report the cloning and heterologous expression of Nostoc punctiforme HupS as a fusion protein, f-HupS. We have characterized the anaerobically purified protein by UV-visible and EPR spectroscopies. Our results show that f-HupS contains three iron-sulfur clusters. UV-visible absorption of f-HupS has bands ∼340 and 420 nm, typical for iron-sulfur clusters. The EPR spectrum of the oxidized f-HupS shows a narrow g = 2.023 resonance, characteristic of a low-spin (S = ½) [3Fe-4S] cluster. The reduced f-HupS presents complex EPR spectra with overlapping resonances centered on g = 1.94, g = 1.91, and g = 1.88, typical of low-spin (S = ½) [4Fe-4S] clusters. Analysis of the spectroscopic data allowed us to distinguish between two species attributable to two distinct [4Fe-4S] clusters, in addition to the [3Fe-4S] cluster. This indicates that f-HupS binds [4Fe-4S] clusters despite the presence of unusual coordinating amino acids. Furthermore, our expression and purification of what seems to be an intact HupS protein allows future studies on the significance of ligand nature on redox properties of the iron-sulfur clusters of HupS.

Catalytic Properties of the Isolated Diaphorase Fragment of the NAD+-Reducing [NiFe]-Hydrogenase from Ralstonia eutropha

Science.gov (United States)

Lauterbach, Lars; Idris, Zulkifli; Vincent, Kylie A.; Lenz, Oliver

2011-01-01

The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha H16 catalyzes the H2-driven reduction of NAD+, as well as reverse electron transfer from NADH to H+, in the presence of O2. It comprises six subunits, HoxHYFUI2, and incorporates a [NiFe] H+/H2 cycling catalytic centre, two non-covalently bound flavin mononucleotide (FMN) groups and an iron-sulfur cluster relay for electron transfer. This study provides the first characterization of the diaphorase sub-complex made up of HoxF and HoxU. Sequence comparisons with the closely related peripheral subunits of Complex I in combination with UV/Vis spectroscopy and the quantification of the metal and FMN content revealed that HoxFU accommodates a [2Fe2S] cluster, FMN and a series of [4Fe4S] clusters. Protein film electrochemistry (PFE) experiments show clear electrocatalytic activity for both NAD+ reduction and NADH oxidation with minimal overpotential relative to the potential of the NAD+/NADH couple. Michaelis-Menten constants of 56 µM and 197 µM were determined for NADH and NAD+, respectively. Catalysis in both directions is product inhibited with K I values of around 0.2 mM. In PFE experiments, the electrocatalytic current was unaffected by O2, however in aerobic solution assays, a moderate superoxide production rate of 54 nmol per mg of protein was observed, meaning that the formation of reactive oxygen species (ROS) observed for the native SH can be attributed mainly to HoxFU. The results are discussed in terms of their implications for aerobic functioning of the SH and possible control mechanism for the direction of catalysis. PMID:22016788

Photoinduced reduction of the medial FeS center in the hydrogenase small subunit HupS from Nostoc punctiforme.

Science.gov (United States)

Raleiras, Patrícia; Hammarström, Leif; Lindblad, Peter; Styring, Stenbjörn; Magnuson, Ann

2015-07-01

The small subunit from the NiFe uptake hydrogenase, HupSL, in the cyanobacterium Nostoc punctiforme ATCC 29133, has been isolated in the absence of the large subunit (P. Raleiras, P. Kellers, P. Lindblad, S. Styring, A. Magnuson, J. Biol. Chem. 288 (2013) 18,345-18,352). Here, we have used flash photolysis to reduce the iron-sulfur clusters in the isolated small subunit, HupS. We used ascorbate as electron donor to the photogenerated excited state of Ru(II)-trisbipyridine (Ru(bpy)3), to generate Ru(I)(bpy)3 as reducing agent. Our results show that the isolated small subunit can be reduced by the Ru(I)(bpy)3 generated through flash photolysis. Copyright © 2015 Elsevier Inc. All rights reserved.

A novel endo-hydrogenase activity recycles hydrogen produced by nitrogen fixation.

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Gordon Ng

Full Text Available BACKGROUND: Nitrogen (N(2 fixation also yields hydrogen (H(2 at 1:1 stoichiometric amounts. In aerobic diazotrophic (able to grow on N(2 as sole N-source bacteria, orthodox respiratory hupSL-encoded hydrogenase activity, associated with the cell membrane but facing the periplasm (exo-hydrogenase, has nevertheless been presumed responsible for recycling such endogenous hydrogen. METHODS AND FINDINGS: As shown here, for Azorhizobium caulinodans diazotrophic cultures open to the atmosphere, exo-hydrogenase activity is of no consequence to hydrogen recycling. In a bioinformatic analysis, a novel seven-gene A. caulinodans hyq cluster encoding an integral-membrane, group-4, Ni,Fe-hydrogenase with homology to respiratory complex I (NADH: quinone dehydrogenase was identified. By analogy, Hyq hydrogenase is also integral to the cell membrane, but its active site faces the cytoplasm (endo-hydrogenase. An A. caulinodans in-frame hyq operon deletion mutant, constructed by "crossover PCR", showed markedly decreased growth rates in diazotrophic cultures; normal growth was restored with added ammonium--as expected of an H(2-recycling mutant phenotype. Using A. caulinodans hyq merodiploid strains expressing beta-glucuronidase as promoter-reporter, the hyq operon proved strongly and specifically induced in diazotrophic culture; as well, hyq operon induction required the NIFA transcriptional activator. Therefore, the hyq operon is constituent of the nif regulon. CONCLUSIONS: Representative of aerobic N(2-fixing and H(2-recycling alpha-proteobacteria, A. caulinodans possesses two respiratory Ni,Fe-hydrogenases: HupSL exo-hydrogenase activity drives exogenous H(2 respiration, and Hyq endo-hydrogenase activity recycles endogenous H(2, specifically that produced by N(2 fixation. To benefit human civilization, H(2 has generated considerable interest as potential renewable energy source as its makings are ubiquitous and its combustion yields no greenhouse gases. As

A novel endo-hydrogenase activity recycles hydrogen produced by nitrogen fixation.

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Ng, Gordon; Tom, Curtis G S; Park, Angela S; Zenad, Lounis; Ludwig, Robert A

2009-01-01

Nitrogen (N(2)) fixation also yields hydrogen (H(2)) at 1:1 stoichiometric amounts. In aerobic diazotrophic (able to grow on N(2) as sole N-source) bacteria, orthodox respiratory hupSL-encoded hydrogenase activity, associated with the cell membrane but facing the periplasm (exo-hydrogenase), has nevertheless been presumed responsible for recycling such endogenous hydrogen. As shown here, for Azorhizobium caulinodans diazotrophic cultures open to the atmosphere, exo-hydrogenase activity is of no consequence to hydrogen recycling. In a bioinformatic analysis, a novel seven-gene A. caulinodans hyq cluster encoding an integral-membrane, group-4, Ni,Fe-hydrogenase with homology to respiratory complex I (NADH: quinone dehydrogenase) was identified. By analogy, Hyq hydrogenase is also integral to the cell membrane, but its active site faces the cytoplasm (endo-hydrogenase). An A. caulinodans in-frame hyq operon deletion mutant, constructed by "crossover PCR", showed markedly decreased growth rates in diazotrophic cultures; normal growth was restored with added ammonium--as expected of an H(2)-recycling mutant phenotype. Using A. caulinodans hyq merodiploid strains expressing beta-glucuronidase as promoter-reporter, the hyq operon proved strongly and specifically induced in diazotrophic culture; as well, hyq operon induction required the NIFA transcriptional activator. Therefore, the hyq operon is constituent of the nif regulon. Representative of aerobic N(2)-fixing and H(2)-recycling alpha-proteobacteria, A. caulinodans possesses two respiratory Ni,Fe-hydrogenases: HupSL exo-hydrogenase activity drives exogenous H(2) respiration, and Hyq endo-hydrogenase activity recycles endogenous H(2), specifically that produced by N(2) fixation. To benefit human civilization, H(2) has generated considerable interest as potential renewable energy source as its makings are ubiquitous and its combustion yields no greenhouse gases. As such, the reversible, group-4 Ni,Fe-hydrogenases, such

New hypotheses for hydrogenase implication in the corrosion of mild steel

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Mehanna, Maha; Basseguy, Regine; Delia, Marie-Line [Laboratoire de Genie Chimique (LGC) CNRS-INPT, 5 rue Paulin Talabot BP 1301, 31106 Toulouse (France); Girbal, Laurence; Demuez, Marie [Laboratoire d' Ingenierie des Systemes Biologiques et des Procedes (LISBP) CNRS-INSA, 135 Avenue de Rangueil, 31077 Toulouse (France); Bergel, Alain [Laboratoire de Genie Chimique (LGC) CNRS-INPT, 5 rue Paulin Talabot BP 1301, 31106 Toulouse (France)], E-mail: Alain.Bergel@ensiacet.fr

2008-12-01

The influence of [Fe]-hydrogenase from Clostridium acetobutylicum was studied on the anaerobic corrosion of mild steel. Two short-circuited mild steel electrodes were exposed to the same solution and hydrogenase was retained on the surface of only one electrode thanks to a dialysis membrane. The galvanic current and the electrode potential were measured as a function of time in order to monitor the difference in electrochemical behaviour induced by the presence of hydrogenase. A sharp potential decrease of around 500 mV was controlled by the deoxygenating phase. When hydrogenase was introduced after complete deoxygenation, significant heterogeneous corrosion was observed under the vivianite deposit on the electrode in contact with hydrogenase, while the other electrode only showed the vivianite deposit, which was analysed by MEB and EDX. The effect of hydrogenase was then confirmed by monitoring the free potential of single coupons exposed or not to the enzyme in a classical cell after complete deoxygenating. In both phosphate and Tris-HCl buffers, the presence of hydrogenase increased the free potential around 60 mV and induced marked general corrosion. It was concluded that [Fe]-hydrogenase acts in the absence of any final electron acceptor by catalysing direct proton reduction on the mild steel surface.

New hypotheses for hydrogenase implication in the corrosion of mild steel

International Nuclear Information System (INIS)

Mehanna, Maha; Basseguy, Regine; Delia, Marie-Line; Girbal, Laurence; Demuez, Marie; Bergel, Alain

2008-01-01

The influence of [Fe]-hydrogenase from Clostridium acetobutylicum was studied on the anaerobic corrosion of mild steel. Two short-circuited mild steel electrodes were exposed to the same solution and hydrogenase was retained on the surface of only one electrode thanks to a dialysis membrane. The galvanic current and the electrode potential were measured as a function of time in order to monitor the difference in electrochemical behaviour induced by the presence of hydrogenase. A sharp potential decrease of around 500 mV was controlled by the deoxygenating phase. When hydrogenase was introduced after complete deoxygenation, significant heterogeneous corrosion was observed under the vivianite deposit on the electrode in contact with hydrogenase, while the other electrode only showed the vivianite deposit, which was analysed by MEB and EDX. The effect of hydrogenase was then confirmed by monitoring the free potential of single coupons exposed or not to the enzyme in a classical cell after complete deoxygenating. In both phosphate and Tris-HCl buffers, the presence of hydrogenase increased the free potential around 60 mV and induced marked general corrosion. It was concluded that [Fe]-hydrogenase acts in the absence of any final electron acceptor by catalysing direct proton reduction on the mild steel surface

Magnetic Properties and Microstructure of FeOx/Fe/FePt and FeOx/FePt Films

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Jai-Lin Tsai

2013-01-01

Full Text Available The Fe(6 nm/FePt film with perpendicular magnetization was deposited on the glass substrate. To study the oxygen diffusion effect on the coupling of Fe/FePt bilayer, the plasma oxidation with 0.5~7% oxygen flow ratio was performed during sputtered part of Fe layer and formed the FeOx(3 nm/Fe(3 nm/FePt trilayer. Two-step magnetic hysteresis loops were found in trilayer with oxygen flow ratio above 1%. The magnetization in FeOx and Fe/FePt layers was decoupled. The moments in FeOx layer were first reversed and followed by coupled Fe/FePt bilayer. The trilayer was annealed again at 500°C and 800°C for 3 minutes. When the FeOx(3 nm/Fe(3 nm/FePt trilayer was annealed at 500°C, the layers structure was changed to FeOx(6 nm/FePt bilayer due to oxygen diffusion. The hard-magnetic FeOx(6 nm/FePt film was coupled with single switching field. The FeOx/(disordered FePt layer structure was observed with further annealing at 800°C and presented soft-magnetic loop. In summary, the coupling between soft-magnetic Fe, FeOx layer, and hard-magnetic L10 FePt layer can be controlled by the oxygen diffusion behavior, and the oxidation of Fe layer was tuned by the annealing temperature. The ordered L10 FePt layer was deteriorated by oxygen and became disordered FePt when the annealed temperature was up to 800°C.

Cyanobacterial Hydrogenases and Hydrogen Metabolism Revisited: Recent Progress and Future Prospects

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Namita Khanna

2015-05-01

Full Text Available Cyanobacteria have garnered interest as potential cell factories for hydrogen production. In conjunction with photosynthesis, these organisms can utilize inexpensive inorganic substrates and solar energy for simultaneous biosynthesis and hydrogen evolution. However, the hydrogen yield associated with these organisms remains far too low to compete with the existing chemical processes. Our limited understanding of the cellular hydrogen production pathway is a primary setback in the potential scale-up of this process. In this regard, the present review discusses the recent insight around ferredoxin/flavodoxin as the likely electron donor to the bidirectional Hox hydrogenase instead of the generally accepted NAD(PH. This may have far reaching implications in powering solar driven hydrogen production. However, it is evident that a successful hydrogen-producing candidate would likely integrate enzymatic traits from different species. Engineering the [NiFe] hydrogenases for optimal catalytic efficiency or expression of a high turnover [FeFe] hydrogenase in these photo-autotrophs may facilitate the development of strains to reach target levels of biohydrogen production in cyanobacteria. The fundamental advancements achieved in these fields are also summarized in this review.

Structural and gene expression analyses of uptake hydrogenases ...

Indian Academy of Sciences (India)

2013-10-01

Oct 1, 2013 ... subunits resemble the structures of known [NiFe] hydrogenases (Volbeda et al. 1995) ..... abundant lipid in Frankia cells and in nitrogen-fixing nodule tissue. .... Vignais PM and Billoud B 2007 Occurrence, classification, and.

Hydrogen evolution in [NiFe] hydrogenases and related biomimetic systems: similarities and differences.

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Das, Ranjita; Neese, Frank; van Gastel, Maurice

2016-09-21

In this work, a detailed quantum chemical study of the mechanism of [Ni(bdt)(dppf)] (Ni(II)L) catalyzed hydrogen formation [A. Gan, T. L. Groy, P. Tarakeshwar, S. K. S. Mazinani, J. Shearer, V. Mujica and A. K. Jones, J. Am. Chem. Soc., 2015, 137, 1109-1115] following an electro-chemical-electro-chemical (ECEC) pathway is reported. The complex exclusively catalyzes the reduction of protons to molecular hydrogen. The calculations suggest that the first one-electron reduction of the [Ni(II)L] catalyst is the rate limiting step of the catalytic cycle and hence, the buildup of detectable reaction intermediates is not expected. The catalytic activity of the [Ni(II)L] complex is facilitated by the flexibility of the ligand system, which allows the ligand framework to adapt to changes in the Ni oxidation state over the course of the reaction. Additionally, a comparison is made with the catalytic activity of [NiFe] hydrogenase. It is argued that the directionality of the reversible hydrogen formation reaction is controlled by the ligand field of the nickel ion and the possibility for side-on (η(2)) binding of H2: if the ligand framework does not allow for η(2) binding of H2, as is the case for [Ni(II)L], the catalyst irreversibly reduces protons. If the ligand field allows η(2) binding of H2, the catalyst can in principle work reversibly. The conditions for η(2) binding are discussed.

Electrochemistry of metalloproteins: protein film electrochemistry for the study of E. coli [NiFe]-hydrogenase-1.

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Evans, Rhiannon M; Armstrong, Fraser A

2014-01-01

Protein film electrochemistry is a technique which allows the direct control of redox-active enzymes, providing particularly detailed information on their catalytic properties. The enzyme is deposited onto a working electrode tip, and through control of the applied potential the enzyme activity is monitored as electrical current, allowing for direct study of inherent activity as electrons are transferred to and from the enzyme redox center(s). No mediators are used. Because the only enzyme present in the experiment is bound at the electrode surface, gaseous and liquid phase inhibitors can be introduced and removed whilst the enzyme remains in situ. Potential control means that kinetics and thermodynamics are explored simultaneously; the kinetics of a reaction can be studied as a function of potential. Steady-state catalytic rates are observed directly as current (for a given potential) and non-steady-state rates (such as interconversions between different forms of the enzyme) are observed from the change in current with time. The more active the enzyme, the higher the current and the better the signal-to-noise. In this chapter we outline the practical aspects of PFE for studying electroactive enzymes, using the Escherichia coli [NiFe]-hydrogenase 1 (Hyd-1) as an example.

Purification and characterization of the hydrogen uptake hydrogenase from the hyperthermpholic archaebacterium Pyrodictium brockii

International Nuclear Information System (INIS)

Pihl, T.D.; Maier, R.J.

1991-01-01

Pyrodictium brockii is a hyperthermophilic archaebacterium with an optimal growth temperature of 105C. P. brokii is also a chemolithotroph, requiring H 2 and CO 2 for growth. The authors have purified the hydrogen uptake hydrogenase from membranes of P. brockii by reactive red affinity chromatography and sucrose gradient centrifugation. Colorometric analysis of Fe and S content in reactive red-purified hydrogenase revealed 8.7 ± 0.6 mol of Fe and 6.2 ± 1.2 mol of S per mol of hydrogenase. Growth of cells in 63 NiCl 2 resulted in label incorporation into reactive red-purified hydrogenase. Temperature stability studies indicated that the membrane-bound form of the enzyme was more stable than the solubilized purified form over a period of minutes with respect to temperature. However, the membranes were not able to protect the enzyme from thermal inactivation over a period of hours. The artificial electron acceptor specificity of the pure enzyme was similar to that of the membrane-bound form, but the purified enzyme was able to evolve H 2 in the presence of reduced methyl viologen. The K m of membrane-bound hydrogenase for H 2 was approximately 19 μM with methylene blue as the electron acceptor, whereas the purified enzyme had a higher K m value

Is engineering O{sub 2}-tolerant hydrogenases just a matter of reproducing the active sites of the naturally occurring O{sub 2}-resistant enzymes?

Energy Technology Data Exchange (ETDEWEB)

Leroux, Fanny; Liebgott, Pierre-Pol; Kpebe, Arlette; Leger, Christophe; Rousset, Marc; Dementin, Sebastien [CNRS, Laboratoire de Bioenergetique et Ingenierie des Proteines, Institut de Microbiologie de la Mediterranee, 31 chemin Joseph Aiguier, 13402 Marseille Cedex 20 (France); Cournac, Laurent; Richaud, Pierre [CEA, DSV, IBEB, Laboratoire de Bioenergetique et Biotechnologie des Bacteries et Microalgues, 13108 Saint-Paul-lez-Durance (France); Aix-Marseille Universite, 3 place Victor-Hugo, 13331 Marseille (France); CNRS, UMR Biologie Vegetale et Microbiologie Environnementales, 13108 Saint-Paul-lez-Durance (France); Burlat, Benedicte; Guigliarelli, Bruno; Bertrand, Patrick [CNRS, Laboratoire de Bioenergetique et Ingenierie des Proteines, Institut de Microbiologie de la Mediterranee, 31 chemin Joseph Aiguier, 13402 Marseille Cedex 20 (France); Aix-Marseille Universite, 3 place Victor-Hugo, 13331 Marseille (France)

2010-10-15

Reproducing the naturally occurring O{sub 2}-tolerant hydrogenases is a potential strategy to make the oxygen sensitive enzymes, produced by organisms of biotechnological interest, more resistant. The search for resistance ''hotspots'' that could be transposed into sensitive hydrogenases is underway. Here, we replaced two residues (Y77 and V78) of the oxygen sensitive [NiFe] hydrogenase from Desulfovibrio fructosovorans with Gly and with Cys, respectively, to copy the active site pocket of the resistant membrane-bound [NiFe] enzyme from Ralstonia eutropha and we examined how this affected oxygen sensitivity. The results are discussed in the light of a short review of the recent results dealing with the reactivity of hydrogenases towards oxygen. (author)

HupW Protease Specifically Required for Processing of the Catalytic Subunit of the Uptake Hydrogenase in the Cyanobacterium Nostoc sp. Strain PCC 7120

Science.gov (United States)

Lindberg, Pia; Devine, Ellenor; Stensjö, Karin

2012-01-01

The maturation process of [NiFe] hydrogenases includes a proteolytic cleavage of the large subunit. We constructed a mutant of Nostoc strain PCC 7120 in which hupW, encoding a putative hydrogenase-specific protease, is inactivated. Our results indicate that the protein product of hupW selectively cleaves the uptake hydrogenase in this cyanobacterium. PMID:22020512

Diversity and transcription of proteases involved in the maturation of hydrogenases in Nostoc punctiforme ATCC 29133 and Nostoc sp. strain PCC 7120

Science.gov (United States)

2009-01-01

Background The last step in the maturation process of the large subunit of [NiFe]-hydrogenases is a proteolytic cleavage of the C-terminal by a hydrogenase specific protease. Contrary to other accessory proteins these hydrogenase proteases are believed to be specific whereby one type of hydrogenases specific protease only cleaves one type of hydrogenase. In cyanobacteria this is achieved by the gene product of either hupW or hoxW, specific for the uptake or the bidirectional hydrogenase respectively. The filamentous cyanobacteria Nostoc punctiforme ATCC 29133 and Nostoc sp strain PCC 7120 may contain a single uptake hydrogenase or both an uptake and a bidirectional hydrogenase respectively. Results In order to examine these proteases in cyanobacteria, transcriptional analyses were performed of hupW in Nostoc punctiforme ATCC 29133 and hupW and hoxW in Nostoc sp. strain PCC 7120. These studies revealed numerous transcriptional start points together with putative binding sites for NtcA (hupW) and LexA (hoxW). In order to investigate the diversity and specificity among hydrogeanse specific proteases we constructed a phylogenetic tree which revealed several subgroups that showed a striking resemblance to the subgroups previously described for [NiFe]-hydrogenases. Additionally the proteases specificity was also addressed by amino acid sequence analysis and protein-protein docking experiments with 3D-models derived from bioinformatic studies. These studies revealed a so called "HOXBOX"; an amino acid sequence specific for protease of Hox-type which might be involved in docking with the large subunit of the hydrogenase. Conclusion Our findings suggest that the hydrogenase specific proteases are under similar regulatory control as the hydrogenases they cleave. The result from the phylogenetic study also indicates that the hydrogenase and the protease have co-evolved since ancient time and suggests that at least one major horizontal gene transfer has occurred. This co

Diversity and transcription of proteases involved in the maturation of hydrogenases in Nostoc punctiforme ATCC 29133 and Nostoc sp. strain PCC 7120

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Lindblad Peter

2009-03-01

Full Text Available Abstract Background The last step in the maturation process of the large subunit of [NiFe]-hydrogenases is a proteolytic cleavage of the C-terminal by a hydrogenase specific protease. Contrary to other accessory proteins these hydrogenase proteases are believed to be specific whereby one type of hydrogenases specific protease only cleaves one type of hydrogenase. In cyanobacteria this is achieved by the gene product of either hupW or hoxW, specific for the uptake or the bidirectional hydrogenase respectively. The filamentous cyanobacteria Nostoc punctiforme ATCC 29133 and Nostoc sp strain PCC 7120 may contain a single uptake hydrogenase or both an uptake and a bidirectional hydrogenase respectively. Results In order to examine these proteases in cyanobacteria, transcriptional analyses were performed of hupW in Nostoc punctiforme ATCC 29133 and hupW and hoxW in Nostoc sp. strain PCC 7120. These studies revealed numerous transcriptional start points together with putative binding sites for NtcA (hupW and LexA (hoxW. In order to investigate the diversity and specificity among hydrogeanse specific proteases we constructed a phylogenetic tree which revealed several subgroups that showed a striking resemblance to the subgroups previously described for [NiFe]-hydrogenases. Additionally the proteases specificity was also addressed by amino acid sequence analysis and protein-protein docking experiments with 3D-models derived from bioinformatic studies. These studies revealed a so called "HOXBOX"; an amino acid sequence specific for protease of Hox-type which might be involved in docking with the large subunit of the hydrogenase. Conclusion Our findings suggest that the hydrogenase specific proteases are under similar regulatory control as the hydrogenases they cleave. The result from the phylogenetic study also indicates that the hydrogenase and the protease have co-evolved since ancient time and suggests that at least one major horizontal gene transfer

Moessbauer-spectroscopic study of structure and magnetism of the exchange-coupled layer systems Fe/FeSn{sub 2}, and Fe/FeSi/Si and the ion-implanted diluted magnetic semiconductor SiC(Fe); Moessbauerspektroskopische Untersuchung von Struktur und Magnetismus der austauschgekoppelten Schichtsysteme Fe/FeSn{sub 2} und Fe/FeSi/Si und des ionenimplantierten verduennten magnetischen Halbleiters SiC(Fe)

Energy Technology Data Exchange (ETDEWEB)

Stromberg, Frank

2009-07-07

In line with this work the structural and magnetic properties of the exchange coupled layered systems Fe/FeSn{sub 2} and Fe/FeSi/Si and of the Fe ion implanted diluted magnetic semiconductor (DMS) SiC(Fe) were investigated. The main measuring method was the isotope selective {sup 57}Fe conversion electron Moessbauer spectroscopy (CEMS), mostly in connection with the {sup 57}Fe tracer layer technique, in a temperature range from 4.2 K to 340 K. Further measurement techniques were X-ray diffraction (XRD), electron diffraction (LEED, RHEED), SQUID magnetometry and FMR (Ferromagnetic Resonance). In the first part of this work the properties of thin AF FeSn{sub 2}(001) films and of the exchange-bias system Fe/FeSn{sub 2}(001) on InSb(001) were investigated. With the application of {sup 57}Fe-tracer layers and CEMS both the Fe-spin structure and the temperature dependence of the magnetic hyperfine field (B{sub hf}) of FeSn{sub 2} could be examined. The evaporation of Fe films on the FeSn{sub 2} films produced in the latter ones a high perpendicular spin component at the Fe/FeSn{sub 2} interface. In some distance from the interface the Fe spins rotate back into the sample plane. Furthermore {sup 57}Fe-CEMS provided a correlation between the absolute value of the exchange field vertical stroke He vertical stroke and the amount of magnetic defects within the FeSn{sub 2}. Temperature dependent CEMS-measurements yielded informations about the spin dynamics within the AF. The transition temperatures T{sub B}{sup *}, which were interpreted as superparamagnetic blocking temperatures, obtain higher values compared to the temperatures T{sub B} of the exchange-bias effect, obtained with magnetometry measurements. The second part of this work deals with the indirect exchange coupling within Fe/FeSi/Si/FeSi/Fe multilayers and FeSi diffusion barriers. The goal was to achieve Fe free Si interlayers. The CEMS results show that starting from a thickness of t{sub FeSi}=10-12 A of the

MFM study of NdFeB and NdFeB/Fe/NdFeB thin films

International Nuclear Information System (INIS)

Gouteff, P.C.; Folks, L.; Street, R.

1998-01-01

Domain structures of NdFeB thin films, ranging in thickness between 1500 and 29 nm, have been studied qualitatively by magnetic force microscopy (MFM). Samples were prepared using a range of sputtering conditions resulting in differences in properties such as texture, coercivity and magnetic saturation. MFM images of all the films showed extensive interaction domain structures, similar to those observed in nanocrystalline bulk NdFeB. An exchange-coupled NdFeB/Fe/NdFeB trilayer with layer thicknesses 18 nm/15 nm/18 nm, respectively, was also examined using MFM. (orig.)

Fundamental Studies of Recombinant Hydrogenases

Energy Technology Data Exchange (ETDEWEB)

Adams, Michael W. [Univ. of Georgia, Athens, GA (United States)

2014-01-25

This research addressed the long term goals of understanding the assembly and organization of hydrogenase enzymes, of reducing them in size and complexity, of determining structure/function relationships, including energy conservation via charge separation across membranes, and in screening for novel H2 catalysts. A key overall goal of the proposed research was to define and characterize minimal hydrogenases that are produced in high yields and are oxygen-resistant. Remarkably, in spite of decades of research carried out on hydrogenases, it is not possible to readily manipulate or design the enzyme using molecular biology approaches since a recombinant form produced in a suitable host is not available. Such resources are essential if we are to understand what constitutes a “minimal” hydrogenase and design such catalysts with certain properties, such as resistance to oxygen, extreme stability and specificity for a given electron donor. The model system for our studies is Pyrococcus furiosus, a hyperthermophile that grows optimally at 100°C, which contains three different nickel-iron [NiFe-] containing hydrogenases. Hydrogenases I and II are cytoplasmic while the other, MBH, is an integral membrane protein that functions to both evolve H2 and pump protons. Three important breakthroughs were made during the funding period with P. furiosus soluble hydrogenase I (SHI). First, we produced an active recombinant form of SHI in E. coli by the co-expression of sixteen genes using anaerobically-induced promoters. Second, we genetically-engineered P. furiosus to overexpress SHI by an order of magnitude compared to the wild type strain. Third, we generated the first ‘minimal’ form of SHI, one that contained two rather than four subunits. This dimeric form was stable and active, and directly interacted with a pyruvate-oxidizing enzyme with any intermediate electron carrier. The research resulted in five peer-reviewed publications.

Preparation and Mechanical Properties of TiC-Fe Cermets and TiC-Fe/Fe Bilayer Composites

Science.gov (United States)

Zheng, Yong; Zhou, Yang; Li, Runfeng; Wang, Jiaqi; Chen, Lulu; Li, Shibo

2017-10-01

TiC-Fe cermets and TiC-Fe/Fe bilayer composites consisting of a pure Fe layer and a TiC-Fe cermets layer were fabricated by hot-pressing sintering. The pure Fe layer contributes to the toughness of composites, and the TiC-Fe cermets layer endows the composites with an improved tensile strength and hardness. The effect of TiC contents (30-60 vol.%) on the mechanical properties of TiC-Fe cermets and TiC-Fe/Fe bilayer composites was investigated. Among the TiC-Fe cermets, the 40 vol.% TiC-Fe cermets possessed the highest tensile strength of 581 MPa and Vickers hardness of 5.1 GPa. The maximum fracture toughness of 17.0 MPa m1/2 was achieved for the TiC-Fe cermets with 30 vol.% TiC. For the TiC-Fe/Fe bilayer composites, the 40 vol.% TiC-Fe/Fe bilayer composite owns the maximum tensile strength of 588 MPa, which is higher than that of 40 vol.% TiC-Fe cermets. In addition, the 33.5% increment of tensile strength of 30 vol.% TiC-Fe/Fe bilayer composite comparing with the 30 vol.% TiC-Fe cermets, which is attributed to the 30 vol.% TiC-Fe/Fe bilayer composite exhibited the largest interlaminar shear strength of 335 MPa. The bilayer composites are expected to be used as wear resistance components in some heavy wear conditions.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

Science.gov (United States)

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-09-21

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

Fe atom exchange between aqueous Fe2+ and magnetite.

Science.gov (United States)

Gorski, Christopher A; Handler, Robert M; Beard, Brian L; Pasakarnis, Timothy; Johnson, Clark M; Scherer, Michelle M

2012-11-20

The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

The Moessbauer effect in Fe(III) HEDTA, Fe(III) EDTA, and Fe(III) CDTA compounds

International Nuclear Information System (INIS)

Prado, F.R.

1989-01-01

The dependence of Moessbauer spectra with pH value of Fe(III)HEDTA and Fe(III)CDTA compounds is studied. Informations on formation processes of LFe-O-FeL (L=ligand) type dimers by the relation of titration curves of Fe(III)EDTA, Fe(III)HEDTA and Fe(III)CDTA compounds with the series of Moessbauer spectra, are obtained. Some informations on Fe-O-Fe bond structure are also obtained. Comparing the titration curves with the series of Moessbauer spectra, it is concluded that the dimerization process begins when a specie of the form FeXOH α (X = EDTA, HEDTA, CDTA; α = -1, -2) arises. (M.C.K.) [pt

Effectiveness of FeEDDHA, FeEDDHMA, and FeHBED in Preventing Iron-Deficiency Chlorosis in Soybean.

Science.gov (United States)

Bin, Levi M; Weng, Liping; Bugter, Marcel H J

2016-11-09

The performance of FeHBED in preventing Fe deficiency chlorosis in soybean (Glycine max (L.) Merr.) in comparison to FeEDDHA and FeEDDHMA was studied, as well as the importance of the ortho-ortho and ortho-para/rest isomers in defining the performance. To this end, chlorophyll production (SPAD), plant dry matter yield, and the mass fractions of important mineral elements in the plant were quantified in a greenhouse pot experiment. All three Fe chelates increased SPAD index and dry matter yield compared to the control. The effect of FeHBED on chlorophyll production was visible over a longer time span than that of FeEDDHA and FeEDDHMA. Additionally, FeHBED did not suppress Mn uptake as much as the other Fe chelates. Compared to the other Fe chelates, total Fe content in the young leaves was lower in the FeHBED treatment; however, total Fe content was not directly related to chlorophyll production and biomass yield. For each chelate, the ortho-ortho isomer was found to be more effective than the other isomers evaluated.

Purification and characterization of Desulfovibrio vulgaris (Hildenborough) hydrogenase expressed in Escherichia coli.

NARCIS (Netherlands)

Voordouw, G.; Hagen, W.R.; Kruse-Wolters, M.; Berkel-Arts, van A.; Veeger, C.

1987-01-01

Hydrogenase from Desulfovibrio vulgaris (Hildenborough) is a heterologous dimer of molecular mass 46 + 13.5 kDa. Its two structural genes have been cloned on a 4664-base-pair fragment of known sequence in the vector pUC9. Expression of hydrogenase polypeptides in Escherichia coli transformed with

Structure and magnetism in Co/X, Fe/Si, and Fe/(FeSi) multilayers

Science.gov (United States)

Franklin, Michael Ray

Previous studies have shown that magnetic behavior in multilayers formed by repeating a bilayer unit comprised of a ferromagnetic layer and a non-magnetic spacer layer can be affected by small structural differences. For example, a macroscopic property such as giant magnetoresistance (GMR) is believed to depend significantly upon interfacial roughness. In this study, several complimentary structural probes were used to carefully characterize the structure of several sputtered multilayer systems-Co/Ag, Co/Cu, Co/Mo, Fe/Si, and Fe//[FeSi/]. X-ray diffraction (XRD) studies were used to examine the long-range structural order of the multilayers perpendicular to the plane of the layers. Transmission electron diffraction (TED) studies were used to probe the long-range order parallel to the layer plane. X-ray Absorption Fine Structure (XAFS) studies were used to determine the average local structural environment of the ferromagnetic atoms. For the Co/X systems, a simple correlation between crystal structure and saturation magnetization is discovered for the Co/Mo system. For the Fe/X systems, direct evidence of an Fe-silicide is found for the /[FeSi/] spacer layer but not for the Si spacer layer. Additionally, differences were observed in the magnetic behavior between the Fe in the nominally pure Fe layer and the Fe contained in the /[FeSi/] spacer layers.

Strong 3D and 1D magnetism in hexagonal Fe-chalcogenides FeS and FeSe vs. weak magnetism in hexagonal FeTe.

Science.gov (United States)

Parker, David S

2017-06-13

We present a comparative theoretical study of the hexagonal forms of the Fe-chalcogenides FeS, FeSe and FeTe with their better known tetragonal forms. While the tetragonal forms exhibit only an incipient antiferromagnetism and experimentally show superconductivity when doped, the hexagonal forms of FeS and FeSe display a robust magnetism. We show that this strong magnetism arises from a van Hove singularity associated with the direct Fe-Fe c-axis chains in the generally more three-dimensional NiAs structure. We also find that hexagonal FeTe is much less magnetic than the other two hexagonal materials, so that unconventional magnetically-mediated superconductivity is possible, although a large T c value is unlikely.

Strong 3D and 1D magnetism in hexagonal Fe-chalcogenides FeS and FeSe vs. weak magnetism in hexagonal FeTe

Energy Technology Data Exchange (ETDEWEB)

Parker, David S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-06-13

We present a comparative theoretical study of the hexagonal forms of the Fe-chalcogenides FeS, FeSe and FeTe with their better known tetragonal forms. While the tetragonal forms exhibit only an incipient antiferromagnetism and experimentally show superconductivity when doped, the hexagonal forms of FeS and FeSe display a robust magnetism. We show that this strong magnetism arises from a van Hove singularity associated with the direct Fe-Fe c-axis chains in the generally more three-dimensional NiAs structure. We also find that hexagonal FeTe is much less magnetic than the other two hexagonal materials, so that unconventional magnetically-mediated superconductivity is possible, although a large T_c value is unlikely.

Enhanced photocatalytic hydrogen production from an MCM-41-immobilized photosensitizer-[Fe-Fe] hydrogenase mimic dyad.

Science.gov (United States)

Wang, Wen; Yu, Tianjun; Zeng, Yi; Chen, Jinping; Yang, Guoqiang; Li, Yi

2014-11-01

A covalently linked photosensitizer-catalytic center dyad Ps-Hy, consisting of two bis(2-phenylpyridine)(2,2'-bipyridine)iridium(iii) chromophores (Ps) and a diiron hydrogenase mimic (Hy) was constructed by using click reaction. Ps-Hy was incorporated into K(+)-exchanged molecular sieve MCM-41 to form a composite (Ps-Hy@MCM-41), which has been successfully applied to the photochemical production of hydrogen. The catalytic activity of Ps-Hy@MCM-41 is ∼3-fold higher as compared with that of Ps-Hy in the absence of MCM-41. The incorporation of Ps-Hy into MCM-41 stabilizes the catalyst, and consequently, advances the photocatalysis. The present study provides a potential strategy for improving catalytic efficiency of artificial photosynthesis systems using mesoporous molecular sieves.

Influence of FeEDDS, FeEDTA, FeDTPA, FeEDDHA, and FeSO4 on Marigold Growth and Nutrition, and Substrate and Runoff Chemistry

Science.gov (United States)

Objectives of the study were to determine effects of Fe source on plant growth, plant nutrition, substrate chemistry and runoff chemistry. Iron source (FS) treatments consisted of Fe-aminopolycarboxylic acid (APCA) complexones iron ethylenediaminetetraacetic acid (FeEDTA), iron [S, S']-ethylenediam...

Anomalous superconducting spin-valve effect in NbN/FeN/Cu/FeN/FeMn multilayers

Energy Technology Data Exchange (ETDEWEB)

Hwang, Tae Jong; Kim, Dong Ho [Yeungnam University, Gyeongsan (Korea, Republic of)

2017-09-15

We have studied magnetic and transport properties of NbN/FeN/Cu/FeN/FeMn spin-valve structure. In-plane magnetic moment exhibited typical hysteresis loops of spin valves in the normal state of NbN film at 20 K. On the other hand, the magnetic hysteresis loop in the superconducting state exhibited more complex behavior in which exchange bias provided by antiferrmagnetic FeMn layer to adjacent FeN layer was disturbed by superconductivity. Because of this, the ideal superconducting spin-valve effect was not detected. Instead the stray field originated from unsaturated magnetic states dominated the transport properties of NbN/FeN/Cu/FeN/FeMn multilayer.

Soft magnetic properties of hybrid ferromagnetic films with CoFe, NiFe, and NiFeCuMo layers

Energy Technology Data Exchange (ETDEWEB)

Choi, Jong-Gu [Eastern-western Biomedical Engineering, Sangji University, Wonju 220-702 (Korea, Republic of); Hwang, Do-Guwn [Dept. of Oriental Biomedical Engineering, Sangji University, Wonju 220-702 (Korea, Republic of); Rhee, Jang-Roh [Dept. of Physics, Sookmyung Women' s University, Seoul 140-742 (Korea, Republic of); Lee, Sang-Suk, E-mail: sslee@sangji.ac.kr [Dept. of Oriental Biomedical Engineering, Sangji University, Wonju 220-702 (Korea, Republic of)

2011-09-30

Two-layered ferromagnetic alloy films (NiFe and CoFe) with intermediate NiFeCuMo soft magnetic layers of different thicknesses were investigated to understand the relationship between coercivity and magnetization process by taking into account the strength of hard-axis saturation field. The thickness dependence of H{sub EC} (easy-axis coercivity), H{sub HS} (hard-axis saturation field), and {chi} (susceptibility) of the NiFeCuMo thin films in glass/Ta(5 nm)/[CoFe or NiFe(5 nm-t/2)]/NiFeCuMo(t = 0, 4, 6, 8, 10 nm)/[CoFe or NiFe(5 nm-t/2)]/Ta(5 nm) films prepared using the ion beam deposition method was determined. The magnetic properties (H{sub EC}, H{sub HS}, and {chi}) of the ferromagnetic CoFe, NiFe three-layers with an intermediate NiFeCuMo super-soft magnetic layer were strongly dependent on the thickness of the NiFeCuMo layer.

MIL-100-Fe derived N-doped Fe/Fe3C@C electrocatalysts for efficient oxygen reduction reaction

Science.gov (United States)

Guo, Dakai; Han, Sancan; Wang, Jiacheng; Zhu, Yufang

2018-03-01

N-doped porous Fe/Fe3C@C electrocatalysts were prepared by the pyrolysis of the hexamethylenetetramine (HMT)-incorporated MIL-100-Fe at different temperatures (700-1000 °C) under N2 atmosphere. Rotary evaporation of MIL-100-Fe and HMT solution could make more N-enriched HMT molecules enter into the pores of MIL-100-Fe, thus improving nitrogen contents of the final pyrolyzed samples. All pyrolyzed samples show porous textures with middle specific surface areas. The X-ray photoelectron spectroscopy (XPS) results demonstrate the successful introduction of N atoms into carbon framework. Sample Fe-N2-800 prepared by annealing the precursors with the HMT/MIL-100-Fe weight ratio of 2 at 800 °C exhibits the best electrocatalytic activity towards the oxygen reduction reaction (ORR) in terms of onset potential and current density because of high graphitic N and pyridinic N content. The enwrapped Fe/Fe3C nanoparticles and Fe-Nx active sites in these samples could also boost the ORR activity synergistically. Moreover, sample Fe-N2-800 demonstrates a dominant four electron reduction process, as well as excellent long-term operation stability and methanol crossover resistance. Thus, the N-doped Fe/Fe3C@C composites derived from the HMT-incorporated MIL-100-Fe are promising electrocatalysts to replace Pt/C for ORR in practical applications.

The 54Fe(d,t)53Fe reaction and the neutron configuration in 54Fe

International Nuclear Information System (INIS)

England, J.B.A.; Ophel, T.R.; Johnston, A.; Zeller, A.F.

1980-07-01

The 54 Fe(d,t) 53 Fe reaction has been used to study the levels populated in 54 Fe in an attempt to establish the neutron configuration in 54 Fe. The states observed show clear evidence for a 2p-4h admixture in 54 Fe. In particular, the strength of the first 3/2 - level relative to the 7/2 - ground state transition is 3-4 times that in neighbouring N = 28 nuclei

Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

Science.gov (United States)

Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

2015-08-14

The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

Spin structure of exchange biased heterostructures. Fe/MnF{sub 2} and Fe/FeF{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Sahoo, B

2006-12-18

In this work, the {sup 57}Fe probe layer technique is used in order to investigate the depth- and temperature-dependent Fe-layer spin structure of exchange biased Fe/MnF{sub 2} and Fe/FeF{sub 2} (pseudo-twinned) antiferromagnetic (AFM) systems by conversion electron Moessbauer spectroscopy (CEMS) and nuclear resonant scattering (NRS) of synchrotron radiation. Two kinds of samples with a 10 A {sup 57}Fe probe layer directly at or 35 A away from the interface, labeled as interface and center sample, respectively, were studied in this work. The results obtained by CEMS for Fe/MnF{sub 2} suggests that, at 80 K, i.e., above T{sub N}=67 K of MnF{sub 2}, the remanent state Fe-layer spin structure of the two studied samples are slightly different due to their different microstructure. In the temperature range from 300 K to 80 K, the Fe-layer spin structure does not change just by zero-field cooling the sample in remanence. For Fe/FeF{sub 2}, a continuous non-monotonic change of the remanent-state Fe spin structure was observed by cooling from 300 K to 18 K. NRS of synchrotron radiation was used to investigate the temperature- and depth-dependent Fe-layer spin structure during magnetization reversal in pseudo-twinned Fe/MnF{sub 2}. A depthdependent Fe spin structure in an applied magnetic field (applied along the bisector of the twin domains) was observed at 10 K, where the Fe spins closer to the interface are not aligned along the field direction. The depth-dependence disappears at 150 K. (orig.)

Fe-vacancy and superconductivity in FeSe-based superconductors

Science.gov (United States)

Wang, C. H.; Chen, T. K.; Chang, C. C.; Lee, Y. C.; Wang, M. J.; Huang, K. C.; Wu, P. M.; Wu, M. K.

2018-06-01

This review summarizes recent advancements in FeSe and related systems. The FeSe and related superconductors are currently receiving considerable attention for the high Tcs observed and for many similar features to the high Tc cuprate superconductors. These similarities suggest that understanding the FeSe based compounds could potentially help our understanding of the cuprates. We shall first review the common features observed in the FeSe-based system. It was found that with a careful control of material synthesizing processes, numerous rich phases have been observed in the FeSe-based system. Detailed studies show that the Fe-vacancy ordered phases found in the FeSe based compounds, which are non-superconducting Mott insulators, are the parent compounds of the superconductors. Superconductivity emerges from the parent phases by disordering the Fe vacancy order, often by a simple annealing treatment. Recent high temperature X-ray diffraction experiments show that the degree of structural distortion associated with the disorder of Fe-vacancy is closely related to volume fraction of the superconductivity observed. These results suggest the strong lattice to spin coupling are important for the occurrence of superconductivity in FeSe based superconductors.

Exchange bias variations of the seed and top NiFe layers in NiFe/FeMn/NiFe trilayer as a function of seed layer thickness

International Nuclear Information System (INIS)

Sankaranarayanan, V.K.; Yoon, S.M.; Kim, C.G.; Kim, C.O.

2005-01-01

Development of exchange bias at the seed and top NiFe layers in the NiFe (t nm)/FeMn(10 nm)/NiFe(5 nm) trilayer structure is investigated as a function of seed layer thickness, in the range of 2-20 nm. The seed NiFe layer shows maximum exchange bias at 4 nm seed layer thickness. The bias shows inverse thickness dependence with increasing thickness. The top NiFe layer on the other hand shows only half the bias of the seed layer which is retained even after the sharp fall in seed layer bias. The much smaller bias for the top NiFe layer is related to the difference in crystalline texture and spin orientations at the top FeMn/NiFe interface, in comparison to the bottom NiFe/FeMn interface which grows on a saturated NiFe layer with (1 1 1) orientation

Structural and magnetic properties of NdFeB and NdFeB/Fe films with Mo addition

Energy Technology Data Exchange (ETDEWEB)

Urse, M; Grigoras, M; Lupu, N; Chiriac, H, E-mail: urse@phys-iasi.ro [National Institute of R and D for Technical Physics, 47 Mangeron Blvd., 700050 Iasi (Romania)

2011-07-06

The influence of the Mo addition on the microstructure and magnetic properties of Nd-Fe-B and Nd-Fe-B/Fe films was studied. The coercivity is a key parameter in the control of technical performances of Nd-Fe-B films. A small amount of about 1 at.% Mo can enhance the coercivity of Nd-Fe-B film by controlling the growth of soft and hard magnetic grains. A coercivity of 22.1 kOe, a remanence ratio, M{sub r}/M{sub s}, of 0.83 and a maximum energy product of 8 MGOe were obtained for Ta/[NdFeBMo(1at.%)(540nm)/Ta films annealed at 650{sup 0}C for 20 minutes due to Mo precipitates formed at the Nd{sub 2}Fe{sub 14}B phase boundaries which prevent the nucleation and expansion of the magnetic domains. Simultaneous use of Mo as addition and the stratification of Nd-Fe-B-Mo films using Fe as spacer layer are important tools for the improvement of the hard magnetic properties of Nd-Fe-B films. The Ta/[NdFeBMo(1at.%)(180nm)/Fe(1nm)]x3/Ta multilayer film annealed at 620{sup 0}C exhibits an increase in the coercivity from 12.1 kOe to 22.8 kOe, in the remanence ratio from 0.77 to 0.80, and in the maximum energy product from 4.5 to 7.1 MGOe in comparison with Ta/Nd-Fe-B/Ta film. As compared to Ta/Nd-Fe-B/Ta film, the Ta/[NdFeBMo(1at.%)(180nm)/Fe(1nm)]x3/Ta film presents a decrease in the crystallization temperature of about 30{sup 0}C.

Influence of an Fe cap layer on the structural and magnetic properties of Fe49Pt51/Fe bi-layers

International Nuclear Information System (INIS)

Chao-Yang, Duan; Bin, Ma; Zong-Zhi, Zhang; Qing-Yuan, Jin; Fu-Lin, Wei

2009-01-01

The influences of an Fe cap layer on the structural and magnetic properties of FePt/Fe bi-layers are investigated. Compared with single FePt alloy films, a thin Fe layer can affect the crystalline orientation and improve the chemical ordering of L1 0 FePt films. Moreover, the coercivity increases when a thin Fe layer covers the FePt layer. Beyond a critical thickness, however, the Fe cover layer quickens the magnetization reversal of Fe 49 Pt 51 /Fe bi-layers by their exchange coupling

A Model Study on the Possible Effects of an External Electrical Field on Enzymes Having Dinuclear Iron Cluster [2Fe-2S

Directory of Open Access Journals (Sweden)

Lemi Türker

2012-01-01

Full Text Available Hydrogenases which catalyze the H2 ↔ 2H+ + 2e− reaction are metalloenzymes that can be divided into two classes, the NiFe and Fe enzymes, on the basis of their metal content. Iron-sulfur clusters [2Fe-2S] and [4Fe-4S] are common in ironhydrogenases. In the present model study, [2Fe-2S] cluster has been considered to visualize the effect of external electric field on various quantum chemical properties of it. In the model, all the cysteinyl residues are in the amide form. The PM3 type semiempirical calculations have been performed for the geometry optimization of the model structure in the absence and presence of the external field. Then, single point DFT calculations (B3LYP/6-31+G(d have been carried out. Depending on the direction of the field, the chemical reactivity of the model enzyme varies which suggests that an external electric field could, under proper conditions, improve the enzymatic hydrogen production.

Microstructure and properties of multiphase sintered cermets Fe-Fe{sub 2}B; Mikrostruktura i wlasnosci spiekanych reakcyjnie cermetali Fe-Fe{sub 2}B

Energy Technology Data Exchange (ETDEWEB)

Nowacki, J. [Wydzial Inzynierii Materialowej, Politechnika Szczecinska, Szczecin (Poland); Klimek, L. [Instytut Inzynierii Materialowej i Technik Bezwiorowych, Politechnika Lodzka, Lodz (Poland)

1998-12-31

The process of multiphase sintering of iron in the vacuum has been analysed. As a result of the process iron-iron boride cermets have been produced. Fe-Fe{sub 2}B cermets were obtained as a result of sintering of the Fe and B pure elements in the vacuum. Attemps at sintering in the solid phase and with the participation of the liquid phase, the Fe-Fe{sub 2}B eutectic, have been made. Metallographic qualitative and quantitative studies, X-ray structural qualitative and qauantitative analysis allowed to determine the structure of Fe{sub 2}B cermets, as well as a description of the kinetics of quantitative changes in phase proportions in the course of sintering. It has been found that their structure varies widely depending on sintering parameters and the composition of the sinters. Measurements of the Fe-Fe{sub 2}B cermets hardness and measurements on wear during dry friction by the pin-on-disc method have shown distinct advantages of the cermets as a modern constructional materials. The hardness of Fe-Fe{sub 2}B cermets, depending on their chemical composition and sintering parameters, ranges widely from 150 to 1500 HV, and their resistance to wear is comparable to that of diffusively boronized steels. FeFe{sub 2}B cermets are a composite material in which iron boride, Fe{sub 2}B, with a hardness of about 1800 HV plays the role of the reinforcement,while iron-iron boride, Fe-Fe{sub 2}B, with a hardness of about 500 HV plays the role of matrix. The eutectic in the spaces between iron boride grains is composed of boron solid solution plates in iron with a hardness of arround 250 HV, and iron boride, Fe{sub 2}B, plates with a hardness of approximaly 1800 HV. The combination of such different materials, a hard reinforcement and a relatively plastic matrix produces favourable properties of the cermet thus produced high hardness (1500 HV) constant over whole cross section of the material, resistance of abrasive wear and acceptable ductility. The properties mentioned above

Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

DEFF Research Database (Denmark)

Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

2008-01-01

be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two......-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of a56Fesolution-solid=1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically...... and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within...

Effectiveness of FeEDDHA, FeEDDHMA, and FeHBED in Preventing Iron-Deficiency Chlorosis in Soybean

NARCIS (Netherlands)

Bin, Levi M.; Weng, Liping; Bugter, Marcel H.J.

2016-01-01

The performance of FeHBED in preventing Fe deficiency chlorosis in soybean (Glycine max (L.) Merr.) in comparison to FeEDDHA and FeEDDHMA was studied, as well as the importance of the ortho-ortho and ortho-para/rest isomers in defining the performance. To this end, chlorophyll production (SPAD),

Raman-spectroscopic (Fe/Fe+Mg, CO2) and Structural studies of Mg-Fe cordierites

International Nuclear Information System (INIS)

Haefeker, U.

2013-01-01

In the course of this dissertation synthetic hexagonal and orthorhombic Mg-Fe-cordierites have been investigated with Raman-spectroscopy and XRD methods. Cordierite´s Mg- and Fe-end-members as well as their Mg-Fe solid solutions with the chemical formula (Mg, Fe 2+ ) 2 Al 4 Si 5 O 18 *nH 2 O have been synthesized. Raman-data of synthetic hydrous Mg- and Fe-cordierites have been obtained in the wavenumber-region 100-1250 cm-1 and the experimental data were then compared with the results of quantum-mechanical calculations. 86 theoretical bands could be related to specific vibrational modes of the tetrahedral and octahedral sites of the cordierite structure. Maximum and mean deviation between experimentally-derived bands and calculated modes were ±7 cm -1 for Mg-cordierite and ±19 cm -1 for Fe-cordierite. Spectra comparison revealed a trend of peak downshifting as a consequence of Fe-incorporation. The calculations now allow more accurate interpretation of the Raman spectra with respect to structural changes of cordierite, resulting from Al-Si ordering and Mg-Fe exchange. Atomic motions in cordierite have been compared with those of the structurally similar mineral beryl. Investigations of 16 H 2 O-bearing synthetic well-ordered Mg-Fe-cordierites (XFe =0-1) with micro-Raman spectroscopy revealed a linear correlation between the Fe/Mg ratio and the position of certain Raman peaks. The peaks (wave-number Mg-/Fe-cordierite) at 122/111, 262/257, 430/418, 579/571, 974/967, and 1012/1007 cm -1 were selected for a detailed deconvolution analysis . The shifts of these peaks were then plotted vs. XFe and regression of the data lead to the formulation of a set of linear equations. In addition, the effect of different H 2 O contents and the degree of Al-Si ordering on the Fe/Mg determination were also investigated. Testing the calibration against data from six well-characterized natural cordierite samples yielded excellent agreement. Existing calibration diagrams for CO 2

Giant magnetoimpedance effect in sputtered single layered NiFe film and meander NiFe/Cu/NiFe film

International Nuclear Information System (INIS)

Chen, L.; Zhou, Y.; Lei, C.; Zhou, Z.M.; Ding, W.

2010-01-01

Giant magnetoimpedance (GMI) effect on NiFe thin film is very promising due to its application in developing the magnetic field sensors with highly sensitivity and low cost. In this paper, the single layered NiFe thin film and NiFe/Cu/NiFe thin film with a meander structure are prepared by the MEMS technology. The influences of sputtering parameters, film structure and conductor layer width on GMI effect in NiFe single layer and meander NiFe/Cu/NiFe film are investigated. Maximum of the GMI ratio in single layer and sandwich film is 5% and 64%, respectively. The results obtained are useful for developing the high-performance magnetic sensors based on NiFe thin film.

Molecular [(Fe3)–(Fe3)] and [(Fe4)–(Fe4)] coordination cluster pairs as single or composite arrays.

Science.gov (United States)

Sañudo, E Carolina; Uber, Jorge Salinas; Pons Balagué, Alba; Roubeau, Olivier; Aromí, Guillem

2012-08-06

The synthesis of molecular cluster pairs is a challenge for coordination chemists due to the potential applications of these species in molecular spintronics or quantum computing. The ligand H(4)L, 1,3-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-2-methoxybenzene, has been successfully used to obtain a series of such complexes using the basic Fe(III) trinuclear carboxylates as starting materials. Synthetic control has allowed the isolation of the two molecular cluster pairs that form the composite [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2)[Fe(3)O(PhCO(2))(5)(py)(H(2)L)](2) (1). The dimers of trinuclear units, [Fe(3)O(PhCO(2))(5)(H(2)O)(H(2)L)](2) (2) and [Fe(3)O(o-MePhCO(2))(5)(H(2)L)(py)](2) (3), and the dimers of tetranuclear units, [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2) (4) and [Fe(4)O(2)(o-MePhCO(2))(6)(H(2)L)(pz)](2) (5), are presented here. The magnetic properties of the reported aggregates show that they are pairs of semi-independent clusters weakly interacting magnetically as required for two-qubit quantum gates.

Study on adsorption of 99Tc on Fe, Fe2O3 and Fe3O4

International Nuclear Information System (INIS)

Liu Dejun; Fan Xianhua; Zhang Yingjie; Yao Jun; Zhou Duo; Wang Yong

2004-01-01

The absorption behavior of 99 Tc on Fe, Fe 2 O 3 and Fe 3 O 4 powders from aqueous 99 TcO 4 - solutions is studied by batch method in atmospheric conditions. After the adsorption reaches equilibrium, the valence state of 99 Tc in the aqueous solution is examined by extraction with tetraphenylarsonium chloride. The experimental results show that the adsorption ratio of 99 Tc on iron powders decreases with the increase of pH (in the range of 5-8) and of CO 3 2- concentration (in the range of 1 x 10 -8 -1 x 10 -2 mol/L). In opposite, the two factors have no significant influence on the absorption of 99 Tc on both Fe 2 O 3 and Fe 3 O 4 powders. The adsorption isotherms of 99 TcO 4 - on Fe, Fe 2 O 3 and Fe 3 O 4 powders can be well described by the Freundlich's equation. The major valence state of 99 Tc is deduced to be Tc(IV) when iron powders is used as the absorbent. In the case of Fe 2 O 3 or Fe 3 O 4 as an absorbent, the 99 Tc remains as the TcO 4 - form

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

Science.gov (United States)

Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

2015-03-03

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Photoelectron spectroscopy study of Fe-diluted Au-Fe alloys

CERN Document Server

Nahm, T U; Choi, B; Park, J S; Oh, S J; Cho, E J

2003-01-01

The electronic structure of Fe-diluted Au-Fe alloys has been studied by taking core-level and valence-band spectra using x-ray photoemission spectroscopy and synchrotron radiation. From the core-level spectroscopy, we found that the Fe 2p spectrum is composed of d sup 6 and d sup 7 multiplets from Fe impurity atoms. This behaviour is qualitatively discussed within the context of electron-electron interaction. In order to explore the electron-correlation effects in the valence band, we obtained Fe 3d partial spectral weights by taking advantage of the Cooper-minimum phenomenon of an Au 5d photoionization cross section. It was found that the spin-down states have an appreciable amount of spectral weights throughout the host Au 5d band, contrary to previous one-electron calculations predicting two-peak structure of the Fe 3d states. We suggest that this discrepancy results from the correlation effect of the Fe 3d electrons.

Colorimeter determination of Fe(II)/Fe(III) ratio in glass

International Nuclear Information System (INIS)

Baumann, E.W.; Coleman, C.J.; Karraker, D.G.; Scott, W.H.

1987-01-01

A colorimetric method has been developed to determine the Fe(II)/Fe(III) ratio in glass containing nuclear waste. Fe(II) is stabilized with pentavalent vanadium during dissolution in sulfuric and hydrofluoric acids. The chromogen is FerroZine (Hach Chemical Company), which forms a magenta complex with Fe(II). The two-step color development consists of determining the Fe(II) by adding FerroZine, followed by determining total Fe after the Fe(III) present is reduced with ascorbic acid. The method was validated by analyzing mixtures of ferrous/ferric solutions and nonferrous glass frit, and by comparison with Moessbauer spectroscopy. The effect of gamma radiation was established. The procedure is generally applicable to nonradioactive materials such as minerals and other glasses

Nature of impurities in fertilizers containing EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+) chelates.

Science.gov (United States)

Alvarez-Fernández, Ana; Cremonini, Mauro A; Sierra, Miguel A; Placucci, Giuseppe; Lucena, Juan J

2002-01-16

Iron chelates derived from ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA), ethylenediaminedi(o-hydroxy-p-methylphenylacetic) acid (EDDHMA), ethylenediaminedi(2-hydroxy-5-sulfophenylacetic) acid (EDDHSA), and ethylenediaminedi(5-carboxy-2-hydroxyphenylacetic) acid (EDDCHA) are remarkably efficient in correcting iron chlorosis in plants growing in alkaline soils. This work reports the determination of impurities in commercial samples of fertilizers containing EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+). The active components (EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+)) were separated easily from other compounds present in the fertilizers by HPLC. Comparison of the retention times and the UV-visible spectra of the peaks obtained from commercial EDDHSA/Fe(3+) and EDDCHA/Fe(3+) samples with those of standard solutions showed that unreacted starting materials (p-hydroxybenzenesulfonic acid and p-hydroxybenzoic acid, respectively) were always present in the commercial products. 1D and 2D NMR experiments showed that commercial fertilizers based on EDDHMA/Fe(3+) contained impurities having structures tentatively assigned to iron chelates of two isomers of EDDHMA. These findings suggest that current production processes of iron chelates used in agriculture need to be improved.

Melting relations in the Fe-rich portion of the system FeFeS at 30 kb pressure

Science.gov (United States)

Brett, R.; Bell, P.M.

1969-01-01

The melting relations of FeFeS mixtures covering the composition range from Fe to Fe67S33 have been determined at 30 kb pressure. The phase relations are similar to those at low pressure. The eutectic has a composition of Fe72.9S27.1 and a temperature of 990??C. Solubility of S in Fe at elevated temperatures at 30 kb is of the same order of magnitude as at low pressure. Sulfur may have significantly lowered the melting point of iron in the upper mantle during the period of coalescence of metal prior to core formation in the primitive earth. ?? 1969.

Comparison of Ab initio low-energy models for LaFePO, LaFeAsO, BaFe2As2, LiFeAs, FeSe, and FeTe. Electron correlation and covalency

International Nuclear Information System (INIS)

Miyake, Takashi; Nakamura, Kazuma; Arita, Ryotaro; Imada, Masatoshi

2010-01-01

Effective low-energy Hamiltonians for several different families of iron-based superconductors are compared after deriving them from the downfolding scheme based on first-principles calculations. Systematic dependences of the derived model parameters on the families are elucidated, many of which are understood from the systematic variation of the covalency between Fe-3d and pnictogen-/chalcogen-p orbitals. First, LaFePO, LaFeAsO (1111), BaFe 2 As 2 (122), LiFeAs (111), FeSe, and FeTe (11) have overall similar band structures near the Fermi level, where the total widths of 10-fold Fe-3d bands are mostly around 4.5 eV. However, the derived effective models of the 10-fold Fe-3d bands (d model) for FeSe and FeTe have substantially larger effective onsite Coulomb interactions U - 4.2 and 3.4 eV, respectively, after the screening by electrons on other bands and after averaging over orbitals, as compared to ∼2.5 eV for LaFeAsO. The difference is similar in the effective models containing p orbitals of As, Se or Te (dp or dpp model), where U ranges from ∼4 eV for the 1111 family to ∼7 eV for the 11 family. The exchange interaction J has a similar tendency. The family dependence of models indicates a wide variation ranging from weak correlation regime (LaFePO) to substantially strong correlation regime (FeSe). The origin of the larger effective interaction in the 11 family is ascribed to smaller spread of the Wannier orbitals generating larger bare interaction, and to fewer screening channels by the other bands. This variation is primarily derived from the distance h between the pnictogen/chalcogen position and the Fe layer: The longer h for the 11 family generates more ionic character of the bonding between iron and anion atoms, while the shorter h for the 1111 family leads to more covalent-bonding character, the larger spread of the Wannier orbitals, and more efficient screening by the anion p orbitals. The screened interaction of the d model is strongly orbital

Magnetostrictive GMR spin valves with composite FeGa/FeCo free layers

Energy Technology Data Exchange (ETDEWEB)

Liu, Luping [Key Laboratory of Magnetic Materials and Devices & Zhejiang Province Key Laboratory of Magnetic Materials and Application Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai 200072 (China); Zhan, Qingfeng, E-mail: zhanqf@nimte.ac.cn, E-mail: runweili@nimte.ac.cn; Yang, Huali; Li, Huihui; Zhang, Shuanglan; Liu, Yiwei; Wang, Baomin; Li, Run-Wei, E-mail: zhanqf@nimte.ac.cn, E-mail: runweili@nimte.ac.cn [Key Laboratory of Magnetic Materials and Devices & Zhejiang Province Key Laboratory of Magnetic Materials and Application Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Tan, Xiaohua [Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai 200072 (China)

2016-03-15

We have fabricated strain-sensitive spin valves on flexible substrates by utilizing the large magnetostrictive FeGa alloy to promote the strain sensitivity and the composite free layer of FeGa/FeCo to avoid the drastic reduction of giant magnetoresistance (GMR) ratio. This kind of spin valve (SV-FeGa/FeCo) displays a MR ratio about 5.9%, which is comparable to that of the conventional spin valve (SV-FeCo) with a single FeCo free layer. Different from the previously reported works on magnetostrictive spin valves, the SV-FeGa/FeCo displays an asymmetric strain dependent GMR behavior. Upon increasing the lateral strain, the MR ratio for the ascending branch decreases more quickly than that for the descending branch, which is ascribed to the formation of a spiraling spin structure around the FeGa/FeCo interface under the combined influences of both magnetic field and mechanical strain. A strain sensitivity of GF = 7.2 was achieved at a magnetic bias field of -30 Oe in flexible SV-FeGa/FeCo, which is significantly larger than that of SV-FeCo.

Magnetostrictive GMR spin valves with composite FeGa/FeCo free layers

International Nuclear Information System (INIS)

Liu, Luping; Zhan, Qingfeng; Yang, Huali; Li, Huihui; Zhang, Shuanglan; Liu, Yiwei; Wang, Baomin; Li, Run-Wei; Tan, Xiaohua

2016-01-01

We have fabricated strain-sensitive spin valves on flexible substrates by utilizing the large magnetostrictive FeGa alloy to promote the strain sensitivity and the composite free layer of FeGa/FeCo to avoid the drastic reduction of giant magnetoresistance (GMR) ratio. This kind of spin valve (SV-FeGa/FeCo) displays a MR ratio about 5.9%, which is comparable to that of the conventional spin valve (SV-FeCo) with a single FeCo free layer. Different from the previously reported works on magnetostrictive spin valves, the SV-FeGa/FeCo displays an asymmetric strain dependent GMR behavior. Upon increasing the lateral strain, the MR ratio for the ascending branch decreases more quickly than that for the descending branch, which is ascribed to the formation of a spiraling spin structure around the FeGa/FeCo interface under the combined influences of both magnetic field and mechanical strain. A strain sensitivity of GF = 7.2 was achieved at a magnetic bias field of -30 Oe in flexible SV-FeGa/FeCo, which is significantly larger than that of SV-FeCo.

Magnetostrictive GMR spin valves with composite FeGa/FeCo free layers

Science.gov (United States)

Liu, Luping; Zhan, Qingfeng; Yang, Huali; Li, Huihui; Zhang, Shuanglan; Liu, Yiwei; Wang, Baomin; Tan, Xiaohua; Li, Run-Wei

2016-03-01

We have fabricated strain-sensitive spin valves on flexible substrates by utilizing the large magnetostrictive FeGa alloy to promote the strain sensitivity and the composite free layer of FeGa/FeCo to avoid the drastic reduction of giant magnetoresistance (GMR) ratio. This kind of spin valve (SV-FeGa/FeCo) displays a MR ratio about 5.9%, which is comparable to that of the conventional spin valve (SV-FeCo) with a single FeCo free layer. Different from the previously reported works on magnetostrictive spin valves, the SV-FeGa/FeCo displays an asymmetric strain dependent GMR behavior. Upon increasing the lateral strain, the MR ratio for the ascending branch decreases more quickly than that for the descending branch, which is ascribed to the formation of a spiraling spin structure around the FeGa/FeCo interface under the combined influences of both magnetic field and mechanical strain. A strain sensitivity of GF = 7.2 was achieved at a magnetic bias field of -30 Oe in flexible SV-FeGa/FeCo, which is significantly larger than that of SV-FeCo.

Computed oscillator strengths and energy levels for Fe III, Fe IV, Fe V, and Fe VI with calculated wavelengths and wavelengths derived from established data

International Nuclear Information System (INIS)

Fawcett, B.C.

1989-01-01

Calculated weighted oscillator strengths are tabulated for spectral lines of Fe III, Fe IV, Fe V, and Fe VI. The lines belong to transition arrays 3d 6 -3d 5 4p and 3d 5 4s-3d 5 4p in Fe III, 3d 5 -3d 4 4p and 3d 4 4s-3d 4 4p in Fe IV, 3d 4 -3d 3 4p and 3d 3 4s-3d 3 4p in Fe V, and 3d 3 -3d 2 4p and 3d 2 4s-3d 2 4p in Fe VI. For the calculations, Slater parameters are optimized on the basis of minimizing the discrepancies between observed and computed wavelengths. Configuration interaction was included among the 3d n , 3d n-1 4s, 3d n-2 4s 2 , 3d n-1 4d, and 3d n-1 5s even configurations and among the 3d n-1 4p, 3d n-2 4s4p, and 3d n-1 5p odd configurations, with 3p 5 3d n+1 added for Fe VI. Calculated wavelengths are compared with observational data, and the compositions of energy levels are listed. This completes a series of similar computations for these complex configurations covering Fe I to Fe VI

Clarifying roughness and atomic diffusion contributions to the interface broadening in exchange-biased NiFe/FeMn/NiFe heterostructures

Energy Technology Data Exchange (ETDEWEB)

Nascimento, V.P., E-mail: valberpn@yahoo.com.br [Departamento de Física, Universidade Federal do Espírito Santo, 29075-910 Vitória (Brazil); Merino, I.L.C.; Passamani, E.C. [Departamento de Física, Universidade Federal do Espírito Santo, 29075-910 Vitória (Brazil); Alayo, W. [Departamento de Física, Universidade de Pelotas, 96010-610 Pelotas (Brazil); Tafur, M. [Instituto de Ciências Exatas, Universidade Federal de Itajubá, 37500-903 Itajubá (Brazil); Pelegrini, F. [Instituto de Física, Universidade Federal de Goiás, 74001-970 Goiânia (Brazil); Magalhães-Paniago, R. [Universidade Federal de Minas Gerais, Belo Horizonte (Brazil); Alvarenga, A.D. [Instituto Nacional de Metrologia, 25250-020 Xerém (Brazil); Saitovitch, E.B. [Coordenação de Física Experimental e Baixas Energias, Centro Brasileiro de Pesquisas Físicas, 22290-180 Rio de Janeiro (Brazil)

2013-09-02

NiFe(30 nm)/FeMn(13 nm)/NiFe(10 nm) heterostructures prepared by magnetron sputtering at different argon working pressures (0.27, 0.67 and 1.33 Pa) were systematically investigated by using specular and off-specular diffuse X-ray scattering experiments, combined with ferromagnetic resonance technique, in order to distinguish the contribution from roughness and atomic diffusion to the total structural disorder at NiFe/FeMn interfaces. It was shown that an increase in the working gas pressure from 0.27 to 1.33 Pa causes an enhancement of the atomic diffusion at the NiFe/FeMn interfaces, an effect more pronounced at the top FeMn/NiFe interface. In particular, this atomic diffusion provokes a formation of non-uniform magnetic dead-layers at the NiFe/FeMn interfaces (NiFeMn regions with paramagnetic or weak antiferromagnetic properties); that are responsible for the substantial reduction of the exchange bias field in the NiFe/FeMn system. Thus, this work generically helps to understand the discrepancies found in the literature regarding the influence of the interface broadening on the exchange bias properties (e.g., exchange bias field) of the NiFe/FeMn system. - Highlights: • Roughness and atomic diffusion contributions to the interface broadening • Clarification of the exchange bias field dependence on the interface disorder • Ferromagnetic, paramagnetic and antiferromagnetic phases at the magnetic interface • Magnetic dead layers formed by increasing the argon work pressure • Atomic diffusion in heterostructures prepared at higher argon pressure.

Point defects in B.C.C. Fe-Al, Fe-Co, and Fe-Co-V ordered alloys

International Nuclear Information System (INIS)

Riviere, J.P.; Dinhut, J.F.

1982-01-01

Radiation damage produced at 20 K by 2.5 MeV electrons is studied in three B 2 type Fe-40 at % Al, Fe-Co, Fe-Co-V ordered alloys. The resistivity damage in Fe-40 at % Al ordered single crystals is found less effective in the directions. The results suggest that replacement collision chains are difficult to propagate along the direction. Frenkel pair creation superimposed with disordering can account for the resistivity damage in the initially ordered Fe-Co alloy. Informations concerning replacement collision sequences in direction are derived. During the recovery of all the alloys, three main stages are observed and an ordering enhancement occurs. (author)

Thermodynamics of the Mo-Fe-C and W-Fe-C systems

International Nuclear Information System (INIS)

Kleykamp, H.

1978-01-01

A study on the reaction behaviour of the components of the Mo 2 C-Fe and WC-Fe systems is presented. Both systems are stable if the mono-phase carbides are in equilibrium with the Fe-C solid solution within fixed carbon concentrations, the limits of which are calculated in this paper. Gibbs energies of formation at 1273 K of the intermetallic phases, of the binary and of the ternary carbides in the Mo-Fe-C and W-Fe-C systems were determined. The Fe corner in the phase diagrams of both systems and the calculated C boundaries in the two-phase field γ-Fe(Mo,C)-Mo 2 C and the γ-Fe(W,C)-WC, respectively, based on this study, are shown in figures. (GSC) [de

Al/Fe isomorphic substitution versus Fe{sub 2}O{sub 3} clusters formation in Fe-doped aluminosilicate nanotubes (imogolite)

Energy Technology Data Exchange (ETDEWEB)

Shafia, Ehsan [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy); Esposito, Serena [Università degli Studi di Cassino e del Lazio Meridionale, Department of Civil and Mechanical Engineering (Italy); Manzoli, Maela; Chiesa, Mario [Università di Torino, Dipartimento di Chimica and Centro Interdipartimentale NIS (Italy); Tiberto, Paola [Electromagnetism, I.N.Ri.M. (Italy); Barrera, Gabriele [Università di Torino, Dipartimento di Chimica and Centro Interdipartimentale NIS (Italy); Menard, Gabriel [Harvard University, Department of Chemistry and Chemical Biology (United States); Allia, Paolo, E-mail: paolo.allia@polito.it [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy); Freyria, Francesca S. [Massachusetts Institute of Technology, Department of Chemistry (United States); Garrone, Edoardo; Bonelli, Barbara, E-mail: barbara.bonelli@polito.it [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy)

2015-08-15

Textural, magnetic and spectroscopic properties are reported of Fe-doped aluminosilicate nanotubes (NTs) of the imogolite type, IMO, with nominal composition (OH){sub 3}Al{sub 2−x}Fe{sub x}O{sub 3}SiOH (x = 0, 0.025, 0.050). Samples were obtained by either direct synthesis (Fe-0.025-IMO, Fe-0.050-IMO) or post-synthesis loading (Fe-L-IMO). The Fe content was either 1.4 wt% (both Fe-0.050-IMO and Fe-L-IMO) or 0.7 wt% (Fe-0.025-IMO). Textural properties were characterized by High-Resolution Transmission Electron Microscopy, X-ray diffraction and N{sub 2} adsorption/desorption isotherms at 77 K. The presence of different iron species was studied by magnetic moment measurements and three spectroscopies: Mössbauer, UV–Vis and electron paramagnetic resonance, respectively. Fe{sup 3+}/Al{sup 3+} isomorphic substitution (IS) at octahedral sites at the external surface of NTs is the main process occurring by direct synthesis at low Fe loadings, giving rise to the formation of isolated high-spin Fe{sup 3+} sites. Higher loadings give rise, besides IS, to the formation of Fe{sub 2}O{sub 3} clusters. IS occurs up to a limit of Al/Fe atomic ratio of ca. 60 (corresponding to x = 0.032). A fraction of the magnetism related to NCs is pinned by the surface anisotropy; also, clusters are magnetically interacting with each other. Post-synthesis loading leads to a system rather close to that obtained by direct synthesis, involving both IS and cluster formations. Slightly larger clusters than with direct synthesis samples, however, are formed. The occurrence of IS indicates a facile cleavage/sealing of Al–O–Al bonds: this opens the possibility to exchange Al{sup 3+} ions in pre-formed IMO NTs, a much simpler procedure compared with direct synthesis.

Diffusion of Nb in Fe and in some Fe alloys

International Nuclear Information System (INIS)

Kurokawa, S.; Ruzzante, J.E.; Hey, A.M.; Dyment, F.

1981-01-01

Diffusion data of microalloying elements such as Nb, V, Ti, are required when analysing the transformation and recrystallization behaviour of HSLA steels in order to optimize grain refinement and precipitation hardening. The diffusion behaviour of Nb in pure Fe, Fe 1.5 Mn, Fe 0.6 Si and Fe 1.5 Mn 0.6 Si has been measured between 1080 and 1200 0 C. Results indicate that Si increases Nb diffusivity while Mn decreases it. The sequence of diffusion coeficients values is: D sup(Nb) sub(Fe 1.5 Mn) [pt

First principles calculations of the magnetic and hyperfine properties of Fe/N/Fe and Fe/O/Fe multilayers in the ground state of cohesive energy

Science.gov (United States)

dos Santos, A. V.; Samudio Pérez, C. A.; Muenchen, D.; Anibele, T. P.

2015-01-01

The ground state properties of Fe/N/Fe and Fe/O/Fe multilayers were investigated using the first principles calculations. The calculations were performed using the Linearized Augmented Plane Wave (LAPW) method implemented in the Wien2k code. A supercell consisting of one layer of nitride (or oxide) between two layers of Fe in the bcc structure was used to model the structure of the multilayer. The research in new materials also stimulated theoretical and experimental studies of iron-based nitrides due to their variety of structural and magnetic properties for the potential applications as in high strength steels and for high corrosion resistance. It is obvious from many reports that magnetic iron nitrides such as γ-Fe4N and α-Fe16N2 have interesting magnetic properties, among these a high magnetisation saturation and a high density crimp. However, although Fe-N films and multilayers have many potential applications, they can be produced in many ways and are being extensively studied from the theoretical point of view there is no detailed knowledge of their electronic structure. Clearly, efforts to understand the influence of the nitrogen atoms on the entire electronic structure are needed as to correctly interpret the observed changes in the magnetic properties when going from Fe-N bulk compounds to multilayer structures. Nevertheless, the N atoms are not solely responsible for electronics alterations in solid compounds. Theoretical results showed that Fe4X bulk compounds, where X is a variable atom with increasing atomic number (Z), the nature of bonding between X and adjacent Fe atoms changes from more covalent to more ionic and the magnetic moments of Fe also increase for Z=7, i.e. N. This is an indicative that atoms with a Z number higher than 7, i.e., O, can produce several new alterations in the entire magnetic properties of Fe multilayers. This paper presents the first results of an ab-initio electronic structure calculations, performed for Fe-N and Fe

Influence of the surface topography, morphology and structure on magnetic properties of ion beam sputtered iron layers, Fe/Cr/Fe- and Fe/MgO/Fe multilayers; Untersuchung der Morphologie und magnetische Eigenschaften von ionenstrahl-gesputterten Eisen-Einzelschichten, Fe/Cr/Fe- und Fe/MgO/Fe-Schichtsystemen

Energy Technology Data Exchange (ETDEWEB)

Steeb, Alexandra

2007-04-05

In this PhD Thesis, the influence of the surface topography, morphology and structure on magnetic properties of ion beam sputtered iron layers on GaAs is examined. To analyze the structure of the produced iron films, low energy electron diffraction and scanning tunneling microscopy is employed. The utilized methods to investigate the magnetic properties are Kerr- and SQUID-magnetometry and ferromagnetic resonance. It is demonstrated that on untreated as well as on presputtered and heated GaAs substrates the sputtered iron films grow epitaxially. The least surface roughness of 1 A exhibit iron films grown on untreated GaAs, while iron films on heated GaAs have the highest roughness of 30 A. The largest crystal anisotropy constant is found for the presputtered GaAs/Fe-System. For this preparation method, two monolayers of iron are determined to be magnetically dead layers. At a film thickness of 100 A, 83% of the value for saturation magnetization of bulk iron are achieved. The small observed FMR-linewidths confirm the good bulk properties of the ion beam sputtered iron. Furthermore, an antiferromagnetic interlayer exchange coupling in sputtered Fe/Cr/Fe-films was achieved. For a thickness of 12 to 17 A of the chrome interlayer, a coupling strength up to 0.2 mJ/m{sup 2} is found. To account for the small coupling strength, a strong intermixing at the interface is assumed. Finally, epitaxial Fe/MgO/Fe/FeMn multilayers are deposited on GaAs. After the structuring, it is possible to detect tunneling processes in the tunneling contacts with current-voltage measurements. The tunnel magneto resistance values of 2% are small, which can be explained by the absence of sharp, well-defined interfaces between the Fe/FeMn and the Fe/MgO interfaces. These results demonstrate, that analog to MBE the ion beam sputtering method realizes good magnetic bulk properties. However, interface sensitive phenomena are weakened because of a strong intermixing at the interfaces. (orig.)

Fe65-PTB2 Dimerization Mimics Fe65-APP Interaction

Directory of Open Access Journals (Sweden)

Lukas P. Feilen

2017-05-01

Full Text Available Physiological function and pathology of the Alzheimer’s disease causing amyloid precursor protein (APP are correlated with its cytosolic adaptor Fe65 encompassing a WW and two phosphotyrosine-binding domains (PTBs. The C-terminal Fe65-PTB2 binds a large portion of the APP intracellular domain (AICD including the GYENPTY internalization sequence fingerprint. AICD binding to Fe65-PTB2 opens an intra-molecular interaction causing a structural change and altering Fe65 activity. Here we show that in the absence of the AICD, Fe65-PTB2 forms a homodimer in solution and determine its crystal structure at 2.6 Å resolution. Dimerization involves the unwinding of a C-terminal α-helix that mimics binding of the AICD internalization sequence, thus shielding the hydrophobic binding pocket. Specific dimer formation is validated by nuclear magnetic resonance (NMR techniques and cell-based analyses reveal that Fe65-PTB2 together with the WW domain are necessary and sufficient for dimerization. Together, our data demonstrate that Fe65 dimerizes via its APP interaction site, suggesting that besides intra- also intermolecular interactions between Fe65 molecules contribute to homeostatic regulation of APP mediated signaling.

Fe65-PTB2 Dimerization Mimics Fe65-APP Interaction.

Science.gov (United States)

Feilen, Lukas P; Haubrich, Kevin; Strecker, Paul; Probst, Sabine; Eggert, Simone; Stier, Gunter; Sinning, Irmgard; Konietzko, Uwe; Kins, Stefan; Simon, Bernd; Wild, Klemens

2017-01-01

Physiological function and pathology of the Alzheimer's disease causing amyloid precursor protein (APP) are correlated with its cytosolic adaptor Fe65 encompassing a WW and two phosphotyrosine-binding domains (PTBs). The C-terminal Fe65-PTB2 binds a large portion of the APP intracellular domain (AICD) including the GYENPTY internalization sequence fingerprint. AICD binding to Fe65-PTB2 opens an intra-molecular interaction causing a structural change and altering Fe65 activity. Here we show that in the absence of the AICD, Fe65-PTB2 forms a homodimer in solution and determine its crystal structure at 2.6 Å resolution. Dimerization involves the unwinding of a C-terminal α-helix that mimics binding of the AICD internalization sequence, thus shielding the hydrophobic binding pocket. Specific dimer formation is validated by nuclear magnetic resonance (NMR) techniques and cell-based analyses reveal that Fe65-PTB2 together with the WW domain are necessary and sufficient for dimerization. Together, our data demonstrate that Fe65 dimerizes via its APP interaction site, suggesting that besides intra- also intermolecular interactions between Fe65 molecules contribute to homeostatic regulation of APP mediated signaling.

Formation mechanisms of neutral Fe layers in the thermosphere at Antarctica studied with a thermosphere-ionosphere Fe/Fe+ (TIFe) model

Science.gov (United States)

Chu, Xinzhao; Yu, Zhibin

2017-06-01

With a thermosphere-ionosphere Fe/Fe+ (TIFe) model developed from first principles at the University of Colorado, we present the first quantitative investigation of formation mechanisms of thermospheric Fe layers observed by lidar in Antarctica. These recently discovered neutral metal layers in the thermosphere between 100 and 200 km provide unique tracers for studies of fundamental processes in the space-atmosphere interaction region. The TIFe model formulates and expands the TIFe theory originally proposed by Chu et al. that the thermospheric Fe layers are produced through the neutralization of converged Fe+ layers. Through testing mechanisms and reproducing the 28 May 2011 event at McMurdo, we conceive the lifecycle of meteoric metals via deposition, transport, chemistry, and wave dynamics for thermospheric Fe layers with gravity wave signatures. While the meteor injection of iron species is negligible above 120 km, the polar electric field transports metallic ions Fe+ upward from their main deposition region into the E-F regions, providing the major source of Fe+ (and accordingly Fe) in the thermosphere. Atmospheric wave-induced vertical shears of vertical and horizontal winds converge Fe+ to form dense Fe+ layers. Direct electron-Fe+ recombination is the major channel to neutralize Fe+ layers to form Fe above 120 km. Fe layer shapes are determined by multiple factors of neutral winds, electric field, and aurora activity. Gravity-wave-induced vertical wind plays a key role in forming gravity-wave-shaped Fe layers. Aurora particle precipitation enhances Fe+ neutralization by increasing electron density while accelerating Fe loss via charge transfer with enhanced NO+ and O2+ densities.Plain Language SummaryThe discoveries of neutral metal layers reaching near 200 km in the thermosphere have significant scientific merit because such discoveries challenge the current understandings of upper atmospheric composition, chemistry, dynamics, electrodynamics, and

Effects of Fe fine powders doping on hot deformed NdFeB magnets

International Nuclear Information System (INIS)

Lin, Min; Wang, Huijie; Zheng, Jingwu; Yan, Aru

2015-01-01

The composite NdFeB magnets with blending melt-spun flakes and Fe fine powders were prepared by the hot-pressed and hot-deformed route. Characterizations of the hot-deformed NdFeB magnets affected by the doped Fe powders were tested. The doped Fe powders decrease the hot-deformed pressure when the strain is between 15 and 50%. XRD patterns show that the doped Fe powders have little influence on the c-axis alignment of hot-deformed NdFeB magnets in the press direction. The B r and the (BH) max get improved when the doped Fe powders are less than 3 wt%. The doped Fe of hot-deformed NdFeB magnets exists in the elongated state and the spherical state surrounded by the Nd-rich phase. With the Fe fraction increasing, the potential of magnet moves to the positive direction and the diameter of the Nyquist arc becomes larger, which indicate that the corrosion resistance improved effectively. The bending strength was enhanced by the elongated α-Fe phase embedded in the matrix 2:14:1 phase. - Highlights: • The doped Fe powders have little influence on the c-axis alignment of magnets. • The elongated Fe powders are more than the spherical Fe powders in the magnets. • The corrosion resistance is improved effectively with the increasing Fe fraction. • The bending strength is enhanced by the elongated α-Fe phase embedded in the matrix

Effects of Fe fine powders doping on hot deformed NdFeB magnets

Energy Technology Data Exchange (ETDEWEB)

Lin, Min, E-mail: linm@nimte.ac.cn [Ningbo Institute of Material Technology & Engineering Chinese Academy of Science, Ningbo 315201 (China); Wang, Huijie [Ningbo Jinji Strong Magnetic Material Company, Ningbo 315041 (China); Zheng, Jingwu [Zhejiang University of Technology, Hangzhou 310014 (China); Yan, Aru [Ningbo Institute of Material Technology & Engineering Chinese Academy of Science, Ningbo 315201 (China)

2015-04-01

The composite NdFeB magnets with blending melt-spun flakes and Fe fine powders were prepared by the hot-pressed and hot-deformed route. Characterizations of the hot-deformed NdFeB magnets affected by the doped Fe powders were tested. The doped Fe powders decrease the hot-deformed pressure when the strain is between 15 and 50%. XRD patterns show that the doped Fe powders have little influence on the c-axis alignment of hot-deformed NdFeB magnets in the press direction. The B{sub r} and the (BH){sub max} get improved when the doped Fe powders are less than 3 wt%. The doped Fe of hot-deformed NdFeB magnets exists in the elongated state and the spherical state surrounded by the Nd-rich phase. With the Fe fraction increasing, the potential of magnet moves to the positive direction and the diameter of the Nyquist arc becomes larger, which indicate that the corrosion resistance improved effectively. The bending strength was enhanced by the elongated α-Fe phase embedded in the matrix 2:14:1 phase. - Highlights: • The doped Fe powders have little influence on the c-axis alignment of magnets. • The elongated Fe powders are more than the spherical Fe powders in the magnets. • The corrosion resistance is improved effectively with the increasing Fe fraction. • The bending strength is enhanced by the elongated α-Fe phase embedded in the matrix.

Pr2Fe14B/α-Fe nanocomposites for thermal applications

International Nuclear Information System (INIS)

Silva, Suelanny Carvalho da

2012-01-01

In this work, Pr x Fe 94 - x B 6 (x = 6, 8, 10 and 12) nanostructured powders were prepared by a combination of hydrogenation, disproportionation, desorption and recombination (HDDR) process with high energy milling applied to the mixture of an as-cast alloy (Pr 14 Fe 80 B 6 ) and α-Fe. The produced nanoparticles showed magnetic properties comparable to those reported in hyperthermia studies. The optimal time to obtain the magnetic nanoparticles is 5 hours (at 900 rpm). It was verified that longer milling times cause an increase in carbon percentage on the particles. The carbon is derived from oleic acid added as a surfactant in the milling step. The nanocomposites exhibit coercive force ranging from 80 Oe (6.5 kAm -1 ) to 170 Oe (13.5 kAm -1 ) and magnetic moments in the range of 81 129 Am2kg -1 . From the X-ray diffraction analyses, only two phases were found in all samples: α-Fe and the magnetic phase Pr 2 Fe 14 B. Individual nanoparticles with diameter of about 20 nm were verified. The samples studied presented heating when exposed to an alternating magnetic field (f = 222 kHz e H max ∼3.7 kAm -1 ) comparable to reported in literature. Temperature variations (ΔT) of the powders were: 51 K for Pr 6 Fe 88 B 6 , 41 K for Pr 8 Fe 86 B 6 , 38 K for Pr 10 Fe 8 4 B 6 and T = 34 K for Pr 12 Fe 82 B 6 . The specific absorption rates (SARs) of the powders were 201 Wkg -1 for Pr 6 Fe 88 B 6 composition, 158 Wkg -1 on the composition Pr 8 Fe 86 B 6 , and 114 Wkg -1 for Pr 10 Fe 84 B 6 and Pr 12 Fe 82 B 6 compositions. (author)

Microstructure and properties of multiphase sintered cermets Fe-Fe2B

International Nuclear Information System (INIS)

Nowacki, J.; Klimek, L.

1998-01-01

The process of multiphase sintering of iron in the vacuum has been analysed. As a result of the process iron-iron boride cermets have been produced. Fe-Fe 2 B cermets were obtained as a result of sintering of the Fe and B pure elements in the vacuum. Attemps at sintering in the solid phase and with the participation of the liquid phase, the Fe-Fe 2 B eutectic, have been made. Metallographic qualitative and quantitative studies, X-ray structural qualitative and qauantitative analysis allowed to determine the structure of Fe 2 B cermets, as well as a description of the kinetics of quantitative changes in phase proportions in the course of sintering. It has been found that their structure varies widely depending on sintering parameters and the composition of the sinters. Measurements of the Fe-Fe 2 B cermets hardness and measurements on wear during dry friction by the pin-on-disc method have shown distinct advantages of the cermets as a modern constructional materials. The hardness of Fe-Fe 2 B cermets, depending on their chemical composition and sintering parameters, ranges widely from 150 to 1500 HV, and their resistance to wear is comparable to that of diffusively boronized steels. FeFe 2 B cermets are a composite material in which iron boride, Fe 2 B, with a hardness of about 1800 HV plays the role of the reinforcement,while iron-iron boride, Fe-Fe 2 B, with a hardness of about 500 HV plays the role of matrix. The eutectic in the spaces between iron boride grains is composed of boron solid solution plates in iron with a hardness of arround 250 HV, and iron boride, Fe 2 B, plates with a hardness of approximaly 1800 HV. The combination of such different materials, a hard reinforcement and a relatively plastic matrix produces favourable properties of the cermet thus produced high hardness (1500 HV) constant over whole cross section of the material, resistance of abrasive wear and acceptable ductility. The properties mentioned above, resulting from the cermet

Tuning high frequency magnetic properties and damping of FeGa, FeGaN and FeGaB thin films

Directory of Open Access Journals (Sweden)

Derang Cao

2017-11-01

Full Text Available A series of FeGa, FeGaN and FeGaB films with varied oblique angles were deposited by sputtering method on silicon substrates, respectively. The microstructure, soft magnetism, microwave properties, and damping factor for the films were investigated. The FeGa films showed a poor high frequency magnetic property due to the large stress itself. The grain size of FeGa films was reduced by the additional N element, while the structure of FeGa films was changed from the polycrystalline to amorphous phase by the involved B element. As a result, N content can effectively improve the magnetic softness of FeGa film, but their high frequency magnetic properties were still poor both when the N2/Ar flow rate ratio is 2% and 5% during the deposition. The additional B content significantly led to the excellent magnetic softness and the self-biased ferromagnetic resonance frequency of 1.83 GHz for FeGaB film. The dampings of FeGa films were adjusted by the additional N and B contents from 0.218 to 0.139 and 0.023, respectively. The combination of these properties for FeGa films are helpful for the development of magnetostrictive microwave devices.

Dissecting the hydrogenase expression and activity of transformed escherichia coli with the bidirectional NiFe-hydrogenase from synechocystis sp. PCC 6803

International Nuclear Information System (INIS)

Moon, Yu Ran; Lee, Min Hee; An, Byung Chull; Chung, Byung Yeoup; Kim, Jae Sung; Kim, Jin Hong; Park, Youn Il; Kim, Cha Soon

2009-01-01

Synechocystis bidirectional hydrogenase genes (hoxEFUYH) and their putative promoter regions and transformed into E. coli. The hox genes were transcribed in the E. coli cells carrying the vector construct of pCCIFOS::phox::hox or pCCIFOS::pT7::hox and translated into HoxEFUYH proteins, suggesting that the putative hox promoter can be constitutively activated in E. coli. Accordingly, the total hydrogenase activity was markedly increased up to 192% or 169% in the transformed cells, while the hydrogen uptake was decreased up to about 30% of the negative control. Although the gene expression of LexA, the only one transcription regulator proven for the hox genes, was substantially decreased in the pCCIFOS::phox::hox cells after γ-irradiation of 30 Gy, the expression levels of HoxEFUYH proteins were not altered significantly. Thus, it is also suggested that other transcription regulators as well as LexA might contribute to activation of the hox promoter in E. coli

Interparticle interactions of FePt core and Fe{sub 3}O{sub 4} shell in FePt/Fe{sub 3}O{sub 4} magnetic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Akbari, Hossein, E-mail: Akbari.ph@iauardabil.ac.ir [Department of Physics, Ardabil Branch, Islamic Azad University, Ardabil (Iran, Islamic Republic of); Zeynali, Hossein [Department of Physics, Kashan Branch, Islamic Azad University, Kashan (Iran, Islamic Republic of); Bakhshayeshi, Ali [Department of Physics, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of)

2016-02-22

Monodisperse FePt nanoparticles were successfully synthesized using simple wet chemical method. Fe{sub 3}O{sub 4} was used as a magnetic shell around each FePt nanoparticles. In FePt/Fe{sub 3}O{sub 4} core/shell system, core thickness is 2 nm and shell thickness varies from zero to 2.5 nm. A theoretical model presented to calculate the shell thickness dependence of Coercivity. Presented model is compared with the results from Stoner–Wohlfarth model to interpret the shell thickness dependence of Coercivity in FePt/Fe{sub 3}O{sub 4} core/shell nanoparticles. There is a difference between the results from Stoner–Wohlfarth model and experimental data when the shell thickness increases. In the presented model, the effects of interparticle exchange and random magneto crystalline anisotropy are added to the previous models of magnetization reversal for core/shell nanostructures in order to achieve a better agreement with experimental data. For magnetic shells in FePt/Fe{sub 3}O{sub 4} core/shell, effective coupling between particles increases with increasing shell thickness which leads to Coercivity destruction for stronger couplings. According to the boundary conditions, in the harder regions with higher exchange stiffness, there is small variation in magnetization and so the magnetization modes become more localized. We discussed both localized and non-localized magnetization modes. For non-zero shell thickness, non-localized modes propagate in the soft phase which effects the quality of particle exchange interactions. - Highlights: • Monodisperse FePt nanoparticles were successfully synthesized using simple wet chemical method. • Fe{sub 3}O{sub 4} was used as a magnetic shell around each FePt nanoparticles. • A theoretical model presented to calculate the shell thickness dependence of Coercivity. • Magnetic shells increase effective coupling between particles with increasing shell thickness. • Magnetization modes are more localized in the regions with

Strengthening mechanisms of Fe nanoparticles for single crystal Cu–Fe alloy

International Nuclear Information System (INIS)

Shi, Guodong; Chen, Xiaohua; Jiang, Han; Wang, Zidong; Tang, Hao; Fan, Yongquan

2015-01-01

A single crystal Cu–Fe alloy with finely dispersed precipitate Fe nanoparticles was fabricated in this study. The interface relationship of iron nanoparticle and copper matrix was analyzed with a high-resolution transmission electron microscope (HRTEM), and the effect of Fe nanoparticles on mechanical properties of single crystal Cu–Fe alloy was discussed. Results show that, the finely dispersed Fe nanoparticles can be obtained under the directional solidification condition, with the size of 5–50 nm and the coherent interface between the iron nanoparticle and the copper matrix. Single crystal Cu–Fe alloy possesses improved tensile strength of 194.64 MPa, and total elongation of 44.72%, respectively, at room temperature, in contrast to pure Cu sample. Nanoparticles which have coherent interface with matrix can improve the dislocation motion state. Some dislocations can slip through the nanoparticle along the coherent interface and some dislocations can enter into the nanoparticles. Thus to improve the tensile strength of single crystal Cu–Fe alloy without sacrificing the ductility simultaneously. Based on the above analyses, strengthening mechanisms of Fe nanoparticles for single crystal Cu–Fe alloy was described

Experimental phases diagram Zr-Fe and Zr-Sn-Fe of the Fe rich zone at a temperature of 1100oC

International Nuclear Information System (INIS)

Nieva, N.; Jimenez, J.; Gomez, A; Granovsky, M.S

2010-01-01

Zr-based alloys are frequently used in the nuclear energy industry; among these are the Zr-based Zircaloys whose main alloys are Sn and Fe. In order to experimentally evaluate part of the diagram of the binary Zr-Fe phases and the ternary Zr-Sn-Fe in the Fe-rich zone, different binary alloys in the area closest to the composition of the ZrFe 2 and Zr 6 Fe 23 compounds were designed as well as a ternary alloy of Zr-Sn-Fe in the Fe-rich region of the ternary system. All the alloys underwent a two month heat treatment at a temperature of 1100 o C. Later the phases that were present were identified using different complementary techniques (mainly X-ray diffraction and microanalysis). The clear presence of the Zr 6 Fe 23 phase was not observed in any of the alloys. A new ternary phase consisting approximately of Zr 2 0Sn 14 Fe 66 was verified in the ternary alloy

Modification of interlayer exchange coupling in Fe/V/Fe trilayers using hydrogen

Energy Technology Data Exchange (ETDEWEB)

Skoryna, J., E-mail: jskoryna@ifmpan.poznan.pl [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17 St., 60-179 Poznań (Poland); Marczyńska, A. [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17 St., 60-179 Poznań (Poland); Lewandowski, M. [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85 St., 61-614 Poznań (Poland); Smardz, L. [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17 St., 60-179 Poznań (Poland)

2015-10-05

Highlights: • Magnetic films and multilayers. • Thin films. • Hydrogen absorbing materials. • Magnetic measurements. • Exchange coupling. - Abstract: Fe/V/Fe trilayers with constant-thickness Fe and step-like wedged V sublayers were prepared at room temperature using UHV magnetron sputtering. The bottom Fe layer grows onto oxidised Si(1 0 0) substrate and shows relatively high coercivity. The top Fe layer grows on vanadium spacer and shows considerably lower coercivity. The planar growth of the Fe and V sublayers was confirmed in-situ by X-ray photoelectron spectroscopy. Results show that the Fe sublayers are weakly exchange coupled for d{sub V} > 1.4 nm. Results on the coercivity studies as a function of the V interlayer thickness show near d{sub V} ∼ 1.95 nm (∼2.45 nm) weak antiferromagnetic (ferromagnetic) coupling, respectively. The hydrogenation of the Fe/V/Fe trilayers leads to increase of the strength of the ferromagnetic interlayer exchange coupling.

Adhesive and Cohesive Strength in FeB/Fe2B Systems

Science.gov (United States)

Meneses-Amador, A.; Blancas-Pérez, D.; Corpus-Mejía, R.; Rodríguez-Castro, G. A.; Martínez-Trinidad, J.; Jiménez-Tinoco, L. F.

2018-05-01

In this work, FeB/Fe2B systems were evaluated by the scratch test. The powder-pack boriding process was performed on the surface of AISI M2 steel. The mechanical parameters, such as yield stress and Young's modulus of the boride layer, were obtained by the instrumented indentation technique. Residual stresses produced on the boride layer were estimated by using the x-ray diffraction (XRD) technique. The scratch test was performed in order to evaluate the cohesive/adhesive strength of the FeB/Fe2B coating. In addition, a numerical evaluation of the scratch test on boride layers was performed by the finite element method. Maximum principal stresses were related to the failure mechanisms observed by the experimental scratch test. Shear stresses at the interfaces of the FeB/Fe2B/substrate system were also evaluated. Finally, the results obtained provide essential information about the effect of the layer thickness, the residual stresses, and the resilience modulus on the cohesive/adhesive strength in FeB/Fe2B systems.

Lattice locations and properties of Fe in Co/Fe co-implanted ZnO

DEFF Research Database (Denmark)

Gunnlaugsson, H.P.; Johnston, K.; Mølholt, T.E.

2012-01-01

The lattice locations and electronic configurations of Fe in 57Co/57Fe implanted ZnO (to (5‐6) × 1014 Fe/cm−2) have been studied by 57Fe Mössbauer emission spectroscopy. The spectra acquired upon room temperature implantation show ∼20% of the probe atoms as Fe2+ on perturbed Zn sites and the rema......The lattice locations and electronic configurations of Fe in 57Co/57Fe implanted ZnO (to (5‐6) × 1014 Fe/cm−2) have been studied by 57Fe Mössbauer emission spectroscopy. The spectra acquired upon room temperature implantation show ∼20% of the probe atoms as Fe2+ on perturbed Zn sites...... and the remaining fraction as Fe2+ in damage sites of interstitial character. After annealing at 773 K, ∼20% remain on crystalline sites, while the damage fraction has partly disappeared and instead a ∼30% fraction occurs as high‐spin Fe3+, presumably in precipitates. This suggests that precipitation of Co/Fe in ZnO...... likely takes place at relatively low temperatures, thus explaining some of the discrepancies in the literature regarding magnetic properties of 3d metal‐doped ZnO....

Moessbauer Study of Electrodeposited Fe/Fe-Oxide Multilayers

International Nuclear Information System (INIS)

Kuzmann, E.; Homonnay, Z.; Klencsar, Z.; Vertes, A.; Lakatos-Varsanyi, M.; Miko, A.; Varga, L.K.; Kalman, E.; Nagy, F.

2005-01-01

Iron has been deposited electrochemically by short current pulses in Na-saccharin containing FeII-chloride and sulphate solution electrolytes. Combined electrochemical techniques with initial pulse plating of iron nanolayer and its subsequent anodic oxidation under potential control have been used for production of Fe/Fe-oxide multilayers. 57Fe CEM spectra of pulse plated iron revealed the presence of a minor doublet attributed mainly to γ-FeOOH in addition to the dominant sextet of α-iron. In the case of anodically oxidized pulse plated iron and of samples after repeated deposition of anodically oxidized pulse plated iron an additional minor doublet, assigned to ferrous chloride, also appears in the Moessbauer spectra. A significant change in the magnetic anisotropy of α-iron was observed with the anodic oxidation. The thickness of the layers were estimated from the CEM spectrum data by a modified computer program of the Liljequist method. The coercive field and the power loss versus frequency data showed that the pulse plated iron cores are good inductive elements up to several kHz frequencies

Colorimetric determination of Fe2+/Fe3+ ratio in radioactive glasses

International Nuclear Information System (INIS)

Coleman, C.J.; Baumann, E.W.; Bibler, N.E.

1992-01-01

In the vitrification of nuclear wastes, the Fe 2+ /Fe 3+ ratio in the glass is a measure of the redox properties of the glass melt. It is necessary to measure this ratio to ensure that the melt redox properties are suitable for the glass melter. A colorimetric method for measuring the Fe 2+ /Fe 3+ ratio in highly radioactive glasses was developed and tested remotely in a shielded cell. The tests were performed on glasses similar in composition and radioactivity to those that will be produced in the Savannah River Site Defense Waste Processing Facility. The first step of the method is dissolution of finely crushed glass with a hydrofluoric/sulfuric acid mixture with ammonium vanadate added to preserve the Fe 2+ content of the glass during the dissolution. Boric acid is then added to complex fluoride and to destroy iron-fluoride complexes. After adjusting the solution to pH 5, FerroZine TM (trademark of the Hach Company, Loveland, CO) reagent is added to form a magenta-colored complex with Fe 2+ . The absorbance at 562 nm is measured by using a fiber optic-coupled photodiode array spectrophotometer. Ascorbic acid is then used to reduce all the iron in solution to Fe 2+ and the absorbance is again measured. The difference in absorbance measurements corresponds to the Fe 3+ in the sample and the Fe 2+ /Fe 3+ ratio can be calculated

Behaviour of Fe4O5-Mg2Fe2O5 solid solutions and their relation to coexisting Mg-Fe silicates and oxide phases

Science.gov (United States)

Uenver-Thiele, Laura; Woodland, Alan B.; Miyajima, Nobuyoshi; Ballaran, Tiziana Boffa; Frost, Daniel J.

2018-03-01

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5-Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg-Fe silicates. Multi-anvil experiments were performed at 11-20 GPa and 1100-1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least 1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot = 0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+ + [6]Mg2+ = 2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential "water-storing" mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298 = - 1981.5 kJ mol- 1. Solid solution is complete across the Fe4O5-Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg-Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.

57Fe Moessbauer and magnetic studies of ErFe12-xNbx

International Nuclear Information System (INIS)

Wang, J L; Campbell, S J; Cadogan, J M; Tegus, O; Edge, A V J

2005-01-01

The structural and magnetic properties of ErFe 12-x Nb x compounds (x 0.6, 0.7 and 0.8) have been investigated by x-ray diffraction, ac susceptibility and dc magnetization measurements and 57 Fe Moessbauer spectroscopy. Refinements of the x-ray diffraction patterns show that the Nb atoms preferentially occupy the 8i sites; this can be understood in the terms of enthalpy effects and differences in the metallic radii. The average Fe-Fe distance at the different sites is found to behave as d Fe-Fe (8i)> d Fe-Fe (8j)> d Fe-Fe (8f). The unit cell volume increases slightly with increasing Nb content, consistent with the larger radius of Nb compared with Fe. A spin reorientation from easy-axis at room temperature to easy-cone at low temperatures has been detected for all compounds. The spin reorientation temperatures T sr in ErFe 12-x Nb x compounds remain essentially unchanged (T sr ∼42-44 K) with increasing Nb concentration, whereas a significant decrease in T sr (T sr1 ∼236-204 K; T sr2 ∼154-94 K) is obtained in DyFe 12-x Nb x from x = 0.6 to 0.8. This can be understood by taking the different crystal-field terms responsible for the spin reorientation in the two systems into account. We find that the spin-reorientation process is particularly sensitive to the sixth-order term B 60 O 60 of the crystal field acting on the Er 3+ ion, due to its large and positive value of γ J . 57 Fe hyperfine interaction parameters and magnetic moments values have been determined for the 8i, 8j and 8f sites from the Moessbauer spectra. The weighted average 57 Fe hyperfine field values were found to follow a T 2 dependence; this suggests that a single-particle excitation mechanism is responsible for reduction of the 3d-sublattice magnetization with increasing temperature

Hyperfine fields of Fe in Nd2Fe14BandSm2Fe17N3

Science.gov (United States)

Akai, Hisazumi; Ogura, Masako

2015-03-01

High saturation magnetization of rare-earth magnets originates from Fe and the strong magnetic anisotropy stems from f-states of rare-earth elements such as Nd and Sm. Therefore the hyperfine fields of both Fe and rare-earth provide us with important pieces of information: Fe NMR enable us to detect site dependence of the local magnetic moment and magnetic anisotropy (Fe sites also contribute to the magnetic anisotropy) while rare-earth NQR directly give the information of electric field gradients (EFG) that are related to the shape of the f-electron cloud as well as the EFG produced by ligands. In this study we focus on the hyperfine fields of materials used as permanent magnets, Nd2Fe14BandSm2Fe17N3 from theoretical points of view. The detailed electronic structure together with the hyperfine interactions are discussed on the basis of the first-principles calculation. In particular, the relations between the observed hyperfine fields and the magnetic properties are studies in detail. The effects of doping of those materials by other elements such as Dy and the effects of N adding in Sm2Fe17N3 will be discussed. This work was supported by Elements Strategy Initiative Center for Magnetic Materials Project, the Ministry of Education, Culture, Sports, Science and Technology, Japan.

Ferromagnetic resonance on oxideless magnetic Fe and FeRh nanoparticles; Ferromagnetische Resonanz an oxidfreien magnetischen Fe und FeRh Nanopartikeln

Energy Technology Data Exchange (ETDEWEB)

Trunova, Anastasia

2009-05-25

This work is dedicated to investigations of structural and magnetic properties of the colloidal Fe/Fe{sub x}O{sub y} nanocubes (13 nm) and the Fe{sub x}Rh{sub 100-x} core/shell nanoparticles (2 nm). As compared with other works, where the measurements on oxidized nanoparticles were carried out, we additionally performed investigations on nanoparticles in an oxide free state. In order to make the measurements on oxide free particles possible, oxygen- and hydrogenplasma was used to remove the ligands and reduce the oxide shell of the Fe nanocubes. The oxide free Fe nanocubes were covered with a Ag/Pt protective coating to prevent them from new oxidation. This method allowed carrying out the magnetic measurements on oxide free Fe nanocubes. Micromagnetic simulations as well as simulations of the high frequency susceptibility were used for the data analysing. It was found that both the g-factor g=2.09{+-}0.01 and the anisotropy constant K{sub 4}=(4.8{+-}0.5).10{sup 4} J/m{sup 3} coincide with that of bulk iron. However, the saturation magnetization M{sub S}(5 K)=(1.2{+-}0.12).10{sup 6} A/m differs from the bulk value by 30%. The reduction by 30% compared to the bulk value in the case of nanoparticles may be caused by the following possible reasons: a) the presence of inner oxide layer (approx. 10 at.%) that cannot be reduced; b) the anti-parallel order between magnetic moments of iron core and magnetic moments of antiferomagnetic iron oxide; c) some structural changes of the surface after plasma treatment. The obtained damping parameter {alpha}=0.03{+-}0.005 is ten times larger than that of the Fe layers as it is known for nanoparticles systems in general. The core/shell Fe{sub x}Rh{sub 100-x} nanoparticles (x=80,50) were produced under Ar-atmosphere and were sealed into a quartz tube to prevent oxidation. The analysis of g-factors shows that the value for the FePh nanoparticles with Fe-rich core is larger (g=2.08{+-}0.01) than that for the nanoparticles with Rh

Kerr microscopy study of exchange-coupled FePt/Fe exchange spring magnets

Energy Technology Data Exchange (ETDEWEB)

Hussain, Zaineb; Kumar, Dileep [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001 (India); Reddy, V. Raghavendra, E-mail: varimalla@yahoo.com [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001 (India); Gupta, Ajay [Amity Center for Spintronic Materials, Amity University, Noida 201303 (India)

2017-05-15

Magnetization reversal and magnetic microstructure of top soft magnetic layer (Fe) in exchange spring coupled L1{sub 0} FePt/Fe is studied using high resolution Kerr microscopy. With remnant state of the hard magnetic layer (L1{sub 0} FePt) as initial condition, magnetization loops along with magnetic domains are recorded for the top soft magnetic layer (Fe) using Kerr microscopy. Considerable shifting of Fe layer hysteresis loop from center which is similar to exchange bias phenomena is observed. It is also observed that one can tune the magnitude of hysteresis shift by reaching the remanent state from different saturating fields (H{sub SAT}) and also by varying the angle between measuring field and H{sub SAT}. The hysteresis loops and magnetic domains of top soft Fe layer demonstrate unambiguously that soft magnetic layer at remanent state in such exchange coupled system is having unidirectional anisotropy. An analogy is drawn and the observations are explained in terms of established model of exchange bias phenomena framed for field-cooled ferromagnetic - antiferromagnetic bilayer systems. - Highlights: • Kerr microscopy of top soft magnetic Fe layer in exchange spring coupled L1{sub 0} FePt (30 nm)/Fe (22 nm) is reported. • Considerable shifting of Fe layer hysteresis loop from center which is similar to exchange bias phenomena is observed. • Tuneable nature of magnitude of hysteresis shift is shown. • It is unambiguously shown that the top soft Fe magnetic layer at remanent state is having unidirectional anisotropy.

Fe2O3/Reduced Graphene Oxide/Fe3O4 Composite in Situ Grown on Fe Foil for High-Performance Supercapacitors.

Science.gov (United States)

Zhao, Chongjun; Shao, Xiaoxiao; Zhang, Yuxiao; Qian, Xiuzhen

2016-11-09

A Fe 2 O 3 /reduced graphene oxide (RGO)/Fe 3 O 4 nanocomposite in situ grown on Fe foil was synthesized via a simple one-step hydrothermal growth process, where the iron foil served as support, reductant of graphene oxide, Fe source of Fe 3 O 4 , and also the current collector of the electrode. When it directly acted as the electrode of a supercapacitor, as-synthesized Fe 2 O 3 /RGO/Fe 3 O 4 @Fe exhibited excellent electrochemical performance with a high capability of 337.5 mF/cm 2 at 20 mA/cm 2 and a superior cyclability with 2.3% capacity loss from the 600th to the 2000th cycle.

Ferromagnetic resonance study of sputtered NiFe/V/NiFe heterostructures

Energy Technology Data Exchange (ETDEWEB)

Alayo, W., E-mail: willian.rodriguez@ufpel.edu.br [Departamento de Física – IFM, Universidade Federal de Pelotas, 96010-900 Rio Grande do Sul (Brazil); Pelegrini, F. [Instituto de Física, Universidade Federal de Goiás, Goiânia, 74001-970 (Brazil); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro, RJ, 22290-180 (Brazil)

2015-03-01

The Ni{sub 81}Fe{sub 19}/V/Ni{sub 81}Fe{sub 19} heterostructures has been produced by magnetron sputtering and analyzed by ferromagnetic resonance. Two systems were investigated: the non symmetrical NiFe(50 Å)/V(t)/NiFe(30 Å) trilayers and the symmetrical NiFe(80 Å)/V(t)/NiFe(80 Å) trilayers, with variable ultrathin V thickness t. Ferromagnetic exchange coupling was evidenced for t below 10 Å by the excitation of the optic mode, in the case of the non symmetrical samples, and by the observation of a single resonance mode for the symmetrical trilayers. For larger V thickness, all samples exhibited two modes, which were attributed to the resonance of the individual NiFe layers with different effective magnetizations. The analysis with the equilibrium and resonance conditions provided the exchange coupling constants and effective magnetizations. - Highlights: • We present a study of symmetrical and non symmetrical NiFe/V/NiFe trilayers deposited on Si single crystals by ferromagnetic resonance (FMR) at room temperature. • For the non symmetrical trilayers, the FMR spectra show the optic and acoustic modes for samples with very thin V layer thicknesses, evidencing ferromagnetic exchange coupling, whereas, for larger V thickness, the spectra exhibited two well resolved modes associated to each independent NiFe layer. For the symmetrical trilayers, strong ferromagnetic exchange coupling is evidenced by the observation of a single resonance mode. • The analysis with the equilibrium condition and dispersion relation provides the exchange coupling constants and effective magnetizations.

Fe-Vacancy-Induced Ferromagnetism in Tetragonal FeSe Thin Films

International Nuclear Information System (INIS)

Yong-Feng, Li; Gui-Bin, Liu; Li-Jie, Shi; Bang-Gui, Liu

2009-01-01

Motivated by recent experiments, we investigate structural, electronic, and magnetic properties of tetragonal FeSe with Fe vacancies using the state-of-the-art first-principles method. We show that Fe vacancies tend to stay in the same one of the two sublattices and thus induce ferromagnetism in the ground-state phase. Our calculated net moment is in good agreement with the experimental data available. Therefore, the ferromagnetism observed in tetragonal FeSe thin films is explained. It could be made controllable soon for spintronic applications

Mössbauer Studies of Core-Shell FeO/Fe3O4 Nanoparticles

Science.gov (United States)

Kamzin, A. S.; Valiullin, A. A.; Khurshid, H.; Nemati, Z.; Srikanth, H.; Phan, M. H.

2018-02-01

FeO/Fe3O4 nanoparticles were synthesized by thermal decomposition. Electron microscopy revealed that these nanoparticles were of the core-shell type and had a spherical shape with an average size of 20 nm. It was found that the obtained FeO/Fe3O4 nanoparticles had exchange coupling. The effect of anisotropy on the efficiency of heating (hyperthermic effect) of FeO/Fe3O4 nanoparticles by an external alternating magnetic field was examined. The specific absorption rate (SAR) of the studied nanoparticles was 135 W/g in the experiment with an external alternating magnetic field with a strength of 600 Oe and a frequency of 310 kHz. These data led to an important insight: the saturation magnetization is not the only factor governing the SAR, and the efficiency of heating of magnetic FeO/Fe3O4 nanoparticles may be increased by enhancing the effective anisotropy. Mössbauer spectroscopy of the phase composition of the synthesized nanoparticles clearly revealed the simultaneous presence of three phases: magnetite Fe3O4, maghemite γ-Fe2O3, and wustite FeO.

Neutron irradiation effects in Fe and Fe-Cr at 300 °C

International Nuclear Information System (INIS)

Chen, Wei-Ying; Miao, Yinbin; Gan, Jian; Okuniewski, Maria A.; Maloy, Stuart A.; Stubbins, James F.

2016-01-01

Fe and Fe-Cr (Cr = 10–16 at.%) specimens were neutron-irradiated at 300 °C to 0.01, 0.1 and 1 dpa. The TEM observations indicated that the Cr significantly reduced the mobility of dislocation loops and suppressed vacancy clustering, leading to distinct damage microstructures between Fe and Fe-Cr. Irradiation-induced dislocation loops in Fe were heterogeneously observed in the vicinity of grown-in dislocations, whereas the loop distribution observed in Fe-Cr is much more uniform. Voids were observed in the irradiated Fe samples, but not in irradiated Fe-Cr samples. Increasing Cr content in Fe-Cr results in a higher density, and a smaller size of irradiation-induced dislocation loops. Orowan mechanism was used to correlate the observed microstructure and hardening, which showed that the hardening in Fe-Cr can be attributed to the formation of dislocation loops and α′ precipitates. -- Graphical abstract: Addition of Cr in Fe suppressed the mobility of mobile 1/2<111> dislocation loops and increased the proportion of immobile <100> dislocation loops, leading to a transition of loop distribution from highly heterogeneous to uniform. Display Omitted

Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording

International Nuclear Information System (INIS)

Chen Ziyu; Li Fashen

1998-01-01

Combining Moessbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core (α-Fe)/shell (γ'-Fe 4 N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in γ'-Fe 4 N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future

Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording

Energy Technology Data Exchange (ETDEWEB)

Chen Ziyu; Li Fashen [Lanzhou University, Department of Physics (China)

1998-12-15

Combining Moessbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core ({alpha}-Fe)/shell ({gamma}'-Fe{sub 4}N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in {gamma}'-Fe{sub 4}N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future.

Exchange biased FeNi/FeMn bilayers with coercivity and switching field enhanced by FeMn surface oxidation

Directory of Open Access Journals (Sweden)

A. V. Svalov

2013-09-01

Full Text Available FeNi/FeMn bilayers were grown in a magnetic field and subjected to heat treatments at temperatures of 50 to 350 °C in vacuum or in a gas mixture containing oxygen. In the as-deposited state, the hysteresis loop of 30 nm FeNi layer was shifted. Low temperature annealing leads to a decrease of the exchange bias field. Heat treatments at higher temperatures in gas mixture result in partial oxidation of 20 nm thick FeMn layer leading to a nonlinear dependence of coercivity and a switching field of FeNi layer on annealing temperature. The maximum of coercivity and switching field were observed after annealing at 300 °C.

Spin-dependent electronic transport characteristics in Fe4N/BiFeO3/Fe4N perpendicular magnetic tunnel junctions

Science.gov (United States)

Yin, Li; Wang, Xiaocha; Mi, Wenbo

2018-01-01

Perpendicular magnetic tunnel junctions (MTJs) have attracted increasing attention owing to the low energy consumption and wide application prospects. Herewith, against Julliere's formula, an inverse tunnel magnetoresistance (TMR) appears in tetragonal Fe4N/BiFeO3/Fe4N perpendicular MTJs, which is attributed to the binding between the interface resonant tunneling state and central (bordered) hot spots. Especially, antiferromagnetic BiFeO3 shows an extra spin-polarized resonant state in the barrier, which provides a magnetic-barrier factor to affect the tunneling transport in MTJs. Meanwhile, due to the spin-polarized transport in Fe4N/BiFeO3/Fe4N MTJs, the sign of TMR can be tuned by the applied bias. The tunable TMR and resonant magnetic barrier effect pave the way for clarifying the tunneling transport in other junctions and spintronic devices.

Effect of Fe-Mn addition on microstructure and magnetic properties of NdFeB magnetic powders

Science.gov (United States)

Kurniawan, C.; Purba, A. S.; Setiadi, E. A.; Simbolon, S.; Warman, A.; Sebayang, P.

2018-03-01

In this paper, the effect of Fe-Mn alloy addition on microstructures and magnetic properties of NdFeB magnetic powders was investigated. Varied Fe-Mn compositions of 1, 5, and 10 wt% were mixed with commercial NdFeB type MQA powders for 15 minutes using shaker mill. The characterizations were performed by powder density, PSA, XRD, SEM, and VSM. The Fe-Mn addition increased the powder density of NdFeB/Fe-Mn powders. On the other side, particle size distribution slightly decreased as the Fe-Mn composition increases. Magnetic properties of NdFeB/Fe-Mn powders changed with the increasing of Fe-Mn content. SEM analysis showed the particle size of NdFeB/Fe-Mn powder was smaller as the Fe-Mn composition increases. It showed that NdFeB/Fe-Mn particles have different size and shape for NdFeB and Fe-Mn particles separately. The optimum magnetic properties of NdFeB/Fe-Mn powder was achieved on the 5 wt% Fe-Mn composition with remanence M r = 49.45 emu/g, coercivity H c = 2.201 kOe, and energy product, BH max = 2.15 MGOe.

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

Science.gov (United States)

Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

2013-05-01

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

Science.gov (United States)

Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

2014-04-01

Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

Asymmetric interfaces in Fe/Ag and Ag/Fe bilayers prepared by molecular beam evaporation

Energy Technology Data Exchange (ETDEWEB)

Tunyogi, A. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary)]. E-mail: tunyogi@rmki.kfki.hu; Paszti, F. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary); Osvath, Z. [MTA Research Institute for Technical Physics and Materials Science, P.O. Box 49, H-1525 Budapest (Hungary); Tancziko, F. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary); Major, M. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary); Szilagyi, E. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary)

2006-08-15

Single layers of Fe and Ag, as well as Fe/Ag (iron deposited first) and Ag/Fe bilayers were prepared by molecular beam evaporation onto Si. The samples were investigated with backscattering spectrometry (BS) and atomic force microscopy (AFM). BS spectra of Fe/Ag and Ag/Fe indicate a significant difference at the interface. In the case of Fe/Ag the Ag peak has a long tail at the interface, while for Ag/Fe the interface is abrupt. The tail in the Fe/Ag spectrum is too large to be caused by double or plural scattering. According to AFM, the effect of surface roughness is also negligible. In spite of the fact that Fe and Ag are completely immiscible in equilibrium, this tail, however, suggests that some Ag is located in the Fe layer. After annealing, both samples show mixing between the two layers; this is much larger again for Fe/Ag.

Influence of ruthenium ions on the precipitation of α-FeOOH, α-Fe2O3 and Fe3O4 in highly alkaline media

International Nuclear Information System (INIS)

Krehula, Stjepko; Music, Svetozar

2006-01-01

The influence of ruthenium ions on the precipitation of goethite (α-FeOOH), α-Fe 2 O 3 and Fe 3 O 4 in highly alkaline media was investigated by 57 Fe Moessbauer and FT-IR spectroscopies, thermal field emission scanning electron microscope (FE SEM) and EDS. The presence of Ru-dopant strongly affected the precipitation of α-FeOOH at highly alkaline pH, i.e. the formation of α-Fe 2 O 3 was also noticed. A decrease of hyperfine magnetic field (HMF) at RT from 35.1 T (undoped α-FeOOH) to 31.3 T for sample with [Ru]/([Ru] + [Fe]) = 0.0196 was assigned to the incorporation of ruthenium ions into the α-FeOOH structure. Moessbauer spectroscopy showed the formation of stoichiometric Fe 3 O 4 for [Ru]/([Ru] + [Fe]) = 0.0291-0.0909. α-Fe 2 O 3 and Fe 3 O 4 did not show a tendency to the formation of solid solutions with ruthenium ions. FE SEM observations of the samples showed that reference α-FeOOH sample contained acicular particles of good uniformity, which increased the length up to ∼5 times with increase of concentration of ruthenium ions. On the other hand, large octahedral Fe 3 O 4 crystals (particles) were associated with small particles of ruthenium (hydrous) oxide with a size in the range ∼100 nm or less. A possible catalytic action of ruthenium that created reduction conditions for Fe 3+ ions and formation of Fe 2+ ions for precipitation of Fe 3 O 4 was discussed

Experimental and thermodynamic assessments of substitutions in the AlFeSi, FeMnSi, FeSiZr and AlCaFeSi systems (65 wt % Si) - solidification simulation

International Nuclear Information System (INIS)

Gueneau, C.; Ansara, I.

1994-01-01

The substitutions of Al Si, Fe Mn and Fe Zr in some intermetallic compounds of the Al-Fe-Si, Fe-Mn-Si and Fe-Si-Zr systems are modelled in the Si-rich corner using a two sublattice model. The solidification paths of the studied alloys are determined at equilibrium. The ascalculated phase volume fractions of the alloys are compared to the experimental ones. Finally, a solidification simulation using the Gulliver-Scheil's model is performed in order to explain the formation of some precipitates experimentally observed. (authors). 14 figs., 19 refs

FeEDDHA-facilitated Fe uptake in relation to the behaviour of FeEDDHA components in the soil-plant system as a function of time and dosage.

OpenAIRE

Schenkeveld, W.D.C.; Temminghoff, E.J.M.; Reichwein, A.M.; Riemsdijk, van, W.H.

2010-01-01

FeEDDHA products are widely used to prevent and remedy Fe chlorosis in crops grown on calcareous soils. These products consist of a mixture of FeEDDHA components: racemic o,o-FeEDDHA, meso o,o-FeEDDHA, o,p-FeEDDHA and rest-FeEDDHA. The FeEDDHA components differ in physical and chemical properties, and as a consequence also in effectiveness as Fe fertilizer. In order to efficiently match dose, frequency and moment of FeEDDHA application with the Fe requirements of plants, it is important to un...

Synthesis and characterization of magnetic Fe/CNTs composites with controllable Fe nanoparticle concentration

International Nuclear Information System (INIS)

Zhao Fan; Duan Hongyan; Wang Weigao; Wang Jun

2012-01-01

Fe/CNTs composites, with different concentrations of Fe nanoparticles (NPs) on carbon nanotube (CNT) surfaces, were successfully fabricated via a facile solvothermal method. The lengths of CNTs are up to 10 μm and the mean diameter of the Fe nanoparticles is about 25 nm. The structures, composition and magnetic properties of the Fe/CNTs were characterized by XRD, FTIR, FE-SEM, TEM and PPMS. We found that the concentrations of Fe nanoparticles depositing on the CNTs could be controlled by adjusting the initial mass ratio of ferrocene to CNTs. The Fe/CNTs composites display good ferromagnetic properties at room temperature, with a saturation magnetization of 125 emu/g-Fe and a coercivity of 276 Oe. The Curie temperature of the sample is about 1038 K, slightly lower than that (1043 K) of the bulk iron.

Formation and stability of Fe-rich precipitates in dilute Zr(Fe) single-crystal alloys

International Nuclear Information System (INIS)

Zou, H.; Hood, G.M.; Roy, J.A.; Schultz, R.J.

1993-02-01

The formation and stability of Fe-rich precipitates in two α-Zr(Fe) single-crystal alloys with nominal compositions (I, 50 ppma Fe, and II, 650 ppma Fe) have been investigated (the maximum solid solubility of Fe in α-Zr is 180 ppma - 800 C). Optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to examine the characteristics of Fe-rich precipitates. SEM and TEM micrographs show that in as-grown alloy II, Zr 2 Fe precipitates are located at 'stringers'. Precipitates were not observed in as-grown alloy I. During annealing, below the solvus, Fe diffuses to the surfaces to form Zr 3 Fe precipitates in both alloys. The precipitates on the surfaces of alloy I tend to be star-like (0001) or pyramidal (1010), and their distribution is heterogeneous. Dissolution of Zr 3 Fe surface precipitates of alloy I (annealing above the solvus) leaves precipitate-like features on the surfaces. Zr 2 Fe precipitates in as-grown alloy II can be dissolved only by β-phase annealing. (Author) 8 figs., 18 refs

FeEDDHA-facilitated Fe uptake in relation to the behaviour of FeEDDHA components in the soil-plant system as a function of time and dosage.

NARCIS (Netherlands)

Schenkeveld, W.D.C.; Temminghoff, E.J.M.; Reichwein, A.M.; Riemsdijk, van W.H.

2010-01-01

FeEDDHA products are widely used to prevent and remedy Fe chlorosis in crops grown on calcareous soils. These products consist of a mixture of FeEDDHA components: racemic o,o-FeEDDHA, meso o,o-FeEDDHA, o,p-FeEDDHA and rest-FeEDDHA. The FeEDDHA components differ in physical and chemical properties,

Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

Science.gov (United States)

Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

2018-02-02

The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

Mössbauer spectroscopic studies in U-Fe and U-Fe-Zr alloys

Energy Technology Data Exchange (ETDEWEB)

Panda, Alaka; Singh, L. Herojit; Rajagopalan, S.; Govindaraj, R., E-mail: govind@igcar.gov.in; Ramachandran, Renjith; Kalavathi, S.; Amarendra, G. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India)

2016-05-23

{sup 57}Fe Mössbauer studies have been carried out in an alloy of U and Fe with atomic percentage in the ratio of 68%:32% in order to understand the local structure and valence of Fe atoms associated with different phases that may get formed. The effect of changes in the hyperfine parameters such as isomer shift and quadrupole splitting at Fe sites due to additional alloying of Zr has been studied in an alloy of U, Fe and Zr in the ratio of 44%:33%:23% respectively with respect to that of the U-Fe alloy chosen in the present study. Possible effect of solute clustering in these systems has been addressed in an analogous alloy of uranium and zirconium using positron lifetime spectroscopy.

Reactions of laser-ablated iron atoms and cations with carbon monoxide: Infrared spectra of FeCO+, Fe(CO)2+, Fe(CO)x, and Fe(CO)x- (x=1-4) in solid neon

Science.gov (United States)

Zhou, Mingfei; Andrews, Lester

1999-06-01

Laser-ablated iron atoms, cations, and electrons have been reacted with CO molecules during condensation in excess neon. The FeCO molecule is observed at 1933.7 cm-1 in solid neon. Based on isotopic shifts and density functional calculations, the FeCO molecule has the same 3Σ- ground state in solid neon that has been observed at 1946.5 cm-1 in a recent high resolution gas phase investigation [Tanaka et al., J. Chem. Phys. 106, 2118 (1997)]. The C-O stretching vibration of the Fe(CO)2 molecule is observed at 1917.1 cm-1 in solid neon, which is in excellent agreement with the 1928.2 cm-1 gas phase value for the linear molecule. Anions and cations are also produced and trapped, absorptions at 1782.0, 1732.9, 1794.5, and 1859.7 cm-1 are assigned to the linear FeCO-, Fe(CO)2-, trigonal planar Fe(CO)3-, and C3v Fe(CO)4- anions, respectively, and 2123.0, 2134.0 cm-1 absorptions to the linear FeCO+ and Fe(CO)2+ cations. Doping these experiments with CCl4 virtually eliminates the anion absorptions and markedly increases the cation absorptions, which confirms the charge identifications. Higher iron carbonyl Fe(CO)3, Fe(CO)4, and Fe(CO)5 absorptions are produced on photolysis.

Stability of the high pressure phase Fe3S2 up to Earth's core pressures in the Fe-S-O and the Fe-S-Si systems

Science.gov (United States)

Zurkowski, C. C.; Chidester, B.; Davis, A.; Brauser, N.; Greenberg, E.; Prakapenka, V. B.; Campbell, A.

2017-12-01

Earth's core is comprised of an iron-nickel alloy that contains 5-15% of a light element component. The abundance and alloying capability of sulfur, silicon and oxygen in the bulk Earth make them important core alloy candidates; therefore, the high-pressure phase equilibria of the Fe-S-O and Fe-S-Si systems are relevant for understanding the possible chemistry of Earth's core. Previously, a Fe3S2 phase was recognized as a low-pressure intermediate phase in the Fe-FeS system that is stable from 14-21 GPa, but the structure of this phase has not been resolved. We report in-situ XRD and chemical analysis of recovered samples to further examine the stability and structure of Fe3S2 as it coexists with other phases in the Fe-S-O and Fe-S-Si systems. In situ high P-T synchrotron XRD experiments were conducted in the laser-heated diamond anvil cell to determine the equilibrium phases in Fe75S7O18 and Fe80S5Si15 compositions between 30 and 174 GPa and up to 3000 K. In the S,O-rich samples, an orthorhombic Fe3S2 phase coexists with hcp-Fe, Fe3S and FeO and undergoes two monoclinic distortions between 60 and 174 GPa. In the S,Si-rich samples, the orthorhombic Fe3S2 phase was observed up to 115 GPa. With increasing pressure, the Fe3S2 phase becomes stable to higher temperatures in both compositions, suggesting possible Fe3(S,O)2 or Fe3(S,Si)2 solid solutions. SEM analysis of a laser heated Fe75S7O18 sample recovered from 40 GPa and 1450 K confirms a Fe3(S,O)2 phase with O dissolved into the structure. Based on the current melting data in the Fe-S-O and Fe-S-Si systems, the Fe3(S,O)2 stability field intersects the solidus in the outer core and could be a possible liquidus phase in Fe,S,O-rich planetary cores, whereas Fe3S is the stable sulfide at outer core pressures in Fe,S,Si-rich systems.

Moessbauer and XRD study of pulse plated Fe-P and Fe-Ni thin layers

International Nuclear Information System (INIS)

Miko, Annamaria; Kuzmann, Erno; Lakatos-Varsanyi, Magda; Kakay, Attila; Nagy, Ferenc; Varga, Lajos Karoly

2005-01-01

57 Fe conversion electron Moessbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe-P and Ni-Fe coatings. XRD and 57 Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe-P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe-P deposits pulse plated at medium long deposition time (t on = 2 ms), with short relaxation time (t off = 9 ms) and low current density (I p = 0.05 Acm -2 ) or at short deposition time (t on = 1 ms) with long relaxation time (t off = 250 ms) and high current density (I p = 1.0 Acm -2 ). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni-Fe alloy with a very fine, 5-8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni-Fe and Fe-P pulse plated thin layers.

Characterization of rust layer formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich environment by Cl and Fe K-edge XANES measurements

International Nuclear Information System (INIS)

Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

2005-01-01

Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akaganeite, lepidocrocite and magnetite. Among these iron oxides, akaganeite in particular is the major component in the rust. Additionally, the amount of akaganeite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akaganeite is generally considered to facilitate the corrosion of steel, but our results indicate that akaganeite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akaganeite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel. (author)

Speciative Determination of Dissolved Inorganic Fe(II), Fe(III) and Total Fe in Natural Waters by Coupling CPE with FAAS

International Nuclear Information System (INIS)

Gurkan, R.; Altunay, N.

2013-01-01

A new cloud point extraction (CPE) method for the preconcentration of trace iron speciation in natural waters prior to determination by flame atomic absorption spectrometry (FAAS) was developed in the present study. In this method, Fe(II) sensitively and selectively reacts with Calcon carboxylic acid (CCA) in presence of cetylpyridinium chloride (CPC) yielding a hydrophobic complex at pH 10.5, which is then entrapped in surfactant-rich phase. Total Fe was accurately and reliably determined after the reduction of Fe(III) to Fe(II) with sulfite. The amount of Fe(III) in samples was determined from the difference between total Fe and Fe(II). CPC was used not only as an auxiliary ligand in CPE, but also as sensitivity enhancement agent in FAAS. The nonionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114) was used as an extracting agent. The analytical variables affecting CPE efficiency were investigated in detail. The preconcentration/enhancement factors of 50 and 82 respectively, were obtained for the preconcentration of Fe(II) with 50 mL solution. Under the optimized conditions, the detection limit of Fe(II) in linear range of 0.2-60 μg L/sup -1/ was 0.06 μg L/sup -1/. The relative standard deviation was 2.7 percentage (20 μg L/sup -1/, N: 5), recoveries for Fe(II) were in range of 99.0-102.0 percentage for all water samples including certified reference materials (CRMs). In order to verify its accuracy, two CRMs were analyzed and the results obtained were statistically in good agreement with the certified values. (author)

Biosynthesis, isolation and characterization of {sup 57}Fe-enriched Phaseolus vulgaris ferritin after heterologous expression in Escherichia coli

Energy Technology Data Exchange (ETDEWEB)

Hoppler, Matthias [ETH Zurich, Laboratory of Human Nutrition, Zurich (Switzerland); Meile, Leo [ETH Zurich, Laboratory of Food Biotechnology, Zurich (Switzerland); Walczyk, Thomas [National University of Singapore, Department of Chemistry and Department of Biochemistry, Singapore (Singapore)

2008-01-15

Ferritin is the major iron storage protein in the biosphere. Iron stores of an organism are commonly assessed by measuring the concentration of the protein shell of the molecule in fluids and tissues. The amount of ferritin-bound iron, the more desirable information, still remains inaccessible owing to the lack of suitable techniques. Iron saturation of ferritin is highly variable, with a maximum capacity of 4,500 iron atoms per molecule. This study describes the direct isotopic labeling of a complex metalloprotein in vivo by biosynthesis, in order to measure ferritin-bound iron by isotope dilution mass spectrometry. [{sup 57}Fe]ferritin was produced by cloning and overexpressing the Phaseolus vulgaris ferritin gene pfe in Escherichia coli in the presence of {sup 57}FeCl{sub 2}. Recombinant ferritin was purified in a fully assembled form and contained approximately 1,000 iron atoms per molecule at an isotopic enrichment of more than 95% {sup 57}Fe. We did not find any evidence of species conversion of the isotopic label for at least 5 months of storage at -20 C. Transfer efficiency of enriched iron into [{sup 57}Fe]ferritin of 20% was sufficient to be economically feasible. Negligible amounts of non-ferritin-bound iron in the purified [{sup 57}Fe]ferritin solution allows for use of this spike for quantification of ferritin-bound iron by isotope dilution mass spectrometry. (orig.)

Properties of porous FeAlOy/FeAlx ceramic matrix composite ...

Indian Academy of Sciences (India)

Home; Journals; Bulletin of Materials Science; Volume 36; Issue 7. Properties of porous FeAlO/FeAl ceramic matrix composite influenced by mechanical activation of FeAl powder. V Usoltsev S Tikhov A Salanov V Sadykov G Golubkova O Lomovskii. Volume 36 Issue 7 December 2013 pp 1195-1200 ...

Obtention of the TiFe compound by high-energy milling of Ti+Fe and TiH{sub 2}+Fe powder mixtures; Obtencao do composto TiFe a partir da moagem de alta energia de misturas Ti+Fe e TiH{sub 2}+Fe

Energy Technology Data Exchange (ETDEWEB)

Falcao, R.B.; Dammann, E.D.C.C.; Rocha, C.J.; Leal Neto, R.M., E-mail: railson.falcao@usp.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencias e Tecnologia de Materiais. Lab. de Intermetalicos

2010-07-01

In this work TiFe compound was obtained by two process routes involving high-energy ball milling: mechanical alloying from Ti and Fe powders (route 1) and mechanical milling from TiH{sub 2} and Fe powders, both followed by an annealing heat treatment. Shaker and planetary ball mills were utilized for times varying from 1-25 hours. Milled and annealed powders were characterized by SEM and X-ray diffraction analyses. TiFe compound was formed in both routes. A strong powder adherence in the milling vial and balls occurred with route 1 in both mills. Powder adherence was significantly reduced by using TiH{sub 2} (route 2) mainly in the planetary mill, in spite of TiFe formation has only occurred after the annealing treatment. (author)

Spectrophotometric speciation of Fe(II) and Fe(III) using hydrazone-micelle systems and flow injections

International Nuclear Information System (INIS)

Khojali, Inas Osman

1999-04-01

Two hydrazones were synthesised, namely salicylhyrazone (SH) and trihydroxyacetophenone (THAPH) were synthesised with the objective of developing a method for determining of Fe(II) and Fe(III) in the presence of each other and hence the total iron.those hydrazones were selected so as to combine the ability of phenolic compounds to complex Fe(III) ions and the complexing characteristics of hydrazones. The complexes of Fe(II) S H and Fe(III) S H as well those of Fe(II)-THAPH and Fe(III)-THAPH had shown maximum absorbance at λ=412 nm which was not not modified by presence of micelles i.e. sodium n-dodecyl sulphate (SDS) and n-hexa dodecyl pyridinium bromide. The maximum absorbance for all complexes takes place around a neutral pH. Generally, in addition, of n-hexa dodecylpyridinium bromide to fe(II)-SH and Fe(III)-SH absorbance of the complexes increases with increasing the concentration of the micelle. The effects of the addition of sodium n-dodecyle sulphate (SDS) to Fe(III)-SH is also studied. Generally, increasing the concentration of the micelle decrease the absorbance of the complexes. To study the effect of the presence of Fe(II) and Fe(III) on the determination of each other,mixtures of Fe(II)-SH and Fe(III)-SH are studied. However, the use of ascorbic acid as a reducing reagent for Fe(III) did not produce the needed results but non reducible results, which may be due to the masking effect of ascorbic acid and thus making the metal not available to the ligand. However, conversion of Fe(II) to Fe(III) prior to the determination was avoided as this requires the use of oxidant, which will oxidise the ligand as well. To establish the condition for the maximum absorbance of THAPH complexes, the effect of the base was investigated by using sodium and ammonium hydroxide. Generally, increasing the concentration of the base decreases the abosrbance. as expected, ammonium hydroxide produced positive results than sodium hydroxide. After establishing the optimum Fi

Magnetic and structural characterizations on nanoparticles of FePt, FeRh and their composites

International Nuclear Information System (INIS)

Ko, Hnin Yu Yu; Suzuki, Takao; Nam, Nguyen T.; Phuoc, Nguyen N.; Cao Jiangwei; Hirotsu, Yoshihiko

2008-01-01

The various compositions of FePt and FeRh nanoparticles, and their composite particles have been fabricated by the solution-phase chemical method and their magnetic properties characterized. High-resolution transmission electron microscopic observations indicate that mono-dispersed FeRh and FePt/FeRh nanoparticles are fabricated with the average size of 3-5 nm. However, larger size particles are distributed in the annealed state. From X-ray diffraction results, the as-deposited FeRh nanoparticles reveal a chemically disordered fcc structure which can be transformed into CsCl-type structure through thermal annealing. Similarly, the annealed FePt nanoparticles show the L1 0 -phase fct structure although the fcc structure is apparent in the as-deposited state. It is also found that the first time in the exchange bias effect in the composite of ferromagnetic (FePt) and anti-ferromagnetic (FeRh) nanoparticles; result in a shift of the hysteresis loop after field cooling process

Moessbauer and XRD study of pulse plated Fe-P and Fe-Ni thin layers

Energy Technology Data Exchange (ETDEWEB)

Miko, Annamaria [Bay Zoltan Institute for Material Science (Hungary); Kuzmann, Erno, E-mail: kuzmann@para.chem.elte.hu [Eoetvoes Lorand University, Research Group for Nuclear Methods in Structural Chemistry, Hungarian Academy of Sciences, Department of Nuclear Chemistry (Hungary); Lakatos-Varsanyi, Magda [Bay Zoltan Institute for Material Science (Hungary); Kakay, Attila [Research Institute for Solid State Physics and Optics (Hungary); Nagy, Ferenc [Eoetvoes Lorand University, Research Group for Nuclear Methods in Structural Chemistry, Hungarian Academy of Sciences, Department of Nuclear Chemistry (Hungary); Varga, Lajos Karoly [Research Institute for Solid State Physics and Optics (Hungary)

2005-09-15

{sup 57}Fe conversion electron Moessbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe-P and Ni-Fe coatings. XRD and {sup 57}Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe-P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe-P deposits pulse plated at medium long deposition time (t{sub on} = 2 ms), with short relaxation time (t{sub off} = 9 ms) and low current density (I{sub p} = 0.05 Acm{sup -2}) or at short deposition time (t{sub on} = 1 ms) with long relaxation time (t{sub off} = 250 ms) and high current density (I{sub p} = 1.0 Acm{sup -2}). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni-Fe alloy with a very fine, 5-8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni-Fe and Fe-P pulse plated thin layers.

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

Science.gov (United States)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

2017-08-01

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

Structural and magnetic study of mechanically deformed Fe rich FeAlSi ternary alloys

International Nuclear Information System (INIS)

Legarra, E.; Apiñaniz, E.; Plazaola, F.

2012-01-01

Highlights: ► Addition of Si to binary Fe–Al alloys makes the disordering more difficult. ► Si addition opposes the large volume increase found in FeAl alloys with deformation. ► Disordering induces a redistribution of non-ferrous atoms around Fe atoms in Fe 75 Al 25−x Si x and Fe 70 Al 30−x Si x . ► Addition of Si to binary Fe 75 Al 25 and Fe 70 Al 30 alloys opposes the magnetic behavior induced by Al in the magnetism of Fe. ► Si inhibits the para-ferro transition found in Fe 60 Al 40 alloy with disordering. - Abstract: In this work we study systematically the influence of different Al/Si ratios on the magnetic and structural properties of mechanically disordered powder Fe 75 Al 25−x Si x , Fe 70 Al 30−x Si x and Fe 60 Al 40−x Si x alloys by means of Mössbauer spectroscopy, X-ray diffraction and magnetic measurements. In order to obtain different stages of disorder the alloys were deformed by different methods: crushing induction melted alloys and ball milling annealed (ordered) alloys using different number of balls and speed. X-ray and Mössbauer data show that mechanical deformation induces the disordered A2 structure in these alloys. The results indicate that addition of Si to binary Fe–Al alloys makes the disordering more difficult. In addition, X-ray diffraction patterns show that the normalized lattice parameter variation of the disordered alloys of each composition decreases monotonically with Si content, indicating clearly that Si addition opposes the large volume increase found in FeAl alloys with deformation. The study of the hyperfine fields indicates that there is a redistribution of non-ferrous atoms around Fe atoms with the disordering; indeed, there is an inversion of the behavior of the hyperfine field of the Fe atoms. On the other hand, the magnetic measurements indicate that addition of Si to binary Fe 75 Al 25 and Fe 70 Al 30 alloys opposes the magnetic behavior induced by Al in the magnetism of Fe.

Spectral distribution of Fe2+ photoionization cross section in InP:Fe

International Nuclear Information System (INIS)

Iikawa, F.

1985-01-01

Measurements of Fe 2+ ( 5 E) photoionization cross section in InP at 80 0 K, using constant current photoconductivity technique, were done. The spectrum presents a threshold energy of ∼ 0,65 eV due to the transition from Fe 2+ charge state, in the ground state, to Fe 3+ with an electron emission for the minimum conduction band. In the measurement of photoluminescence at ∼ 2 0 K, a wide emission of Fe complexe with the strong lattice interaction. In order to analyse the experimental data of Fe 2+ cross section in InP, a theoretical model was used. (M.C.K.) [pt

Insights into Resistance to Fe Deficiency Stress from a Comparative Study of In Vitro-Selected Novel Fe-Efficient and Fe-Inefficient Potato Plants

Directory of Open Access Journals (Sweden)

Georgina A. Boamponsem

2017-09-01

Full Text Available Iron (Fe deficiency induces chlorosis (IDC in plants and can result in reduced plant productivity. Therefore, development of Fe-efficient plants is of great interest. To gain a better understanding of the physiology of Fe-efficient plants, putative novel plant variants were regenerated from potato (Solanum tubersosum L. var. ‘Iwa’ callus cultures selected under Fe deficient or low Fe supply (0–5 μM Fe. Based on visual chlorosis rating (VCR, 23% of callus-derived regenerants were classified as Fe-efficient (EF and 77% as Fe-inefficient (IFN plant lines when they were grown under Fe deficiency conditions. Stem height was found to be highly correlated with internodal distance, leaf and root lengths in the EF plant lines grown under Fe deficiency conditions. In addition, compared to the IFN plant lines and control parental biotype, the EF plants including the lines named A1, B2, and B9, exhibited enhanced formation of lateral roots and root hairs as well as increased expression of ferritin (fer3 in the leaf and iron-regulated transporter (irt1 in the root. These morphological adaptations and changes in expression the fer3 and irt1 genes of the selected EF potato lines suggest that they are associated with resistance to low Fe supply stress.

Interstitial Fe in MgO

CERN Document Server

Mølholt, T E; Gunnlaugsson, H P; Svane, A; Masenda, H; Naidoo, D; Bharuth-Ram, K; Fanciulli, M; Gislason, H P; Johnston, K; Langouche, G; Ólafsson, S; Sielemann, R; Weyer, G

2014-01-01

Isolated Fe-57 atoms were studied in MgO single-crystals by emission Mossbauer spectroscopy following implantation of Mn-57 decaying to Fe-57. Four Mossbauer spectral components were found corresponding to different Fe lattice positions and/or charge states. Two components represent Fe atoms substituting Mg as Fe2+ and Fe3+, respectively; a third component is due to Fe in a strongly implantation-induced disturbed region. The fourth component, which is the focus of this paper, can be assigned to Fe at an interstitial site. Comparison of its measured isomer shift with ab initio calculations suggests that the interstitial Fe is located on, or close to, the face of the rock-salt MgO structure. To harmonize such an assignment with the measured near-zero quadrupole interaction a local motion process (cage motion) of the Fe has to be stipulated. The relation of such a local motion as a starting point for long range diffusion is discussed.

Photosynthetic fuel for heterologous enzymes

DEFF Research Database (Denmark)

Mellor, Silas Busck; Vavitsas, Konstantinos; Nielsen, Agnieszka Janina Zygadlo

2017-01-01

of reducing power. Recent work on the metabolic engineering of photosynthetic organisms has shown that the electron carriers such as ferredoxin and flavodoxin can be used to couple heterologous enzymes to photosynthetic reducing power. Because these proteins have a plethora of interaction partners and rely...... on electrostatically steered complex formation, they form productive electron transfer complexes with non-native enzymes. A handful of examples demonstrate channeling of photosynthetic electrons to drive the activity of heterologous enzymes, and these focus mainly on hydrogenases and cytochrome P450s. However......, competition from native pathways and inefficient electron transfer rates present major obstacles, which limit the productivity of heterologous reactions coupled to photosynthesis. We discuss specific approaches to address these bottlenecks and ensure high productivity of such enzymes in a photosynthetic...

A method for determination of [Fe3+]/[Fe2+] ratio in superparamagnetic iron oxide

Science.gov (United States)

Jiang, Changzhao; Yang, Siyu; Gan, Neng; Pan, Hongchun; Liu, Hong

2017-10-01

Superparamagnetic iron oxide nanoparticles (SPION), as a kind of nanophase materials, are widely used in biomedical application, such as magnetic resonance imaging (MRI), drug delivery, and magnetic field assisted therapy. The magnetic property of SPION has close connection with its crystal structure, namely it is related to the ratio of Fe3+ and Fe2+ which form the SPION. So a simple way to determine the content of the Fe3+ and Fe2+ is important for researching the property of SPION. This review covers a method for determination of the Fe3+ and Fe2+ ratio in SPION by UV-vis spectrophotometry based the reaction of Fe2+ and 1,10-phenanthroline. The standard curve of Fe with R2 = 0.9999 is used for determination the content of Fe2+ and total iron with 2.5 mL 0.01% (w/v) SPION digested by HCl, pH = 4.30 HOAc-NaAc buffer 10 mL, 0.01% (w/v) 1,10-phenanthroline 5 mL and 10% (w/v) ascorbic acid 1 mL for total iron determine independently. But the presence of Fe3+ interfere with obtaining the actual value of Fe2+ (the error close to 9%). We designed a calibration curve to eliminate the error by devising a series of solution of different ratio of [Fe3+]/[Fe2+], and obtain the calibration curve. Through the calibration curve, the error between the measured value and the actual value can be reduced to 0.4%. The R2 of linearity of the method is 0.99441 and 0.99929 for Fe2+ and total iron respectively. The error of accuracy of recovery and precision of inter-day and intra-day are both lower than 2%, which can prove the reliability of the determination method.

Electric-field tunable perpendicular magnetic anisotropy in tetragonal Fe4N/BiFeO3 heterostructures

Science.gov (United States)

Yin, Li; Wang, Xiaocha; Mi, Wenbo

2017-07-01

Electric field control on perpendicular magnetic anisotropy (PMA) is indispensable for spintronic devices. Herewith, in tetragonal Fe4N/BiFeO3 heterostructures with the FeAFeB/Fe-O2 interface, PMA in each Fe4N layer, not merely interfacial layers, is modulated by the electric field, which is attributed to the broken spin screening of the electric field in highly spin-polarized Fe4N. Moreover, the periodical dx y+dy z+dz2 and dx y+dx2-y2 orbital-PMA oscillation enhances the interactions between adjacent FeAFeB and (FeB)2N atomic layers, which benefits the electric field modulation on PMA in the whole Fe4N atomic layers. The electric-field control on PMA in Fe4N/BiFeO3 heterostructures is favored by the electric-field-lifted potential in Fe4N.

Magnetic nanowires (Fe, Fe-Co, Fe-Ni – magnetic moment reorientation in respect of wires composition

Directory of Open Access Journals (Sweden)

Kalska-Szostko Beata

2015-03-01

Full Text Available Magnetic nanowires of Fe, Fe-Co, and Fe-Ni alloy and layered structure were prepared by electrochemical alternating current (AC deposition method. The morphology of the nanowires in and without the matrix was studied by energy dispersive X-ray spectroscopy (EDX, scanning electron microscopy (SEM, and X-ray diffraction (XRD, respectively. The wires either show strong dependence on the combination of elements deposition (alloy or layered or chemical composition (Co or Ni. The magnetic properties of the nanostructures were determined on the basis of Mössbauer spectroscopy (MS.

Fe-Impregnated Mineral Colloids for Peroxide Activation: Effects of Mineral Substrate and Fe Precursor.

Science.gov (United States)

Li, Yue; Machala, Libor; Yan, Weile

2016-02-02

Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.

Rapid thermal annealing of FePt and FePt/Cu thin films

Energy Technology Data Exchange (ETDEWEB)

Brombacher, Christoph

2011-01-10

Chemically ordered FePt is one of the most promising materials to reach the ultimate limitations in storage density of future magnetic recording devices due to its high uniaxial magnetocrystalline anisotropy and a corrosion resistance superior to rare-earth based magnets. In this study, FePt and FePt/Cu bilayers have been sputter deposited at room temperature onto thermally oxidized silicon wafers, glass substrates and self-assembled arrays of spherical SiO{sub 2} particles with diameters down to 10 nm. Millisecond flash lamp annealing, as well as conventional rapid thermal annealing was employed to induce the phase transformation from the chemically disordered A1 phase into the chemically ordered L1{sub 0} phase. The influence of the annealing temperature, annealing time and the film thickness on the ordering transformation and (001) texture evolution of FePt films with near equiatomic composition was studied. Whereas flash lamp annealed FePt films exhibit a polycrystalline morphology with high chemical L1{sub 0} order, rapid thermal annealing can lead to the formation of chemically ordered FePt films with (001) texture on amorphous SiO{sub 2}/Si substrates. The resultant high perpendicular magnetic anisotropy and large coercivities up to 40 kOe are demonstrated. Simultaneously to the ordering transformation, rapid thermal annealing to temperatures exceeding 600 C leads to a break up of the continuous FePt film into separated islands. This dewetting behavior was utilized to create regular arrays of FePt nanostructures on SiO{sub 2} particle templates with periods down to 50 nm. The addition of Cu improves the (001) texture formation and chemical ordering for annealing temperatures T{sub a} {<=}600 C. In addition, the magnetic anisotropy and the coercivity of the ternary FePtCu alloy can be effectively tailored by adjusting the Cu content. The prospects of FePtCu based exchange spring media, as well as the magnetic properties of FePtCu nanostructures fabricated

High-frequency permeability of electroplated CoNiFe and CoNiFe-C alloys

International Nuclear Information System (INIS)

Rhen, Fernando M.F.; McCloskey, Paul; O'Donnell, Terence; Roy, Saibal

2008-01-01

We have investigated CoNiFe and CoNiFe-C electrodeposited by pulse reverse plating (PRP) and direct current (DC) techniques. CoNiFe(PRP) films with composition Co 59.4 Fe 27.7 Ni 12.8 show coercivity of 95 A m -1 (1.2 Oe) and magnetization saturation flux (μ 0 M s ) of 1.8 T. Resistivity of CoNiFe (PRP) is about 24 μΩ cm and permeability remains almost constant μ r ' ∼475 up to 30 MHz with a quality factor (Q) larger than 10. Additionally, the permeability spectra analysis shows that CoNiFe exhibits a classical eddy current loss at zero bias field and ferromagnetic resonance (FMR) when biased with 0.05 T. Furthermore, a crossover between eddy current and FMR loss is observed for CoNiFe-PRP when baised with 0.05 T. DC and PRP plated CoNiFe-C, which have resistivity and permeability of 85, 38 μΩ cm, μ r '=165 and 35 with Q>10 up to 320 MHz, respectively, showed only ferromagnetic resonance losses. The ferromagnetic resonance peaks in CoNiFe and CoNiFe-C are broad and resembles a Gaussian distribution of FMR frequencies. The incorporation of C to CoNiFe reduces eddy current loss, but also reduces the FMR frequency

NifI inhibits nitrogenase by competing with Fe protein for binding to the MoFe protein

International Nuclear Information System (INIS)

Dodsworth, Jeremy A.; Leigh, John A.

2007-01-01

Reduction of substrate by nitrogenase requires direct electron transfer from the Fe protein to the MoFe protein. Inhibition of nitrogenase activity in Methanococcus maripaludis occurs when the regulatory protein NifI 1,2 binds the MoFe protein. This inhibition is relieved by 2-oxoglutarate. Here we present evidence that NifI 1,2 binding prevents association of the two nitrogenase components. Increasing amounts of Fe protein competed with NifI 1,2 , decreasing its inhibitory effect. NifI 1,2 prevented the co-purification of MoFe protein with a mutant form of the Fe protein that forms a stable complex with the MoFe protein, and NifI 1,2 was unable to bind to an AlF 4 - -stabilized Fe protein:MoFe protein complex. NifI 1,2 inhibited ATP- and MoFe protein-dependent oxidation of the Fe protein, and 2OG relieved this inhibition. These results support a model where NifI 1,2 competes with the Fe protein for binding to MoFe protein and prevents electron transfer

Na7 [Fe2S6 ] , Na2 [FeS2 ] and Na2 [FeSe2 ] : New 'reduced' sodium chalcogenido ferrates

Science.gov (United States)

Stüble, Pirmin; Peschke, Simon; Johrendt, Dirk; Röhr, Caroline

2018-02-01

Three new 'reduced' FeII containing sodium chalcogenido ferrates were obtained applying a reductive synthetic route. The mixed-valent sulfido ferrate Na7 [Fe2S6 ] , which forms bar-shaped crystals with metallic greenish luster, was synthesized in pure phase from natural pyrite and elemental sodium at a maximum temperature of 800 °C. Its centrosymmetric triclinic structure (SG P 1 bar , a = 764.15(2), b = 1153.70(2), c = 1272.58(3) pm, α = 62.3325 (7) , β = 72.8345 (8) , γ = 84.6394 (8) ° , Z = 3, R1 = 0.0185) exhibits two crystallographically different [Fe2S6 ] 7 - dimers of edge-sharing [FeS4 ] tetrahedra, with somewhat larger Fe-S distances than in the fully oxidized FeIII dimers of e.g. Na6 [Fe2III S6 ] . In contrast to the localized AFM ordered pure di-ferrates(III), the Curie-Weiss behavior of the magnetic susceptibility proves the rarely observed valence-delocalized S = 9/2 state of the mixed-valent FeIII /FeII dimer. The nearly spin-only value of the magnetic moment combined with the chemical bonding not generally differing from that in pure ferrates(II) and (III), provides a striking argument, that the reduction of the local Fe spin moments observed in all condensed sulfido ferrate moieties is connected with the AFM spin ordering. The two isotypic ferrates(II) Na2 [FeS2 ] and Na2 [FeSe2 ] with chain-like structural units (SG Ibam, a = 643.54(8)/ 660.81(1), b = 1140.2(2)/1190.30(2) c = 562.90(6)/585.59(1) pm, Z = 4, R1 = 0.0372/0.0466) crystallize in the K2 [ZnO2 ] -type structure. Although representing merely further members of the common series of chalcogenido metallates(II) Na2 [MIIQ2 ] , these two new phases, together with Na6 [FeS4 ] and Li2 [FeS2 ] , are the only examples of pure FeII alkali chalcogenido ferrates. The new compounds allow for a general comparison of di- and chain ferrates(II) and (III) and mixed-valent analogs concerning the electronic and magnetic properties (including Heisenberg super-exchange and double-exchange interactions

Structural and magnetic properties of Ce/Fe and Ce/FeCoV multilayers

Energy Technology Data Exchange (ETDEWEB)

Tixier, S; Boeni, P [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Mannix, D; Stirling, W G [Liverpool Univ. (United Kingdom); Lander, G H

1997-09-01

Ce/Fe and Ce/FeCoV multilayers have been grown by magnetron sputtering. The interfaces are well defined and the layers are crystalline down to an individual layer thickness of 20 A. Ce/FeCoV multilayers show sharper interfaces than Ce/Fe but some loss of crystallinity is observed. Hysteresis loops obtained by SQUID show different behaviour of the bulk magnetisation as a function of the layer thickness. Fe moments are found by Moessbauer spectroscopy to be perpendicular to the interfaces for multilayers with small periodicity. (author) 2 figs., 2 refs.

Electronic Properties of LiFePO4 and Li doped LiFePO4

International Nuclear Information System (INIS)

Zhuang, G.V.; Allen, J.L.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

2005-01-01

The potential use of different iron phosphates as cathode materials in lithium-ion batteries has recently been investigated.1 One of the promising candidates is LiFePO4. This compound has several advantages in comparison to the state-of-the-art cathode material in commercial rechargeable lithium batteries. Firstly, it has a high theoretical capacity (170 mAh/g). Secondly, it occurs as mineral triphylite in nature and is inexpensive, thermally stable, non-toxic and non-hygroscopic. However, its low electronic conductivity (∼10-9 S/cm) results in low power capability. There has been intense worldwide research activity to find methods to increase the electronic conductivity of LiFePO4, including supervalent ion doping,2 introducing non-carbonaceous network conduction3 and carbon coating, and the optimization of the carbon coating on LiFePO4 particle surfaces.4 Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL has yield electronic conductivity increase up to 106.5 We studied electronic structure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-ray emission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes the unoccupied partial density of states, while XES the occupied partial density of states. By combining XAS and XES measurements, we obtained information on band gap and orbital character of both LiFePO4 and Li doped LiFePO4. The occupied and unoccupied oxygen partial density of states (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented in Fig. 1. Our experimental results clearly indicate that LiFePO4 has wideband gap (∼ 4 eV). This value is much larger than what is predicted by DFT calculation. For 5 percent Li doped LiFePO4, a new doping state was created closer to the Fermi level, imparting p-type conductivity, consistent with thermopower measurement. Such observation substantiates the suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 is due to available number of charge carriers in the material

Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

Science.gov (United States)

Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

2005-01-01

A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

Magnetic properties of FeZr{sub 2} and Fe{sub 2}Zr intermetallic compounds

Energy Technology Data Exchange (ETDEWEB)

Prajapat, C. L., E-mail: prajapat@barc.gov.in; Singh, M. R.; Mishra, P. K. [Technical Physics Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India); Chattaraj, D. [Product Development Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India); Mishra, R. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India); Ravikumar, G. [Scientific Information Resources Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India)

2016-05-23

Magnetic properties of Fe-Zr system, viz., FeZr{sub 2} and Fe{sub 2}Zr have been studied. Both the compounds show soft ferromagnetic behavior. Curie temperature is well above the room temperature. Lower saturation magnetization for the zirconium rich sample, FeZr{sub 2}, could be due to possible donation of electrons from the Zr-rich neighbors to Fe atoms or diminution of long range magnetic order by defects.

Removal of FePO4 and Fe3(PO4)2 crystals on the surface of passive fillers in Fe0/GAC reactor using the acclimated bacteria

International Nuclear Information System (INIS)

Lai, Bo; Zhou, Yuexi; Yang, Ping; Wang, Juling; Yang, Jinghui; Li, Huiqiang

2012-01-01

Highlights: ► Fe 3 (PO 4 ) 2 and FePO 4 crystals would weaken treatment efficiency of Fe 0 /GAC reactor. ► Fe 3 (PO 4 ) 2 and FePO 4 crystals could be removed by the acclimated bacteria. ► FeS and sulfur in the passive film would be removed by the sulfur-oxidizing bacteria. ► Develop a cost-effective bio-regeneration technology for the passive fillers. - Abstract: As past studies presented, there is obvious defect that the fillers in the Fe 0 /GAC reactor begin to be passive after about 60 d continuous running, although the complicated, toxic and refractory ABS resin wastewater can be pretreated efficiently by the Fe 0 /GAC reactor. During the process, the Fe 3 (PO 4 ) 2 and FePO 4 crystals with high density in the passive film are formed by the reaction between PO 4 3− and Fe 2+ /Fe 3+ . Meanwhile, they obstruct the formation of macroscopic galvanic cells between Fe 0 and GAC, which will lower the wastewater treatment efficiency of Fe 0 /GAC reactor. In this study, in order to remove the Fe 3 (PO 4 ) 2 and FePO 4 crystals on the surface of the passive fillers, the bacteria were acclimated in the passive Fe 0 /GAC reactor. According to the results, it can be concluded that the Fe 3 (PO 4 ) 2 and FePO 4 crystals with high density in the passive film could be decomposed or removed by the joint action between the typical propionic acid type fermentation bacteria and sulfate reducing bacteria (SRB), whereas the PO 4 3− ions from the decomposition of the Fe 3 (PO 4 ) 2 and FePO 4 crystals were released into aqueous solution which would be discharged from the passive Fe 0 /GAC reactor. Furthermore, the remained FeS and sulfur (S) in the passive film also can be decomposed or removed easily by the oxidation of the sulfur-oxidizing bacteria. This study provides some theoretical references for the further study of a cost-effective bio-regeneration technology to solve the passive problems of the fillers in the zero-valent iron (ZVI) or Fe 0 /GAC reactor.

Optimization of Fe2+ supplement in anaerobic digestion accounting for the Fe-bioavailability.

Science.gov (United States)

Cai, Yafan; Zhao, Xiaoling; Zhao, Yubin; Wang, Hongliang; Yuan, Xufeng; Zhu, Wanbin; Cui, Zongjun; Wang, Xiaofen

2018-02-01

Fe is widely used as an additive in anaerobic digestion, but its bioavailability and the mechanism by which it enhances digestion are unclear. In this study, sequential extraction was used to measure Fe bioavailability, while biochemical parameters, kinetics model and Q-PCR (fluorescence quantitative PCR) were used to explore its mechanism of stimulation. The results showed that sequential extraction is a suitable method to assess the anaerobic system bioavailability of Fe, which is low and fluctuates to a limited extent (1.7 to -3.1wt%), indicating that it would be easy for Fe levels to be insufficient. Methane yield increased when the added Fe 2+ was 10-500mg/L. Appropriate amounts of Fe 2+ accelerated the decomposition of rice straw and facilitated methanogen metabolism, thereby improving reactor performance. The modified Gompertz model better fitted the results than the first-order kinetic model. Feasibility analysis showed that addition of Fe 2+ at ≤50mg/L was suitable. Copyright © 2017. Published by Elsevier Ltd.

Chemical consequences of the nuclear reactions 58Fe(n,γ)59Fe and 57Co(EC)57Fe in soluble Prussian Blue

DEFF Research Database (Denmark)

Fenger, Jes; Maddock, A. G.; Siekierska, K. E.

1970-01-01

KFe[Fe(CN)6],H2O was prepared with 58Fe in either the cation or the complex, and both samples were neutron-irradiated and analysed for free and complexed 59Fe. Parallel experiments were performed on K4[Fe(CN)6],3H2O. In Prussian Blue the retention in the hexacyano-complex is ca. 5% and can be inc...

Requirements for construction of a functional hybrid complex of photosystem I and [NiFe]-hydrogenase.

Science.gov (United States)

Schwarze, Alexander; Kopczak, Marta J; Rögner, Matthias; Lenz, Oliver

2010-04-01

The development of cellular systems in which the enzyme hydrogenase is efficiently coupled to the oxygenic photosynthesis apparatus represents an attractive avenue to produce H(2) sustainably from light and water. Here we describe the molecular design of the individual components required for the direct coupling of the O(2)-tolerant membrane-bound hydrogenase (MBH) from Ralstonia eutropha H16 to the acceptor site of photosystem I (PS I) from Synechocystis sp. PCC 6803. By genetic engineering, the peripheral subunit PsaE of PS I was fused to the MBH, and the resulting hybrid protein was purified from R. eutropha to apparent homogeneity via two independent affinity chromatographical steps. The catalytically active MBH-PsaE (MBH(PsaE)) hybrid protein could be isolated only from the cytoplasmic fraction. This was surprising, since the MBH is a substrate of the twin-arginine translocation system and was expected to reside in the periplasm. We conclude that the attachment of the additional PsaE domain to the small, electron-transferring subunit of the MBH completely abolished the export competence of the protein. Activity measurements revealed that the H(2) production capacity of the purified MBH(PsaE) fusion protein was very similar to that of wild-type MBH. In order to analyze the specific interaction of MBH(PsaE) with PS I, His-tagged PS I lacking the PsaE subunit was purified via Ni-nitrilotriacetic acid affinity and subsequent hydrophobic interaction chromatography. Formation of PS I-hydrogenase supercomplexes was demonstrated by blue native gel electrophoresis. The results indicate a vital prerequisite for the quantitative analysis of the MBH(PsaE)-PS I complex formation and its light-driven H(2) production capacity by means of spectroelectrochemistry.

Perpendicular exchange coupling effects in ferrimagnetic TbFeCo/GdFeCo hard/soft structures

Science.gov (United States)

Wang, Ke; Wang, Yahong; Ling, Fujin; Xu, Zhan

2018-04-01

Bilayers consisting of magnetically hard TbFeCo and soft GdFeCo alloy were fabricated. Exchange-spring and sharp switching in a step-by-step fashion were observed in the TbFeCo/GdFeCo hard/soft bilayers with increasing GdFeCo thickness. A perpendicular exchange bias field of several hundred Oersteds is observed from the shift of minor loops pinned by TbFeCo layer. The perpendicular exchange energy is derived to be in the range of 0.18-0.30 erg/cm2. The exchange energy is shown to increase with the thickness of GdFeCo layer in the bilayers, which can be attributed to the enhanced perpendicular anisotropy of GdFeCo layer in our experimental range.

Connection between the membrane electron transport system and Hyn hydrogenase in the purple sulfur bacterium, Thiocapsa roseopersicina BBS.

Science.gov (United States)

Tengölics, Roland; Mészáros, Lívia; Győri, E; Doffkay, Zsolt; Kovács, Kornél L; Rákhely, Gábor

2014-10-01

Thiocapsa. roseopersicina BBS has four active [NiFe] hydrogenases, providing an excellent opportunity to examine their metabolic linkages to the cellular redox processes. Hyn is a periplasmic membrane-associated hydrogenase harboring two additional electron transfer subunits: Isp1 is a transmembrane protein, while Isp2 is located on the cytoplasmic side of the membrane. In this work, the connection of HynSL to various electron transport pathways is studied. During photoautotrophic growth, electrons, generated from the oxidation of thiosulfate and sulfur, are donated to the photosynthetic electron transport chain via cytochromes. Electrons formed from thiosulfate and sulfur oxidation might also be also used for Hyn-dependent hydrogen evolution which was shown to be light and proton motive force driven. Hyn-linked hydrogen uptake can be promoted by both sulfur and nitrate. The electron flow from/to HynSL requires the presence of Isp2 in both directions. Hydrogenase-linked sulfur reduction could be inhibited by a QB site competitive inhibitor, terbutryne, suggesting a redox coupling between the Hyn hydrogenase and the photosynthetic electron transport chain. Based on these findings, redox linkages of Hyn hydrogenase are modeled. Copyright © 2014 Elsevier B.V. All rights reserved.

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

Science.gov (United States)

Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.

Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

[{sup 18}F]FE-SUPPY and [{sup 18}F]FE-SUPPY:2 - metabolic considerations

Energy Technology Data Exchange (ETDEWEB)

Haeusler, Daniela [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Nics, Lukas [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Nutritional Sciences, Univ. of Vienna, A-1090 Vienna (Austria); Mien, Leonhard-Key [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Ungersboeck, Johanna [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Inorganic Chemistry, Univ. of Vienna, A-1090 Vienna (Austria); Lanzenberger, Rupert R. [Dept. of Psychiatry and Psychotherapy, Medical Univ. of Vienna, A-1090 Vienna (Austria); Shanab, Karem [Dept. of Drug and Natural Product Synthesis, Univ. of Vienna, A-1090 Vienna (Austria); Sindelar, Karoline M. [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Viernstein, Helmut [Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Wagner, Karl-Heinz [Dept. of Nutritional Sciences, Univ. of Vienna, A-1090 Vienna (Austria); Dudczak, Robert; Kletter, Kurt [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Wadsak, Wolfgang [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Inorganic Chemistry, Univ. of Vienna, A-1090 Vienna (Austria); Mitterhauser, Markus [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Hospital Pharmacy of the General Hospital of Vienna, A-1090 Vienna (Austria)], E-mail: markus.mitterhauser@meduniwien.ac.at

2010-05-15

Introduction: Recently, [{sup 18}F]FE-SUPPY and [{sup 18}F]FE-SUPPY:2 were introduced as the first positron emission tomography (PET) tracers for the adenosine A{sub 3} receptor. Thus, aim of the present study was the metabolic characterization of the two adenosine A{sub 3} receptor PET tracers. Methods: In vitro carboxylesterase (CES) experiments were conducted using incubation mixtures containing different concentrations of the two substrates, porcine CES and phosphate-buffered saline. Enzymatic reactions were stopped by adding acetonitrile/methanol (10:1) after various time points and analyzed by a high-performance liquid chromatography (HPLC) standard protocol. In vivo experiments were conducted in male wild-type rats; tracers were injected through a tail vein. Rats were sacrificed after various time points (n=3), and blood and brain samples were collected. Sample cleanup was performed by an HPLC standard protocol. Results: The rate of enzymatic hydrolysis by CES demonstrated Michaelis-Menten constants in a micromolar range (FE-SUPPY, 20.15 {mu}M, and FE-SUPPY:2, 13.11 {mu}M) and limiting velocities of 0.035 and 0.015 {mu}M/min for FE-SUPPY and FE-SUPPY:2, respectively. Degree of metabolism in blood showed the following: 15 min pi 47.7% of [{sup 18}F]FE-SUPPY was intact compared to 33.1% of [{sup 18}F]FE-SUPPY:2; 30 min pi 30.3% intact [{sup 18}F]FE-SUPPY was found compared to 15.6% [{sup 18}F]FE-SUPPY:2. In brain, [{sup 18}F]FE-SUPPY:2 formed an early hydrophilic metabolite, whereas metabolism of [{sup 18}F]FE-SUPPY was not observed before 30 min pi Conclusion: Knowing that metabolism in rats is several times faster than in human, we conclude that [{sup 18}F]FE-SUPPY should be stable for the typical time span of a clinical investigation. As a consequence, from a metabolic point of view, one would tend to decide in favor of [{sup 18}F]FE-SUPPY.

Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II-oxidizer

Directory of Open Access Journals (Sweden)

Jennyfer eMIOT

2015-09-01

Full Text Available Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is however thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had however never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry (NanoSIMS. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidences of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasm encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a strategy of survival in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern

Resonant Ni and Fe KLL Auger spectra photoexcited from NiFe alloys

International Nuclear Information System (INIS)

Koever, L.; Cserny, I.; Berenyi, Z.; Egri, S.; Novak, M.

2005-01-01

Complete text of publication follows. KLL Auger spectra of 3d transition metal atoms in solid environment, measured using high energy resolution, give an insight into the details of the local electronic structure surrounding the particular atoms emitting the signal Auger electrons. Fine tuning the energy of the exciting monochromatic photons across the K-absorption edge, features characteristic to resonant phenomena can be identified in the spectra. The shapes of the resonantly photoexcited KLL Auger spectra induced from 3d transition metals and alloys are well interpreted by the single step model of the Auger process, based on the resonant scattering theory. The peak shapes are strongly influenced by the 4p partial density of unoccupied electronic states around the excited atom. High energy resolution studies of KLL Auger spectra of 3d transition metals using laboratory X-ray sources, however, request very demanding experiments and yield spectra of limited statistical quality making the evaluation of the fine details in the spectra difficult. The Tunable High Energy XPS (THE- XPS) instrument at BW2 offers optimum photon x and energy resolution for spectroscopy of deep core Auger transitions. For the present measurements high purity polycrystalline Ni and Fe sheets as well as NiFe alloy samples of different compositions (Ni 80 Fe 20 , Ni 50 Fe 50 , Ni 20 Fe 80 ) were used. The surfaces of the samples were cleaned by in-situ argon ion sputtering. The measurements of the Ni and Fe KL 23 L 23 Auger spectra of the metal and alloy samples were performed with the THE-XPS instrument using high electron energy resolution (0.2 eV). In Fig.1, the measured Fe KL 23 L 23 spectrum, photoexcited at the Fe K absorption edge from Fe metal, is compared with the respective spectrum excited from a Ni 50 Fe 50 alloy. A significant broadening of the 1 D 2 peak and an enhancement of the spectral intensity at the low energy loss part of this peak observed in the alloy sample, while the

Electrical resistivity surface for FeO-Fe2O3-P2O5 glasses

Science.gov (United States)

Vaughan, J. G.; Kinser, D. L.

1975-01-01

The dc electrical properties and microstructure of x(FeO-Fe2O3)-(100-x)P2O5 glasses were investigated up to a maximum of x = 75 mol %. Results indicate that, in general, the minimum resistivity of the glass does not occur at equal Fe(2+) and Fe(3+) concentrations, although for the special case where x = 55 mol % the minimum does occur at Fe(2+)/Fe total = 0.5, as reported by other investigators. Evidence presented shows that the position of the minimum resistivity is a function of total iron content. The minimum shifts to glasses richer in Fe(2+) at higher total iron concentrations.

Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

Science.gov (United States)

Zeng, Yuewu

2015-06-01

Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons. © 2015 Wiley Periodicals, Inc.

Microstructure, magnetic and Moessbauer studies on spark-plasma sintered Sm-Co-Fe/Fe(Co) nanocomposite magnets

Energy Technology Data Exchange (ETDEWEB)

Rao, N V Rama; Saravanan, P; Gopalan, R; Raja, M Manivel; Rao, D V Sreedhara; Chandrasekaran, V [Defence Metallurgical Research Laboratory, Hyderabad-500 058 (India); Sivaprahasam, D [International Advanced Research Centre for Powder Metallurgy and New Materials Hyderabad-500 005 (India); Ranganathan, R [Saha Institute of Nuclear Physics, Kolkata-700 064 (India)], E-mail: rg_gopy@yahoo.com

2008-03-21

Nanocomposite powders comprising Sm-Co-Fe intermetallic phases and Fe(Co) were synthesized by high-energy ball milling and were consolidated into bulk magnets by the spark-plasma sintering (SPS) technique. While the microstructure of the SPS samples was characterized by transmission electron microscopy (TEM), the solubility of Fe in different phases was investigated using Moessbauer spectroscopy. TEM studies revealed that the spark-plasma sintered sample has Sm(Co,Fe){sub 5} as a major phase with Sm{sub 2}(Co,Fe){sub 17}, Sm(Co,Fe){sub 2} and Fe(Co) as secondary phases. The size of the nanocrystalline grains of all these phases was found to be in the range 50-100 nm. The Moessbauer spectra of the as-milled powders exhibited two different subspectra: a sextet corresponding to the Fe phase and a broad sextet associated with the Fe(Co) phase; while that of the SPS sample showed four different subspectra: a sextet corresponding to Fe and other three sextets corresponding to the Fe(Co), Sm(Co,Fe){sub 5} and Sm{sub 2}(Co,Fe){sub 17} phases; these results are in accordance with the TEM observation. Recoil magnetization and reversible susceptibility measurements revealed magnetically single phase behaviour of the SPS magnets.

Exchange bias in sputtered FeNi/FeMn systems: Effect of short low-temperature heat treatments

Energy Technology Data Exchange (ETDEWEB)

Savin, Peter, E-mail: peter.savin@urfu.ru [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Guzmán, Jorge [Instituto de Ciencia de Materiales de Madrid-CSIC, 28049 Madrid (Spain); Lepalovskij, Vladimir [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Svalov, Andrey; Kurlyandskaya, Galina [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), 48940 Leioa, Vizcaya (Spain); Asenjo, Agustina [Instituto de Ciencia de Materiales de Madrid-CSIC, 28049 Madrid (Spain); Vas’kovskiy, Vladimir [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Vazquez, Manuel [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Instituto de Ciencia de Materiales de Madrid-CSIC, 28049 Madrid (Spain)

2016-03-15

Short (5 min) post-deposition thermal treatments under magnetic field at low temperature (up to 200 °C) performed in exchange-coupled FeNi(40 nm)/FeMn(20 nm) bilayer thin films prepared by magnetron sputtering are shown to be effective to significantly modify their exchange field (from around 40 Oe down to 27 Oe) between FeNi and FeMn layers. A similar exchange field decrease was observed for the first deposited FeNi layer of the FeNi(40 nm)/FeMn(20 nm)/FeNi(40 nm) trilayer films after the same thermal treatments. The exchange field value for the second FeNi layer was not substantially changed. The X-ray diffraction patterns indicates that such a heat treatment has no effect on the grain size and crystalline texture of the films, while atomic force microscope studies reveal an increase of the surface roughness after the treatment which is more noticeable in the case of the trilayer film. Analysis of the experimental results leads us to conclude that the variations of the exchange field after heat treatment are likely caused by a modification of interfacial roughness and/or interfacial magnetic structure, but unlikely by the changes in the microstructure and/or changes of composition of the antiferromagnetic FeMn layer. - Highlights: • FeNi/FeMn bilayers and FeNi/FeMn/FeNi trilayers were prepared by magnetron sputtering. • Post-deposition heat treatments at the temperatures below 200 °C during 5 min were made. • Annealing reduces the exchange field for the first FeNi layer in trilayers. • The exchange field value for the second FeNi layer was not substantially changed. • Exchange field changes are most likely caused by a modification of interface roughness.

Fe/V and Fe/Co (0 0 1) superlattices: growth, anisotropy, magnetisation and magnetoresistance

International Nuclear Information System (INIS)

Nordblad, P.; Broddefalk, A.; Mathieu, R.; Blomqvist, P.; Eriksson, O.; Waeppling, R.

2003-01-01

Some physical properties of BCC Fe/V and Fe/Co (0 0 1) superlattices are reviewed. The dependence of the magnetic anisotropy on the in-plane strain introduced by the lattice mismatch between Fe and V is measured and compared to a theoretical derivation. The dependence of the magnetic anisotropy (and saturation magnetisation) on the layer thickness ratio Fe/Co is measured and a value for the anisotropy of BCC Co is derived from extrapolation. The interlayer exchange coupling of Fe/V superlattices is studied as a function of the V layer thickness (constant Fe thickness) and layer thickness of Fe (constant V thickness). A region of antiferromagnetic coupling and GMR is found for V thicknesses 12-14 monolayers. However, surprisingly, a 'cutoff' of the antiferromagnetic coupling and GMR is found when the iron layer thickness exceeds about 10 monolayers

Chapter Eight - Structural Characterization of Poised States in the Oxygen Sensitive Hydrogenases and Nitrogenases

Energy Technology Data Exchange (ETDEWEB)

King, Paul W [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Mulder, David W [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Artz, Jacob H. [Washington State University; Zadvornyy, Oleg A. [Washington State University; Peters, John W. [Washington State University

2017-08-21

The crystallization of FeS cluster-containing proteins has been challenging due to their oxygen sensitivity, and yet these enzymes are involved in many critical catalytic reactions. The last few years have seen a wealth of innovative experiments designed to elucidate not just structural but mechanistic insights into FeS cluster enzymes. Here, we focus on the crystallization of hydrogenases, which catalyze the reversible reduction of protons to hydrogen, and nitrogenases, which reduce dinitrogen to ammonia. A specific focus is given to the different experimental parameters and strategies that are used to trap distinct enzyme states, specifically, oxidants, reductants, and gas-treatments. Other themes presented here include the recent use of Cryo-EM, and how coupling various spectroscopies to crystallization is opening up new approaches for structural and mechanistic analysis.

High Temperature Magnetic Properties of Indirect Exchange Spring FePt/M(Cu,C/Fe Trilayer Thin Films

Directory of Open Access Journals (Sweden)

Anabil Gayen

2013-01-01

Full Text Available We report the investigation of temperature dependent magnetic properties of FePt and FePt(30/M(Cu,C/Fe(5 trilayer thin films prepared by using magnetron sputtering technique at ambient temperature and postannealed at different temperatures. L10 ordering, hard magnetic properties, and thermal stability of FePt films are improved with increasing postannealing temperature. In FePt/M/Fe trilayer, the formation of interlayer exchange coupling between magnetic layers depends on interlayer materials and interface morphology. In FePt/C/Fe trilayer, when the C interlayer thickness was about 0.5 nm, a strong interlayer exchange coupling between hard and soft layers was achieved, and saturation magnetization was enhanced considerably after using interlayer exchange coupling with Fe. In addition, incoherent magnetization reversal process observed in FePt/Fe films changes into coherent switching process in FePt/C/Fe films giving rise to a single hysteresis loop. High temperature magnetic studies up to 573 K reveal that the effective reduction in the coercivity decreases largely from 34 Oe/K for FePt/Fe film to 13 Oe/K for FePt/C(0.5/Fe film demonstrating that the interlayer exchange coupling seems to be a promising approach to improve the stability of hard magnetic properties at high temperatures, which is suitable for high-performance magnets and thermally assisted magnetic recording media.

Ferromagnetic resonance on oxideless magnetic Fe and FeRh nanoparticles

International Nuclear Information System (INIS)

Trunova, Anastasia

2009-01-01

This work is dedicated to investigations of structural and magnetic properties of the colloidal Fe/Fe x O y nanocubes (13 nm) and the Fe x Rh 100-x core/shell nanoparticles (2 nm). As compared with other works, where the measurements on oxidized nanoparticles were carried out, we additionally performed investigations on nanoparticles in an oxide free state. In order to make the measurements on oxide free particles possible, oxygen- and hydrogenplasma was used to remove the ligands and reduce the oxide shell of the Fe nanocubes. The oxide free Fe nanocubes were covered with a Ag/Pt protective coating to prevent them from new oxidation. This method allowed carrying out the magnetic measurements on oxide free Fe nanocubes. Micromagnetic simulations as well as simulations of the high frequency susceptibility were used for the data analysing. It was found that both the g-factor g=2.09±0.01 and the anisotropy constant K 4 =(4.8±0.5).10 4 J/m 3 coincide with that of bulk iron. However, the saturation magnetization M S (5 K)=(1.2±0.12).10 6 A/m differs from the bulk value by 30%. The reduction by 30% compared to the bulk value in the case of nanoparticles may be caused by the following possible reasons: a) the presence of inner oxide layer (approx. 10 at.%) that cannot be reduced; b) the anti-parallel order between magnetic moments of iron core and magnetic moments of antiferomagnetic iron oxide; c) some structural changes of the surface after plasma treatment. The obtained damping parameter α=0.03±0.005 is ten times larger than that of the Fe layers as it is known for nanoparticles systems in general. The core/shell Fe x Rh 100-x nanoparticles (x=80,50) were produced under Ar-atmosphere and were sealed into a quartz tube to prevent oxidation. The analysis of g-factors shows that the value for the FePh nanoparticles with Fe-rich core is larger (g=2.08±0.01) than that for the nanoparticles with Rh-rich core and coincides within error bars with the g-factor of bulk

Effect of Iron Fe (II and Fe (III in a Binary System Evaluated Bioluminescent Method

Directory of Open Access Journals (Sweden)

Elena Sorokina

2013-01-01

Full Text Available The effect of iron ions Fe2+ and Fe3+ on the bioluminescent recombinant strain of Escherichia coli in a single-component and binary system. Found that for the bacteria E. coli Fe3+ ions are more toxic than Fe2+. Under the combined effect of iron toxicity increases, the percentage of luminescence quenching increases, but the value is much less than the sum of the indicator for the Fe2+ and Fe3+. The biological effect of insertion of iron is not proportional to their content in the mixture.

Magnetic structure of molecular magnet Fe[Fe(CN) 6

Indian Academy of Sciences (India)

We have studied the magnetic structure of Fe[Fe(CN)6]·4H2O, prepared by precipitation method, using neutron diffraction technique. Temperature dependent DC magnetization study down to 4.2 K shows that the compound undergoes from a high temperature disordered (paramagnetic) to an ordered magnetic phase ...

57Fe Moessbauer and magnetization study of the Th7Fe3 and the hydride Th7Fe3H/sub n/

International Nuclear Information System (INIS)

Viccaro, P.J.; Shenoy, G.K.; Dunlap, B.D.; Westlake, D.G.; Malik, S.K.; Wallace, W.E.

1978-01-01

Th 7 Fe 3 is known to be a Pauli paramagnet and to undergo a superconducting transition at 1.86K. Its hydride Th 7 Fe 3 H/sub n/ is shown to possess magnetic ordering. The 57 Fe saturated hyperfine field in the hydride is estimated to be aproximately 20kG. A positive isomer shift of 0.30 +- 0.02 mm/s at 300 K relative to Th 7 Fe 3 would be consistent with an increase in d-like electrons on Fe. Preliminary magnetization results indicate a magnetic moment of about 0.5 μ/sub B/ for the hydride and a transition temperature near 300 K

Kinetics and mechanism of diclofenac removal using ferrate(VI): roles of Fe3+, Fe2+, and Mn2.

Science.gov (United States)

Zhao, Junfeng; Wang, Qun; Fu, Yongsheng; Peng, Bo; Zhou, Gaofeng

2018-06-01

In this study, the effect of Fe 3+ , Fe 2+ , and Mn 2+ dose, solution pH, reaction temperature, background water matrix (i.e., inorganic anions, cations, and natural organic matters (NOM)), and the kinetics and mechanism for the reaction system of Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ were investigated systematically. Traces of Fe 3+ , Fe 2+ , and Mn 2+ promoted the DCF removal by Fe(VI) significantly. The pseudo-first-order rate constant (k obs ) of DCF increased with decreasing pH (9-6) and increasing temperature (10-30 °C) due to the gradually reduced stability and enhanced reactivity of Fe(VI). Cu 2+ and Zn 2+ ions evidently improved the DCF removal, while CO 3 2- restrained it. Besides, SO 4 2- , Cl - , NO 3 - , Mg 2+ , and Ca 2+ almost had no influence on the degradation of DCF by Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ within the tested concentration. The addition of 5 or 20 mg L -1 NOM decreased the removal efficiency of DCF. Moreover, Fe 2 O 3 and Fe(OH) 3 , the by-products of Fe(VI), slightly inhibited the DCF removal, while α-FeOOH, another by-product of Fe(VI), showed no influence at pH 7. In addition, MnO 2 and MnO 4 - , the by-products of Mn 2+ , enhanced the DCF degradation due to catalysis and superposition of oxidation capacity, respectively. This study indicates that Fe 3+ and Fe 2+ promoted the DCF removal mainly via the self-catalysis for Fe(VI), and meanwhile, the catalysis of Mn 2+ and the effect of its by-products (i.e., MnO 2 and MnO 4 - ) contributed synchronously for DCF degradation. Graphical abstract ᅟ.

Simulation of radiation damage in Fe and Fe-Cr

International Nuclear Information System (INIS)

Lagerstedt, Christina

2005-11-01

Steel is an important structural material in nuclear reactors used for example in pressure vessels and fast reactor cladding. In reactor environments it has been observed that ferritic steels are more resistant to swelling than the austenitic steels typically used. Much effort has been put into developing basic models of FeCr alloys which can serve as model alloys for describing ferritic steels. As a result, a number of interatomic potentials for Fe and FeCr alloys exist today. For the work in this thesis, basic material properties coming from experiments or ab initio calculations were used to fit interatomic potentials for Fe, Cr and FeCr implementing both the embedded atom method and the Finnis-Sinclair formalisms. The potentials were then validated by molecular dynamic calculations of material properties such as defect formation energies, migration energies and thermal expansion. Further studies of potential performance were carried out in simulations of radiation damage cascades and thermal aging. The influence of the interatomic potential on the primary defect state in materials under irradiation was analyzed in a study comparing results obtained using four different potentials. The objective of the study was to find correlations between potential properties and the primary damage state produced in simulations of displacement cascades. The defect evolution and clustering during different cascade stages were also investigated to try to gain a better understanding of these processes

Investigation of Synthesis and Magnetic Properties of Rod-Shaped CoFe2O4 via Precipitation-Topotactic Reaction Employing α-FeOOH and γ-FeOOH As Templates

Science.gov (United States)

Cao, Xiaohui; Dong, Hongfei; Tan, Yuzhuo; Meng, Jinhong

2018-03-01

Rod-shaped CoFe2O4 was prepared by chemical precipitation-topotactic reaction method, and in this preparation needle-like γ-FeOOH and α-FeOOH were synthesized to use as template materials. The evolution of phase and morphology in the process of calcination exhibits that α-FeOOH and γ-FeOOH experienced different routes to form the α-Fe2O3 middle phase with different crystallinity and morphology. The synthesis process of CoFe2O4 revealed that the crystallinity, purity and morphology of CoFe2O4 depend on the α-Fe2O3 middle phase. The magnetic measurement showed that the CoFe2O4 prepared from α-FeOOH has higher saturation magnetization and coercivity, and the crystallinity and morphology may play important roles in achieving a better magnetic performance.

Fe-Ti/Fe (II)-loading on ceramic filter materials for residual chlorine removal from drinking water.

Science.gov (United States)

Man, Kexin; Zhu, Qi; Guo, Zheng; Xing, Zipeng

2018-06-01

Ceramic filter material was prepared with silicon dioxide (SiO 2 ), which was recovered from red mud and then modified with Fe (II) and Fe-Ti bimetal oxide. Ceramic filter material can be used to reduce the content of residual chlorine from drinking water. The results showed that after a two-step leaching process with 3 M hydrochloric acid (HCl) and 90% sulfuric acid (H 2 SO 4 ), the recovery of SiO 2 exceeded 80%. Fe (II)/Fe-Ti bimetal oxide, with a high adsorption capacity of residual chlorine, was prepared using a 3:1 M ratio of Fe/Ti and a concentration of 0.4 mol/L Fe 2+ . According to the zeta-potential, scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis, Fe (II) and Fe-Ti bimetal oxide altered the zeta potential and structural properties of the ceramic filter material. There was a synergistic interaction between Fe and Ti in which FeOTi bonds on the material surface and hydroxyl groups provided the active sites for adsorption. Through a redox reaction, Fe (II) transfers hypochlorite to chloride, and FeOTiCl bonds were formed after adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Determination of the 54Fe(n, 2n)53gFe and 54Fe(n, 2n)53mFe cross sections averaged over a 235U fission neutron spectrum

International Nuclear Information System (INIS)

Ribeiro Guevara, S.; Arribere, M.; Kestelman, A.J.

2002-01-01

The reaction cross sections averaged over a 235 U fission neutron spectrum have been measured for the 54 Fe(n, 2n) 53g Fe and 54 Fe(n, 2n) 53m Fe threshold reactions. The values found are, respectively: (1.14 ± 0.13) μb, and (0.52 ± 0.16) μb. The measured cross sections are referred to the (111± 3) mb standard cross section of the 58 Ni(n, p) 58m+g Co reaction. The (81.7 ± 2.2) mb standard cross section value for the 54 Fe(n, p) 54 Mn reaction, was also used as a monitor to check the results obtained with the Ni standard, leading to an excellent agreement. (author)

Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

Science.gov (United States)

Domagal-Goldman, S.; Kubicki, J. D.

2006-05-01

Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the

Ferromagnetic alloy material CoFeC with high thermal tolerance in MgO/CoFeC/Pt structure and comparable intrinsic damping factor with CoFeB

Science.gov (United States)

Chen, Shaohai; Zhou, Jing; Lin, Weinan; Yu, Jihang; Guo, Rui; Poh, Francis; Shum, Danny; Chen, Jingsheng

2018-02-01

The thermal tolerance and perpendicular magnetic anisotropy (PMA) of ferromagnetic alloy Co40Fe40C20 in the structure MgO/CoFeC/Pt (or Ta) were investigated and compared with the commonly used CoFeB alloy. It is found that the PMA of CoFeC with {{K}i,CoFeC}=2.21 erg c{{m}-2} , which is 59% higher than that of CoFeB, can be obtained after proper post-annealing treatment. Furthermore, CoFeC alloy provides better thermal tolerance to temperature of 400 °C than CoFeB. The studies on ferromagnetic resonance show that the intrinsic damping constant α in of Co40Fe40C20 alloy is 0.0047, which is similar to the reported value of 0.004 for Co40Fe40B20 alloy. The comprehensive comparisons indicate that CoFeC alloy is a promising candidate for the application of the integration of spin torque transfer magnetic random access memory with complementary metal-oxide semiconductor processes.

Fe++/Fe+++ concentration relationship and mechanical properties of phosphate glasses useful for wastes immobilization

International Nuclear Information System (INIS)

Garcia, D.A.; Prado, Miguel O.

2007-01-01

Under different melting conditions, glasses with different Fe(II)/Fe(III) concentration relationship were prepared within each type of glass 43Fe 2 O 3 -57P 2 O 5 and 33,33Fe 2 O 3 - 66,67P 2 O 5 . Using Moessbauer spectroscopy Fe(II)/Fe(III) concentration values were determined. Vickers and Knoop indentations were used for determining their hardness, toughness, Young modulus and brittleness. The same measurements were carried on some silicate and aluminosilicate glasses. Also Weibull statistics was done to determine the characteristics (Weibull modulus and and fracture probability) of glass fracture. We found that silicate glasses (SG) are harder than phosphate glasses (PG). Toughness values for PG, are in the same range than for SG, although for the same density exhibit larger values or smaller brittleness than silicate glasses. For one of the glasses it was found that the mechanical load P 0 needed for a fracture probability of 63% increases with the Fe(II) content. (author)

Ion-irradiation induced chemical ordering of FePt and FePtAu nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Seetala, Naidu V. [Department of Physics, Grambling State University, RWE Jones Drive, Carver Hall 81, Grambling, LA 71245 (United States)]. E-mail: naidusv@gram.edu; Harrell, J.W. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Lawson, Jeremy [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Nikles, David E. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Williams, John R. [Department of Physics, Auburn University, Auburn, AL 36849 (United States); Isaacs-Smith, Tamara [Department of Physics, Auburn University, Auburn, AL 36849 (United States)

2005-12-15

We have studied the effect of ion-beam irradiation on reducing the ordering temperature of FePt and FePtAu nanoparticles. FePt and FePt(Au14%) 4 nm particles dispersed on a Si-substrate were irradiated by 300 keV Al-ions with a dose of 1 x 10{sup 16} ions/cm{sup 2} at 43 {sup o}C using a water-cooled flange in order to minimize the vacancy migration and voids formation within the collision cascades. Partial chemical ordering has been observed in as-irradiated particles with coercivity of 60-130 Oe. Post-irradiation annealing at 220 {sup o}C enhanced chemical ordering in FePt nanoparticles with coercivity of 3500 Oe, magnetic anisotropy of 1.5 x 10{sup 7} erg/cc, and thermal stability factor of 130. A much higher 375 {sup o}C post-irradiation annealing was required in FePtAu, presumably because Au atoms were trapped at Fe/Pt lattice sites at lower temperatures. As the annealing temperature increased, anomalous features in the magnetization reversal curves were observed that disappeared at higher annealing temperatures.

Magnetic properties of Fe/NiO/Fe(001) trilayers

International Nuclear Information System (INIS)

Biagioni, P.; Brambilla, A.; Portalupi, M.; Rougemaille, N.; Schmid, A.K.; Lanzara, A.; Vavassori, P.; Zani, M.; Finazzi, M.; Duo, L.; Ciccacci, F.

2005-01-01

We have investigated the magnetic properties of epitaxially grown Fe/NiO/Fe(001) trilayers, for different thicknesses of the NiO spacer. Magneto Optical Kerr Effect has been exploited to study the in-plane magnetization reversal processes in the iron layers. We found that the NiO thickness t AFM has a critical value t C for the magnetic coupling between the Fe layers: for t AFM C the magnetization directions align perpendicularly, with zero applied field, while the alignment is collinear for thicker spacers. A phenomenological model has been developed to reproduce and discuss the results. Complementary information has been obtained by means of spin polarized low energy electron microscopy

Magnetic properties of Fe/NiO/Fe(001) trilayers

Energy Technology Data Exchange (ETDEWEB)

Biagioni, P [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Brambilla, A [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Portalupi, M [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Rougemaille, N [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Schmid, A K [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lanzara, A [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Department of Physics, University of California at Berkeley, Berkeley, CA 94720 (United States); Vavassori, P [INFM - Dipartimento di Fisica, Universita di Ferrara, Via Paradiso 12, 44100 Ferrara (Italy); Zani, M [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Finazzi, M [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Duo, L [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Ciccacci, F [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)

2005-04-15

We have investigated the magnetic properties of epitaxially grown Fe/NiO/Fe(001) trilayers, for different thicknesses of the NiO spacer. Magneto Optical Kerr Effect has been exploited to study the in-plane magnetization reversal processes in the iron layers. We found that the NiO thickness t{sub AFM} has a critical value t{sub C} for the magnetic coupling between the Fe layers: for t{sub AFM}

Thermodynamic Description Of Ternary Fe-B-X Systems. Part 2: Fe-B-Ni

Directory of Open Access Journals (Sweden)

Miettinen J.

2014-06-01

Full Text Available Przedstawiono termodynamiczny opis trójskładnikowego układu Fe-B-Ni w kontekście nowej bazy danych dla układów Fe-B-X (X = Cr, Ni, Mn, Si, Ti, V, C. Parametry termodynamiczne dwuskładnikowych stopów Fe-B. Fe-Ni i B-Ni zostały są zaczerpnięte z wcześniejszych opracowań, przy tym opis B-Ni został nieznacznie zmodyfikowany. Parametry dla układu Fe-B-Ni zostały zoptymalizowane w tej pracy w oparciu o eksperymentalne równowagi fazowe i dane termodynamiczne zaczerpnięte z literatury. Roztwory stałe w układzie Fe-B-Ni opisano przy użyciu modelu roztworu substytucyjnego, a borki traktowane są jako fazy stechiometryczne lub półstechiometryczne typu (A.BpCq opisane przy użyciu modelu dwu podsieci.

Structure, magnetism, and interface properties of epitactical thin Fe and FePt films on GaAs(001) substrates; Struktur, Magnetismus und Grenzflaecheneigenschaften epitaktischer duenner Fe- und FePt-Filme auf GaAs(001)-Substraten

Energy Technology Data Exchange (ETDEWEB)

Schuster, Ellen Ursula

2007-12-17

The research in this thesis is focused on the study of the Fe spin structure and interface magnetism of thin epitaxial Fe layers or epitaxial FePt alloy films with chemical L1{sub 0} order on GaAs(001) surfaces. The main method of investigation was isotope-specific conversion electron Moessbauer spectroscopy (CEMS) combined with the {sup 57}Fe probe-layer technique in the temperature range of 4.2-300 K. The film structure was studied using electron diffraction (RHEED) and X-ray diffraction (XRD). The chemical order parameter S determined by XRD was found to increase with rising growth temperature, T{sub S}, to a maximum value of 0.71, until long range order is destroyed at T{sub S}>350 C by alloying with the substrate. As an important result a linear correlation between short-range order (revealed by the relative spectral area of the L1{sub 0} phase) and long-range order S was observed. The observed perpendicular Fe spin texture, characterized by the mean tilting angle left angle {theta} right angle of the Fe spins (relative to the film normal direction), was found to correlate with the L1{sub 0} phase content and with S. Furthermore, epitaxial Fe(001) films on GaAs(001)-(4 x 6) and on GaAs(001)-LED surfaces were grown successfully. In the initial stage of Fe film growth non-monotonous behavior of the in-plane lattice parameter was observed by RHEED. The magnetic hyperfine field distributions P(B{sub hf}) at the Fe/GaAs interface extracted from CEMS spectra for T{sub S}=-140 C or room temperature (RT) were found to be very similar. The observed large mean hyperfine fields of left angle B{sub hf} right angle {approx}25-27 T at the interface indicate the presence of high average Fe moments of 1.7-1.8 {mu}{sub B}. Nonmagnetic interface layers either can be excluded (Fe/GaAs) or are very thin (0.5 ML,Fe/GaAs-LED). Owing to its island structure an ultrathin (1.9 ML thick) uncoated Fe(001) film on GaAs(001)-(4 x 6) shows superparamagnetism with a blocking temperature of

Exchange coupling behavior in bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Leite, G.C.P. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Chagas, E.F., E-mail: efchagas@fisica.ufmt.br [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Pereira, R.; Prado, R.J. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Terezo, A.J. [Departamento de Quimica, Universidade Federal do Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Alzamora, M.; Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Fisicas, Rua Xavier Sigaud 150 Urca, Rio de Janeiro (Brazil)

2012-09-15

In this work we report a study of the magnetic behavior of ferrimagnetic oxide CoFe{sub 2}O{sub 4} and ferrimagnetic oxide/ferromagnetic metal CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite. The latter compound is a good system to study hard ferrimagnet/soft ferromagnet exchange coupled. Two steps were followed to synthesize the bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite: (i) first, preparation of CoFe{sub 2}O{sub 4} nanoparticles using a simple hydrothermal method, and (ii) second, reduction reaction of cobalt ferrite nanoparticles using activated charcoal in inert atmosphere and high temperature. The phase structures, particle sizes, morphology, and magnetic properties of CoFe{sub 2}O{sub 4} nanoparticles were investigated by X-Ray diffraction (XRD), Mossbauer spectroscopy (MS), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM) with applied field up to 3.0 kOe at room temperature and 50 K. The mean diameter of CoFe{sub 2}O{sub 4} particles is about 16 nm. Mossbauer spectra revealed two sites for Fe{sup 3+}. One site is related to Fe in an octahedral coordination and the other one to the Fe{sup 3+} in a tetrahedral coordination, as expected for a spinel crystal structure of CoFe{sub 2}O{sub 4}. TEM measurements of nanocomposite showed the formation of a thin shell of CoFe{sub 2} on the cobalt ferrite and indicate that the nanoparticles increase to about 100 nm. The magnetization of the nanocomposite showed a hysteresis loop that is characteristic of exchange coupled systems. A maximum energy product (BH){sub max} of 1.22 MGOe was achieved at room temperature for CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposites, which is about 115% higher than the value obtained for CoFe{sub 2}O{sub 4} precursor. The exchange coupling interaction and the enhancement of product (BH){sub max} in nanocomposite CoFe{sub 2}O{sub 4}/CoFe{sub 2} are discussed. - Highlights: Black-Right-Pointing-Pointer CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

Treatment of reverse osmosis (RO) concentrate by the combined Fe/Cu/air and Fenton process (1stFe/Cu/air-Fenton-2ndFe/Cu/air).

Science.gov (United States)

Ren, Yi; Yuan, Yue; Lai, Bo; Zhou, Yuexi; Wang, Juling

2016-01-25

To decompose or transform the toxic and refractory reverse osmosis (RO) concentrate and improve the biodegradability, 1stFe/Cu/air-Fenton-2ndFe/Cu/air were developed to treat RO concentrate obtained from an amino acid production plant in northern China. First, their operating conditions were optimized thoroughly. Furthermore, 5 control experiments were setup to confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and synergistic reaction between Fe/Cu/air and Fenton. The results suggest that the developed method could obtain high COD removal (65.1%) and BOD5/COD ratio (0.26) due to the synergistic reaction between Fe/Cu/air and Fenton. Under the optimal conditions, the influent and effluent of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and 5 control experiments were analyzed by using UV, FTIR, EEM and LC, which confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air. Therefore, the developed method in this study is a promising process for treatment of RO concentrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Ordering phenomena in FeCo-films and Fe/Cr-multilayers: an X-ray and neutron scattering study

Energy Technology Data Exchange (ETDEWEB)

Nickel, B.

2001-07-01

The following topics are covered: critical phenomena in thin films, critical adsorption, finite size scaling, FeCo Ising model, kinematical scattering theory for thin films, FeCo thin films, growth and characterisation of single crystal FeCo thin films, X-ray study of ordering in FeCo films, antiferromagnetic coupling in Fe/Cr multilayers, neutron scattering on Fe/Cr multilayers (WL)

Shape anisotropy and hybridization enhanced magnetization in nanowires of Fe/MgO/Fe encapsulated in carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Aryee, Dennis [Army Research Laboratory, Weapons and Materials Research Directorate, Aberdeen Proving Ground, MD 21005 (United States); Department of Physics and Engineering Physics, Morgan State University, Baltimore, MD 21251 (United States); Seifu, Dereje, E-mail: dereje.seifu@morgan.edu [Department of Physics and Engineering Physics, Morgan State University, Baltimore, MD 21251 (United States)

2017-05-01

Arrays of tunneling magnetoresistance (TMR) nanowires were synthesized for the first time by filling Fe/MgO/Fe inside vertically grown and substrate supported carbon nanotubes. The magnetic properties of nanowires and planar nanoscale thin films of Fe/MgO/Fe showed several similarities, such as two-fold magnetic symmetry and ratio of orbital moment to spin moment. Nanowires of Fe/MgO/Fe showed higher saturation magnetization by a factor of 2.7 compared to planar thin films of Fe/MgO/Fe at 1.5 kOe. The enhanced magnetic properties likely resulted from shape anisotropy of the nanowires and as well as the hybridization that occur between the π- electronic states of carbon and 3d-bands of the Fe-surface.

Fabrication and magnetic properties of Fe/GaAs/Fe hybrid structures

OpenAIRE

Wong, P.K.J.; Zhang, W.; Zhang, W.; Wu, J.; Will, I.G.; Xu, Y.B.; Farrer, I.; Ritchie, D.A.

2010-01-01

In this contribution, experimental results on the fabrication and magnetic characterization of a novel type vertical Fe/GaAs(100)/Fe spin-valve (SV) spintronic device are presented. An array of techniques has been developed by combining use of ex-situ chemical and selective etching of GaAs/AlGaAs/n-GaAs epilayers and ultrahigh vacuum deposition of Fe by molecular beam epitaxy (MBE). The thinnest achievable GaAs membrane by these sequences can be as thin as 50 nm.

Molecular magnetism of a linear Fe(III)-Mn(II)-Fe(III) complex. Influence of long-range exchange interaction

International Nuclear Information System (INIS)

Lengen, M.; Chaudhuri, P.

1994-01-01

The magnetic properties of [L-Fe(III)-dmg 3 Mn(II)-Fe(III)-L] (ClO 4 ) 2 have been characterized by magnetic susceptibility, EPR, and Moessbauer studies. L represents 1,4,7-trimethyl-,1,4,7-triazacyclononane and dmg represents dimethylglyoxime. X-ray diffraction measurements yield that the arrangement of the three metal centers is strictly linear with atomic distances d Fe-Mn 0.35 nm and d Fe-Fe = 0.7 nm. Magnetic susceptibility measurements (3-295 K) were analyzed in the framework of the spin-Hamiltonian formalism considering Heisenberg exchange and Zeeman interaction: H = J Fe-Mn (S Fe1 + S Fe2 )S Mn + J Fe-Fe S Fe1 S Fe2 + gμ B S total B. The spins S Fe1 = S Fe2 = S Mn = 5/2 of the complex are antiferromagnetically coupled, yielding a total spin of S total = 5/2 with exchange coupling constants F Fe-Mn = 13.4 cm -1 and J Fe-Fe = 4.5 cm -1 . Magnetically split Moessbauer spectra were recorded at 1.5 K under various applied fields (20 mT, 170 mT, 4 T). The spin-Hamiltonian analysis of these spectra yields isotropic magnetic hyperfine coupling with A total /(g N μ N ) = -18.5 T. The corresponding local component A Fe is related to A total via spin-projection: A total = (6/7)A Fe . The resulting A Fe /(g N μ N ) -21.6 T is in agreement with standard values of ferric high-spin complexes. Spin-Hamiltonian parameters as obtained from Moessbauer studies and exchange coupling constants as derived from susceptibility measurements are corroborated by temperature-dependent EPR studies. (orig.)

Characterization of Bi and Fe co-doped PZT capacitors for FeRAM.

Science.gov (United States)

Cross, Jeffrey S; Kim, Seung-Hyun; Wada, Satoshi; Chatterjee, Abhijit

2010-08-01

Ferroelectric random access memory (FeRAM) has been in mass production for over 15 years. Higher polarization ferroelectric materials are needed for future devices which can operate above about 100 °C. With this goal in mind, co-doping of thin Pb(Zr 40 ,Ti 60 )O 3 (PZT) films with 1 at.% Bi and 1 at.% Fe was examined in order to enhance the ferroelectric properties as well as characterize the doped material. The XRD patterns of PZT-5% BiFeO 3 (BF) and PZT 140-nm thick films showed (111) orientation on (111) platinized Si wafers and a 30 °C increase in the tetragonal to cubic phase transition temperature, often called the Curie temperature, from 350 to 380 °C with co-doping, indicating that Bi and Fe are substituting into the PZT lattice. Raman spectra revealed decreased band intensity with Bi and Fe co-doping of PZT compared to PZT. Polarization hysteresis loops show similar values of remanent polarization, but square-shaped voltage pulse-measured net polarization values of PZT-BF were higher and showed higher endurance to repeated cycling up to 10 10 cycles. It is proposed that Bi and Fe are both in the +3 oxidation state and substituting into the perovskite A and B sites, respectively. Substitution of Bi and Fe into the PZT lattice likely creates defect dipoles, which increase the net polarization when measured by the short voltage pulse positive-up-negative-down (PUND) method.

Regulation of brain copper homeostasis by the brain barrier systems: Effects of Fe-overload and Fe-deficiency

International Nuclear Information System (INIS)

Monnot, Andrew D.; Behl, Mamta; Ho, Sanna; Zheng, Wei

2011-01-01

Maintaining brain Cu homeostasis is vital for normal brain function. The role of systemic Fe deficiency (FeD) or overload (FeO) due to metabolic diseases or environmental insults in Cu homeostasis in the cerebrospinal fluid (CSF) and brain tissues remains unknown. This study was designed to investigate how blood-brain barrier (BBB) and blood-SCF barrier (BCB) regulated Cu transport and how FeO or FeD altered brain Cu homeostasis. Rats received an Fe-enriched or Fe-depleted diet for 4 weeks. FeD and FeO treatment resulted in a significant increase (+ 55%) and decrease (− 56%) in CSF Cu levels (p < 0.05), respectively; however, neither treatment had any effect on CSF Fe levels. The FeD, but not FeO, led to significant increases in Cu levels in brain parenchyma and the choroid plexus. In situ brain perfusion studies demonstrated that the rate of Cu transport into the brain parenchyma was significantly faster in FeD rats (+ 92%) and significantly slower (− 53%) in FeO rats than in controls. In vitro two chamber Transwell transepithelial transport studies using primary choroidal epithelial cells revealed a predominant efflux of Cu from the CSF to blood compartment by the BCB. Further ventriculo-cisternal perfusion studies showed that Cu clearance by the choroid plexus in FeD animals was significantly greater than control (p < 0.05). Taken together, our results demonstrate that both the BBB and BCB contribute to maintain a stable Cu homeostasis in the brain and CSF. Cu appears to enter the brain primarily via the BBB and is subsequently removed from the CSF by the BCB. FeD has a more profound effect on brain Cu levels than FeO. FeD increases Cu transport at the brain barriers and prompts Cu overload in the CNS. The BCB plays a key role in removing the excess Cu from the CSF.

Regulation of brain copper homeostasis by the brain barrier systems: Effects of Fe-overload and Fe-deficiency

Energy Technology Data Exchange (ETDEWEB)

Monnot, Andrew D.; Behl, Mamta; Ho, Sanna; Zheng, Wei, E-mail: wzheng@purdue.edu

2011-11-15

Maintaining brain Cu homeostasis is vital for normal brain function. The role of systemic Fe deficiency (FeD) or overload (FeO) due to metabolic diseases or environmental insults in Cu homeostasis in the cerebrospinal fluid (CSF) and brain tissues remains unknown. This study was designed to investigate how blood-brain barrier (BBB) and blood-SCF barrier (BCB) regulated Cu transport and how FeO or FeD altered brain Cu homeostasis. Rats received an Fe-enriched or Fe-depleted diet for 4 weeks. FeD and FeO treatment resulted in a significant increase (+ 55%) and decrease (- 56%) in CSF Cu levels (p < 0.05), respectively; however, neither treatment had any effect on CSF Fe levels. The FeD, but not FeO, led to significant increases in Cu levels in brain parenchyma and the choroid plexus. In situ brain perfusion studies demonstrated that the rate of Cu transport into the brain parenchyma was significantly faster in FeD rats (+ 92%) and significantly slower (- 53%) in FeO rats than in controls. In vitro two chamber Transwell transepithelial transport studies using primary choroidal epithelial cells revealed a predominant efflux of Cu from the CSF to blood compartment by the BCB. Further ventriculo-cisternal perfusion studies showed that Cu clearance by the choroid plexus in FeD animals was significantly greater than control (p < 0.05). Taken together, our results demonstrate that both the BBB and BCB contribute to maintain a stable Cu homeostasis in the brain and CSF. Cu appears to enter the brain primarily via the BBB and is subsequently removed from the CSF by the BCB. FeD has a more profound effect on brain Cu levels than FeO. FeD increases Cu transport at the brain barriers and prompts Cu overload in the CNS. The BCB plays a key role in removing the excess Cu from the CSF.

Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

Science.gov (United States)

Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

2009-01-01

Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

Influence of chemical composition of CoFeB on tunneling magnetoresistance and microstructure in polycrystalline CoFeB/MgO/CoFeB magnetic tunnel junctions

International Nuclear Information System (INIS)

Tsunekawa, Koji; Choi, Young-Suk; Nagamine, Yoshinori; Djayaprawira, David D.; Takeuchi, Takashi; Kitamoto, Yoshitaka

2006-01-01

We report, for the first time, the correlation between tunneling magnetoresistance (TMR) and the microstructure of polycrystalline CoFeB/MgO/CoFeB magnetic tunnel junctions with various Co/Fe ratios in the (CoFe) 81 B 19 reference and free layers. It is found that the Co/Fe ratio in the (CoFe) 81 B 19 reference layer strongly affects the (001) out-of-plane texture of the MgO tunnel barrier, resulting in the variation in TMR ratio. Further microstructure characterization of the magnetic tunnel junction with a higher TMR ratio and a stronger (001) out-of-plane texture in the MgO tunnel barrier reveals a grain-to-grain lattice match between the crystallized bcc CoFeB reference layer and MgO with a 45deg rotational epitaxial relationship, that is, CoFeB(001)[110]//MgO(001)[100]. (author)

A pulse synthesis of beta-FeSi sub 2 layers on silicon implanted with Fe sup + ions

CERN Document Server

Batalov, R I; Terukov, E I; Kudoyarova, V K; Weiser, G; Kuehne, H

2001-01-01

The synthesis of thin beta-FeSi sub 2 films was performed by means of the Fe sup + ion implantation into Si (100) and the following nanosecond pulsed ion treatment of implanted layer. Using the beta-FeSi sub 2 beta-FeSi sub 2 e X-ray diffraction it is shown that the pulsed ion treatment results in the generation of the mixture of two phases: FeSi and beta-FeSi sub 2 with stressed crystal lattices. The following short-time annealing leads to the total transformation of the FeSi phase into the beta-FeSi sub 2 one. The Raman scattering data prove the generation of the beta-FeSi sub 2 at the high degree of the silicon crystallinity. The experimental results of the optical absorption testify to the formation of beta-FeSi sub 2 layers and precipitates with the straight-band structure. The photoluminescence signal at lambda approx = 1.56 mu m observes up to 210 K

In situ QXAFS observation of the reduction of Fe2O3 and CaFe2O4

International Nuclear Information System (INIS)

Kimura, Masao; Takayama, Toru; Murao, Reiko; Nomura, Masaharu; Uemura, Yohei; Asakura, Kiyotaka

2013-01-01

In situ QXAFS studies of the reduction of α-Fe 2 O 3 and CaFe 2 O 4 were conducted to determine their reduction kinetics and mechanisms. The reduction of α-Fe 2 O 3 involved two steps, the first being a very fast process in which Fe 3+ was reduced to Fe 2+ and the second being the reduction of Fe 2+ to Fe metal over a longer period. In contrast, the reduction of Fe in CaFe 2 O 4 was a single first-order reaction, although an induction period was clearly observed at the beginning of the reduction process. The reduction processes were successfully studied using a combination of in situ QXAFS spectra at the Ca and Fe K-edges.

Presence of 60Fe in eucrite Piplia Kalan: A new perspective to the initial 60Fe/ 56Fe in the early solar system

Digital Repository Service at National Institute of Oceanography (India)

Rudraswami, N.G.; Sahijpal, S.; Bhandari, N.

Fe-Ni isotope measurements of ferrous pyroxenes of the Piplia Kalan eucrite using Secondary Ion Mass Spectrometer revealed the presence of sup (60) Ni excess corresponding to the initial 60Fe/56Fe of (5.2 + or - 2.4) × 10 sup(-9). Combining...

Coercivity Recovery Effect of Sm-Fe-Cu-Al Alloy on Sm2Fe17N3 Magnet

Science.gov (United States)

Otogawa, Kohei; Asahi, Toru; Jinno, Miho; Yamaguchi, Wataru; Takagi, Kenta; Kwon, Hansang

2018-03-01

The potential of a Sm-Fe-Cu-Al binder for improvement of the magnetic properties of Sm2Fe17N3 was examined. Transmission electron microscope (TEM) observation of a Sm-Fe-Cu-Al alloy-bonded Sm2Fe17N3 magnet which showed high coercivity revealed that the Sm-Fe-Cu-Al alloy had an effect of removing the surface oxide layer of the Sm2 Fe17N3 grains. However, the Sm-Fe-Cu-Al binder was contaminated by carbon and nitrogen, which originated from the organic solvent used as the milling medium during pulverization. To prevent carbon and nitrogen contamination, the Sm-Fe- Cu-Al alloy was added directly on the surface of the Sm2Fe17N3 grains by sputtering. Comparing the recovered coercivity per unit amount of the added binder the uncontaminated binder-coated sample had a higher coercivity recovery effect than the milled binder-added sample. These results suggested that sufficient addition of the contamination-free Sm-Fe-Cu-Al binder has the possibility to reduce the amount of binder necessary to produce a high coercive Sm2Fe17N3 magnet.

Effect of Soil Parameters on the Kinetics of the Displacement of Fe from FeEDDHA Chelates by Cu

NARCIS (Netherlands)

Schenkeveld, W.D.C.; Reichwein, A.M.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

2012-01-01

In soil application, o,o-FeEDDHA (iron (3+) ethylene diamine-N,N'-bis(2-hydroxy phenyl acetic acid) complex) is the active ingredient of FeEDDHA chelate-based Fe fertilizers. The effectiveness of o,o-FeEDDHA is potentially compromised by the displacement of Fe from FeEDDHA by Cu. The actual impact

A new rhodamine-based fluorescent probe for the discrimination of Fe"3"+ from Fe"2"+

International Nuclear Information System (INIS)

You, Qi Hua; Huang, Hua Bin; Zhuang, Zhi Xia; Wang, Xiao Ru; Chan, Wing Hong

2016-01-01

A new rhodamine-based fluorescent probe for the discrimination of Fe"3"+ from Fe"2"+ has been designed and investigated. The probe shows an immediate visual color change in response to Fe"3"+ and Cu"2"+, while only Fe"3"+ triggers the fluorescent change of the probe. The existence of large amount of other metal ions shows negligible interference in the detection of Fe"3"+. The association constant K_a_s_s of 4.64 × 10"8 M"-"2 (R"2 = 0.994) and 5.38 × 10"8 M"-"2 (R"2 = 0.991) of the complex was derived from UV/Vis and fluorescence titration assuming 1:2 stoichiometry of probe–Fe"3"+ complex, respectively

Determination of K shell fluorescence cross-section and Kβ/Kα intensity ratios for Fe, Se, Te, FeSe, FeTe and TeSe

International Nuclear Information System (INIS)

Saydam, M.; Aksoy, C.; Cengiz, E.; Alaşalvar, C.; Tıraşoğlu, E.; Apaydın, G.

2012-01-01

The fluorescence cross-sections (σ Ki ) and the intensity ratios K β /K α for pure Fe, Se, Te elements and FeSe, FeTe, TeSe complexes have been investigated. The samples were excited by 59.5 keV γ-rays from 241 Am annular radioactive source and emitted X-rays. They were counted by an Ultra-LEGe detector with resolution of 150 eV at 5.9 keV. For pure elements results have been compared with the theoretical calculated values. According to our results band length and mutual interaction of atoms affected the results. We claimed that these effects would help researchers who study on superconductors, especially determining which compound can be show the superconductor properties. - Highlights: ► TeSe, FeSe and FeTe complexes have affected each other in terms of charge transfer. ► Fe excitement and enhancement have been made by Se and Te. ► Attractive interactions between electrons can help to becoming superconductivity.

Crystallization behavior and magnetic properties in High Fe content FeBCSiCu alloy system

Energy Technology Data Exchange (ETDEWEB)

Fan, X.D., E-mail: fanxd@seu.edu.cn; Shen, B.L., E-mail: blshen@seu.edu.cn

2015-07-01

High Fe content FeBCSiCu nanocrystalline alloys are prepared by annealing melt-spun amorphous ribbons with aim at increasing saturation magnetic flux density. Microstructures identified by XRD and TEM reveal that Cu addition inhibits the surface crystallization of Fe{sub 86}B{sub 7}C{sub 7} alloy and improve its glass-forming ability. Activation energy of crystallization calculated by Kissinger's equation indicates that both Cu and Si addition promotes the precipitation of α-Fe phase and improves the thermal stability. VSM and DC B–H loop tracer measurements show that the Fe{sub 85.5}B{sub 7}C{sub 6}Si{sub 1}Cu{sub 0.5} nanocrystalline alloy exhibits high saturation magnetic flux density of 1.8 T and low coercivity of 10 A/m, respectively. AC properties measured by AC B–H analyzer show this alloy exhibits low core loss of 0.35 W/kg at 1 T at 50 Hz. Low material cost and convenient productivity make the Fe{sub 85.5}B{sub 7}C{sub 6}Si{sub 1}Cu{sub 0.5} nanocrystalline alloy an economical application in industry. - Highlights: • Cu addition inhibits the surface crystallization and improves the GFA. • The competitive formation of Fe{sub 3}C and α-Fe phase impedes the devitrification. • Fe{sub 85.5}B{sub 7}C{sub 6}Si{sub 1}Cu{sub 0.5} nanocrystalline alloy exhibits excellent magnetic properties. • The alloy system has an economical advantage and convenient productivity.

Gas phase synthesis of core-shell Fe@FeO{sub x} magnetic nanoparticles into fluids

Energy Technology Data Exchange (ETDEWEB)

Aktas, Sitki, E-mail: aksitki61@gmail.com; Thornton, Stuart C.; Binns, Chris [University of Leicester, Department of Physics and Astronomy (United Kingdom); Denby, Phil [Ensol As, Nesttun (Norway)

2016-12-15

Sorbitol, short chain molecules, have been used to stabilise of Fe@FeO{sub x} nanoparticles produced in the gas phase under the ultra-high vacuum (UHV) conditions. The sorbitol coated Fe@FeO{sub x} nanoparticles produced by our method have a narrow size distribution with a hydrodynamic diameter of 35 nm after NaOH is added to the solution. Magnetisation measurement shows that the magnetic nanoparticles are superparamagnetic at 100 K and demonstrate hysteresis at 5 K with an anisotropy constant of 5.31 × 10{sup 4} J/m{sup 3} (similar to bulk iron). Also, it is shown that sorbitol is only suitable for stabilising the Fe@FeO{sub x} suspensions, and it does not prevent further oxidation of the metallic Fe core. According to MRI measurement, the nanoparticles have a high transverse relaxation rate of 425 mM{sup −1} s{sup −1}.

Sulfide phase in the Fe-Ti-S and Fe-C-Ti-S alloys

International Nuclear Information System (INIS)

Malinochka, Ya.N.; Balakina, N.A.; Shmelev, Yu.S.

1976-01-01

The nature of the sulfide phases in Fe-Ti-S and Fe-C-Ti-S alloys was studied. The carbide and the sulfide phase were identified the aid of X-ray spectral microanalysis. It was established that for a small content of titanium and sulfur in ternary Fe-Ti-S alloys the solidification of the γ-solution on the boundaries of dendritic branches is accompanied, along with the precipitation of a sulfide rich in iron of the (Fe, Ti) S type where a small quantity of titanium is dissolved, by the formation of a titanium-bearing sulfide eutectic γ + TiS. The amount of the sulfide eutectic increases with the contents of titanium and sulfur until a purely eutectic alloy is formed. Both carbides and sulfides may be formed in the solidification of quaternary alloys Fe-C-Ti-S

Physiology, Fe(II oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

Directory of Open Access Journals (Sweden)

Elizabeth D. Swanner

2015-10-01

Full Text Available Evidence for Fe(II oxidation and deposition of Fe(III-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF. While the exact mechanisms of Fe(II oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II-rich waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM and confocal laser scanning microscopy (CLSM are consistent with extracellular precipitation of Fe(III (oxyhydroxide minerals, but that >10% of Fe(III sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS in Fe(II toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II. These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

Science.gov (United States)

Paolella, Andrea; Turner, Stuart; Bertoni, Giovanni; Hovington, Pierre; Flacau, Roxana; Boyer, Chad; Feng, Zimin; Colombo, Massimo; Marras, Sergio; Prato, Mirko; Manna, Liberato; Guerfi, Abdelbast; Demopoulos, George P; Armand, Michel; Zaghib, Karim

2016-04-13

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

Fabrication of FeSi and Fe{sub 3}Si compounds by electron beam induced mixing of [Fe/Si]{sub 2} and [Fe{sub 3}/Si]{sub 2} multilayers grown by focused electron beam induced deposition

Energy Technology Data Exchange (ETDEWEB)

Porrati, F.; Sachser, R.; Huth, M. [Physikalisches Institut, Goethe-Universität, Max-von-Laue-Str. 1, D-60438 Frankfurt am Main (Germany); Gazzadi, G. C. [S3 Center, Nanoscience Institute-CNR, Via Campi 213/a, 41125 Modena (Italy); Frabboni, S. [S3 Center, Nanoscience Institute-CNR, Via Campi 213/a, 41125 Modena (Italy); FIM Department, University of Modena and Reggio Emilia, Via G. Campi 213/a, 41125 Modena (Italy)

2016-06-21

Fe-Si binary compounds have been fabricated by focused electron beam induced deposition by the alternating use of iron pentacarbonyl, Fe(CO){sub 5}, and neopentasilane, Si{sub 5}H{sub 12} as precursor gases. The fabrication procedure consisted in preparing multilayer structures which were treated by low-energy electron irradiation and annealing to induce atomic species intermixing. In this way, we are able to fabricate FeSi and Fe{sub 3}Si binary compounds from [Fe/Si]{sub 2} and [Fe{sub 3}/Si]{sub 2} multilayers, as shown by transmission electron microscopy investigations. This fabrication procedure is useful to obtain nanostructured binary alloys from precursors which compete for adsorption sites during growth and, therefore, cannot be used simultaneously.

Magnetic properties of Fe-oxide and (Fe, Co) oxide nanoparticles synthesized in polystyrene resin matrix

Science.gov (United States)

Rodak, D.; Kroll, E.; Tsoi, G. M.; Vaishnava, P. P.; Naik, R.; Wenger, L. E.; Suryanarayanan, R.; Naik, V. M.; Boolchand, P.

2003-03-01

Magnetic nanoparticles have potential applications ranging from drug delivery and imaging in the medical field to sensing and memory storage in technology. The preparation, structure, and physical properties of iron oxide-based nanoparticles synthesized by ion exchange in a polystyrene resin matrix have been investigated. Employing a synthesis method developed originally by Ziolo, et. al^1, nanoparticles were prepared in a sulfonated divinyl benzene polystyrene resin matrix using various aqueous solutions of (1) FeCl_2, (2) FeCl_3, (3) FeCl2 : 2FeCl3 , (4) 9FeCl2 : CoCl_2, and (5) 4FeCl2 : CoCl_2. Powder x-ray diffraction measurements were used to identify the phases present while transmission electron microscopy was used for particle size distribution determinations. SQUID magnetization measurements (field-cooled and zero-field-cooled) and Fe^57 Mössbauer effect measurements indicate the presence of ferromagnetic iron oxide phases and a superparamagnetic behavior with blocking temperatures (T_B) varying from 50 K to room temperature. Nanoparticles synthesized using a stoichiometric mixture of FeCl2 and FeCl3 exhibit the lowest TB and smallest particle size distribution. The Mössbauer effect measurements have also been used to identify the iron oxides phases present and their relative amounts in the nanoparticles ^1R.F. Ziolo, et al., Science 207, 219 (1992). *Permanent address: Kettering University, Flint, MI 48504

Magnetism and metal insulator transition in FeSi and FeGe. Ab Initio investigations of the electronic structure; Magnetismus und Metall-Isolator-Uebergang in FeSi und FeGe. Ab-initio-Untersuchungen der elektronischen Struktur

Energy Technology Data Exchange (ETDEWEB)

Neef, Matthias

2007-03-19

Aim of this thesis was to reach by a systematic study of different ab initio procedures an improved description of the electronic properties of FeSi and FeGe. Central result is the itinerant description of FeSi as a semiconductor in the neighbourhood of a ferromagnetic instability. The regardment of the nonlocal exchange in the effective one-particle approximation leads to a metastable magnetic state scarcely above the magnetic ground state. The application of the hybrid functional leads to a 1st order metal-isolator transition for large lattice parameters: FeSi transforms at increasement of the lattice parameter from an unmagnetic isolator to a magnetic metal. A similar behavior is found in the isostructural compound FeGe. The two systems FeSi and FeGe were systematically and detailedly analyzed by means of ab initio procedures. Thereby the structural, electronic, and magnetic properties were studied with DFT and HF calculations. Both calculations with spin polarization and without spin polarization were performed.

Timing for a sustainable fertilisation of Glycine max by using HBED/Fe3+ and EDDHA/Fe3+ chelates.

Science.gov (United States)

Martín-Fernández, Clara; López-Rayo, Sandra; Hernández-Apaolaza, Lourdes; Lucena, Juan J

2017-07-01

Efficient use of Fe chelates is crucial to avoid environmental risks and reduce economic losses. HBED/Fe 3+ has been recently approved by the European Union for soil fertilisation, but studies delving into the best timing for its application are necessary. In this work, a batch incubation experiment and two biological experiments were developed to determine the optimal physiological stage for a sustainable application of HBED/Fe 3+ in soil fertilisation compared with EDDHA/Fe 3+ fertilisers using 57 Fe. HBED/Fe 3+ demonstrated a high durability in soils and soil materials, maintaining more than 80% of Fe chelated after 70 days, and its application at an early physiological stage resulted in a high Fe accumulation in soybean and soil after 36 days. In contrast, the stability of EDDHA/Fe 3+ decreased because of the retention of its lowest stable isomers. The best timing for chelates application was confirmed in a 52 day experiment. The application of HBED/Fe 3+ at the early stage increased the Fe translocation to fruits; while o,o-EDDHA/Fe 3+ accumulated more Fe in fruits when added at the fructification stage. The high HBED/Fe 3+ stability in calcareous soil requires a differentiate application timing, and its addition at early physiological stages leads into the most efficient fertilisation. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

N2O decomposition over Fe/ZSM-5: reversible generation of highly active cationic Fe species

NARCIS (Netherlands)

Zhu, Q.; Hensen, E.J.M.; Mojet, B.L.; Wolput, van J.H.M.C.; Santen, van R.A.

2002-01-01

Fe-oxide species in Fe/ZSM-5 (prepared by chemical vapor deposition of FeCl3)-active in N2O decomposition-react with zeolite protons during high temperature calcination to give highly active cationic Fe species, this transformation being reversible upon exposure to water vapor at lower temperature

Magnetic properties of ball-milled TbFe2 and TbFe2B

Indian Academy of Sciences (India)

Unknown

1. Introduction. The RFe2 (R = rare earth) Laves phase compounds are known to possess large cubic anisotropy (Clark et al 1972) and highest Curie temperature (TC) of all RT2 compounds. (T = transition metal). RFe2 ... TbFe2 and TbFe2B were prepared by arc melting the high pure elements (Tb and B, 99⋅9% purity; Fe, ...

μ(4)-Orthothio-carbonato-tetra-kis-[tri-carbonyl-iron(I)](2 Fe-Fe).

Science.gov (United States)

Shi, Yao-Cheng; Cheng, Huan-Ren; Yuan, Li-Min; Li, Qian-Kun

2011-11-01

The fused bis-butterfly-shaped title compound, [Fe(4)(CS(4))(CO)(12)], possesses an orthothio-carbonate (CS(4) (4-)) ligand that acts as a bridge between two Fe(2)(CO)(6) units. A short intra-molecular S⋯S contact [2.6984 (8) and 2.6977 (8) Å] occurs in each S(2)Fe(2)(CO)(6) fragment.

Protein profile of Beta vulgaris leaf apoplastic fluid and changes induced by Fe deficiency and Fe resupply

Directory of Open Access Journals (Sweden)

Laura eCeballos-Laita

2015-03-01

Full Text Available The fluid collected by direct leaf centrifugation has been used to study the proteome of the sugar beet apoplastic fluid as well as the changes induced by Fe deficiency and Fe resupply to Fe-deficient plants in the protein profile. Plants were grown in Fe-sufficient and Fe-deficient conditions, and Fe resupply was carried out with 45 μM Fe(III-EDTA for 24 h. Protein extracts of leaf apoplastic fluid were analyzed by two-dimensional isoelectric focusing-SDS-PAGE electrophoresis. Gel image analysis revealed 203 consistent spots, and proteins in 81% of them (164 were identified by nLC-MS/MS using a custom made reference repository of beet protein sequences. When redundant UniProt entries were deleted, a non-redundant leaf apoplastic proteome consisting of 109 proteins was obtained. TargetP and SecretomeP algorithms predicted that 63% of them were secretory proteins. Functional classification of the non-redundant proteins indicated that stress and defense, protein metabolism, cell wall and C metabolism accounted for approximately 75% of the identified proteome. The effects of Fe-deficiency on the leaf apoplast proteome were limited, with only five spots (2.5% changing in relative abundance, thus suggesting that protein homeostasis in the leaf apoplast fluid is well maintained upon Fe shortage. The identification of three chitinase isoforms among proteins increasing in relative abundance with Fe-deficiency suggests that one of the few effects of Fe deficiency in the leaf apoplast proteome includes cell wall modifications. Iron resupply to Fe deficient plants changed the relative abundance of 16 spots when compared to either Fe-sufficient or Fe-deficient samples. Proteins identified in these spots can be broadly classified as those responding to Fe-resupply, which included defense and cell wall related proteins, and non-responsive, which are mainly protein metabolism related proteins and whose changes in relative abundance followed the same trend as

Phase analysis of Fe-nanowires encapsulated into multi-walled carbon nanotubes via 57Fe Moessbauer spectroscopy

International Nuclear Information System (INIS)

Ruskov, T.; Spirov, I.; Ritschel, M.; Mueller, C.; Leonhardt, A.; Ruskov, R.

2007-01-01

We have performed morphological analysis of samples of Fe-nanowires encapsulated into aligned multi-walled carbon nanotubes (Fe-MWCNT) via 57 Fe Moessbauer spectroscopy. The aligned Fe-MWCNTs were obtained by pyrolysis of ferrocene onto an oxidized Si substrate. Transmission Moessbauer spectroscopy (TMS) and back scattered conversion electron Moessbauer spectroscopy (CEMS) were applied in order to distinguish different Fe-phases and their spatial distribution within the whole sample and along the tubes' height. A characterization (on a large spatial scale) of the aligned CNT samples were performed by obtaining TMS spectra for selected spots positioned at different locations of the sample. While the total Fe content changes considerably from one location to another, the γ-Fe/α-Fe phase ratio is constant onto a relatively large area. Using TMS and CEMS for all aligned Fe-MWCNTs samples it is also shown that along the CNT axes, going to the top of the nanotube the relative content of the γ-Fe phase increases. Going to the opposite direction, i.e. towards the silicon substrate, the relative content of the Fe 3 C phase increases, that is in agreement with our previous works. The results of an additional Moessbauer spectroscopy experiment in TMS and CEMS modes performed on a non-aligned sample support the conclusion that in our case the iron phases in the channels of carbon nanotubes are spatially separated as individual nanoparticles. The relative intensity ratio of the α-Fe phase Moessbauer sextets show good magnetic texture along nanotubes axis for one of the aligned samples and the lack of such orientation for the others. (authors)

Magnetic properties of {alpha}-Fe and Fe{sub 3}C nanowires

Energy Technology Data Exchange (ETDEWEB)

Lutz, M U; Weissker, U; Wolny, F; Mueller, C; Loeffler, M; Muehl, T; Leonhardt, A; Buechner, B; Klingeler, R, E-mail: m.lutz@ifw-dresden.d [Leibniz Institute for Solid State and Materials Research IFW Dresden, Helmholtzstrasse 20, 01069 Dresden (Germany)

2010-01-01

The magnetic properties of single domain {alpha}-Fe and Fe{sub 3}C nanowires encapsulated within Multi Walled Carbon Nanotubes (MWNT) are investigated with a Magnetic Force Microscope (MFM). The wires are formed during the Chemical Vapour Deposition growth process, partially filling the hollow center of the MWNTs. The wires have a diameter variation of 10-60nm and can be several {mu}m long. The phase and crystal orientation of the filling relative to the long tube axis are probed by Transmission Electron Microscopy. The remanent magnetization states of the wires are investigated by MFM imaging. The {alpha}-Fe wires show shape dominated magnetization along the tube axis, whereas the FesC wires show a perpendicular magnetization imposed by magneto-crystalline anisotropy. Switching fields of {alpha}-Fe nanowires are determined by the application of an in-situ magnetic field, revealing a tip triggered magnetization reversal by localized nucleation.

A subsurface Fe-silicate weathering microbiome

Science.gov (United States)

Napieralski, S. A.; Buss, H. L.; Roden, E. E.

2017-12-01

Traditional models of microbially mediated weathering of primary Fe-bearing minerals often invoke organic ligands (e.g. siderophores) used for nutrient acquisition. However, it is well known that the oxidation of Fe(II) governs the overall rate of Fe-silicate mineral dissolution. Recent work has demonstrated the ability of lithtrophic iron oxidizing bacteria (FeOB) to grow via the oxidation of structural Fe(II) in biotite as a source of metabolic energy with evidence suggesting a direct enzymatic attack on the mineral surface. This process necessitates the involvement of dedicated outer membrane proteins that interact with insoluble mineral phases in a process known as extracellular electron transfer (EET). To investigate the potential role FeOB in a terrestrial subsurface weathering system, samples were obtained from the bedrock-saprolite interface (785 cm depth) within the Rio Icacos Watershed of the Luquillo Mountains in Puerto Rico. Prior geochemical evidence suggests the flux of Fe(II) from the weathering bedrock supports a robust lithotrophic microbial community at depth. Current work confirms the activity of microorganism in situ, with a marked increase in ATP near the bedrock-saprolite interface. Regolith recovered from the interface was used as inoculum to establish enrichment cultures with powderized Fe(II)-bearing minerals serving as the sole energy source. Monitoring of the Fe(II)/Fe(total) ratio and ATP generation suggests growth of microorganisms coupled to the oxidation of mineral bound Fe(II). Analysis of 16S rRNA gene and shotgun metagenomic libraries from in situ and enrichment culture samples lends further support to FeOB involvement in the weathering process. Multiple metagenomic bins related to known FeOB, including Betaproteobacteria genera, contain homologs to model EET systems, including Cyc2 and MtoAB. Our approach combining geochemistry and metagenomics with ongoing microbiological and genomic characterization of novel isolates obtained

Epitaxial Fe3Si/Ge/Fe3Si thin film multilayers grown on GaAs(001)

International Nuclear Information System (INIS)

Jenichen, B.; Herfort, J.; Jahn, U.; Trampert, A.; Riechert, H.

2014-01-01

We demonstrate Fe 3 Si/Ge/Fe 3 Si/GaAs(001) structures grown by molecular-beam epitaxy and characterized by transmission electron microscopy, electron backscattered diffraction, and X-ray diffraction. The bottom Fe 3 Si epitaxial film on GaAs is always single crystalline. The structural properties of the Ge film and the top Fe 3 Si layer depend on the substrate temperature during Ge deposition. Different orientation distributions of the grains in the Ge and the upper Fe 3 Si film were found. The low substrate temperature T s of 150 °C during Ge deposition ensures sharp interfaces, however, results in predominantly amorphous films. We find that the intermediate T s (225 °C) leads to a largely [111] oriented upper Fe 3 Si layer and polycrystal films. The high T s of 325 °C stabilizes the [001] oriented epitaxial layer structure, i.e., delivers smooth interfaces and single crystal films over as much as 80% of the surface area. - Highlights: • Fe 3 Si/Ge/Fe 3 Si/GaAs(001) structures are grown by MBE. • The bottom Fe 3 Si film is always single crystalline. • The properties of the Ge film depend on the substrate temperature during deposition. • Optimum growth conditions lead to almost perfect epitaxy of Ge on Fe 3 Si

Study of the reaction of astrophysical interest 60Fe(n,γ)61Fe via (d,pγ) transfer reaction

International Nuclear Information System (INIS)

Giron, S.

2011-12-01

60 Fe is of special interest in nuclear astrophysics. Indeed the recent observations of 60 Fe characteristic gamma-ray lines by the RHESSI and INTEGRAL spacecrafts allowed to measure the total flux of 60 Fe over the Galaxy. Moreover the observation in presolar grains of an excess of the daughter-nuclei of 60 Fe, 60 Ni, gives constraints on the conditions of formation of the early solar system. However, the cross-sections of some reactions involved in 60 Fe nucleosynthesis and included to stellar models are still uncertain. The destruction reaction of 60 Fe, 60 Fe(n, γ) 61 Fe, is one of them. The total cross-section can be separate into two contributions: the direct one, involving states below the neutron separation threshold of 61 Fe, and the resonant one.We improved 61 Fe spectroscopy in order to evaluate the direct capture part of the 60 Fe(n, γ) 61 Fe reaction cross-section. 60 Fe(n, γ) 61 Fe was thus studied via d( 60 Fe, pγ) 61 Fe transfer reaction with the CATS/MUST2/EXOGAM setup at LISE-GANIL. DWBA analysis of experimental proton differential cross-sections allowed to extract orbital angular momentum and spectroscopic factors of different populated states identified below the neutron threshold. A comparison of experimental results for 61 Fe with experimental results for similar nuclei and with shell-model calculations was also performed. (author) [fr

Magnetization reversal in textured NdFeB-Fe composites observed by domain imaging

Energy Technology Data Exchange (ETDEWEB)

Thielsch, Juliane, E-mail: j.thielsch@ifw-dresden.d [IFW Dresden, Institute for Metallic Materials, P.O. Box 27 01 16, D-01171 Dresden (Germany); Hinz, Dietrich; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 27 01 16, D-01171 Dresden (Germany)

2010-10-15

Textured composite samples consisting of Nd{sub 13.6}Fe{sub 73.6}Ga{sub 0.6}Co{sub 6.6}B{sub 5.6} (MQU-F{sup TM}) and micron-sized Fe particles with weight ratios from 100:0 to 70:30 have been prepared by hot deformation. Microstructure studies revealed a layered structure of both phases with the layer normal parallel to the pressing direction. Magnetic measurements showed single-phase hysteresis curves for all samples when measured along the pressing direction, which is also the easy axis of magnetization. Coercivity decreased drastically from 1.32 T for pure NdFeB samples to 0.154 T for a sample with 30 wt% Fe. Magneto-optical Kerr microscopy with a digitally enhanced imaging technique has been used to examine the evolution of magnetic domains in the hard and soft phase during demagnetizing a sample consisting of 70 wt% NdFeB and 30 wt% Fe. It is shown that demagnetization takes place via domain rearrangements within the soft phase, which lead to and support the nucleation of reversed interaction domains at phase boundaries. Also nucleation of interaction domains within the hard magnetic phase could be revealed.

Magnetization reversal in textured NdFeB-Fe composites observed by domain imaging

International Nuclear Information System (INIS)

Thielsch, Juliane; Hinz, Dietrich; Schultz, Ludwig; Gutfleisch, Oliver

2010-01-01

Textured composite samples consisting of Nd 13.6 Fe 73.6 Ga 0.6 Co 6.6 B 5.6 (MQU-F TM ) and micron-sized Fe particles with weight ratios from 100:0 to 70:30 have been prepared by hot deformation. Microstructure studies revealed a layered structure of both phases with the layer normal parallel to the pressing direction. Magnetic measurements showed single-phase hysteresis curves for all samples when measured along the pressing direction, which is also the easy axis of magnetization. Coercivity decreased drastically from 1.32 T for pure NdFeB samples to 0.154 T for a sample with 30 wt% Fe. Magneto-optical Kerr microscopy with a digitally enhanced imaging technique has been used to examine the evolution of magnetic domains in the hard and soft phase during demagnetizing a sample consisting of 70 wt% NdFeB and 30 wt% Fe. It is shown that demagnetization takes place via domain rearrangements within the soft phase, which lead to and support the nucleation of reversed interaction domains at phase boundaries. Also nucleation of interaction domains within the hard magnetic phase could be revealed.

High saturation magnetization FeB(C) nanocapsules

International Nuclear Information System (INIS)

Ma, S.; Si, P.Z.; Zhang, Y.; Wu, B.; Li, Y.B.; Liu, J.J.; Feng, W.J.; Ma, X.L.; Zhang, Z.D.

2007-01-01

FeB(C) nanocapsules were prepared by arc-discharging Fe 80 B 20 alloy in Ar and CH 4 . X-ray diffraction and transmission electron microscopy analyses showed that the FeB(C) nanocapsules had a core-shell structure with α-Fe and Fe 3 B as cores and graphite as shells. The formation mechanism of the FeB(C) nanocapsules is discussed. The graphite shells display a strong anti-acid effect. The saturation magnetization at room temperature of the FeB(C) nanocapsules is much higher than that of Fe(B) nanocapsules. The blocking temperature of FeB(C) nanocapsules is above 300 K

Enhanced antibacterial performance of Fe3O4–Ag and MnFe2O4 ...

Indian Academy of Sciences (India)

sity in our daily life. ... enhances the biological activity of Ag NPs, but many stud- ... against Gram-positive and Gram-negative bacteria in this ..... Antimicrobial effects of Fe3O4@Nico@Ag, Fe3O4@His@Ag and Fe3O4@HA@Ag against Fe3O4 ...

Microstructure and Properties of Fe3Al-Fe3AlC x Composite Prepared by Reactive Liquid Processing

Science.gov (United States)

Verona, Maria Nalu; Setti, Dalmarino; Paredes, Ramón Sigifredo Cortés

2018-04-01

A Fe3Al-Fe3AlC x composite was prepared using reactive liquid processing (RLP) through controlled mixture of carbon steel and aluminum in the liquid state. The microstructure and phases of the composite were assessed using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, optical microscopy, and differential scanning calorimetry. In addition, the density, hardness, microhardness, and elastic modulus were evaluated. The Fe3Al-Fe3AlC x composite consisted of 65 vol pct Fe3Al and 35 vol pct Fe3AlC x ( κ). The κ phase contained 10.62 at. pct C, resulting in the stoichiometry Fe3AlC0.475. The elastic modulus of the Fe3Al-Fe3AlC0.475 composite followed the rule of mixtures. The RLP technique was shown to be capable of producing Fe3Al-Fe3AlC0.475 with a microstructure and properties similar to those achieved using other processing techniques reported in the literature.

Efficacy of Fe(o,o-EDDHA) and Fe(o,p-EDDHA) isomers in supplying Fe to strategy I plants differs in nutrient solution and calcareous soil.

Science.gov (United States)

Rojas, Carmen L; Romera, Francisco J; Alcántara, Esteban; Pérez-Vicente, Rafael; Sariego, Cristina; Garcaí-Alonso, J Ignacio; Boned, Javier; Marti, Gabriel

2008-11-26

The FeEDDHA [iron(3+) ethylenediamine di(o-hydroxyphenylacetic) acid] is one of the most efficient iron chelates employed in the correction of iron clorosis in calcareous soils. FeEDDHA presents different positional isomers: the ortho-ortho (o,o), the ortho-para (o,p), and the para-para (p,p). Of these isomers, the p,p cannot chelate Fe in soil solution in a wide range of pH values, while both o,o and o,p can. The objective of this work was to compare the efficiency of both isomers (o,o and o,p) to provide Fe to two Strategy I plants (tomato and peach) in nutrient solution (pH approximately 6.0), as well as in calcareous soil (pH approximately 8.4; CALCIXEREPT). For this, chelates of both o,o-EDDHA and o,p-EDDHA with 57Fe (a nonradioactive isotope of Fe) were used, where the 57Fe acts as a tracer. The results obtained showed that the o,o isomer is capable of providing sufficient Fe to plants in both nutrient solution and calcareous soil. However, the o,p isomer is capable of providing sufficient Fe to plants in nutrient solution but not in calcareous soil.

Fabrication of NdFeB microstructures using a silicon molding technique for NdFeB/Ta multilayered films and NdFeB magnetic powder

International Nuclear Information System (INIS)

Jiang Yonggang; Fujita, Takayuki; Uehara, Minoru; Iga, Yuki; Hashimoto, Taichi; Hao, Xiuchun; Higuchi, Kohei; Maenaka, Kazusuke

2011-01-01

The silicon molding technique is described for patterning of NdFeB/Ta multilayered magnetic films and NdFeB magnetic powder at the micron scale. Silicon trenches are seamlessly filled by 12-μm-thick NdFeB/Ta multilayered magnetic films with a magnetic retentivity of 1.3 T. The topography image and magnetic field distribution image are measured using an atomic force microscope and a magnetic force microscope, respectively. Using a silicon molding technique complemented by a lift-off process, NdFeB magnetic powder is utilized to fabricate magnetic microstructures. Silicon trenches as narrow as 20 μm are filled by a mixture of magnetic powder and wax powder. The B-H hysteresis loop of the patterned magnetic powder is characterized using a vibrating sample magnetometer, which shows a magnetic retentivity of approximately 0.37 T. - Highlights: → We demonstrate the fabrication of micro-magnets using silicon molding processes. → NdFeB/Ta films are well filled in silicon trenches with a thickness of 12 μm. → The 12-μm-thick NdFeB/Ta magnetic film shows a retentivity of 1.3 T. → Magnetic structures as narrow as 20 μm are fabricated using NdFeB magnetic powder. → VSM measurement shows a retentivity of 0.37 T for patterned NdFeB magnetic powder.

Fabrication of NdFeB microstructures using a silicon molding technique for NdFeB/Ta multilayered films and NdFeB magnetic powder

Energy Technology Data Exchange (ETDEWEB)

Jiang Yonggang, E-mail: yonggangj@gmail.com [School of Mechanical Engineering and Automation, Beihang University, Xueyuan Road No. 37, Haidian District, Beijing 100191 (China); Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Fujita, Takayuki [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Uehara, Minoru [NEOMAX Co. Ltd., 2-15-17, Egawa, Shimamoto-Cho, Mishima-gun, Osaka 618-0013 (Japan); Iga, Yuki [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Hashimoto, Taichi [Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Hao, Xiuchun; Higuchi, Kohei [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Maenaka, Kazusuke [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan)

2011-11-15

The silicon molding technique is described for patterning of NdFeB/Ta multilayered magnetic films and NdFeB magnetic powder at the micron scale. Silicon trenches are seamlessly filled by 12-{mu}m-thick NdFeB/Ta multilayered magnetic films with a magnetic retentivity of 1.3 T. The topography image and magnetic field distribution image are measured using an atomic force microscope and a magnetic force microscope, respectively. Using a silicon molding technique complemented by a lift-off process, NdFeB magnetic powder is utilized to fabricate magnetic microstructures. Silicon trenches as narrow as 20 {mu}m are filled by a mixture of magnetic powder and wax powder. The B-H hysteresis loop of the patterned magnetic powder is characterized using a vibrating sample magnetometer, which shows a magnetic retentivity of approximately 0.37 T. - Highlights: > We demonstrate the fabrication of micro-magnets using silicon molding processes. > NdFeB/Ta films are well filled in silicon trenches with a thickness of 12 {mu}m. > The 12-{mu}m-thick NdFeB/Ta magnetic film shows a retentivity of 1.3 T. > Magnetic structures as narrow as 20 {mu}m are fabricated using NdFeB magnetic powder. > VSM measurement shows a retentivity of 0.37 T for patterned NdFeB magnetic powder.

Fabrication of α-Fe/Fe3C/Woodceramic Nanocomposite with Its Improved Microwave Absorption and Mechanical Properties

Directory of Open Access Journals (Sweden)

Weihong Zhou

2018-05-01

Full Text Available Furan resin and fir powder pretreated by FeCl3 and aqueous ammonia solution were used to fabricate α-Fe/Fe3C/woodceramic nanocomposite. The bands of the pretreated wood powder were characterized by Fourier transform infrared spectroscopy (FTIR. The structural characterization of the nanocomposites was performed by scanning electron microscopy (SEM and X-ray diffraction (XRD. The microwave absorption of the nanocomposites was measured by a vector network analyzer in the range of 2–18 GHz. The mechanical properties of the composites were also investigated. XRD and SEM results show that the α-Fe and Fe3C nanoparticles are in-situ generated and disperse in the matrix of the woodceramic. The diameters of these nanoparticles increase with the increasing of concentration of FeCl3 solution. The experimental results show that both the complex permittivity and the complex permeability of α-Fe/Fe3C/woodceramic nanocomposites increase as the concentration of FeCl3 solution increases. The composites pretreated with 0.60 mol·L−1 FeCl3 have the best absorption properties. The maximum value of reflection loss (RL at 3 mm thickness reaches −25.60 dB at 10.16 GHz and the bandwidth below −10 dB is about 2.5 GHz. Compared to woodceramic, the bending strength and compressive strength of α-Fe/Fe3C/woodceramic nanocomposites increase by 22.5% and 18.7% at most, respectively.

Swelling of Fe-Mn and Fe-Cr-Mn alloys at high neutron fluence

International Nuclear Information System (INIS)

Garner, F.A.; Brager, H.R.

1986-06-01

Swelling data on neutron-irradiated simple Fe-Cr-Mn and Fe-Mn alloys, as well as commercial Fe-Cr-Mn base alloys are now becoming available at exposure levels approaching 50 dpa. The swelling rate decreases from the ∼1%/dpa found at lower exposures, probably due to the extensive formation of ferritic phases. As expected, commercial alloys swell less than the simple alloys

Structural Investigation of Fe-Ni-S and Fe-Ni-Si Melts by High-temperature Fluorescence XAFS Measurements

International Nuclear Information System (INIS)

Manghnani, Murli H.; Balogh, John; Hong Xinguo; Newville, Matthew; Amulele, G.

2007-01-01

Iron-nickel (Fe-Ni) alloy is regarded as the most abundant constituent of Earth's core, with an amount of 5.5 wt% Ni in the core based on geochemical and cosmochemical models. The structural role of nickel in liquid Fe-Ni alloys with light elements such as S or Si is poorly understood, largely because of the experimental difficulties of high-temperature melts. Recently, we have succeeded in acquiring Ni K-edge fluorescence x-ray absorption fine structure (XAFS) spectra of Fe-Ni-S and Fe-Ni-Si melts and alloys. Different structural environment of Ni atoms in Fe-Ni-S and Fe-Ni-Si melts is observed, supporting the effect of light elements in Fe-Ni melts

Silicon induced Fe deficiency affects Fe, Mn, Cu and Zn distribution in rice (Oryza sativa L.) growth in calcareous conditions.

Science.gov (United States)

Carrasco-Gil, Sandra; Rodríguez-Menéndez, Sara; Fernández, Beatriz; Pereiro, Rosario; de la Fuente, Vicenta; Hernandez-Apaolaza, Lourdes

2018-04-01

A protective effect by silicon in the amelioration of iron chlorosis has recently been proved for Strategy 1 species, at acidic pH. However in calcareous conditions, the Si effect on Fe acquisition and distribution is still unknown. In this work, the effect of Si on Fe, Mn, Cu and Zn distribution was studied in rice (Strategy 2 species) under Fe sufficiency and deficiency. Plants (+Si or-Si) were grown initially with Fe, and then Fe was removed from the nutrient solution. The plants were then analysed using a combined approach including LA-ICP-MS images for each element of interest, the analysis of the Fe and Si concentration at different cell layers of root and leaf cross sections by SEM-EDX, and determining the apoplastic Fe, total micronutrient concentration and oxidative stress indexes. A different Si effect was observed depending on plant Fe status. Under Fe sufficiency, Si supply increased Fe root plaque formation, decreasing Fe concentration inside the root and increasing the oxidative stress in the plants. Therefore, Fe acquisition strategies were activated, and Fe translocation rate to the aerial parts was increased, even under an optimal Fe supply. Under Fe deficiency, +Si plants absorbed Fe from the plaque more rapidly than -Si plants, due to the previous activation of Fe deficiency strategies during the growing period (+Fe + Si). Higher Fe plaque formation due to Si supply during the growing period reduced Fe uptake and could activate Fe deficiency strategies in rice, making it more efficient against Fe chlorosis alterations. Silicon influenced Mn and Cu distribution in root. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Magnetostrictive properties of FeAl/polyester and FeAl/silicone composites

Energy Technology Data Exchange (ETDEWEB)

Riesgo, G. [Dpto. de Ciencias y Técnicas de la Navegación, Universidad de Oviedo, Campus universitario de Gijón, 33203 Gijón (Spain); Carrizo, J. [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain); Elbaile, L., E-mail: elbaile@uniovi.es [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain); Crespo, R.D. [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain); Sepúlveda, R. [Dpto. de Ingeniería Mecánica y de los Materiales, Universidad de Sevilla, Isla Cartuja, 41092 Sevilla (Spain); García, J.A. [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain)

2017-01-15

Highlights: • Nanocrystalline powders of FeAl have been obtained from the Fe{sub 81}Al{sub 19} ribbon produced by melt spinning. • The method allows the obtainment of a FeAl solid solution from the starting process. • The microstructure and magnetic properties of the powders were investigated. • Composites with a magnetostriction of 45 ppm have been obtained. - Abstract: Ribbons of composition Fe{sub 81}Al{sub 19} obtained by the melt spinning method have been used to yield powder by mechanical milling. Using this method, a rapid nanocrystallization and a FeAl solid solution phase was obtained from the start of the process. The microstructural and magnetic properties as well as the XRD patterns of the powders were studied in function of the milling time. Grain refinement and an increase of the coercive field were the main transformations resulting from increasing the milling time. Two sets of magnetostrictive composites were produced from the 100 h-milled powder. In one of them polyester was used as matrix and in the other one silicone. In the case of the silicone composites cured in a magnetic field of 140 mT in the longitudinal direction a saturation magnetostriction as high as 45 ppm was obtained.

Fe II/Fe III mixed-valence state induced by Li-insertion into the metal-organic-framework Mil53(Fe): A DFT+U study

Science.gov (United States)

Combelles, C.; Ben Yahia, M.; Pedesseau, L.; Doublet, M.-L.

The iron-based metal-organic-framework MIL53(Fe) has recently been tested as a cathode materials for Li-Ion batteries, leading to promising cycling life and rate capability. Despite a poor capacity of 70 mAh g -1 associated with the exchange of almost 0.5Li/Fe, this result is the first evidence of a reversible lithium insertion never observed in a MOF system. In the present study, the MIL53(Fe) redox mechanism is investigated through first-principles DFT+U calculations. The results show that MIL53(Fe) is a weak antiferromagnetic charge transfer insulator at T = 0 K, with iron ions in the high-spin S = 5/2 state. Its reactivity vs elemental lithium is then investigated as a function of lithium composition and distribution over the most probable Li-sites of the MOF structure. The redox mechanism is fully interpreted as a two-step insertion/conversion mechanism, associated with the stabilization of the Fe 3+/Fe 2+ mixed-valence state prior to the complete decomposition of the inorganic-organic interactions within the porous MOF architecture.

Acetone sensors based on microsheet-assembled hierarchical Fe2O3 with different Fe3+ concentrations

Science.gov (United States)

Wang, Han; Yan, Lei; Li, Shuo; Li, Yu; Liu, Li; Du, Liting; Duan, Haojie; Cheng, Yali

2018-02-01

Several different morphologies of microsheet-assembled Fe2O3 have been fabricated by hydrothermal method using diverse concentrations of Fe3+ precursor solutions (0.025, 0.020, 0.015, 0.010 mol/L Fe3+). The as-synthesized materials have been characterized by scanning electron microscope (SEM), X-ray powder diffraction (XRD), and energy-dispersive X-ray spectrometry (EDS). The SEM images reflect that the morphologies of as-synthesized materials are affected by the concentrations of Fe3+ in precursor solutions. The less concentration of Fe3+, the more porous of Fe2O3 microflowers, and thinner of slices distributed on the surface. Furthermore, gas sensors based on these Fe2O3 microflowers manufactured and tested to various common gases. The optimum response value to 100 ppm acetone is 52 at the working temperature of 220 °C. Meanwhile, the Fe2O3 microflower sensors possess ultrafast response-recovery speed, which are 8 and 19 s, respectively. The possible sensing mechanism was mainly attributed to the high surface area, three-dimensional porous structure.

Chemical synthesis of magnetic Fe-B and Fe-Co-B particles and chains

International Nuclear Information System (INIS)

Fulmer, P.; Kim, J.; Manthiram, A.; Sanchez, J.M.

1999-04-01

With an objective to develop magnetic materials with high saturation magnetization for the Magnetically Assisted Chemical Separation (MACS) process the chemical synthesis of Fe-B and Fe-Co-B alloys by reducing iron and cobalt chloride solutions with potassium borohydride has been investigated systematically. The influence of the concentration of the reactants, applied magnetic field, reaction atmosphere, and method of mixing the reactants on the microstructure, particle size, composition and magnetic properties has been studied. Both M-B (M = Fe and Co) particles and elongated chains composed of nanometer size M-B particles have been obtained depending on the reaction conditions. The Fe-B samples exhibit saturation magnetization of M S of 120--190 emu/g, remanent magnetization M r of 10--22 emu/g, and coercive field H c of 400--900 Oe. A high M S value of 190 emu/g, which is close to the theoretical value of 218 emu/g for pure Fe, has been achieved particularly for samples with well-defined chain structures. Increasing the Co content in the Fe-Co-B alloys increases the boron content and thereby decreases the crystallinity and M S values although marginal increase in H c (1,250 Oe) and M r (36 emu/g) values could be made in some Fe-Co-B compositions. The chain structure with high M S may be attractive for other magnetic separation processes as well

Uptake and Release of Cerium During Fe-Oxide Formation and Transformation in Fe(II) Solutions

DEFF Research Database (Denmark)

Nedel, Sorin; Dideriksen, Knud; Christiansen, Bo C.

2010-01-01

Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption......(III) release. X-ray photoelectron spectroscopy revealed Ce(III) adsorbed on magnetite. When Fe-oxides were synthesized by air oxidation of Fe(II) solutions at pH 7, GR(Na,SO4) played a catalytic role in the oxidation of Ce(III) to Ce(IV) by O-2, removing more than 90% of the dissolved Ce. Transmission electron...

Adsorption induced modification of in-plane magnetic anisotropy in epitaxial Co and Fe/Co films on Fe(110)

Science.gov (United States)

Ślezak, M.; Ślezak, T.; Matlak, K.; DróŻdŻ, P.; Korecki, J.

2018-05-01

A study of in-plane magnetic anisotropy (MA) in epitaxial bcc Co films and Fe/Co bilayers on a Fe(110) surface is reported. Surface MA of as-deposited Co films and Fe/Co bilayers strongly depends on the Co (dCo) and Fe (dFe) thickness. Adsorption of residual gases drastically modifies in-plane MA of both Co films and Fe/Co bilayers. We present two dimensional MA maps in the (dCo, dFe) space for both as grown and adsorption-modified films. Our results indicate how to precisely engineer in-plane MA that can be controlled by dCo, dFe and is sensitive to the residual gas adsorption.

Thermodynamical properties of 56Fe

International Nuclear Information System (INIS)

Tavukcu, E.; Becker, J. A.; Bernstein, L. A.; Garrett, P. E.; Younes, W.; Guttormsen, M.; Rekstad, J.; Siem, S.; Mitchell, G. E.; Schiller, A.; Voinov, A.

2003-01-01

Average nuclear level densities close to the nuclear binding energy in 56Fe and 57Fe are extracted from primary γ-ray spectra. A step structure is observed in the level density for both isotopes, and is interpreted as breaking of Cooper pairs. Thermal properties of 56Fe are studied within the statistical canonical ensemble. The experimental heat capacity in 56Fe is compared with the theoretical heat capacity calculated within the shell model Monte Carlo approach

Ab-initio study of the interfacial properties in ultrathin MgO films on O-rich FeO/Fe(001) surfaces

Energy Technology Data Exchange (ETDEWEB)

Jeon, Junjin; Yu, Byungdeok [University of Seoul, Seoul (Korea, Republic of)

2014-09-15

Using ab-initio simulations based on density functional theory, we systematically studied the interfacial properties of MgO films on O-rich FeO/Fe(001) surfaces with increasing number of MgO layers from one to three monolayers (MLs). The structural and the adhesion properties of the MgO/FeO/Fe(001) system were assessed and compared with those of simple MgO/Fe(001) interfaces. Our calculated results showed that the adhesion energy for MgO/FeO/Fe(001) was smaller than that for simple MgO/Fe(001). An analysis of the electronic structures and the charge rearrangements of the MgO/FeO/Fe(001) interfaces was also performed. The work functions of the MgO/FeO/Fe(001) systems upon the deposition of MgO films exhibited smaller decreases (0.45 - 0.67 eV) than those (1.43 - 1.74 eV) of the MgO/Fe(001) systems. In addition, the obtained work functions (3.77 - 3.99 eV) for MgO/FeO/Fe(001) were much larger than those (2.12 - 2.43 eV) for MgO/Fe(001).

Fabricating Fe3O4/Fe/Biocarbon Fibers using Cellulose Nanocrystals for High-Rate Li-ion Battery Anode

International Nuclear Information System (INIS)

Zhang, Shuzhen; He, Wen; Zhang, Xudong; Yang, Guihua; Ma, Jingyun; Yang, Xuena; Song, Xin

2015-01-01

Highlights: • Mesoporous biocarbon fibers adhered with Fe 3 O 4 /Fe nanoparticles (Fe 3 O 4 /Fe/MBCFs) are synthesized. • This method uses the natural cotton as a template and carbon source. • Fe 3 O 4 /Fe/MBCFs exhibit excellent cycling performance at higher current. - ABSTRACT: Searching the high rate Fe 3 O 4 -based materials for lithium ion batteries (LIBs) is still a great challenge. Here we tackle this problem by developing a facile and green method which uses the natural cotton as a biotemplate and a activity biocarbon source. By this new method, we synthesized the mesoporous biocarbon fibers adhered with Fe 3 O 4 /Fe nanoparticles (Fe 3 O 4 /Fe/MBCFs). Fe 3 O 4 /Fe/MBCFs are a highly stable anode material for high-rate LIBs due to its excellent cycling performance at higher current and fast charging feature. This anode shows a high reversible capacity of 472 mAh g −1 after 500 cycles and can be rapidly charge to 100% in 28.3 min. After 160 cycles at varied current densities from 1 A g −1 to 10 A g −1 , it still delivered a high discharge capacity of 524.6 mAh g −1 and an ultra-high coulombic efficiency close to 100%. This is attributed to the synergistic effects of several factors including the unique mesoporous hybrid construction, the graphitized biocarbon fibers and the chemical bonding between Fe 3 O 4 and Fe nanoparticles. This work is instructive for fabrication and design of nanostructured electrodes with extraordinary properties from biomass renewable resources

Formation of hard magnetic L1{sub 0}-FePt/FePd monolayers from elemental multilayers

Energy Technology Data Exchange (ETDEWEB)

Goo, Nam Hoon

2007-06-18

In this thesis, ordered L1{sub 0}-FePt and FePd films of different nominal compositions are prepared from Fe/Pt and Fe/Pd multilayers by annealing. In case of the L1{sub 0}-FePt films the composition of the films is modified by changing the individual elemental layer thicknesses in the multilayer precursors. This simple variation of the composition is the great advantage of the multilayer approach compared to sputtering single alloy layer from an alloy target. The formation mechanism of the fct phase from the multilayers and the microstructural properties are investigated. The characteristics of the hysteresis loop (coercivity {mu}{sub 0}H{sub c}, remanence J{sub r}) and of the intrinsic magnetic properties (anisotropy constant K{sub l}, spontaneous polarization J{sub s}, exchange constant A) of the ordered L1{sub 0}-FePt and FePd films are studied. The effects of the composition of the L1{sub 0}-FePt films on the microstructural and magnetic properties are investigated. The microstructure of these ordered L1{sub 0}-FePt films are then correlated to the magnetic properties with microstructural parameters by investigating the temperature dependence of the coercivity. (orig.)

CoFeRh alloys

International Nuclear Information System (INIS)

Tabakovic, Ibro; Qiu Jiaoming; Riemer, Steve; Sun Ming; Vas'ko, Vlad; Kief, Mark

2008-01-01

The electrochemical behavior of Rh(III) species in CoFe solution containing RhCl 3 , NH 4 Cl, H 3 BO 3 , CoSO 4 , FeSO 4 , saccharin, and NaLS (Na lauryl sulfate) has been investigated. The electrochemistry of Rh(III) species is influenced by each of the compounds present in CoFe plating solution, but especially by addition of saccharin and H 3 BO 3 to the RhCl 3 -NH 4 Cl solution. The nucleation and growth of Rh on GC (glassy carbon), Ru, and Cu electrodes from NH 4 Cl solution was studied using the potentiostatic current-transient methods. The results support a predominantly progressive nucleation of Rh on all three-electrode surfaces. The nucleation kinetic parameters ANo (steady state nucleation rate) and Ns (saturation nuclear number density) were found to vary with potential and are electrode-dependent in order: GC > Ru∼Cu. The electrodeposited Rh films obtained from NH 4 Cl solution and nonmagnetic CoFeRh film obtained from CoFe solution were characterized in terms of the following properties: morphology, surface roughness, crystal structure and chemical composition. The origin of light elements found in Rh and CoFeRh films (O, Cl, S, C, N) was discussed

Impact of Fe(III)-OM complexes and Fe(III) polymerization on SOM pools reactivity under different land uses

Science.gov (United States)

Giannetta, B.; Plaza, C.; Zaccone, C.; Siebecker, M. G.; Rovira, P.; Vischetti, C.; Sparks, D. L.

2017-12-01

Soil organic matter (SOM) protection and long-term accumulation are controlled by adsorption to mineral surfaces in different ways, depending on its molecular structure and pedo-climatic conditions. Iron (Fe) oxides are known to be key regulators of the soil carbon (C) cycle, and Fe speciation in soils is highly dependent on environmental conditions and chemical interactions with SOM. However, the molecular structure and hydrolysis of Fe species formed in association with SOM is still poorly described. We hypothesize the existence of two pools of Fe which interact with SOM: mononuclear Fe(III)-SOM complexes and precipitated Fe(III) hydroxides. To verify our hypothesis, we investigated the interactions between Fe(III) and physically isolated soil fractions by means of batch experiments at pH 7. Specifically, we examined the fine silt plus clay (FSi+C) fraction, obtained by ultrasonic dispersion and wet sieving. The soil samples spanned several land uses, including coniferous forest (CFS), grassland (GS), technosols (TS) and agricultural (AS) soils. Solid phase products and supernatants were analyzed for C and Fe content. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis were also performed. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was used to assess the main C functional groups involved in C complexation and desorption experiments. Preliminary linear combination fitting (LCF) of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra suggested the formation of ferrihydrite-like polymeric Fe(III) oxides in reacted CFS and GS samples, with higher C and Fe concentration. Conversely, mononuclear Fe(III) OM complexes dominated the speciation for TS and AS samples, characterized by lower C and Fe concentration, inhibiting the hydrolysis and polymerization of Fe (III). This approach will help revealing the mechanisms by which SOM pools can control Fe(III) speciation, and will elucidate how both Fe

Nano-sized magnetic instabilities in Fe/NiO/Fe(001) epitaxial thin films

Energy Technology Data Exchange (ETDEWEB)

Brambilla, A [Dipartimento di Fisica-Politecnico di Milano, P.za Leonardo da Vinci 32, 20133 Milan (Italy); Biagioni, P [Dipartimento di Fisica-Politecnico di Milano, P.za Leonardo da Vinci 32, 20133 Milan (Italy); Rougemaille, N [National Center for Electron Microscopy, Lawrence Berkeley National Lab, Berkeley, CA 94720 (United States); Schmid, A K [National Center for Electron Microscopy, Lawrence Berkeley National Lab, Berkeley, CA 94720 (United States); Lanzara, A [Department of Physics, University of California at Berkeley, Berkeley, CA 94720 (United States); Duo, L [Dipartimento di Fisica-Politecnico di Milano, P.za Leonardo da Vinci 32, 20133 Milan (Italy); Ciccacci, F [Dipartimento di Fisica-Politecnico di Milano, P.za Leonardo da Vinci 32, 20133 Milan (Italy); Finazzi, M [Dipartimento di Fisica-Politecnico di Milano, P.za Leonardo da Vinci 32, 20133 Milan (Italy)

2006-10-25

We report on a magnetic imaging study of the Fe/NiO/Fe(001) trilayer structure, by means of X-ray photoemission electron microscopy (XPEEM) and spin-polarised low-energy electron microscopy (SPLEEM). Two different magnetic couplings between the Fe layers are observed depending on the NiO thickness being greater or smaller than a critical value. Very small magnetic domains and domain walls are observed in the top Fe layer. They are dramatically smaller than those observed in the Fe substrate, and have a convoluted topology. Furthermore they seem to be unstable with respect to an applied magnetic field for any NiO thickness except that corresponding to the transition between the different coupling regimes. The phenomenology of such magnetic nano-structures and the dependence of the magnetic behaviour of the layered structure on the NiO spacer thickness are discussed on the basis of the experimental results and of state-of-the-art theoretical models.

Nano-sized magnetic instabilities in Fe/NiO/Fe(001) epitaxial thin films

International Nuclear Information System (INIS)

Brambilla, A.; Biagioni, P.; Rougemaille, N.; Schmid, A.K.; Lanzara, A.; Duo, L.; Ciccacci, F.; Finazzi, M.

2006-01-01

We report on a magnetic imaging study of the Fe/NiO/Fe(001) trilayer structure, by means of X-ray photoemission electron microscopy (XPEEM) and spin-polarised low-energy electron microscopy (SPLEEM). Two different magnetic couplings between the Fe layers are observed depending on the NiO thickness being greater or smaller than a critical value. Very small magnetic domains and domain walls are observed in the top Fe layer. They are dramatically smaller than those observed in the Fe substrate, and have a convoluted topology. Furthermore they seem to be unstable with respect to an applied magnetic field for any NiO thickness except that corresponding to the transition between the different coupling regimes. The phenomenology of such magnetic nano-structures and the dependence of the magnetic behaviour of the layered structure on the NiO spacer thickness are discussed on the basis of the experimental results and of state-of-the-art theoretical models

Diffusion in ordered Fe-Si alloys

International Nuclear Information System (INIS)

Sepiol, B.; Vogl, G.

1995-01-01

The measurement of the diffusional Moessbauer line broadening in single crystalline samples at high temperatures provides microscopic information about atomic jumps. We can separate jumps of iron atoms between the various sublattices of Fe-Si intermetallic alloys (D0 3 structure) and measure their frequencies. The diffusion of iron in Fe-Si samples with Fe concentrations between 75 and 82 at% shows a drastic composition dependence: the jump frequency and the proportion between jumps on Fe sublattices and into antistructure (Si) sublattice positions change greatly. Close to Fe 3 Si stoichiometry iron diffusion is extremely fast and jumps are performed exclusively between the three Fe sublattices. The change in the diffusion process when changing the alloy composition from stoichiometric Fe 3 Si to the iron-rich side is discussed. (orig.)

Microstructure and magnetic properties of nanocomposite FePt/MgO and FePt/Ag films

International Nuclear Information System (INIS)

Chen, S.C.; Kuo, P.C.; Sun, A.C.; Chou, C.Y.; Fang, Y.H.; Wu, T.H.

2006-01-01

An in-plane magnetic anisotropy of FePt film is obtained in the MgO 5 nm/FePt t nm/MgO 5 nm films (where t=5, 10 and 20 nm). Both the in-plane coercivity (H c- parallel ) and the perpendicular magnetic anisotropy of FePt films are increased when introducing an Ag-capped layer instead of MgO-capped layer. An in-plane coercivity is 3154 Oe for the MgO 5 nm/FePt 10 nm/MgO 5 nm film, and it can be increased to 4846 Oe as a 5 nm Ag-capped layer instead of MgO-capped layer. The transmission electron microscopy (TEM)-energy disperse spectrum (EDS) analysis shows that the Ag mainly distributed at the grain boundary of FePt, that leads the increase of the grain boundary energy, which will enhance coercivity and perpendicular magnetic anisotropy of FePt film

Fe magnetic moment formation and exchange interaction in Fe{sub 2}P: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Liu, X.B., E-mail: liuxubo@uta.edu [Department of Physics, University of Texas at Arlington, Arlington, TX 76019 (United States); Ping Liu, J.; Zhang, Qiming [Department of Physics, University of Texas at Arlington, Arlington, TX 76019 (United States); Altounian, Z. [Center for the Physics of Materials and Department of Physics, McGill University, 3600 University Street, Montreal, Quebec, H3A 2T8 (Canada)

2013-03-15

Electronic structure and magnetic properties of Fe{sub 2}P have been studied by a first-principles density functional theory calculation. The ground state is ferromagnetic and the calculated magnetic moments for Fe{sub 1} (3f) and Fe{sub 2} (3g) are 0.83 and 2.30μ{sub B}, respectively. The nearest neighbor inter-site magnetic exchange coupling parameter at the Fe{sub 1} layer (0.02 mRy) is much smaller than that at the Fe{sub 2} layer (1.29 mRy). The Fe moment at the 3f site is metastable and sensitive to the inter-site exchange interaction with its magnetic neighbors, which is responsible for the first order magnetic transition and large magneto-caloric effect around T{sub C}.

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

Science.gov (United States)

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

NARCIS (Netherlands)

Grift, B. van der; Behrends, T.; Osté, L.A.; Schot, P.P.; Wassen, M.J.; Griffioen, J.

2016-01-01

Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction

Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

NARCIS (Netherlands)

van der Grift, B.; Behrends, T.; Osté, L.A.; Schot, P.P.; Wassen, M.J.; Griffioen, J.

2016-01-01

Abstract Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition,

Mechanism of thermal decomposition of K{sub 2}FeO{sub 4} and BaFeO{sub 4}: A review

Energy Technology Data Exchange (ETDEWEB)

Sharma, Virender K., E-mail: vsharma@sph.tamhsc.edu [Texas A& M University, Department of Environmental and Occupational Health, School of Public Health (United States); Machala, Libor [Palacky University, Regional Centre of Advanced Technologies and Materials, Departments of Experimental Physics and Physical Chemistry, Faculty of Science (Czech Republic)

2016-12-15

This paper presents thermal decomposition of potassium ferrate(VI) (K{sub 2}FeO{sub 4}) and barium ferrate(VI) (BaFeO{sub 4}) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe {sup V} and Fe {sup IV} as intermediate iron species using the applied techniques are given. Thermal decomposition of K{sub 2}FeO{sub 4} involved Fe {sup V}, Fe {sup IV}, and K{sub 3}FeO{sub 3} as intermediate species while BaFeO{sub 3} (i.e. Fe {sup IV}) was the only intermediate species during the decomposition of BaFeO{sub 4}. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K{sub 2}FeO{sub 4} and BaFeO{sub 4} under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

Adsorption of As(V) from water using Mg-Fe-based hydrotalcite (FeHT)

Energy Technology Data Exchange (ETDEWEB)

Tuerk, T. [Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon (Turkey); Alp, I., E-mail: ialp@ktu.edu.tr [Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon (Turkey); Deveci, H. [Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon (Turkey)

2009-11-15

This paper describes a study of the sorptive removal of arsenate (As(V)) from aqueous solutions by synthetically prepared Mg-Fe-based hydrotalcites (FeHT) as layered double hydroxide (LDH) adsorbents. The synthesis of Fe{sup 3+}-substituted hydrotalcites (FeHT) with the chemical formula [Mg(II){sub 6}Fe(III){sub 2}(OH){sub 16}]{sup 2+}[CO{sub 3} x yH{sub 2}O]{sup 2-} was achieved by a co-precipitation method. The reaction products were characterized by powder X-ray diffraction analysis. The influences of solution pH, initial arsenate (As(V)) concentration, and sorbent concentration were investigated in multiple kinetic runs. The adsorption rates and isotherms were investigated in batch experiments. The pseudo-first-order and second-order kinetic models were tested and the latter was found to fit better to the experimental data. Langmuir and Freundlich isotherms were used to describe the adsorption data from equilibrium experiments. The results have shown that FeHT has a high arsenate removal efficiency, with the ability to reduce the concentration of arsenate in the aqueous solution from an initial value of 330 {mu}g/l to <10 {mu}g/l (i.e. below the limit value specified by WHO).

Probing Fe (III)/Fe (II) redox potential in a clayey material

International Nuclear Information System (INIS)

Tournassat, Christophe; Chainet, Fabien; Betelu, Stephanie; Hadi, Jebril; Gaucher, Eric C.; Ignatiadis, Ioannis; Greneche, Jean-Marc; Charlet, Laurent

2010-01-01

Document available in extended abstract form only. Redox is one of the main factors affecting the migration of redox-sensitive radionuclides. As a consequence reducing conditions are considered of strategic importance for the confinement properties of a clayey formation towards nuclear waste. A representative redox potential of clay formation such as Callovian- Oxfordian (COx) can be derived from thermodynamic calculations considering equilibrium between observed redox phases such as pyrite and siderite. However, there is little information on the reactivity of the different reservoirs of redox constituents in this type of complex material. The present study aims at investigating the reactivity of the Fe(III)/Fe(II) redox couple in the structure of clay minerals using different investigation methods: electrochemistry and O 2 reduction kinetic experiments. Clay modified electrodes were specifically designed to probe Fe(III)/Fe(II) redox potential in the structure of clay minerals. The clay fraction of a Callovian-Oxfordian argillite sample originating from the same level than ANDRA underground research laboratory was used after pre-treatment to remove organic matter and accessory minerals such as pyrite that could influence redox potential measurements. These electrodes were used to verify the validity of the model of Favre et al. (2006) that links the redox potential (E clay ) to the the Fe(II)/Fe tot ratio in the structure (m rel ), the pH and the sodium concentration in solution: equation 1. The good agreement between direct potential measurements and model prediction provides a strong evidence of the relevance of this model in our experimental conditions although the clay composition and its too low Fe content do not a priori fulfil the conditions set by Drits and Manceau (2000) for the calculation of K 0 parameter. Following the verification of the model, we tried to apply it to the specific case of a Callovian-Oxfordian sample that had been very well preserved

A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

International Nuclear Information System (INIS)

Wen, Y.H.; Zhang, H.M.; Qian, P.; Zhou, H.T.; Zhao, P.; Yi, B.L.; Yang, Y.S.

2006-01-01

The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br 2 cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application

Electronic structures and magnetism of CaFeAsH and CaFeAsF

International Nuclear Information System (INIS)

Wang Guangtao; Shi Xianbiao; Liu Haipeng; Liu Qingbo

2015-01-01

We studied the electronic structures, magnetism, and Fermi surface (FS) nesting of CaFeAsH and CaFeAsF by first-principles calculations. In the nonmagnetic (NM) states, we found strong FS nesting, which induces magnetic instability and a spin density wave (SDW). Our calculations indicate that the ground state of CaFeAsH and CaFeAsF is the stripe antiferromagnetic state. The calculated bare susceptibility χ 0 (q) peaked at the M-point and was clearly suppressed and became slightly incommensurate with both electron doping and hole doping for both materials. (author)

Profound Interfacial Effects in CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4 Core/Shell Nanoparticles

Science.gov (United States)

Polishchuk, Dmytro; Nedelko, Natalia; Solopan, Sergii; Ślawska-Waniewska, Anna; Zamorskyi, Vladyslav; Tovstolytkin, Alexandr; Belous, Anatolii

2018-03-01

Two sets of core/shell magnetic nanoparticles, CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4, with a fixed diameter of the core ( 4.1 and 6.3 nm for the former and latter sets, respectively) and thickness of shells up to 2.5 nm were synthesized from metal chlorides in a diethylene glycol solution. The nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, and magnetic measurements. The analysis of the results of magnetic measurements shows that coating of magnetic nanoparticles with the shells results in two simultaneous effects: first, it modifies the parameters of the core-shell interface, and second, it makes the particles acquire combined features of the core and the shell. The first effect becomes especially prominent when the parameters of core and shell strongly differ from each other. The results obtained are useful for optimizing and tailoring the parameters of core/shell spinel ferrite magnetic nanoparticles for their use in various technological and biomedical applications.

{sup 57}Fe Mössbauer spectroscopic studies of single-crystalline K{sub x}Fe{sub 2-y}S{sub 2} and K{sub x}Fe{sub 2-y}Se{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tsuchiya, Yuu, E-mail: tsuchiya.yuu1990@gmail.com; Ikeda, Shugo; Kobayashi, Hisao [University of Hyogo (Japan)

2016-12-15

We have investigated the physical properties of single-crystalline K{sub x}Fe{sub 2-y}S{sub 2} and K{sub x}Fe{sub 2-y}Se{sub 2} samples using {sup 57}Fe Mössbauer spectroscopy. The observed {sup 57}Fe Mössbauer spectra were reconstructed using a major antiferromagnetic ordered K{sub 2}Fe{sub 4}Se{sub 5} phase and a minor paramagnetic phase down to 5 K, despite being superconducting below 32.2 K in K{sub x}Fe{sub 2-y}Se{sub 2}. The analysis of {sup 57}Fe Mössbauer spectrum for K{sub x}Fe{sub 2-y}S{sub 2} at 290 K confirms the presence of a major antiferromagnetic ordered K{sub 2}Fe{sub 4}S{sub 5} phase and a minor paramagnetic phase in the K{sub x}Fe{sub 2-y}S{sub 2} single crystal. The derived hyperfine interaction parameters of the paramagnetic phase in K{sub x}Fe{sub 2-y}S{sub 2} suggest that the microstructure of this phase in K{sub x}Fe{sub 2-y}S{sub 2} is similar to that of the superconducting phase in K{sub x}Fe{sub 2-y}Se{sub 2} although the K{sub x}Fe{sub 2-y}S{sub 2} single crystals exhibit no superconductivity down to 5 K.

Texturing for bulk α-Fe/Nd2Fe14B nanocomposites with enhanced magnetic properties

International Nuclear Information System (INIS)

Lou, L.; Hou, F.C.; Wang, Y.N.; Cheng, Y.; Li, H.L.; Li, W.; Guo, D.F.; Li, X.H.; Zhang, X.Y.

2014-01-01

In the present study, the texturing of bulk α-Fe/Nd 2 Fe 14 B nanocomposites produced from Nd-lean amorphous Nd x Fe 92.5−x Cu 1.5 B 6 (x=9 to 11.5 at%) via a hot deformation under a uniaxial stress of ∼350 MPa at 973 K has been studied. An enhanced (00l) texture of the hard phase is observed with increasing Nd content, which results in an increase in the magnetic anisotropy of the nanocomposite magnets. As a result, both the coercivity and the remanence of the magnets increase simultaneously with increasing Nd content from x=9–11.5 at%, yielding a significant enhancement of the maximum energy product from (BH) max =13.2 to 17.5 MGOe in the direction parallel to stress axis. - Highlights: • Textured bulk α-Fe/Nd 2 Fe 14 B nanocomposites have been produced from Nd-lean alloys. • Nd content has an effect on the texturing of α-Fe/Nd 2 Fe 14 B nanocomposite magnets. • An enhanced (00l) texture of hard phase is observed with increasing Nd content. • Both the coercivity and remanence increase simultaneously with Nd content

Action of a clay suspension on an Fe(0) surface under anoxic conditions: Characterization of neoformed minerals at the Fe(0)/solution and Fe(0)/atmosphere interfaces

International Nuclear Information System (INIS)

Le Pape, Pierre; Rivard, Camille; Pelletier, Manuel; Bihannic, Isabelle; Gley, Renaud; Mathieu, Sandrine; Salsi, Lise; Migot, Sylvie; Barres, Odile; Villiéras, Frédéric; Michau, Nicolas

2015-01-01

Highlights: • Immersion of an Fe(0) foil in a clay suspension at 90 °C and in anoxic conditions. • Magnetite was observed on the atmospheric part. • Iron-rich 7 Å serpentines were observed on the clay suspension part. • A gradient in serpentine cristallochemistry was observed. • A pure Fe–Si phyllosilicate was identified at the Fe(0)/clay suspension contact. - Abstract: To better understand the reaction mechanisms involved at the Fe(0)/clay minerals interface, we investigate in the present study the reaction between an Fe(0) surface and a clay suspension extracted from the Callovo-Oxfordian claystone (COx). Batch experiments were carried out under anoxic conditions in sealed autoclave, at 90 °C to mimic predicted radioactive waste disposal conditions. An Fe(0) foil was introduced into the autoclave so that the lower part of the foil was immersed in the clay suspension while the upper part was contacted with the atmosphere of the experimental setup. After two months, the mineralogical deposits that precipitated at the surface of the Fe(0) foil were analyzed using multiple techniques, namely X-ray diffraction (XRD), scanning/transmission electron microscopy associated to microanalysis (SEM/TEM–EDXS), and micro-spectroscopic measurements (μ-FTIR and μ-Raman). Both parts of the Fe(0) foil were then shown to react: magnetite was the main resulting mineral formed at the Fe(0) surface in the atmospheric conditions whereas serpentine 1:1 phyllosilicates were the main end-products in the clay suspension. The analyses performed on the immersed part of the foil revealed a spatial heterogeneity in both serpentine cristallochemistry and morphology, with a gradient from the Fe(0) contact point toward the clay suspension. A pure Fe–Si phyllosilicate ring was observed at the direct contact point with the Fe(0) foil and a progressive incorporation of Al instead of Fe into the clay phases was identified as deposit thickness increased from the Fe(0) surface to

Structure and dynamics of hydrated Fe(II) and Fe(III) ions. Quantum mechanical and molecular mechanical simulations

International Nuclear Information System (INIS)

Remsungnen, T.

2002-11-01

Classical molecular dynamics (MD) and combined em ab initio quantum mechanical/molecular mechanical molecular dynamics (QM/MM-MD) simulations have been performed to investigate structural, dynamical and energetical properties of Fe(II), and Fe(III) transition metal ions in aqueous solution. In the QM/MM-MD simulations the ion and its first hydration sphere were treated at the Hartree-Fock ab initio quantum mechanical level, while ab initio generated pair plus three-body potentials were employed for the remaining system. For the classical MD simulation the pair plus three-body potential were employed for all ion-water interactions. The coordination number of the first hydration shell is 100 % of 6 in both cases. The number of waters in the second hydration shell obtained from classical simulations are 13.4 and 15.1 for Fe(II) and Fe(III), respectively, while QM/MM-MD gives the values of 12.4 and 13.4 for Fe(II) and Fe(III). The energies of hydration obtained from MD and QM/MM-MD for Fe(II) are 520 and 500 kcal/mol, and for Fe(III) 1160 and 1100 kcal/mol respectively. The mean residence times of water in the second shell obtained from QM/MM-MD are 24 and 48 ps for Fe(II) and Fe(III), respectively. In contrast to the data obtained from classical MD simulation, the QM/MM-MD values are all in good agreement with the experimental data available. These investigations and results clearly indicate that many-body effects are essential for the proper description of all properties of the aqueous solution of both Fe(II) and Fe(III) ions. (author)

Use of Fe(III) oxalate for oxidativewastewater treatment; Einsatz von Fe(III)-Oxalat zur chemisch-oxidativen Abwasserbehandlung

Energy Technology Data Exchange (ETDEWEB)

Kim, S.M.; Vogelpohl, A. [Clausthal Univ., Clausthal-Zellerfeld (Germany). Inst. fuer Thermische Verfahrenstechnik

1998-08-01

Iron(III)-oxalate was used as an iron catalyst for the Photo Fenton reaction. Iron(III) oxalations ([Fe(C{sub 2}O{sub 4}){sub 3}]{sup 3-}) are reduced to Fe(II) by irradiation using near UV-light ({lambda} = 300 - 400 nm) or visible light ({lambda} > 400 nm). At the same time, CO{sub 2}{sup -} or C{sub 2}O{sub 4}{sup -}-radicals originate, which cause the secondary reduction of Fe(III) to Fe(II). By means of the photolytically regenerated Fe(II) ions, hydroxyl radicals are increasingly formed, so that the degradation of organic substances is accelerated. The work aimed to assess the catalytic effect of Fe(III) oxalate for photochemical oxidation processes and to establish the parameters influencing further treatment of leachate from a municipal waste sanitary landfill by means of technical-scale experiments. (orig.) [Deutsch] In der vorliegenden Arbeit wurde Eisen(III)-Oxalat als Eisenkatalysator fuer die Photo-Fenton-Reaktion eingesetzt. Eisen(III)-Oxalationen ([Fe(C{sub 2}O{sub 4}){sub 3}]{sup 3-}) werden durch Strahlung mit nahem UV-Licht ({lambda}=300 bis 400 nm) oder mit sichtbarem Licht ({lambda}>400 nm) zu Fe(II) reduziert. Gleichzeitig entstehen CO{sub 2}{sup .-} oder C{sub 2}O{sub 4}{sup .-}-Radikale, die eine sekundaere Reduktion von Fe(III) zu Fe(II) bewirken. Mit Hilfe der photolytiisch regenerierten Fe(II)-Ionen werden vermehrt Hydroxylradikale gebildet und damit die Abbaugeschwindigkeit der organischen Substanzen beschleunigt. Ziel der hier vorgestellten Arbeit war es, die katalytische Wirkung von Fe(III)-Oxalat fuer photochemische Oxidationsverfahren abzuschaetzen und die Einflussparameter zur weitergehenden Behandlung eines Deponiesickerwassers aus Hausmuelldeponie anhand von Technikumsversuchen zu ermitteln. (orig.)

Design and Micromagnetic Simulation of Fe/L10-FePt/Fe Trilayer for Exchange Coupled Composite Bit Patterned Media at Ultrahigh Areal Density

Directory of Open Access Journals (Sweden)

Warunee Tipcharoen

2015-01-01

Full Text Available Exchange coupled composite bit patterned media (ECC-BPM are one candidate to solve the trilemma issues, overcome superparamagnetic limitations, and obtain ultrahigh areal density. In this work, the ECC continuous media and ECC-BPM of Fe/L10-FePt/Fe trilayer schemes are proposed and investigated based on the Landau-Lifshitz-Gilbert equation. The switching field, Hsw, of the hard phase in the proposed continuous ECC trilayer media structure is reduced below the maximum write head field at interlayer exchange coupling between hard and soft phases, Aex, higher than 20 pJ/m and its value is lower than that for continuous L10-FePt single layer media and L10-FePt/Fe bilayer. Furthermore, the Hsw of the proposed ECC-BPM is lower than the maximum write head field with exchange coupling coefficient between neighboring dots of 5 pJ/m and Aex over 10 pJ/m. Therefore, the proposed ECC-BPM trilayer has the highest potential and is suitable for ultrahigh areal density magnetic recording technology at ultrahigh areal density. The results of this work may be gainful idea for nanopatterning in magnetic media nanotechnology.

Physical conditions in CaFe interstellar clouds

OpenAIRE

Gnacinski, P.; Krogulec, M.

2007-01-01

Interstellar clouds that exhibit strong Ca I and Fe I lines were called CaFe clouds. The ionisation equilibrium equations were used to model the column densities of Ca II, Ca I, K I, Na I, Fe I and Ti II in CaFe clouds. The chemical composition of CaFe clouds is that of the Solar System and no depletion of elements onto dust grains is seen. The CaFe clouds have high electron densities n=1 cm^-3 that leads to high column densities of neutral Ca and Fe.

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

Science.gov (United States)

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

Reduction under hydrogen of ferrite MFe{sub 2}O{sub 4} (M: Fe, Co, Ni) nanoparticles obtained by hydrolysis in polyol medium: A novel route to elaborate CoFe{sub 2}, Fe and Ni{sub 3}Fe nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Ballot, N.; Schoenstein, F.; Mercone, S.; Chauveau, T.; Brinza, O. [Laboratoire des Sciences des Procedes et des Materiaux, CNRS, LSPM - UPR 3407, Universite Paris 13, PRES Sorbonne-Paris-Cite, 99 Avenue J.-B. Clement, 93430 Villetaneuse (France); Jouini, N., E-mail: jouini@univ-paris13.fr [Laboratoire des Sciences des Procedes et des Materiaux, CNRS, LSPM - UPR 3407, Universite Paris 13, PRES Sorbonne-Paris-Cite, 99 Avenue J.-B. Clement, 93430 Villetaneuse (France)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Spinels nano-particles MFe{sub 2}O{sub 4} (M: Co, Fe or Ni) are obtained by hydrolysis in polyol medium. Black-Right-Pointing-Pointer Gentle reduction under hydrogen flow of spinel nano-particles yields metal and alloy nanoparticles. Black-Right-Pointing-Pointer TEM and X-ray analysis show that CoFe{sub 2}, Fe and Ni{sub 3}Fe nano-particles are monocrystalline particles with size less than 160 nm. Black-Right-Pointing-Pointer Iron with size of 150 nm presents ferromagnetic behavior. Black-Right-Pointing-Pointer CoFe{sub 2} alloy with size of 55 nm could be considered as a superparamagnetic material. - Abstract: A novel method to process metal and various alloy particles of nanometric size is described. The first step consists in the elaboration of MFe{sub 2}O{sub 4} (M: Fe, Ni or Co) spinel nanoparticles in polyol medium via hydrolysis and the second one in gently reducing these latter under hydrogen at 300 Degree-Sign C. X-ray diffraction analysis shows that pure Fe and CoFe{sub 2} alloy are well obtained by reducing Fe{sub 3}O{sub 4} and CoFe{sub 2}O{sub 4}, respectively. This is not the case when we try to reduce NiFe{sub 2}O{sub 4}. A mixture of Fe and Ni{sub 3}Fe is observed. TEM analysis reveals that the size of metal particles stays within the range of a few tenths of nm up to 150 nm, while the precursors (MFe{sub 2}O{sub 4}) never exceed 5 nm. Our results show that the formation of metal particles occurs via two main steps: (i) reduction of the spinel oxide nanoparticles into metal ones and (ii) aggregation of the latter, leading to larger metal nanoparticles. Magnetic measurements indicate that the as-obtained metallic materials have good magnetic properties mainly affected by the sizes of the nanoparticles and the purity of the reduced phases.

CoFeRh alloys

Energy Technology Data Exchange (ETDEWEB)

Tabakovic, Ibro [Seagate Technology, Research and Development, Bloomington, MN 55435 (United States)], E-mail: ibro.m.tabakovic@seagate.com; Qiu Jiaoming; Riemer, Steve; Sun Ming; Vas' ko, Vlad; Kief, Mark [Seagate Technology, Research and Development, Bloomington, MN 55435 (United States)

2008-01-01

The electrochemical behavior of Rh(III) species in CoFe solution containing RhCl{sub 3}, NH{sub 4}Cl, H{sub 3}BO{sub 3}, CoSO{sub 4}, FeSO{sub 4}, saccharin, and NaLS (Na lauryl sulfate) has been investigated. The electrochemistry of Rh(III) species is influenced by each of the compounds present in CoFe plating solution, but especially by addition of saccharin and H{sub 3}BO{sub 3} to the RhCl{sub 3}-NH{sub 4}Cl solution. The nucleation and growth of Rh on GC (glassy carbon), Ru, and Cu electrodes from NH{sub 4}Cl solution was studied using the potentiostatic current-transient methods. The results support a predominantly progressive nucleation of Rh on all three-electrode surfaces. The nucleation kinetic parameters ANo (steady state nucleation rate) and Ns (saturation nuclear number density) were found to vary with potential and are electrode-dependent in order: GC > Ru{approx}Cu. The electrodeposited Rh films obtained from NH{sub 4}Cl solution and nonmagnetic CoFeRh film obtained from CoFe solution were characterized in terms of the following properties: morphology, surface roughness, crystal structure and chemical composition. The origin of light elements found in Rh and CoFeRh films (O, Cl, S, C, N) was discussed.

Synthesis, characterization, and comparative gas-sensing properties of Fe{sub 2}O{sub 3} prepared from Fe{sub 3}O{sub 4} and Fe{sub 3}O{sub 4}-chitosan

Energy Technology Data Exchange (ETDEWEB)

Cuong, Nguyen Duc [Faculty of Hospitality and Tourism, Hue University, 22 Lam Hoang, Vy Da Ward, Hue City (Viet Nam); College of Sciences, Hue University, 77 Nguyen Hue, Phu Nhuan Ward, Hue City (Viet Nam); International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST), Hanoi (Viet Nam); Hoa, Tran Thai; Khieu, Dinh Quang [College of Sciences, Hue University, 77 Nguyen Hue, Phu Nhuan Ward, Hue City (Viet Nam); Lam, Tran Dai [Institute of Materials Science, Vietnamese Academy of Science and Technology, Hanoi (Viet Nam); Hoa, Nguyen Duc [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST), Hanoi (Viet Nam); Van Hieu, Nguyen, E-mail: hieu@itims.edu.vn [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST), Hanoi (Viet Nam)

2012-05-15

Highlights: Black-Right-Pointing-Pointer We have demonstrated a facile method to prepare Fe{sub 3}O{sub 4} nanoparticles and chitosan-coated Fe{sub 3}O{sub 4} nanoparticles. Black-Right-Pointing-Pointer {alpha}-Fe{sub 2}O{sub 3} sensors prepared from those Fe{sub 3}O{sub 4} materials have been investigated and compared. Black-Right-Pointing-Pointer The results show potential application of {alpha}-Fe{sub 2}O{sub 3} for CO sensors in environmental monitoring. - Abstract: In this paper, Fe{sub 3}O{sub 4} and chitosan (CS)-coated Fe{sub 3}O{sub 4} nanoparticles were synthesized via co-precipitation method and subsequent covalent binding of CS onto the surface for functionalization, respectively. Characterization of the crystal structures and morphologies of as-synthesized nanoparticles by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy demonstrated that Fe{sub 3}O{sub 4} had a cubic spinal structure with irregular shapes and average diameters of 10-20 nm. The surface states and magnetic properties of Fe{sub 3}O{sub 4}-CS nanoparticles were characterized by Fourier transform infrared spectra and vibrating sample magnetometry. Results showed that Fe{sub 3}O{sub 4}-CS nanoparticles possessed super-paramagnetic properties, with saturated magnetization up to 60 emu/g. In addition, Fe{sub 3}O{sub 4} and CS-coated Fe{sub 3}O{sub 4} nanoparticles were used in the fabrication of {alpha}-Fe{sub 2}O{sub 3} based gas sensors. Gas sensing measurements revealed that the {alpha}-Fe{sub 2}O{sub 3} gas sensor prepared from Fe{sub 3}O{sub 4}-CS had a better response to H{sub 2}, CO, C{sub 2}H{sub 5}OH, and NH{sub 3} compared with the device prepared from pristine Fe{sub 3}O{sub 4}. Furthermore, the {alpha}-Fe{sub 2}O{sub 3} sensor prepared from Fe{sub 3}O{sub 4}-CS nanoparticles exhibited the highest response to CO among the test gases, suggesting that it has great potential for practical applications in environmental monitoring.

Pressure effect on Fe3+/FeT in silicate melts and applications to magma redox, particularly in magma oceans

Science.gov (United States)

Zhang, H.; Hirschmann, M. M.

2014-12-01

The proportions of Fe3+ and Fe2+ in magmas reflect the redox conditions of their origin and influence the chemical and physical properties of natural silicate liquids, but the relationship between Fe3+/FeT and oxygen fugacity depends on pressure owing to different molar volumes and compressibilities of Fe3+ and Fe2+ in silicates. An important case where the effect of pressure effect may be important is in magma oceans, where well mixed (and therefore potentially uniform Fe3+/FeT) experiencses a wide range of pressures, and therefore can impart different ƒO2 at different depths, influencing magma ocean degassing and early atmospheres, as well as chemical gradients within magma oceans. To investigate the effect of pressure on magmatic Fe3+/FeT we conducted high pressure expeirments on ƒO2-buffered andestic liquids. Quenched glasses were analyzed by Mössbauer spectroscopy. To verify the accuracy of Mössbauer determinations of Fe3+/FeT in glasses, we also conducted low temperature Mössbauer studies to determine differences in the recoilless fraction (ƒ) of Fe2+ and Fe3. These indicate that room temperature Mössbauer determinations of on Fe3+/FeT glasses are systematically high by 4% compared to recoilless-fraction corrected ratios. Up to 7 GPa, pressure decreases Fe3+/FeT, at fixed ƒO2 relative to metal-oxide buffers, meaning that an isochemical magma will become more reduced with decreasing pressure. Consequently, for small planetary bodies such as the Moon or Mercury, atmospheres overlying their MO will be highly reducing, consisting chiefly of H2 and CO. The same may also be true for Mars. The trend may reverse at higher pressure, as is the case for solid peridotite, and so for Earth, Venus, and possibly Mars, more oxidized atmospheres above MO are possible. Diamond anvil experiments are underway to examine this hypothesis.

Efficient spin injection and giant magnetoresistance in Fe / MoS 2 / Fe junctions

KAUST Repository

Dolui, Kapildeb

2014-07-02

We demonstrate giant magnetoresistance in Fe/MoS2/Fe junctions by means of ab initio transport calculations. We show that junctions incorporating either a monolayer or a bilayer of MoS2 are metallic and that Fe acts as an efficient spin injector into MoS2 with an efficiency of about 45%. This is the result of the strong coupling between the Fe and S atoms at the interface. For junctions of greater thickness, a maximum magnetoresistance of ∼300% is obtained, which remains robust with the applied bias as long as transport is in the tunneling limit. A general recipe for improving the magnetoresistance in spin valves incorporating layered transition metal dichalcogenides is proposed. © 2014 American Physical Society.

Thermodynamic study of NaFe complex oxides. High temperature properties of Na sub 5 FeO sub 4 and Na sub 3 FeO sub 3

CERN Document Server

Furukawa, T

2002-01-01

In order to contribute the investigation into corrosion mechanism of the structural materials by leakage sodium, thermodynamic study of Na-Fe complex oxides formed by the reactions was carried out. Na sub 5 FeO sub 4 and Na sub 3 FeO sub 3 were used as the sample. Its high temperature properties (i.e. melting, solidification and transformation) were observed by Differential Scanning Calorimetry, DSC. Moreover, the original test named 'melting point confirmation test' was performed for the observation of traces of melting and solidification after the tests. Following contents have been obtained by this study. (1) Na sub 5 FeO sub 4 was stably as the solid without phase transformation and melting until 800degC. However, the compound was showing a tendency to change into Na sub 4 FeO sub 3 with temperature increasing under the low oxygen potential. (2) The stability of Na sub 3 FeO sub 3 is the same as that of Na sub 5 FeO sub 4 until 700degC. Over the temperature, the compound was changed differential compound ...

Effect of Fe on the phases and microstructure of TiC-Fe cermets by combustion synthesis/quasi-isostatic pressing

International Nuclear Information System (INIS)

Zhang Weifang; Zhang Xinghong; Wang Jianli; Hong Changqing

2004-01-01

Fully dense TiC-Fe cermets (x = 10, 20, 30, and 40 wt.%) were produced from Ti-C-Fe powder mixtures by combustion synthesis with quasi-isostatic pressing. The effect of Fe content on combustion temperature, combustion wave velocity, and final product density was investigated. The final product was characterized by XRD, SEM, and TEM. The combustion temperature and wave velocity decreased with increasing Fe content. Product density increased with increasing Fe content (96% at 30 wt.%). X-ray diffraction and transmission electron microscopy (TEM) revealed the final product to contain TiC, Fe phases, lath martensite, and Fe 2 Ti. The TiC particle size decreased with increasing Fe content. In addition, a low density of dislocations was observed in both the TiC particles and Fe binder, indicative of annealing and recrystallization, respectively

Structural investigations of LiFePO4 electrodes and in situ studies by Fe X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Deb, Aniruddha; Bergmann, Uwe; Cramer, S.P.; Cairns, Elton J.

2005-01-01

Fe K-edge X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) have been performed on electrodes containing LiFePO 4 to determine the local atomic and electronic structure and their stability with electrochemical cycling. A versatile electrochemical in situ cell has been constructed for long-term soft and hard X-ray experiments for the structural investigation on battery electrodes during the lithium-insertion/extraction processes. The device is used here for an X-ray absorption spectroscopic study of lithium insertion/extraction in a LiFePO 4 electrode, where the electrode contained about 7.7 mg of LiFePO 4 on a 20 μm thick Al-foil. Fe K-edge X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) have been performed on this electrode to determine the local atomic and electronic structure and their stability with electrochemical cycling. The initial state (LiFePO 4 ) showed iron to be in the Fe 2+ state corresponding to the initial state (0.0 mAh) of the cell, whereas in the delithiated state (FePO 4 ) iron was found to be in the Fe 3+ state corresponding to the final charged state (3 mAh). XANES region of the XAS spectra revealed a high spin configuration for the two states (Fe (II), d 6 and Fe (III), d 5 ). The results confirm that the olivine structure of the LiFePO 4 and FePO 4 is retained by the electrodes in agreement with the XRD observations reported previously. These results confirm that LiFePO 4 cathode material retains good structural short-range order leading to superior cycling capability

Study of structural, electronic and magnetic properties of CoFeIn and Co2FeIn Heusler alloys

International Nuclear Information System (INIS)

El Amine Monir, M.; Khenata, R.; Baltache, H.; Murtaza, G.; Abu-Jafar, M.S.; Bouhemadou, A.; Bin Omran, S.

2015-01-01

The structural, electronic and magnetic properties of half-Heusler CoFeIn and full-Heusler Co 2 FeIn alloys have been investigated by using the state of the art full-potential linearized augmented plane wave (FP-LAPW) method. The exchange-correlation potential was treated with the generalized gradient approximation (PBE-GGA) for the calculation of the structural properties, whereas the PBE-GGA+U approximation (where U is the Hubbard Coulomb energy term) is applied for the computation of the electronic and magnetic properties in order to treat the “d” electrons. The structural properties have been calculated in the paramagnetic and ferromagnetic phases where we have found that both the CoFeIn and Co 2 FeIn alloys have a stable ferromagnetic phase. The obtained results of the spin-polarized band structure and the density of states show that the CoFeIn alloy is a metal and the Co 2 FeIn alloy has a complete half-metallic nature. Through the obtained values of the total spin magnetic moment, we conclude that in general, the Co 2 FeIn alloy is half-metallic ferromagnet material whereas the CoFeIn alloy has a metallic nature. - Highlights: • Based on DFT calculations, CoFeIn and Co2FeIn Heusler alloys were investigated. • The magnetic phase stability was determined from the total energy calculations. • Electronic properties reveal the metallic (half-metallic) nature for CoFeIn (Co2FeIn)

Cl K-edge XANES spectra of atmospheric rust on Fe, Fe-Cr and Fe-Ni alloys exposed to saline environment

International Nuclear Information System (INIS)

Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

2004-01-01

Cl K-edge XANES measurements of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys in chloride pollution have been performed using synchrotron radiation in order to clarify roles of anticorrosive alloying elements and of Cl in the corrosion resistance of weathering steel. The spectra of binary alloys show a shoulder structure near the absorption edge. The intensity of the shoulder peak depends on the kind and amount of the alloying element, whereas the energy position is invariant. This indicates that Cl is not combined directly with alloying elements in the rust. (author)

Thick CoFeB with perpendicular magnetic anisotropy in CoFeB-MgO based magnetic tunnel junction

Directory of Open Access Journals (Sweden)

V. B. Naik

2012-12-01

Full Text Available We have investigated the effect of an ultra-thin Ta insertion in the CoFeB (CoFeB/Ta/CoFeB free layer (FL on magnetic and tunneling magnetoresistance (TMR properties of a CoFeB-MgO system with perpendicular magnetic anisotropy (PMA. It is found that the critical thickness (tc to sustain PMA is doubled (tc = 2.6 nm in Ta-inserted CoFeB FL as compared to single CoFeB layer (tc = 1.3 nm. While the effective magnetic anisotropy is found to increase with Ta insertion, the saturation magnetization showed a slight reduction. As the CoFeB thickness increasing, the thermal stability of Ta inserted structure is significantly increased by a factor of 2.5 for total CoFeB thickness less than 2 nm. We have observed a reasonable value of TMR for a much thicker CoFeB FL (thickness = 2-2.6 nm with Ta insertion, and without significant increment in resistance-area product. Our results reveal that an ultra-thin Ta insertion in CoFeB might pay the way towards developing the high-density memory devices with enhanced thermal stability.

High quality β-FeSi2 thin films prepared on silicon (100) by using pulsed laser ablation of Fe target

International Nuclear Information System (INIS)

Xu, S.C.; Yang, C.; Liu, M.; Jiang, S.Z.; Ma, Y.Y.; Chen, C.S.; Gao, X.G.; Sun, Z.C.; Hu, B.; Wang, C.C.; Man, B.Y.

2012-01-01

High quality β-FeSi 2 thin films have been fabricated on silicon (100) substrate by the pulsed laser deposition (PLD) technique with the Fe and sintered FeSi 2 targets. The crystalline quality and surface morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. These results indicate that the samples prepared with a Fe target can acquire a better crystalline quality and a smoother surface than those with a sintered FeSi 2 target. The reasons were discussed with subsurface superheating mechanism. The intrinsic PL spectrum attributed to the interband transition of β-FeSi 2 for all the samples was compared, showing that the film prepared with Fe target can acquire a good PL property by optimizing experimental parameters. It is suggested that sputtering Fe on Si substrate by the pulsed laser offers a cheap and convenient way to prepare the β-FeSi 2 thin films. -- Highlights: ► β-FeSi 2 films were fabricated by PLD technique with the Fe and FeSi 2 targets. ► The films prepared with Fe target have good crystalline quality and smooth surface. ► The Fe target prepared film acquired a high PL intensity. ► Sputtering Fe on Si substrate offers a convenient way to prepare the β-FeSi 2 films.

Nematicity and Magnetism in FeSe and Other Families of Fe-Based Superconductors

Directory of Open Access Journals (Sweden)

Youichi Yamakawa

2016-06-01

Full Text Available Nematicity and magnetism are two key features in Fe-based superconductors, and their interplay is one of the most important unsolved problems. In FeSe, the magnetic order is absent below the structural transition temperature T_{str}=90  K, in stark contrast to the fact that the magnetism emerges slightly below T_{str} in other families. To understand such amazing material dependence, we investigate the spin-fluctuation-mediated orbital order (n_{xz}≠n_{yz} by focusing on the orbital-spin interplay driven by the strong-coupling effect, called the vertex correction. This orbital-spin interplay is very strong in FeSe because of the small ratio between the Hund’s and Coulomb interactions (J[over ¯]/U[over ¯] and large d_{xz}, d_{yz}-orbital weight at the Fermi level. For this reason, in the FeSe model, the orbital order is established irrespective of the fact that the spin fluctuations are very weak, so the magnetism is absent below T_{str}. In contrast, in the LaFeAsO model, the magnetic order appears just below T_{str} both experimentally and theoretically. Thus, the orbital-spin interplay due to the vertex correction is the key ingredient in understanding the rich phase diagram with nematicity and magnetism in Fe-based superconductors in a unified way.

Research Progress on Fe-based Amorphous Coatings

Directory of Open Access Journals (Sweden)

LIANG Xiu-bing

2017-09-01

Full Text Available The latest research progresses on Fe-based amorphous coatings were reviewed. The typical alloy system and the classification of Fe-based amorphous coatings were clarified. The status, progress and development of the Fe-based amorphous coatings prepared by thermal spray processing and laser cladding process were discussed. The main mechanical properties and potential applications of the Fe-based amorphous coatings were also described. Furthermore, based on the main problems mentioned above, the future development of the Fe-based amorphous coatings was discussed, including the exploitation preparation technologies of high amorphous content of the Fe-based coatings, the development of the low cost and high performance Fe-based coating alloys system, the broadening application of Fe-based amorphous coatings, and so on.

Amorphous NiFe-OH/NiFeP Electrocatalyst Fabricated at Low Temperature for Water Oxidation Applications

KAUST Repository

Liang, Hanfeng

2017-04-11

Water splitting driven by electricity or sunlight is one of the most promising ways to address the global terawatt energy needs of future societies; however, its large-scale application is limited by the sluggish kinetics of the oxygen evolution reaction (OER). NiFe-based compounds, mainly oxides and hydroxides, are well-known OER catalysts and have been intensively studied; however, the utilization of the synergistic effect between two different NiFe-based materials to further boost the OER performance has not been achieved to date. Here, we report the rapid conversion of NiFe double hydroxide into metallic NiFeP using PH3 plasma treatment and further construction of amorphous NiFe hydroxide/NiFeP/Ni foam as efficient and stable oxygen-evolving anodes. The strong electronic interactions between NiFe hydroxide and NiFeP significantly lower the adsorption energy of H2O on the hybrid and thus lead to enhanced OER performance. As a result, the hybrid catalyst can deliver a geometrical current density of 300 mA cm–2 at an extremely low overpotential (258 mV, after ohmic-drop correction), along with a small Tafel slope of 39 mV decade–1 and outstanding long-term durability in alkaline media.

Thermodynamical Properties of 56Fe

International Nuclear Information System (INIS)

Tavukcu, E.; Becker, J.A.; Bernstein, L.A.; Garrett, P.E.; Guttormsen, M.; Mitchell, G.E.; Rekstad, J.; Schiller, A.; Siem, S.; Voinov, A.; Younes, W.

2002-01-01

Average nuclear level densities close to the nuclear binding energy in 56 Fe and 57 Fe are extracted from primary γ-ray spectra. Thermal properties of 56 Fe are studied within the statistical canonical ensemble. The experimental heat capacity is compared with the theoretical heat capacity calculated within the shell model Monte Carlo approach

The reduction of 4-chloronitrobenzene by Fe(II)-Fe(III) oxide systems - correlations with reduction potential and inhibition by silicate

Energy Technology Data Exchange (ETDEWEB)

Jones, Adele M., E-mail: adele.jones1@unsw.edu.au; Kinsela, Andrew S.; Collins, Richard N.; Waite, T. David, E-mail: d.waite@unsw.edu.au

2016-12-15

Recent studies have demonstrated that the rate at which Fe(II)-Fe(III) oxyhydroxide systems catalyze the reduction of reducible contaminants, such as 4-chloronitrobenzene, is well correlated to their thermodynamic reduction potential. Here we confirm this effect in the presence of Fe(III) oxyhydroxide phases not previously assessed, namely ferrihydrite and nano-goethite, as well as Fe(III) oxyhydroxide phases previously examined. In addition, silicate is found to decrease the extent of Fe(II) sorption to the Fe(III) oxyhydroxide surface, increasing the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspension and, accordingly, decreasing the rate of 4-chloronitrobenzene reduction. A linear relationship between the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspensions and the reduction rate of 4-chloronitrobenzene (normalized to surface area and concentration of sorbed Fe(II)) was obtained in the presence and absence of silicate. However, when ferrihydrite was doped with Si (through co-precipitation) the reduction of 4-chloronitrobenzene was much slower than predicted from its reduction potential. The results obtained have significant implications to the likely effectiveness of naturally occurring contaminant degradation processes involving Fe(II) and Fe(III) oxyhydroxides in groundwater environments containing high concentrations of silicate, or other species which compete with Fe(II) for sorption sites.

Transport and superconducting properties of Fe-based superconductors: a comparison between SmFeAsO1-xFx and Fe1+yTe1-xSex

Science.gov (United States)

Tropeano, M.; Pallecchi, I.; Cimberle, M. R.; Ferdeghini, C.; Lamura, G.; Vignolo, M.; Martinelli, A.; Palenzona, A.; Putti, M.

2010-05-01

In this paper we carry out a direct comparison between transport and superconducting properties—namely resistivity, magnetoresistivity, Hall effect, Seebeck effect, thermal conductivity, upper critical field—of two different families of Fe-based superconductors, which can be viewed in many respects as end members: SmFeAsO1 - xFx with the largest Tc and the largest anisotropy and Fe1 + yTe1 - xSex, with the largest Hc2, the lowest Tc and the lowest anisotropy. In the case of the SmFeAsO1 - xFx series, we find that a single-band description allows us to extract an approximate estimation of band parameters such as carrier density and mobility from experimental data, although the behaviour of the Seebeck effect as a function of doping demonstrates that a multiband description would be more appropriate. On the contrary, experimental data for the Fe1 + y(Te1 - x, Sex) series exhibit a strongly compensated behaviour, which can be described only within a multiband model. In the Fe1 + y(Te1 - x, Sex) series, the role of the excess Fe, tuned by Se stoichiometry, is found to be twofold: on one hand it dopes electrons in the system and on the other hand it introduces localized magnetic moments, responsible for Kondo like scattering and likely pairbreaking of Cooper pairs. Hence, Fe excess also plays a crucial role in determining superconducting properties such as the Tc and the upper critical field Hc2. The huge Hc2 values of the Fe1 + yTe1 - xSex samples are described by a dirty limit law, opposed to the clean limit behaviour of the SmFeAsO1 - xFx samples. Hence, magnetic scattering by excess Fe seems to drive the system in the dirty regime, but its detrimental pairbreaking role seems not to be as severe as predicted by theory. This issue has yet to be clarified, addressing the more fundamental issue of the interplay between magnetism and superconductivity.

Thermodynamic properties of Y/sub 3/Fe/sub 5/O/sub 12/ and TbFeO/sub 3/

Energy Technology Data Exchange (ETDEWEB)

Shchelkotunov, V A; Danilov, V N; Reznitskii, L A; Korobeinikova, A V [Moskovskij Gosudarstvennyj Univ. (USSR)

1975-01-01

Two types of chemical compounds-garnets and perovskites - exist in Fe/sub 2/O/sub 3/-Y/sub 2/O/sub 3/ and Fe/sub 2/O/sub 3/-Tb/sub 2/..omega../sub 3/ systems. Both of them are noncompensated antiferromagnetics. Thermal-physical properties of TbFeO/sub 3/ were determined. Values of Csub(p),(Hsub(t)-Hsub(o)) and Ssub(T) in the temperature range 298 to 700 deg K for Y/sub 3/Fe/sub 5/O/sub 12/ and in the range 298 to 600 deg K for TbFeO/sub 3/ were calculated using the experimental data on TbFeO/sub 3/ and Y/sub 3/Fe/sub 5/O/sub 12/ thermal capacity. Magnetic contribution for Y/sub 3/Fe/sub 5/O/sub 12/ Usub(mag)=1617 cal/mol and ..delta..S=3.44 cal/mol.deg. was determined.

Erosion resistance of FeAl-TiB2 and FeAl-WC at room and elevated temperatures

International Nuclear Information System (INIS)

Alman, D.E.; Tylczak, J.H.; Hawk, J.A.

2000-01-01

The resistance of FeAl-40%TiB 2 and FeAl-80%WC cermets to solid particle erosion at 25, 180, 500 and 700 C was evaluated and compared to the behavior of WC-6%Co (Co-90%WC) cemented carbides. Even though the WC-Co contained a higher volume fraction of the hard phase, the erosion rates of the FeAl-cermets were similar in magnitude to the erosion rates of the WC-Co. However, the erosion rates of the FeAl-cermets either were constant (FeAl-TiB 2 ) or decreased (FeAl-WC) with increasing test temperature; whereas, the erosion rates of the WC-Co cemented carbides increased with increasing test temperature. This indicated that once the microstructures of the FeAl-cermets are optimized for wear resistance, these materials might make promising candidates for high-temperature wear applications

Magnetism mediated by a majority of [Fe³⁺ + VO²⁻] complexes in Fe-doped CeO₂ nanoparticles.

Science.gov (United States)

Paidi, V K; Ferreira, N S; Goltz, D; van Lierop, J

2015-08-26

We examine the role of Fe(3+) and vacancies (V(O)) on the magnetism of Fe-doped CeO2 nanoparticles. Magnetic nanoparticles of Ce(100-x)Fe(x)O2 (x  =  0, 0.26, 1.82, 2.64, 5.26, 6.91, and 7.22) were prepared by a co-precipitation method, and their structural, compositional and magnetic properties were investigated. The CeO2 nanoparticles had a mixed valance of Ce(4+) and Ce(3+) ions, and doping introduced Fe(3+) ions. The decrease in Ce(3+) and increase in Fe(3+) concentrations indicated the presence of more [Fe(3+) + V(O)(2-)] complexes with Fe loading in the particles. Charge neutralization, Fe(3+) + V(O)(2-) + 2Ce(4+) ↔ 2Ce(3+) + Fe(3+), identified the impact of V(O) on the magnetism, where our results suggest that the Fe-doped CeO2 nanoparticle magnetism is mediated by a majority of [Fe(3+) + V(O)(2-)]-Ce(3+) -[Fe(3+) + V(O)(2-)] complexes.

The effect of Fe-coverage on the structure, morphology and magnetic properties of α-FeSi2 nanoislands

International Nuclear Information System (INIS)

Tripathi, J K; Goldfarb, I; Garbrecht, M; Kaplan, W D; Markovich, G

2012-01-01

Self-assembled α-FeSi 2 nanoislands were formed using solid-phase epitaxy of low (∼1.2 ML) and high (∼21 ML) Fe coverages onto vicinal Si(111) surfaces followed by thermal annealing. At a resulting low Fe-covered Si(111) surface, we observed in situ, by real-time scanning tunneling microscopy and surface electron diffraction, the entire sequence of Fe–silicide formation and transformation from the initially two-dimensional (2 × 2)-reconstructed layer at 300 °C into (2 × 2)-reconstructed nanoislands decorating the vicinal step-bunch edges in a self-ordered fashion at higher temperatures. In contrast, the silicide nanoislands at a high Fe-covered surface were noticeably larger, more three-dimensional, and randomly distributed all over the surface. Ex situ x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy indicated the formation of an α-FeSi 2 island phase, in an α-FeSi 2 { 112} ∥ Si{ 111} orientation. Superconducting quantum interference device magnetometry showed considerable superparamagnetism, with ∼1.9 μ B /Fe atom at 4 K for the low Fe-coverage, indicating stronger ferromagnetic coupling of individual magnetic moments, as compared to high Fe-coverage, where the calculated moments were only ∼0.8 μ B /Fe atom. Such anomalous magnetic behavior, particularly for the low Fe-coverage case, is radically different from the non-magnetic bulk α-FeSi 2 phase, and may open new pathways to high-density magnetic memory storage devices. (paper)

Single peak parameters technique for simultaneous measurements: Spectrophotometric sequential injection determination of Fe(II) and Fe(III).

Science.gov (United States)

Kozak, J; Paluch, J; Węgrzecka, A; Kozak, M; Wieczorek, M; Kochana, J; Kościelniak, P

2016-02-01

Spectrophotometric sequential injection system (SI) is proposed to automate the method of simultaneous determination of Fe(II) and Fe(III) on the basis of parameters of a single peak. In the developed SI system, sample and mixture of reagents (1,10-phenanthroline and sulfosalicylic acid) are introduced into a vessel, where in an acid environment (pH≅3) appropriate compounds of Fe(II) and Fe(III) with 1,10-phenanthroline and sulfosalicylic acid are formed, respectively. Then, in turn, air, sample, EDTA and sample again, are introduced into a holding coil. After the flow reversal, a segment of air is removed from the system by an additional valve and as EDTA replaces sulfosalicylic acid forming a more stable colorless compound with Fe(III), a complex signal is registered. Measurements are performed at wavelength 530 nm. The absorbance measured at minimum of the negative peak and the area or the absorbance measured at maximum of the signal can be used as measures corresponding to Fe(II) and Fe(III) concentrations, respectively. The time of the peak registration is about 2 min. Two-component calibration has been applied to analysis. Fe(II) and Fe(III) can be determined within the concentration ranges of 0.04-4.00 and 0.1-5.00 mg L(-1), with precision less than 2.8% and 1.7% (RSD), respectively and accuracy better than 7% (RE). The detection limit is 0.04 and 0.09 mg L(-1) for Fe(II) and Fe(III), respectively. The method was applied to analysis of artesian water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Fe-V redox flow batteries

Science.gov (United States)

Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Xia, Guanguang

2014-07-08

A redox flow battery having a supporting solution that includes Cl.sup.- anions is characterized by an anolyte having V.sup.2+ and V.sup.3+ in the supporting solution, a catholyte having Fe.sup.2+ and Fe.sup.3+ in the supporting solution, and a membrane separating the anolyte and the catholyte. The anolyte and catholyte can have V cations and Fe cations, respectively, or the anolyte and catholyte can each contain both V and Fe cations in a mixture. Furthermore, the supporting solution can contain a mixture of SO.sub.4.sup.2- and Cl.sup.- anions.

Study of magnetization and magnetoelectricity in CoFe2O4/BiFeO3 core-shell composites

Science.gov (United States)

Kuila, S.; Tiwary, Sweta; Sahoo, M. R.; Barik, A.; Babu, P. D.; Siruguri, V.; Birajdar, B.; Vishwakarma, P. N.

2018-02-01

CoFe2O4 (core)/BiFeO3 (shell) nanoparticles are prepared by varying the relative molar concentration of core and shell materials (40%CoFe2O4-60%BiFeO3, 50%CoFe2O4-50%BiFeO3, and 60%CoFe2O4-40%BiFeO3). The core-shell nature is confirmed from transmission electron microscopy on these samples. A plot of ΔM (=MFC-MZFC) vs temperature suggests the presence of two types of spin dynamics: (a) particle size dependent spin blocking and (b) spin-disorder. These two spin dynamic processes are found to contribute independently to the generation of magnetoelectric voltage. Very clear first order and second order magnetoelectric voltages are recorded. The resemblance of the first order magnetoelectric coefficient vs temperature plot to that of building up of order parameters in the mean field theory suggests that spin disorder can act like one of the essential ingredients in building the magnetoelectric coupling. The best result is obtained for the 50-50 composition sample, which may be due to better coupling of magnetostrictive CoFe2O4, and piezoelectric BiFeO3, because of the optimum thickness of shell and core.

Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}, and Cs{sub 7}[Fe{sub 4}Se{sub 8}]. Missing links of known chalcogenido ferrate series

Energy Technology Data Exchange (ETDEWEB)

Stueble, Pirmin; Roehr, Caroline [Institut fuer Anorganische und Analytische Chemie, Universitaet Freiburg (Germany)

2017-11-17

The three cesium selenido ferrate title compounds with an Se:Fe ratio of 2:1 were synthesized from stoichiometric samples reacting elemental Cs either (A) with Fe and Se in a double-crucible setup (Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}) or (B) with previously prepared FeSe{sub 2} (Cs{sub 3}[FeSe{sub 2}]{sub 2}, Cs{sub 7}[Fe{sub 4}S{sub 8}]) (T{sub max} = 800-1000 C). The pure Fe{sup III} ferrate Cs[FeSe{sub 2}] crystallizes in the Tl[FeSe{sub 2}] type [monoclinic, space group C2/m, a = 1392.95(10), b = 564.43(3), c = 737.44(6) pm, β = 119.163(5) , Z = 4, R{sub 1} = 0.0550]. It is thus not isotypic to all other alkali ferrates(III) A[FeS{sub 2}] and A[FeSe{sub 2}] containing chains of edge-sharing tetrahedra, but crystallizes in a t2 subgroup of the Immm structure of Cs[FeS{sub 2}]. The mixed-valent chain compound Cs{sub 3}[FeSe{sub 2}]{sub 2} is isotypic to its sulfido analogue [orthorhombic, space group Pnma, a = 777.88(6), b = 1151.02(6), c = 1341.61(7) pm, Z = 4, R{sub 1} = 0.0470]. In contrast to the isopunctal Na{sub 3}[FeSe{sub 2}]{sub 2} type K/Rb compounds the chains are only slightly corrugated. The monoclinic, likewise mixed-valent Fe{sup II/III} selenido ferrate Cs{sub 7}[Fe{sub 4}Se{sub 8}] [monoclinic, space group C2/c, a = 1953.79(10), b = 879.71(5), c = 1717.03(10) pm, β = 117.890(2) , Z = 4, R{sub 1} = 0.0816] is isostructural both to the cesium sulfido and tellurido compound. The structure contains oligomeric moieties of four edge sharing [FeSe{sub 4}] tetrahedra forming slightly distorted tetrahedral clusters [Fe{sub 4}Se{sub 8}]{sup 7-}, which are surrounded by a cube of 26 Cs cations. Based on a structure map, the crystal chemistry of the three title compounds is discussed together with all chain/cluster ferrates of the general series A{sub 1+x}[Fe{sup III}{sub 1-x}Fe{sup II}{sub x}Q{sub 2}] (x = 0-1; A = Na, K, Rb, Cs; Q = S, Se, Te). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Fe(III) and Fe(II) ions different effects on Enterococcus hirae cell growth and membrane-associated ATPase activity

Energy Technology Data Exchange (ETDEWEB)

Vardanyan, Zaruhi [Department of Biophysics of the Biology Faculty, Yerevan State University, 1 A. Manoukian Str., 0025 Yerevan (Armenia); Trchounian, Armen, E-mail: trchounian@ysu.am [Department of Biophysics of the Biology Faculty, Yerevan State University, 1 A. Manoukian Str., 0025 Yerevan (Armenia)

2012-01-06

Highlights: Black-Right-Pointing-Pointer Fe{sup 3+} stimulates but Fe{sup 2+} suppresses Enterococcus hirae wild-type and atpD mutant growth. Black-Right-Pointing-Pointer Fe ions change oxidation-reduction potential drop during cell growth. Black-Right-Pointing-Pointer Fe{sup 3+} and Fe{sup 2+} have opposite effects on a membrane-associated ATPase activity. Black-Right-Pointing-Pointer These effects are either in the presence of F{sub 0}F{sub 1} inhibitor or non-functional F{sub 0}F{sub 1}. Black-Right-Pointing-Pointer Fe ions decrease protons and coupled potassium ions fluxes across the membrane. -- Abstract: Enterococcus hirae is able to grow under anaerobic conditions during glucose fermentation (pH 8.0) which is accompanied by acidification of the medium and drop in its oxidation-reduction potential (E{sub h}) from positive values to negative ones (down to {approx}-200 mV). In this study, iron (III) ions (Fe{sup 3+}) have been shown to affect bacterial growth in a concentration-dependent manner (within the range of 0.05-2 mM) by decreasing lag phase duration and increasing specific growth rate. While iron(II) ions (Fe{sup 2+}) had opposite effects which were reflected by suppressing bacterial growth. These ions also affected the changes in E{sub h} values during bacterial growth. It was revealed that ATPase activity with and without N,N Prime -dicyclohexylcarbodiimide (DCCD), an inhibitor of the F{sub 0}F{sub 1}-ATPase, increased in the presence of even low Fe{sup 3+} concentration (0.05 mM) but decreased in the presence of Fe{sup 2+}. It was established that Fe{sup 3+} and Fe{sup 2+} both significantly inhibited the proton-potassium exchange of bacteria, but stronger effects were in the case of Fe{sup 2+} with DCCD. Such results were observed with both wild-type ATCC9790 and atpD mutant (with defective F{sub 0}F{sub 1}) MS116 strains but they were different with Fe{sup 3+} and Fe{sup 2+}. It is suggested that the effects of Fe{sup 3+} might be due to

Modeling thermodynamics of Fe-N phases; characterisation of e-Fe2N1-z

DEFF Research Database (Denmark)

Pekelharing, M.I.; Böttger, A.; Somers, Marcel A.J.

1999-01-01

In order to arrive at modeling the thermodynamics of Fe-N phases, including long-range (LRO) and short-range ordering (SRO) of the N atoms, it is important to understand the role of N interstitially dissolved in an Fe-host lattice. The crystal structure of -Fe2N1-z consists of an h.c.p. iron...... sublattice and a hexagonal nitrogen sublattice formed by octahedral interstices of the Fe sublattice [1]. Two ground-state structures have been proposed for the ordered arrangement of the N atoms on their own sublattice [1], which were shown to be thermodynamically favourable [2]: configuration A for Fe2N1...... investigated with X-ray diffraction (XRD) and Mössbauer spectroscopy. A thermodynamic model accounting for the two configurations of LRO of the N atoms [2,3] was fitted to the N-absorption isotherm at 723 K and resulted in the occupancies of the sites of the nitrogen sublattice. A miscibility gap between...

Enhancement of plasticity of Fe-based bulk metallic glass by Ni substitution for Fe

Energy Technology Data Exchange (ETDEWEB)

Guo, S.F. [State Key Laboratory of Material Processing and Die and Mould Technology, Huazhong University of Science and Technology, 430074 Wuhan (China); State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China); Li, N.; Zhang, C. [State Key Laboratory of Material Processing and Die and Mould Technology, Huazhong University of Science and Technology, 430074 Wuhan (China); Liu, L., E-mail: sfguo2005@163.co [State Key Laboratory of Material Processing and Die and Mould Technology, Huazhong University of Science and Technology, 430074 Wuhan (China)

2010-08-15

Bulk metallic glasses (BMGs) (Fe{sub 1-x}Ni{sub x}){sub 71}Mo{sub 5}P{sub 12}C{sub 10}B{sub 2} (x = 0, 0.1 and 0.2) with a diameter of 3 mm were synthesized by copper mold casting. The effect of Ni substitution for Fe on the structure, thermal and mechanical properties has been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and compressive testing. It was found that the substitution of Ni for Fe enhances the glass forming ability, and improves the plasticity of Fe{sub 71}Mo{sub 5}P{sub 12}C{sub 10}B{sub 2} BMG as indicated by the increase in the plastic strain from 3.1% (x = 0) to 5.2% (x = 0.2). The improvement of the plasticity is discussed in term of the reduction of glass transition temperature and the supercooled liquid region due to the substitution of Ni for Fe.

Crystal and magnetic structures of CaCu3Fe4O12 and LaCu3Fe4O12: distinct charge transitions of unusual high valence Fe

International Nuclear Information System (INIS)

Shimakawa, Yuichi

2015-01-01

New 134-type perovskites, CaCu 3 Fe 4 O 12 (CCFO) and LaCu 3 Fe 4 O 12 (LCFO), were prepared by means of high-pressure synthesis. The compounds contain unusual high valence Fe 4+ in CCFO and Fe 3.75+ in LCFO at high temperatures. With decreasing temperature, the instabilities of the high valence states of Fe are relieved by distinct charge transitions, which are charge disproportionation (4Fe 4+   →  2Fe 3+   +  2Fe 5+ ) in CCFO and intermetallic charge transfer (3Cu 2+   +  4Fe 3.75+   →  3Cu 3+   +  4Fe 3+ ) in LCFO. Crystal structure analysis with synchrotron x-ray diffraction and magnetic structure analysis with neutron diffraction revealed the nature of the transitions. Although the two behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of low-lying Fe-d and oxygen p orbitals in the oxides. The ligand holes in the charge disproportionated CCFO are localized at the Fe–O sites alternately (4d 5 L  →  2d 5   +  2d 5 L 2 ) and the ligand holes in the charge transferred LCFO are localized at the Cu–O sites (3d 9   +  4d 5 L 0.75   →  3d 9 L  +  4d 5 ). (review)

Cd Mobility in Anoxic Fe-Mineral-Rich Environments - Potential Use of Fe(III)-Reducing Bacteria in Soil Remediation

Science.gov (United States)

Muehe, E. M.; Adaktylou, I. J.; Obst, M.; Schröder, C.; Behrens, S.; Hitchcock, A. P.; Tylsizczak, T.; Michel, F. M.; Krämer, U.; Kappler, A.

2014-12-01

Agricultural soils are increasingly burdened with heavy metals such as Cd from industrial sources and impure fertilizers. Metal contaminants enter the food chain via plant uptake from soil and negatively affect human and environmental health. New remediation approaches are needed to lower soil metal contents. To apply these remediation techniques successfully, it is necessary to understand how soil microbes and minerals interact with toxic metals. Here we show that microbial Fe(III) reduction initially mobilizes Cd before its immobilization under anoxic conditions. To study how microbial Fe(III) reduction influences Cd mobility, we isolated a new Cd-tolerant, Fe(III)-reducing Geobacter sp. from a heavily Cd-contaminated soil. In lab experiments, this Geobacter strain first mobilized Cd from Cd-loaded Fe(III) hydroxides followed by precipitation of Cd-bearing mineral phases. Using Mössbauer spectroscopy and scanning electron microscopy, the original and newly formed Cd-containing Fe(II) and Fe(III) mineral phases, including Cd-Fe-carbonates, Fe-phosphates and Fe-(oxyhydr)oxides, were identified and characterized. Using energy-dispersive X-ray spectroscopy and synchrotron-based scanning transmission X-ray microscopy, Cd was mapped in the Fe(II) mineral aggregates formed during microbial Fe(III) reduction. Microbial Fe(III) reduction mobilizes Cd prior to its precipitation in Cd-bearing mineral phases. The mobilized Cd could be taken up by phytoremediating plants, resulting in a net removal of Cd from contaminated sites. Alternatively, Cd precipitation could reduce Cd bioavailability in the environment, causing less toxic effects to crops and soil microbiota. However, the stability and thus bioavailability of these newly formed Fe-Cd mineral phases needs to be assessed thoroughly. Whether phytoremediation or immobilization of Cd in a mineral with reduced Cd bioavailability are feasible mechanisms to reduce toxic effects of Cd in the environment remains to be

New method for simultaneous determination of 55Fe and 59Fe in blood serum samples

International Nuclear Information System (INIS)

Saukkonen, H.; Uhlenius, R.

1978-01-01

Routine methods for the measurement of 55 Fe and 59 Fe activities in biological samples are frequently required in metabolic studies of iron. A new simple method for the simultaneous determination of 59 Fe and 55 Fe concentration in 5 cm 3 samples of blood is described and carefully evaluated. Before the measurement of the activity, organic matter was eliminated by HNO 3 -HClO 4 wet ashing and iron was electroplated onto a copper plate. The accuracy of results was studied by assessing samples, which contained known amounts of radioactivity and determining the counts per nanocurie in each case. The accuracy of the results of 59 Fe and 55 Fe determinations was found to be about 5%. The method has been routinely used to determine iron resorption in patients using the double isotope method. The determination proved to be satisfactory and not too laborious. When performing the yield determination there is a way of detecting and correcting mistakes or incompleteness in different stages of the measurement, thus leading to a high degree of reliability. (T.G.)

Experimental investigation and thermodynamic calculation of the Fe-Mg-Mn and Fe-Mg-Ni systems

Energy Technology Data Exchange (ETDEWEB)

Wang, Peisheng; Zhao, Jingrui; Xu, Honghui; Liu, Shuhong; Ouyang, Hongwu [Central South Univ., Hunan (China). State Key Lab. of Powder Metallurgy; Du, Yong [Central South Univ., Hunan (China). State Key Lab. of Powder Metallurgy; Harbin Institute of Technology (China). State Key Lab. of Advanced Welding Production Technology; Gang, Tie; Fen, Jicai [Harbin Institute of Technology (China). State Key Lab. of Advanced Welding Production Technology; Zhang, Lijun [Central South Univ., Hunan (China). State Key Lab. of Powder Metallurgy; Bochum Univ. (Germany). ICAMS Inst.; He, Cuiyun [Guangxi Univ. (China). College of Physical Science and Technology

2011-01-15

Based on the thermodynamic calculations extrapolated from the corresponding binary sub-systems, four decisive alloys in the Fe-Mg-Mn system and three in the Fe-Mg-Ni system were selected and prepared using a powder metallurgy method to measure the isothermal sections at 500 C in both systems. The prepared samples were annealed at 500 C, and then subjected to X-ray diffraction, optical microscopy, scanning electron microscopy with energy-dispersive X-ray spectrometry as well as electron probe microanalysis. Taking into account the presently obtained experimental data and the experimental data available in the literature, thermodynamic modeling was performed for the above systems. It was found that a direct extrapolation from the corresponding three binary systems can well reproduce all the experimental data in the Fe-Mg-Mn system, while two thermodynamic parameters are needed in the Fe-Mg-Ni system to fit all the experimental data. The liquidus projections and reaction schemes for the Fe-Mg-Mn and Fe-Mg-Ni systems are also presented. (orig.)

Synthesis of highly efficient α-Fe{sub 2}O{sub 3} catalysts for CO oxidation derived from MIL-100(Fe)

Energy Technology Data Exchange (ETDEWEB)

Cui, Lifeng; Zhao, Di; Yang, Yang [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China); Wang, Yuxin [Institute of Applied Biotechnology, Taizhou Vocation & Technical College, Taizhou, Zhejiang 318000 (China); Zhang, Xiaodong, E-mail: fatzhxd@126.com [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China)

2017-03-15

Mesoporous hollow α-Fe{sub 2}O{sub 3} bricks were synthesized via a hydrothermal method to create a precursor MIL-100(Fe) and a subsequent calcination process was applied to prepare the Fe{sub 2}O{sub 3} phase. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results showed the morphology of hollow α-Fe{sub 2}O{sub 3} bricks which inherited from the MIL-100(Fe) template. The catalytic activities of hollow α-Fe{sub 2}O{sub 3} bricks for CO oxidation are studied in this work. Due to better low temperature reduction behavior, mesoporous hollow α-Fe{sub 2}O{sub 3} bricks obtained at calcination temperature of 430 °C displayed high catalytic activity and excellent stability with a complete CO conversion temperature (T{sub 100}) of 255 °C. - Graphical abstract: Synthesis of highly efficient α-Fe{sub 2}O{sub 3} catalysts for CO oxidation derived from MIL-100(Fe). - Highlights: • α-Fe{sub 2}O{sub 3} is prepared by the thermolysis of a MIL-100(Fe) template. • The morphology of hollow α-Fe{sub 2}O{sub 3} bricks is inherited from MIL-100(Fe) template. • α-Fe{sub 2}O{sub 3} obtained at calcined temperature of 430 °C displays high activity • Enhanced activity is attributed to crystal plane and reduction behavior.

Compression of Fe-Si-H alloys

Science.gov (United States)

Tagawa, S.; Ohta, K.; Hirose, K.

2014-12-01

The light elements in the Earth's core have not been fully identified yet, but hydrogen is now collecting more attention in part because recent planet formation theory suggests that large amount of water should have been brought to the Earth during its formation (giant-impact stage). Nevertheless, the effect of hydrogen on the property of iron alloys is little known so far. The earlier experimental study by Hirao et al. [2004 GRL] examined the compression behavior of dhcp FeHx (x ≈ 1) and found that it becomes much stiffer than pure iron above 50 GPa, where magnetization disappears. Here we examined the solubility of hydrogen into iron-rich Fe-Si alloys and the compression behavior of dhcp Fe-Si-H alloy at room temperature. Fe+6.5wt.%Si or Fe+9wt.%Si foil was loaded into a diamond-anvil cell (DAC), and then liquid hydrogen was introduced at temperatures below 20 K. X-ray diffraction measurements at SPring-8 revealed the formation of a dhcp phase with or without thermal annealing by laser above 8.4 GPa. The concentration of hydrogen in such dhcp lattice was calculated following the formula reported by Fukai [1992]; y = 0.5 and 0.2 for Fe-6.5wt.%Si-H or Fe-9wt.%Si-H alloys, respectively when y is defined as Fe(1-x)SixHy. Unlike Fe-H alloy, hydrogen didn't fully occupy the octahedral sites even under hydrogen-saturated conditions in the case of Fe-Si-H system. Anomaly was observed in obtained pressure-volume curve around 44 Å3 of unit-cell volume for both Fe-6.5wt.%Si-H and Fe-9wt.%Si-H alloys, which may be related to the spin transition in the dhcp phase. They became slightly stiffer at higher pressures, but their compressibility was still similar to that of pure iron.

Stress impedance effect of FeCoSiB/Cu/FeCoSiB sandwich layers on flexible substrate

International Nuclear Information System (INIS)

Peng, B.; Zhang, W.L.; Liu, J.D.; Zhang, W.X.

2011-01-01

FeCoSiB/Cu/FeCoSiB sandwich layers were deposited on flexible substrate to develop flexible stress/strain sensors. The influence of stress on the impedance of the multilayers is reported. The results show that the variation of the impedance increases with the increase in deflection of the free end of the cantilever. A relative change in impedance of 6.4% is obtained in the FeCoSiB(1.5 μm)/Cu(0.25 μm)/FeCoSiB(1.5 μm) sandwich layers at 1 MHz with deflection of 2 mm. The stress impedance effects are sensitive to the frequency of the current and the thickness of both FeCoSiB and Cu layers. The stress impedance effect increases with the increase in the thickness of FeCoSiB or Cu layers. The stress impedance effect increases slightly with the increase in frequency and decreases with the further increase in frequency, which can be understood by the stress and frequency-dependent permeability of magnetic films. - Research highlights: → We deposited FeCoSiB/Cu/FeCoSiB multilayer on flexible substrate. → We studied the stress impedance effect of FeCoSiB/Cu/FeCoSiB multilayer. → Stress impedance effect increases with thickness of both FeCoSiB and Cu layer.→ Stress impedance effect is dependent on current frequency. → Results are understood using stress and frequency-dependent permeability.

Viscosity of SiO2-"FeO"-Al2O3 System in Equilibrium with Metallic Fe

Science.gov (United States)

Chen, Mao; Raghunath, Sreekanth; Zhao, Baojun

2013-08-01

The present study delivered the measurements of viscosities in SiO2-"FeO"-Al2O3 system in equilibrium with metallic Fe. The rotational spindle technique was used in the measurements at the temperature range of 1473 K to 1773 K (1200 °C to 1500 °C). Molybdenum crucibles and spindles were employed in all measurements. The Fe saturation condition was maintained by an iron plate placed at the bottom of the crucible. The equilibrium compositions of the slags were measured by EPMA after the viscosity measurements. The effect of up to 20 mol. pct Al2O3 on the viscosity of the SiO2-"FeO" slag was investigated. The "charge compensation effect" of the Al2O3 and FeO association has been discussed. The modified quasi-chemical viscosity model has been optimized in the SiO2-"FeO"-Al2O3 system in equilibrium with metallic Fe to describe the viscosity measurements of the present study.

Impact of lattice strain on the tunnel magnetoresistance in Fe/insulator/Fe and Fe/insulator/La0.67Sr0.33MnO3 magnetic tunnel junctions

KAUST Repository

Useinov, Arthur

2013-08-19

The objective of this work is to describe the tunnel electron current in single-barrier magnetic tunnel junctions within an approach that goes beyond the single-band transport model. We propose a ballistic multichannel electron transport model that can explain the influence of in-plane lattice strain on the tunnel magnetoresistance as well as the asymmetric voltage behavior. We consider as an example single-crystal magnetic Fe(110) electrodes for Fe/insulator/Fe and Fe/insulator/La0.67Sr0.33MnO3 tunnel junctions, where the electronic band structures of Fe and La0.67Sr0.33MnO3 are derived by ab initio calculations.

Impact of lattice strain on the tunnel magnetoresistance in Fe/insulator/Fe and Fe/insulator/La0.67Sr0.33MnO3 magnetic tunnel junctions

KAUST Repository

Useinov, Arthur; Saeed, Yasir; Schwingenschlö gl, Udo; Singh, Nirpendra; Useinov, N.

2013-01-01

The objective of this work is to describe the tunnel electron current in single-barrier magnetic tunnel junctions within an approach that goes beyond the single-band transport model. We propose a ballistic multichannel electron transport model that can explain the influence of in-plane lattice strain on the tunnel magnetoresistance as well as the asymmetric voltage behavior. We consider as an example single-crystal magnetic Fe(110) electrodes for Fe/insulator/Fe and Fe/insulator/La0.67Sr0.33MnO3 tunnel junctions, where the electronic band structures of Fe and La0.67Sr0.33MnO3 are derived by ab initio calculations.

V-insertion in Li(Fe,Mn)FePO4

Science.gov (United States)

Wu, T.; Liu, J.; Sun, L.; Cong, L.; Xie, H.; Abdel-Ghany, A.; Mauger, A.; Julien, C. M.

2018-04-01

Insertion of 3% vanadium in LiMn1-yFeyPO4 has been investigated, with y = 0.2 corresponding to the highest manganese concentration before the stress/strain field degrades the electrochemical performance. V substitutes for Fe2+ in the trivalent state V3+. This substitution is accompanied with the formation of Fe vacancies while Mn remains in the Mn2+ valence state, leading to a composition LiMn0.8Fe0.2-0.045V0.03□0.015PO4 where □ is a Fe vacancy. The comparison between electrochemical properties of a pristine sample and a sample with 3 mol.% vanadium made of particles with the same morphology (spherical particles with the same dispersion 100-150 nm in size) and same carbon coating (same conductivity of the carbon layer) is reported. Although the vanadium is in the V3+ state at open circuit voltage (2.6 V) before cycling, a reversible V3+/V2+ is observed when the potential of the half-cell is lowered below the redox potential of 1.8 V vs Li+/Li, due to Li-vacancies. The V-insertion improves the electrochemical properties, due to a synergetic effect of an increase of the lithium diffusion coefficient by a factor two and an increase of the electric conductivity at any Li-concentration during the cycling process, in contradiction with prior claims that attributed the increase of conductivity to V-based impurities.

Switchable transport strategy to deposit active Fe/Fe3C cores into hollow microporous carbons for efficient chromium removal.

Science.gov (United States)

Liu, Dong-Hai; Guo, Yue; Zhang, Lu-Hua; Li, Wen-Cui; Sun, Tao; Lu, An-Hui

2013-11-25

Magnetic hollow structures with microporous shell and highly dispersed active cores (Fe/Fe3 C nanoparticles) are rationally designed and fabricated by solution-phase switchable transport of active iron species combined with a solid-state thermolysis technique, thus allowing selective encapsulation of functional Fe/Fe3 C nanoparticles in the interior cavity. These engineered functional materials show high loading (≈54 wt%) of Fe, excellent chromium removal capability (100 mg g(-1)), fast adsorption rate (8766 mL mg(-1) h(-1)), and easy magnetic separation property (63.25 emu g(-1)). During the adsorption process, the internal highly dispersed Fe/Fe3 C nanoparticles supply a driving force for facilitating Cr(VI) diffusion inward, thus improving the adsorption rate and the adsorption capacity. At the same time, the external microporous carbon shell can also efficiently trap guest Cr(VI) ions and protect Fe/Fe3 C nanoparticles from corrosion and subsequent leaching problems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique

International Nuclear Information System (INIS)

Kozak, J.; Gutowski, J.; Kozak, M.; Wieczorek, M.; Koscielniak, P.

2010-01-01

The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength λ = 530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic 'cut off' peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 2 2 factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L -1 of both analytes, respectively.

Using Gas Chromatography/Isotope Ratio Mass Spectrometry to Determine the Fractionation Factor for H2 Production by Hydrogenases

International Nuclear Information System (INIS)

Yang, Hui; Ghandi, H.; Shi, Liang; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

2012-01-01

Hydrogenases catalyze the reversible formation of H2, and they are key enzymes in the biological cycling of H2. H isotopes should be a very useful tool in quantifying proton trafficking in biological H2 production processes, but there are several obstacles that have thus far limited the use of this tool. In this manuscript, we describe a new method that overcomes some of these barriers and is specifically designed to measure isotopic fractionation during enzyme-catalyzed H2 evolution. A key feature of this technique is that purified hydrogenases are employed, allowing precise control over the reaction conditions and therefore a high level of precision. A custom-designed high-throughput gas chromatography-isotope ratio mass spectrometer is employed to measure the isotope ratio of the H2. Using this method, we determined that the fractionation factor of H2 production by the (NiFe)-hydrogenase from Desulfivibrio fructosovran is 0.27. This result indicates that, as expected, protons are highly favored over deuterons during H2 evolution. Potential applications of this new method are discussed.

Protection of Nitrate-Reducing Fe(II)-Oxidizing Bacteria from UV Radiation by Biogenic Fe(III) Minerals

Science.gov (United States)

Gauger, Tina; Konhauser, Kurt; Kappler, Andreas

2016-04-01

Due to the lack of an ozone layer in the Archean, ultraviolet radiation (UVR) reached early Earth's surface almost unattenuated; as a consequence, a terrestrial biosphere in the form of biological soil crusts would have been highly susceptible to lethal doses of irradiation. However, a self-produced external screen in the form of nanoparticular Fe(III) minerals could have effectively protected those early microorganisms. In this study, we use viability studies by quantifying colony-forming units (CFUs), as well as Fe(II) oxidation and nitrate reduction rates, to show that encrustation in biogenic and abiogenic Fe(III) minerals can protect a common soil bacteria such as the nitrate-reducing Fe(II)-oxidizing microorganisms Acidovorax sp. strain BoFeN1 and strain 2AN from harmful UVC radiation. Analysis of DNA damage by quantifying cyclobutane pyrimidine dimers (CPD) confirmed the protecting effect by Fe(III) minerals. This study suggests that Fe(II)-oxidizing microorganisms, as would have grown in association with mafic and ultramafic soils/outcrops, would have been able to produce their own UV screen, enabling them to live in terrestrial habitats on early Earth.

Influence of Fe underlayers on stress evolution of Ti in Ti/Fe multilayers

Energy Technology Data Exchange (ETDEWEB)

Wan, Li; Thompson, Gregory, E-mail: gthompson@eng.ua.edu [Department of Metallurgical Engineering, The University of Alabama, Tuscaloosa, Alabama 35487-0202 (United States)

2016-11-15

A series of 40–2 nm bilayer spacing Ti/Fe multilayers were sputter-deposited. As the length scale of individual Ti layers equaled to 2 nm, Ti phase transforms from a hexagonal close packed (hcp)-to-body centered cubic (bcc) crystal structures for equal layer thicknesses in Ti/Fe multilayers. Further equal reductions in bilayer spacing to less than 1 nm resulted in an additional transformation from a crystalline to amorphous structure. Atom probe tomography reveals significant intermixing between layers which contributes to the observed phase transformations. Real-time, intrinsic growth stress measurements were also performed to relate the adatom mobility to these phase transformations. For the hcp Ti/bcc Fe multilayers of equivalent volume fractions, the multilayers undergo an overall tensile stress state to a compressive stress state with decreasing bilayer thickness for the multilayers. When the above phase transformations occurred, a modest reduction in the overall compressive stress of the multilayer was noted. Depending on the Fe thickness, the Ti growth was observed to be a tensile to compressive growth change to a purely compressive growth for thinner bilayer spacing. Fe retained a tensile growth stress regardless of the bilayer spacing studied.

THE LICK/SDSS LIBRARY. II. [Ca/Fe] AND [Mg/Fe] IN F, G, AND K STARS FROM SDSS-DR7

International Nuclear Information System (INIS)

Franchini, M.; Morossi, C.; Di Marcantonio, P.; Malagnini, M. L.; Chavez, M.

2011-01-01

We analyzed the spectra of 17,600 F, G, and K stars extracted from the seventh Sloan Digital Sky Survey Data Release (SDSS-DR7) database in order to derive ([α/Fe]), [Ca/Fe], and [Mg/Fe] ratios. Particular attention has been devoted to estimating homogeneous and self-consistent atmospheric parameter values, T eff , log g, and [Fe/H], by comparing synthetic and observational Lick/SDSS indices. We present results for the sub-sample of more than 4000 spectra whose overall quality allowed us to derive fairly accurate stellar atmospheric parameter values and, therefore, reliable abundance ratios. A Monte Carlo approach was adopted to evaluate both the errors in the observational Lick/SDSS indices and in the derived parameter estimates. The analysis of the trends of [Ca/Fe] and [Mg/Fe] versus [Fe/H] pointed out that (1) the [Ca/Fe] and [Mg/Fe] ratios increase with decreasing [Fe/H] with different slopes reaching maximum average levels of +0.25 and +0.40 dex at [Fe/H] ≅ -1.75, respectively; (2) our sample contains, at a given [Fe/H], stars characterized by significantly different amounts of α-enhancement, thus belonging to different Galactic populations; and (3) the analyzed sample shows a predominance of thick disk stars for [Fe/H] > - 0.5 and the presence of stars belonging to the h igh-αhalo population for -2.0 < [Fe/H] <-0.5.

A new rhodamine-based fluorescent probe for the discrimination of Fe{sup 3+} from Fe{sup 2+}

Energy Technology Data Exchange (ETDEWEB)

You, Qi Hua; Huang, Hua Bin; Zhuang, Zhi Xia; Wang, Xiao Ru [Dept. of Science and Technology for Inspection, Xiamen Huaxia University, Xiamen (China); Chan, Wing Hong [Dept. of of Chemistry, Hong Kong Bap tist University, Hong Kong (China)

2016-11-15

A new rhodamine-based fluorescent probe for the discrimination of Fe{sup 3+} from Fe{sup 2+} has been designed and investigated. The probe shows an immediate visual color change in response to Fe{sup 3+} and Cu{sup 2+}, while only Fe{sup 3+} triggers the fluorescent change of the probe. The existence of large amount of other metal ions shows negligible interference in the detection of Fe{sup 3+}. The association constant K{sub ass} of 4.64 × 10{sup 8} M{sup -2} (R{sup 2} = 0.994) and 5.38 × 10{sup 8} M{sup -2} (R{sup 2} = 0.991) of the complex was derived from UV/Vis and fluorescence titration assuming 1:2 stoichiometry of probe–Fe{sup 3+} complex, respectively.

Alloying effect on hardening of martensite stainless steels of the Fe-Cr-Ni and Fe-Cr-Co systems

International Nuclear Information System (INIS)

Fel'dgandler, Eh.G.; Savkina, L.Ya.

1975-01-01

The effect of alloying elements is considered on the γ → a-transformation and hardening of certain compositions of the ternary Fe-Cr-Ni- and Fe-Cr-Co alloy systems with the martensite structure. In martensite Fe-(10 to 14)% Cr base steels the elements Co, Cu, W, Ni, Mo, Si, Cr decrease, Mn, Si, Mo, Cu increase, and Cr, Ni, Co decrease the temperature of α → γ-transition. The tempering of martensite steels of the Fe-Cr-Ni- and Fe-Cr-Co-systems containing 10 to 14% Cr, 4 to 9% Ni, and 7 to 12% Co does not lead to hardening. Alloyage of the martensite Fe-Cr-Ni-, Fe-Cr-Co- and Fe-Cr-Ni-Co base separately with Mo, W, Si or Cu leads to a hardening during tempering, the hardening being the higher, the higher is the content of Ni and, especially, of Co. The increase in the content of Mo or Si produces the same effect as the increase in the Co content. In on Fe-Cr-Co or Fe-Cr-Ni-Co based steels alloyed with Mo or Si, two temperature ranges of ageing have been revealed which, evidently, have different hardening natures. The compositions studied could serve as the base material for producing maraging stainless steels having a complex variety of properties

Oxidation of Fe(II) in rainwater.

Science.gov (United States)

Willey, J D; Whitehead, R F; Kieber, R J; Hardison, D R

2005-04-15

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

Mechanisms of Fe biofortification and mitigation of Cd accumulation in rice (Oryza sativa L.) grown hydroponically with Fe chelate fertilization.

Science.gov (United States)

Chen, Zhe; Tang, Ye-Tao; Zhou, Can; Xie, Shu-Ting; Xiao, Shi; Baker, Alan J M; Qiu, Rong-Liang

2017-05-01

Cadmium contaminated rice from China has become a global food safety issue. Some research has suggested that chelate addition to substrates can affect metal speciation and plant metal content. We investigated the mitigation of Cd accumulation in hydroponically-grown rice supplied with EDTANa 2 Fe(II) or EDDHAFe(III). A japonica rice variety (Nipponbare) was grown in modified Kimura B solution containing three concentrations (0, 10, 100 μΜ) of the iron chelates EDTANa 2 Fe(II) or EDDHAFe(III) and 1 μΜ Cd. Metal speciation in solution was simulated by Geochem-EZ; growth and photosynthetic efficiency of rice were evaluated, and accumulation of Cd and Fe in plant parts was determined. Net Cd fluxes in the meristematic zone, growth zone, and maturation zone of roots were monitored by a non-invasive micro-test technology. Expression of Fe- and Cd-related genes in Fe-sufficient or Fe-deficient roots and leaves were studied by QRT-PCR. Compared to Fe deficiency, a sufficient or excess supply of Fe chelates significantly enhanced rice growth by elevating photosynthetic efficiency. Both Fe chelates increased the Fe content and decreased the Cd content of rice organs, except for the Cd content of roots treated with excess EDDHAFe(III). Compared to EDDHAFe(III), EDTANa 2 Fe(II) exhibited better mitigation of Cd accumulation in rice by generating the EDTANa 2 Cd complex in solution, decreasing net Cd influx and increasing net Cd efflux in root micro-zones. Application of EDTANa 2 Fe(II) and EDDHAFe(III) also reduced Cd accumulation in rice by inhibiting expression of genes involved in transport of Fe and Cd in the xylem and phloem. The 'win-win' situation of Fe biofortification and Cd mitigation in rice was achieved by application of Fe chelates. Root-to-stem xylem transport of Cd and redistribution of Cd in leaves by phloem transport can be regulated in rice through the use of Fe chelates that influence Fe availability and Fe-related gene expression. Fe fertilization

Chemical synthesis of Fe/Fe{sub 3}O{sub 4} core-shell composites with enhanced soft magnetic performances

Energy Technology Data Exchange (ETDEWEB)

Yang, Bai, E-mail: byang@buaa.edu.cn [Key Laboratory of Aerospace Advanced Materials and Performance, Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Li, Xiaopan [Key Laboratory of Aerospace Advanced Materials and Performance, Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Yang, Xueying [Hi-tech Industry Standardization Institute, Hubei Standardization and Quality Institution, Wuhan 430061 (China); Yu, Ronghai [Key Laboratory of Aerospace Advanced Materials and Performance, Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China)

2017-04-15

The large-grain Fe/Fe{sub 3}O{sub 4} composite particles with average size of about 1.2 µm have been fabricated by a facile one-step solvothermal method. The formation of high-purity Fe{sub 3}O{sub 4} as the shells (90.14 wt%) and α-Fe as the cores (9.86 wt%) in the Fe/Fe{sub 3}O{sub 4} composites leads to their high saturation magnetization of 119.6 A m{sup 2} Kg{sup -1}. Very low coercivity of 30 Oe is obtained in the composites due to their uniform cubic-shaped morphologies. Compared with Fe-based nanosized particles, these micron-sized magnetic Fe/Fe{sub 3}O{sub 4} composites exhibit high air stability and good compactibility with high compressed density of 5.9 g cm{sup -3}. The fully compacted sample shows good soft magnetic properties including high magnetic induction B{sub 1.2k} {sub (H=1200} {sub A/m)} of 540 mT and good frequency-dependent magnetic properties with operating frequency up to 50 MHz superior to those of the most traditional soft magnetic ferrites, which promotes their potential applications in high-frequency and high-power magnetic devices. - Highlights: • Micron-sized Fe/Fe{sub 3}O{sub 4} composites are prepared by a one-step solvothermal method. • High saturation magnetization and low coercivity are obtained in the composites. • Good air stability and high bulk density occurs in the composites. • High magnetic induction and good frequency-dependent properties are achieved.

Characterization of Fe (III)-reducing enrichment culture and isolation of Fe (III)-reducing bacterium Enterobacter sp. L6 from marine sediment.

Science.gov (United States)

Liu, Hongyan; Wang, Hongyu

2016-07-01

To enrich the Fe (III)-reducing bacteria, sludge from marine sediment was inoculated into the medium using Fe (OH)3 as the sole electron acceptor. Efficiency of Fe (III) reduction and composition of Fe (III)-reducing enrichment culture were analyzed. The results indicated that the Fe (III)-reducing enrichment culture with the dominant bacteria relating to Clostridium and Enterobacter sp. had high Fe (III) reduction of (2.73 ± 0.13) mmol/L-Fe (II). A new Fe (III)-reducing bacterium was isolated from the Fe (III)-reducing enrichment culture and identified as Enterobacter sp. L6 by 16S rRNA gene sequence analysis. The Fe (III)-reducing ability of strain L6 under different culture conditions was investigated. The results indicated that strain L6 had high Fe (III)-reducing activity using glucose and pyruvate as carbon sources. Strain L6 could reduce Fe (III) at the range of NaCl concentrations tested and had the highest Fe (III) reduction of (4.63 ± 0.27) mmol/L Fe (II) at the NaCl concentration of 4 g/L. This strain L6 could reduce Fe (III) with unique properties in adaptability to salt variation, which indicated that it can be used as a model organism to study Fe (III)-reducing activity isolated from marine environment. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Characterisation of a tertiary mixture of {alpha}-Fe{sub 2}O{sub 3}, {gamma}-Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Srinivasan, M.P.; Narasimhan, S.V. [Water and Steam Chemistry Laboratory (Chemistry Group, BARC) BARC Facilities, Kalpakkam, Tamil Nadu 603 102. (India)

1998-12-31

A method has been developed to quantify the individual components of a ternary mixture containing {alpha}-Fe{sub 2}O{sub 3}, {gamma}- Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} based on the preferential dissolution of the components at a fixed time (fixed time - depending on the strength of the chelating agent) in a dilute chemical formulation (containing a chelant and an organic acid) both in presence and absence of reductant. A ternary component diagram was constructed based on the percentage dissolution of the individual components in 2,6-Pyridine dicarboxylic acid (PDCA), Nitrilo triacetic acid (NTA) and EDTA based formulation at 60degC both in presence and absence of reductant. In these formulations, the observed behaviour that the {alpha}-Fe{sub 2}O{sub 3} dissolved very little both in presence and absence of reductant and {gamma}-Fe{sub 2}O{sub 3} dissolved very little in absence of reductant were used for resolving the ternary physical mixture composition. Physical mixtures of Fe{sub 3}O{sub 4}, {alpha}-Fe{sub 2}O{sub 3} and {gamma}-Fe{sub 2}O{sub 3} based on mole ratio were taken such that the total quantity of Fe present would be 1.37 mM for complete dissolution. In presence and absence of reductant, dissolution percentage of Fe observed at fixed time in these formulations, when fit into the already constructed three component phase diagram for each formulation at the same fixed duration, the experimentally resolved composition showed good agreement with that based on individual components. This method is useful to resolve different polymorphs of metal oxides having the metal ions in single and/or multiple oxidation states. (author)

Evaluations of the 58Fe(n,γ)59Fe, and 54Fe(n,p)54Mn reactions for the ENDF/B-V dosimetry file

International Nuclear Information System (INIS)

Schenter, R.E.; Schmittroth, F.; Mann, F.M.

1979-10-01

A generalized least-squares adjustment procedure was used to evaluate two important dosimetry reactions for the ENDF/B-V files. Calculations for the cross section adjustments were made with the computer code FERRET, where input data included both integral and differential experimental data results. For the 54 Fe reaction, important ratio measurements were renormalized to ENDF/B-V evaluations of 235 U(n,f), 238 U(n,f), and 56 Fe(n,p). A priori curves which are required for the calculations were obtained using Hauser-Feshbach calculations from the codes NCAP ( 58 Fe) and HAUSER-5 ( 54 Fe). Covariance matrices were also calculated and are included in the evaluations. 8 figures, 1 table

Modeling Fe II Emission and Revised Fe II (UV) Empirical Templates for the Seyfert 1 Galaxy I Zw 1

Science.gov (United States)

Bruhweiler, F.; Verner, E.

2008-03-01

We use the narrow-lined broad-line region (BLR) of the Seyfert 1 galaxy, I Zw 1, as a laboratory for modeling the ultraviolet (UV) Fe II 2100-3050 Å emission complex. We calculate a grid of Fe II emission spectra representative of BLR clouds and compare them with the observed I Zw 1 spectrum. Our predicted spectrum for log [nH/(cm -3) ] = 11.0, log [ΦH/(cm -2 s-1) ] = 20.5, and ξ/(1 km s-1) = 20, using Cloudy and an 830 level model atom for Fe II with energies up to 14.06 eV, gives a better fit to the UV Fe II emission than models with fewer levels. Our analysis indicates (1) the observed UV Fe II emission must be corrected for an underlying Fe II pseudocontinuum; (2) Fe II emission peaks can be misidentified as that of other ions in active galactic nuclei (AGNs) with narrow-lined BLRs possibly affecting deduced physical parameters; (3) the shape of 4200-4700 Å Fe II emission in I Zw 1 and other AGNs is a relative indicator of narrow-line region (NLR) and BLR Fe II emission; (4) predicted ratios of Lyα, C III], and Fe II emission relative to Mg II λ2800 agree with extinction corrected observed I Zw 1 fluxes, except for C IV λ1549 (5) the sensitivity of Fe II emission strength to microturbulence ξ casts doubt on existing relative Fe/Mg abundances derived from Fe II (UV)/Mg II flux ratios. Our calculated Fe II emission spectra, suitable for BLRs in AGNs, are available at http://iacs.cua.edu/people/verner/FeII. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 05-26555.