Magnetic moments, coupling, and interface interdiffusion in Fe/V(001) superlattices

NASA Astrophysics Data System (ADS)

Schwickert, M. M.; Coehoorn, R.; Tomaz, M. A.; Mayo, E.; Lederman, D.; O'brien, W. L.; Lin, Tao; Harp, G. R.

1998-06-01

Epitaxial Fe/V(001) multilayers are studied both experimentally and by theoretical calculations. Sputter-deposited epitaxial films are characterized by x-ray diffraction, magneto-optical Kerr effect, and x-ray magnetic circular dichroism. These results are compared with first-principles calculations modeling different amounts of interface interdiffusion. The exchange coupling across the V layers is observed to oscillate, with antiferromagnetic peaks near the V layer thicknesses tV~22, 32, and 42 Å. For all films including superlattices and alloys, the average V magnetic moment is antiparallel to that of Fe. The average V moment increases slightly with increasing interdiffusion at the Fe/V interface. Calculations modeling mixed interface layers and measurements indicate that all V atoms are aligned with one another for tV<~15 Å, although the magnitude of the V moment decays toward the center of the layer. This ``transient ferromagnetic'' state arises from direct (d-d) exchange coupling between V atoms in the layer. It is argued that the transient ferromagnetism suppresses the first antiferromagnetic coupling peak between Fe layers, expected to occur at tV~12 Å.

Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

NASA Astrophysics Data System (ADS)

Lohrasbi, Elaheh; Javanbakht, Mehran; Mozaffari, Sayed Ahmad

2017-06-01

The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO3sbnd groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm-2 Pt) reaches to a maximum of 530 mW cm-2 at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

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

Zarzycki, Piotr; Rosso, Kevin M.

Understanding Fe(II)-catalyzed transformations of Fe(III)- (oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014, 48, 11302-11311; Joshi and Gorski Environ. Sci. Technol. 2016, 50, 7315-7324), wemore » developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ~10-5 Fe nm-2 s-1, commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.« less

The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells.

PubMed

Liu, Qingtao; Liu, Xiaofang; Zheng, Lirong; Shui, Jianglan

2018-01-26

The environmentally friendly synthesis of highly active Fe-N-C electrocatalysts for proton-exchange membrane fuel cells (PEMFCs) is desirable but remains challenging. A simple and scalable method is presented to fabricate Fe II -doped ZIF-8, which can be further pyrolyzed into Fe-N-C with 3 wt % of Fe exclusively in Fe-N 4 active moieties. Significantly, this Fe-N-C derived acidic PEMFC exhibits an unprecedented current density of 1.65 A cm -2 at 0.6 V and the highest power density of 1.14 W cm -2 compared with previously reported NPMCs. The excellent PEMFC performance can be attributed to the densely and atomically dispersed Fe-N 4 active moieties on the small and uniform catalyst nanoparticles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of thermal atomic displacements on the Curie temperature of 3 d transition metals

NASA Astrophysics Data System (ADS)

Ruban, A. V.; Peil, O. E.

2018-05-01

It is demonstrated that thermally induced atomic displacements from ideal lattice positions can produce considerable effect on magnetic exchange interactions and, consequently, on the Curie temperature of Fe. Thermal lattice distortion should, therefore, be accounted for in quantitatively accurate theoretical modeling of the magnetic phase transition. At the same time, this effect seems to be not very important for magnetic exchange interactions and the Curie temperature of Co and Ni.

Tuning the Curie temperature of L1{sub 0} ordered FePt thin films through site-specific substitution of Rh

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

Xu, Dongbin, E-mail: dongbin.xu@seagate.com; Department of Materials Science and Engineering, National University of Singapore, Singapore 117576; Sun, Cheng-Jun, E-mail: cjsun@aps.anl.gov, E-mail: msecgm@nus.edu.sg

2014-10-14

In structurally ordered magnetic thin films, the Curie temperature (T{sub C}) of ferromagnetic films depends on the exchange integral of the short range ordered neighboring atoms. The exchange integral may be adjusted by controlling the elemental substitutional concentration at the lattice site of interest. We show how to control the T{sub C} in high anisotropy L1{sub 0} Fe{sub 50}Pt{sub 50} magnetic thin films by substituting Rh into the Pt site. Rh substitution in L1{sub 0} FePt modified the local atomic environment and the corresponding electronic properties, while retaining the ordered L1{sub 0} phase. The analysis of extended x-ray Absorption Finemore » Structure spectra shows that Rh uniformly substitutes for Pt in L1{sub 0} FePt. A model of antiferromagnetic defects caused by controlled Rh substitution of the Pt site, reducing the T{sub C,} is proposed to interpret this phenomenon and its validity is further examined by ab initio density functional calculations.« less

AtomDB Progress Report: Atomic data and new models for X-ray spectroscopy.

NASA Astrophysics Data System (ADS)

Smith, Randall K.; Foster, Adam; Brickhouse, Nancy S.; Stancil, Phillip C.; Cumbee, Renata; Mullen, Patrick Dean; AtomDB Team

2018-06-01

The AtomDB project collects atomic data from both theoretical and observational/experimental sources, providing both a convenient interface (http://www.atomdb.org/Webguide/webguide.php) as well as providing input to spectral models for many types of astrophysical X-ray plasmas. We have released several updates to AtomDB in response to the Hitomi data, including new data for the Fe K complex, and have expanded the range of models available in AtomDB to include the Kronos charge exchange models from Mullen at al. (2016, ApJS, 224, 2). Combined with the previous AtomDB charge exchange model (http://www.atomdb.org/CX/), these data enable a velocity-dependent model for X-ray and EUV charge exchange spectra. We also present a new Kappa-distribution spectral model, enabling plasmas with non-Maxwellian electron distributions to be modeled with AtomDB. Tools are provided within pyAtomDB to explore and exploit these new plasma models. This presentation will review these enhancements and describe plans for the new few years of database and code development in preparation for XARM, Athena, and (hopefully) Arcus.

Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

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

Kaur, Maninder; Dai, Qilin; Bowden, Mark

2013-01-01

Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr2O3 and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (rv25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of r-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs. The giantmore » magnetoresistance (GMR) effect,1,2 where an antiferromagnetic (AFM) exchange coupling exists between two ferromagnetic (FM) layers separated by a certain type of magnetic or non-magnetic spacer,3 has significant potential for application in the magnetic recording industry. Soon after the discovery of the GMR, the magnetic properties of multilayer systems (FeCr) became a subject of intensive study. The application of bulk iron-chromium (Fe-Cr) alloys has been of great interest, as these alloys exhibit favorable prop- erties including corrosion resistance, high strength, hardness, low oxidation rate, and strength retention at elevated temper- ature. However, the structural and magnetic properties of Cr-doped Fe nanoclusters (NCs) have not been investigated in-depth. Of all NCs, Fe-based clusters have unique magnetic properties as well as favorable catalytic characteristics in reactivity, selectivity, and durability.4 The incorporation of dopant of varied type and concentration in Fe can modify its chemical ordering, thereby optimizing its electrical, optical, and magnetic properties and opening up many new applications. The substitution of an Fe atom (1.24 A°) by a Cr atom (1.25 A° ) can easily modify the magnetic properties, since (i) the curie temperature (Tc ) of Fe is 1043 K, while Cr is an itinerant AFM with a bulk Neel temperature TN =311 K, and (ii) Fe and Cr share the same crystal structure (bcc) with only 0.5% difference between their lattice constants.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

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

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE PAGES

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin; ...

2018-01-24

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Xiao Xia; Cullen, David A; Pan, Yung-Tin; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Wang, Jingyun; Engelhard, Mark H; Zhang, Hanguang; He, Yanghua; Shao, Yuyan; Su, Dong; More, Karren L; Spendelow, Jacob S; Wu, Gang

2018-03-01

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mössbauer spectroscopy and the structure of interfaces on the atomic scale in metallic nanosystems

NASA Astrophysics Data System (ADS)

Uzdin, V. M.

2007-10-01

A microscopic model of the formation of an alloy on the interface has been constructed, which takes into account the exchange of atoms with the substrate atoms and the “floating up” of the latter into the upper layers in the process of epitaxial growth. The self-consistent calculations of atomic magnetic moments of spatially inhomogeneous structures obtained in this case are used for the interpretation of data of Mössbauer spectroscopy. The proposed scenario of mixing leads to the appearance of a preferred direction in the sample and the asymmetry of interfaces in the direction of epitaxial growth. In the multilayer M 1/ M 2 ( M 1,2 = Fe, Cr, V, Sn, or Ag) systems, this asymmetry makes it possible to understand the difference in the magnetic behavior of M 1-on M 2 and M 2-on- M 1 interfaces which has been observed experimentally. The correlation between the calculated distributions of magnetic moments and the measured distributions of hyperfine fields at iron atoms confirms the assumption about their proportionality for a broad class of metallic multilayer systems. However, a linear decrease of hyperfine fields at the 57Fe nuclei with increasing number of impurity atoms among the nearest and next-nearest neighbors is not confirmed for Fe/Cr systems, although is correct in Fe/V superlattices. In the Fe/Cr multilayer systems, the experimentally measured value of magnetoresistance grows with increasing fraction of the “floated up” atoms of 57Fe. Thus, it is the bulk scattering by impurity atoms that gives the basic contribution to the effect of giant magnetoresistance. The problem of the influence of mixing and adsorption of hydrogen in the vanadium layers on the state of the spin-density wave in V/Cr superlattices has been considered.

The hybrid lattice of K(x)Fe(2-y)Se2: where superconductivity and magnetism coexist.

PubMed

Louca, Despina; Park, Keeseong; Li, Bing; Neuefeind, Joerg; Yan, Jiaqiang

2013-01-01

Much remains unknown of the microscopic origin of superconductivity in atomically disordered systems of amorphous alloys or in crystals riddled with defects. A manifestation of this conundrum is envisaged in the highly defective superconductor of K(x)Fe(2-y)Se2. How can superconductivity survive under such crude conditions that call for strong electron localization? Here, we show that the Fe sublattice is locally distorted and accommodates two kinds of Fe valence environments giving rise to a bimodal bond-distribution, with short and long Fe bonds. The bimodal bonds are present even as the system becomes superconducting in the presence of antiferromagnetism, with the weight continuously shifting from the short to the long with increasing K content. Such a hybrid state is most likely found in cuprates as well while our results point to the importance of the local atomic symmetry by which exchange interactions between local moments materialize.

Ferromagnetic properties of manganese doped iron silicide

NASA Astrophysics Data System (ADS)

Ruiz-Reyes, Angel; Fonseca, Luis F.; Sabirianov, Renat

We report the synthesis of high quality Iron silicide (FeSi) nanowires via Chemical Vapor Deposition (CVD). The materials exhibits excellent magnetic response at room temperature, especially when doped with manganese showing values of 2.0 X 10-04 emu for the FexMnySi nanowires. SEM and TEM characterization indicates that the synthesized nanowires have a diameter of approximately 80nm. MFM measurements present a clear description of the magnetic domains when the nanowires are doped with manganese. Electron Diffraction and XRD measurements confirms that the nanowires are single crystal forming a simple cubic structure with space group P213. First-principle calculations were performed on (111) FeSi surface using the Vienna ab initio simulation package (VASP). The exchange correlations were treated under the Ceperley-Alder (CA) local density approximation (LDA). The Brillouin Zone was sampled with 8x8x1 k-point grid. A total magnetic moment of about 10 μB was obtained for three different surface configuration in which the Iron atom nearest to the surface present the higher magnetization. To study the effect of Mn doping, Fe atom was replaced for a Mn. Stronger magnetization is presented when the Mn atom is close to the surface. The exchange coupling constant have been evaluated calculating the energy difference between the ferromagnetic and anti-ferromagnetic configurations.

Microstructures, magnetic properties and coercivity mechanisms of Nd-Ce-Fe-B based alloys by Zr substitution

NASA Astrophysics Data System (ADS)

Wang, Lei; Quan, Qichen; Zhang, Lili; Hu, Xianjun; Ur Rehman, Sajjad; Jiang, Qingzheng; Du, Junfeng; Zhong, Zhenchen

2018-03-01

In this paper, the effects of Zr addition on microstructures, magnetic properties, exchange coupling, and coercivity mechanisms of Nd-Ce-Fe-B alloys fabricated by melt-spinning technique are investigated. It is found that the coercivity Hcj is enhanced significantly by Zr substitution in the (Nd0.8Ce0.2)13Fe82-xZrxB5 alloys, while the remanence Jr is reduced slightly. The Hcj increases from 12.2 to 13.7 kOe by adding Zr up to 1.5 at. %, whereas Hcj is decreased with a further increase in Zr content. The larger lattice constants and unit cell volumes of the matrix phase indicate that Zr atoms enter into the hard magnetic phase by substituting Fe sites. The reduction of Tc implies the attenuation of the exchange interaction in the 2:14:1 phase with Zr occupying the Fe sites. The weakened intergranular exchange coupling of the Zr added alloy may be attributed to the formation of a non-magnetic intergranular phase. It is worth noting that the coercivity is dominated by the pinning of domain walls at defect positions even though the nucleation of reversal domains still exists. The synergistic function between the pinning effect and the exchange coupling leads to improved magnetic properties.

Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

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

Kaur, Maninder; Qiang, You, E-mail: youqiang@uidaho.edu; Dai, Qilin

2013-11-11

Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr{sub 2}O{sub 3} and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (∼25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of σ-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs.

Observation and elimination of broken symmetry in L1{sub 0} FePt nanostructures

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

Quarterman, P.; Wang, Hao; Qiu, Jiao-Ming

2015-12-07

An unexplained surface anisotropy effect was observed and confirmed in the magnetization reversal process of both L1{sub 0} phase FePt nanoparticles with octahedral shape and (001) textured L1{sub 0} FePt thin films with island nanostructures. We suggest that the nature of the observed surface effect is caused by broken symmetry on the FePt surface, which results in weakened exchange coupling for surface atoms. Furthermore, we propose, and experimentally demonstrate, a method to repair the broken symmetry by capping the FePt islands with a Pt layer, which could prove invaluable in understanding fundamental limitations of magnetic nanostructures.

Effects of Co doping on the metamagnetic states of the ferromagnetic fcc Fe-Co alloy.

PubMed

Ortiz-Chi, Filiberto; Aguayo, Aarón; de Coss, Romeo

2013-01-16

The evolution of the metamagnetic states in the ferromagnetic face centered cubic (fcc) Fe(1-x)Co(x) alloy as a function of Co concentration has been studied by means of first-principles calculations. The ground state properties were obtained using the full-potential linear augmented plane wave method and the generalized gradient approximation for the exchange-correlation functional. The alloying was modeled using the virtual crystal approximation and the magnetic states were obtained from the calculations of the total energy as a function of the spin moment, using the fixed spin moment method. For ferromagnetic fcc Fe, the binding-energy curve shows metamagnetic behavior, with two minima corresponding to a small-volume, low-spin (LS) state and a large-volume, high-spin (HS) state, which are separated by a small energy (E(LS) ≲ E(HS)). The evolution of the magnetic moment, the exchange integral (J), and the binding-energy curve is analyzed in the whole range of Co concentrations (x). The magnetic moment corresponding to the HS state decreases monotonically from 2.6 μ(B)/atom in fcc Fe to 1.7 μ(B)/atom in fcc Co. In contrast, the exchange integral for the HS state shows a maximum at around x = 0.45. The thermal dependence of the lattice parameter is evaluated with a method based on statistical mechanics using the binding-energy curve as an effective potential. It is observed that the behavior of the lattice parameter with temperature is tuned by Co doping, from negative thermal expansion in fcc Fe to positive thermal expansion in fcc Co, through the modification of the energetics of the metamagnetic states.

Tuning the Curie temperature of L 1 0 ordered FePt thin films through site-specific substitution of Rh

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

Xu, Dongbin; Sun, Cheng-Jun; Chen, Jing-Sheng

2014-10-14

In structurally ordered magnetic thin films, the Curie temperature (TC) of ferromagnetic films depends on the exchange integral of the short range ordered neighboring atoms. The exchange integral may be adjusted by controlling elemental substitutional concentration at the lattice site of interest. We show how to control the TC in high anisotropy L10 Fe50Pt50 magnetic thin films by substituting Rh into the Pt site. Rh substitution in L10 FePt modified the local atomic environment and corresponding electronic properties while retaining the ordered L10 phase. The analysis of extended x-ray Absorption Fine Structure (EXAFS) spectra shows that Rh uniformly substitutes formore » Pt in L10 FePt. With 15 at. % of Rh substitution, temperature-dependent magnetic measurements show that the saturation magnetization (Ms) decreases from 1152 emu/cc to 670 emu/cc, the magnetocrystalline anisotropy (Ku) drops from 5×107 erg/cc to 2×107 erg/cc, and TC decreased from 750 to 500 K. A model of antiferromagnetic (AFM) defects caused by controlled Rh substitution of the Pt site, reducing the TC, is proposed to interpret this phenomenon and the validity is further examined by ab initio density functional calculations.« less

Atomic alignment effect in the dissociative energy transfer reaction of metal carbonyls (Fe(CO)5, Ni(CO)4) with oriented Ar (3P2, M(J) = 2).

PubMed

Ohoyama, H; Matsuura, Y

2011-10-13

The atomic alignment effect has been studied for the dissociative energy transfer reaction of metal carbonyls (Fe(CO)(5), Ni(CO)(4)) with the oriented Ar ((3)P(2), M(J) = 2). The emission intensity from the excited metal products (Fe*, Ni*) has been measured as a function of the atomic alignment in the collision frame. The selectivity of the atomic orbital alignment of Ar ((3)P(2), M(J) = 2) (rank 2 moment, a(2)) is found to be opposite for the two reaction systems; the Fe(CO)(5) reaction is favorable at the Π configuration (positive a(2)), while the Ni(CO)(4) reaction is favorable at the Σ configuration (negative a(2)). Moreover, a significant spin alignment effect (rank 4 moment, a(4)) is recognized only in the Ni(CO)(4) reaction. The atomic alignment effect turns out to be essentially different between the two reaction systems; the Fe(CO)(5) reaction is controlled by the configuration of the half-filled 3p atomic orbital of Ar ((3)P(2)) in the collision frame (L dependence), whereas the Ni(CO)(4) reaction is controlled by the configuration of the total angular moment J (including spin) of Ar ((3)P(2)) in the collision frame (J dependence). As the origin of J dependence observed only in the Ni(CO)(4) reaction, the correlation (and/or the interference) between two electron exchange processes via the electron rearrangements is proposed.

The hybrid lattice of KxFe2−ySe2: where superconductivity and magnetism coexist

PubMed Central

Louca, Despina; Park, Keeseong; Li, Bing; Neuefeind, Joerg; Yan, Jiaqiang

2013-01-01

Much remains unknown of the microscopic origin of superconductivity in atomically disordered systems of amorphous alloys or in crystals riddled with defects. A manifestation of this conundrum is envisaged in the highly defective superconductor of KxFe2−ySe2. How can superconductivity survive under such crude conditions that call for strong electron localization? Here, we show that the Fe sublattice is locally distorted and accommodates two kinds of Fe valence environments giving rise to a bimodal bond-distribution, with short and long Fe bonds. The bimodal bonds are present even as the system becomes superconducting in the presence of antiferromagnetism, with the weight continuously shifting from the short to the long with increasing K content. Such a hybrid state is most likely found in cuprates as well while our results point to the importance of the local atomic symmetry by which exchange interactions between local moments materialize. PMID:23782976

The hybrid lattice of K xFe 2-ySe 2: where superconductivity and magnetism coexist

DOE PAGES

Yang, Junjie; Duan, Chunruo; Huang, Qing; ...

2013-01-01

Much remains unknown of the microscopic origin of superconductivity in atomically disordered systems of amorphous alloys or in crystals riddled with defects. A manifestation of this conundrum is envisaged in the highly defective superconductor of K xFe 2-ySe 2. How can superconductivity survive under such crude conditions that call for strong electron localization? Here, we show that the Fe sublattice is locally distorted and accommodates two kinds of Fe valence environments giving rise to a bimodal bond-distribution, with short and long Fe bonds. The bimodal bonds are present even as the system becomes superconducting in the presence of antiferromagnetism, withmore » the weight continuously shifting from the short to the long with increasing K content. Such a hybrid state is most likely found in cuprates as well while our results point to the importance of the local atomic symmetry by which exchange interactions between local moments materialize.« less

Crystal structure, phase transition and structural deformations in iron borate (Y0.95Bi0.05)Fe3(BO3)4 in the temperature range 90-500 K.

PubMed

Smirnova, Ekaterina S; Alekseeva, Olga A; Dudka, Alexander P; Artemov, Vladimir V; Zubavichus, Yan V; Gudim, Irina A; Bezmaterhykh, Leonard N; Frolov, Kirill V; Lyubutin, Igor S

2018-04-01

An accurate X-ray diffraction study of (Y 0.95 Bi 0.05 )Fe 3 (BO 3 ) 4 single crystals in the temperature range 90-500 K was performed on a laboratory diffractometer and used synchrotron radiation. It was established that the crystal undergoes a diffuse structural phase transition in the temperature range 350-380 K. The complexity of localization of such a transition over temperature was overcome by means of special analysis of systematic extinction reflections by symmetry. The transition temperature can be considered to be T str ≃ 370 K. The crystal has a trigonal structure in the space group P3 1 21 at temperatures of 90-370 K, and it has a trigonal structure in the space group R32 at 375-500 K. There is one type of chain formed by the FeO 6 octahedra along the c axis in the R32 phase. When going into the P3 1 21 phase, two types of nonequivalent chains arise, in which Fe atoms are separated from the Y atoms by a different distance. Upon lowering the temperature from 500 to 90 K, a distortion of the Y(Bi)O 6 , FeO 6 , B(2,3)O 3 coordination polyhedra is observed. The distances between atoms in helical Fe chains and Fe-O-Fe angles change non-uniformly. A sharp jump in the equivalent isotropic displacement parameters of O1 and O2 atoms within the Fe-Fe chains and fluctuations of the equivalent isotropic displacement parameters of B2 and B3 atoms were observed in the region of structural transition as well as noticeable elongation of O1, O2, B2, B3, Fe1, Fe2 atomic displacement ellipsoids. It was established that the helices of electron density formed by Fe, O1 and O2 atoms may be structural elements determining chirality, optical activity and multiferroicity of rare-earth iron borates. Compression and stretching of these helices account for the symmetry change and for the manifestation of a number of properties, whose geometry is controlled by an indirect exchange interaction between iron cations that compete with the thermal motion of atoms in the structure. Structural analysis detected these changes as variations of a number of structural characteristics in the c unit-cell direction, that is, the direction of the helices. Structural results for the local surrounding of the atoms in (Y 0.95 Bi 0.05 )Fe 3 (BO 3 ) 4 were confirmed by EXAFS and Mössbauer spectroscopies.

Nanoscale spatial analysis of clay minerals containing cesium by synchrotron radiation photoemission electron microscopy

NASA Astrophysics Data System (ADS)

Yoshigoe, Akitaka; Shiwaku, Hideaki; Kobayashi, Toru; Shimoyama, Iwao; Matsumura, Daiju; Tsuji, Takuya; Nishihata, Yasuo; Kogure, Toshihiro; Ohkochi, Takuo; Yasui, Akira; Yaita, Tsuyoshi

2018-01-01

A synchrotron radiation photoemission electron microscope (SR-PEEM) was applied to demonstrate the pinpoint analysis of micrometer-sized weathered biotite clay particles with artificially adsorbed cesium (Cs) atoms. Despite the insulating properties of the clay, we observed the spatial distributions of constituent elements (Si, Al, Cs, Mg, and Fe) without charging issues and clarified reciprocal site-correlations among these elements with nanometer resolution. We found that Cs atoms were likely to be adsorbed evenly over the entire particle; however, we identified an occupational conflict between Cs and Mg atoms, implying that Cs sorption involves ion exchange processes. Spatially resolved X-ray absorption spectra (XAS) of the Cs4,5 M-edge region showed Cs to be present in a monocation state (Cs+) as typically observed for Cs compounds. Further pinpoint XAS measurements were also performed at the Fe L2,3-edge to determine the chemical valence of the Fe atoms. The shapes of the spectra were similar to those for Fe2O3, indicating that Fe in the clay was in a 3+ oxidation state. From these observations, we infer that charge compensation facilitates Cs adsorption in the vicinity of a substitution site where Si4+ ions are replaced by Fe3+ ions in SiO4 tetrahedral sheets. Our results demonstrate the utility of SR-PEEM as a tool for spatially resolved chemical analyses of various environmental substances, which is not limited by the poor conductivity of samples.

Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes

NASA Astrophysics Data System (ADS)

Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna

2017-04-01

Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

Defect formation energy and magnetic structure of shape memory alloys Ni-X-Ga (X=Mn, Fe, Co) by first principle calculation

NASA Astrophysics Data System (ADS)

Bai, J.; Raulot, J. M.; Zhang, Y. D.; Esling, C.; Zhao, X.; Zuo, L.

2010-09-01

The crystallographic and magnetic structures of the Ni2XGa (X=Mn, Fe, Co), are systematically investigated by means of the first-principles calculations within the framework of density functional theory using the VIENNA AB INITIO SOFTWARE PACKAGE. The formation energies of several kinds of defects (atomic exchange, antisite, vacancy) are estimated. The Ga atoms stabilize the cubic structure, and the effect of X atoms on the structural stability is opposite. For most cases of the site occupation, the excess atoms of the rich component directly occupy the site(s) of the deficient one(s), except for Ga-rich Ni-deficient type. The magnitude of the variation in Ni moments is much larger than that of Mn in defective Ni2XGa. The value of Ni magnetic moment sensitively depends on the distance between Ni and X. Excess Mn could be ferromagnetic or antiferromagnetic, depending on the distance between the neighboring Mn atoms.

Electronic properties of excess Cr at Fe site in FeCr{sub 0.02}Se alloy

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

Kumar, Sandeep, E-mail: sandeepk.iitb@gmail.com; Singh, Prabhakar P.

2015-06-24

We have studied the effect of substitution of transition-metal chromium (Cr) in excess on Fe sub-lattice in the electronic structure of iron-selenide alloys, FeCr{sub 0.02}Se. In our calculations, we used Korringa-Kohn-Rostoker coherent potential approximation method in the atomic sphere approximation (KKR-ASA-CPA). We obtained different band structure of this alloy with respect to the parent FeSe and this may be reason of changing their superconducting properties. We did unpolarized calculations for FeCr{sub 0.02}Se alloy in terms of density of states (DOS) and Fermi surfaces. The local density approximation (LDA) is used in terms of exchange correlation potential.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles ismore » tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). We report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunablemore » through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. In using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe 3+ to Fe 2+) likely bonded with pyridinic N (FeN 4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H 2SO 4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg Pt/cm 2). Finally, enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O 2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

DOE PAGES

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; ...

2017-09-13

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). We report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunablemore » through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. In using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe 3+ to Fe 2+) likely bonded with pyridinic N (FeN 4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H 2SO 4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg Pt/cm 2). Finally, enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O 2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Coercivity degradation caused by inhomogeneous grain boundaries in sintered Nd-Fe-B permanent magnets

NASA Astrophysics Data System (ADS)

Chen, Hansheng; Yun, Fan; Qu, Jiangtao; Li, Yingfei; Cheng, Zhenxiang; Fang, Ruhao; Ye, Zhixiao; Ringer, Simon P.; Zheng, Rongkun

2018-05-01

Quantitative correlation between intrinsic coercivity and grain boundaries in three dimensions is critical to further improve the performance of sintered Nd-Fe-B permanent magnets. Here, we quantitatively reveal the local composition variation across and especially along grain boundaries using the powerful atomic-scale analysis technique known as atom probe tomography. We also estimate the saturation magnetization, magnetocrystalline anisotropy constant, and exchange stiffness of the grain boundaries on the basis of the experimentally determined structure and composition. Finally, using micromagnetic simulations, we quantify the intrinsic coercivity degradation caused by inhomogeneous grain boundaries. This approach can be applied to other magnetic materials for the analysis and optimization of magnetic properties.

Growth, Structural, Electronic, and Magnetic Characterization of GaN, CrN, Fe Islands on CrN, and Fe/CrN Bilayer Thin Films

NASA Astrophysics Data System (ADS)

Alam, Khan

As a part of my Ph.D research, initially I was involved in construction and calibration of an ultra-high vacuum thin film facility, and later on I studied structural, electronic, and magnetic properties of GaN, CrN, Fe/CrN bilayers, and Fe islands on CrN thin films. All of these films were grown by molecular beam epitaxy and characterized with a variety of state-of-the-art techniques including variable temperature reflection high energy electron diffraction, low temperature scanning tunneling microscopy and spectroscopy, variable temperature vibrating sample magnetometry, variable temperature neutron diffraction and reflectometry, variable temperature x-ray diffraction, x-ray reflectometry, Rutherford backscattering, Auger electron spectroscopy, and cross-sectional tunneling electron microscopy. The experimental results are furthermore understood by comparing with numerical calculations using generalized gradient approximation, local density approximation with Hubbard correction, Refl1D, and data analysis and visual environment program. In my first research project, I studied Ga gas adatoms on GaN surfaces. We discovered frozen-out gallium gas adatoms on atomically smooth c(6x12) GaN(0001¯) surface using low temperature scanning tunneling microscopy. We identified adsorption sites of the Ga adatoms on c(6x12) reconstructed surface. Their bonding is determined by measuring low unoccupied molecular orbital level. Absorption sites of the Ga gas adatoms on centered 6x12 are identified, and their asymmetric absorption on the chiral domains is investigated. In second project, I investigated magneto-structural phase transition in chromium nitride (CrN) thin films. The CrN thin films are grown by molecular beam epitaxy. Structural and magnetic transition are studied using variable temperature reflection high energy electron diffraction and variable temperature neutron diffraction. We observed a structural phase transition at the surface at 277+/-2 K, and a sharp, first-order magnetic phase transition from paramagnetic (room temperature) to antiferromagnetic (low temperature) at 280+/-3 K. Our experiments suggest that the structural transition in CrN thin films occur in out-of-plane direction, and epitaxial constraints suppress the in-plane transition; therefore, the low temperature crystal structure of CrN is tetragonal. This new model explains our structural and magnetic data at low temperatures, but it is different than the previously published orthorhombic model. In third project, I studied exchange bias and exchange spring effect in MBE grown Fe/CrN bilayer thin films. We grew Fe/CrN bilayer thin films on MgO(001) substrate by molecular beam epitaxy, and studied them using variable temperature vibrating sample magnetometry, polarized neutron reflectometry, x-ray reflectivity, and cross-sectional transmission electron microscopy. We observed exchange bias and exchange spring effect in all bilayer thin films. We studied the relationship of exchange bias, blocking temperature, and coercivity with Fe and CrN layers thicknesses. We used polarized neutron beam reflectometry to see if spins at Fe/CrN interface are pinned. We found a thin ferromagnetically ordered CrN layer at the interface. In my final project, I studied growth of submonolayer Fe islands on CrN thin films. These films are prepared in two stages: first, a CrN layer is grown by MBE and then a submonolayer Fe is deposited at room temperature from a carefully degassed e-beam evaporator. The films are studied at liquid helium temperature using low temperature scanning tunneling microscopy and spectroscopy. Islands are seen in STM images, after the Fe deposition, at the edges as well as at the center of atomically flat CrN terraces. However, numerical calculations performed by our collaborator Ponce-P'erez from Benem'erita Universidad Aut'onoma de Puebla show that the Fe islands are energetically unstable on the surface. The Fe atoms substitute Cr atoms in the surface layer and the Cr atoms comes out and form islands. In order to find out elemental composition of the islands, we attempted to map local density of state by measuring differential conductance spectra as a function of bias voltage using LT-STS. We observed three characteristically different spectra; one in the CrN substrate and two in the islands. The CrN substrate curve has a "U" shape near Fermi level and a peak at ≈ 105 mV. The islands spectra show Kondo-like resonances at Fermi level; some islands produce a peak whereas others produce a dip the dI/dV curves near Fermi level. Further investigations are needed to determine the origin of the peak and dip in the island curves, as well as to find the composition of the islands.

Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

PubMed

Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

2018-06-26

It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

NASA Astrophysics Data System (ADS)

Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

2016-06-01

High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

The H(2) sensor of Ralstonia eutropha: biochemical and spectroscopic analysis of mutant proteins modified at a conserved glutamine residue close to the [NiFe] active site.

PubMed

Buhrke, Thorsten; Brecht, Marc; Lubitz, Wolfgang; Friedrich, Bärbel

2002-09-01

[NiFe] hydrogenases contain a highly conserved histidine residue close to the [NiFe] active site which is altered by a glutamine residue in the H(2)-sensing [NiFe] hydrogenases. In this study, we exchanged the respective glutamine residue of the H(2) sensor (RH) of Ralstonia eutropha, Q67 of the RH large subunit HoxC, by histidine, asparagine and glutamate. The replacement by histidine and asparagine resulted in slightly unstable RH proteins which were hardly affected in their regulatory and enzymatic properties. The exchange to glutamate led to a completely unstable RH protein. The purified wild-type RH and the mutant protein with the Gln/His exchange were analysed by continuous-wave and pulsed electron paramagnetic resonance (EPR) techniques. We observed a coupling of a nitrogen nucleus with the [NiFe] active site for the mutant protein which was absent in the spectrum of the wild-type RH. A combination of theoretical calculations with the experimental data provided an explanation for the observed coupling. It is shown that the coupling is due to the formation of a weak hydrogen bond between the protonated N(epsilon) nucleus of the histidine with the sulfur of a conserved cysteine residue which coordinates the metal atoms of the [NiFe] active site as a bridging ligand. The effect of this hydrogen bond on the local structure of the [NiFe] active site is discussed.

Exchange interactions and magnetocaloric effects of the Heusler alloys Ni-Mn-In-R (R = Fe, Co)

NASA Astrophysics Data System (ADS)

Li, Yan-Ru; Su, Hui-Ling; Sun, Ji-Bing; Li, Ying

2018-05-01

The magnetic interactions and magnetocaloric effects in Ni2Mn1.4In0.6‑xRx (x = 0-0.2) (R = Fe, Co) Heusler alloys are investigated by the first-principles and Monte Carlo method. The ab initio calculations provide a basic understanding of the competition of ferromagnetic and antiferromagnetic interactions due to the chemical disorder of the alloy compositions. The thermodynamic properties including magnetization, specific heat and magnetic entropy change are calculated by the finite-temperature Monte Carlo simulations using the exchange couplings and magnetic moments from ab initio calculation as input parameters. The results show that the Fe or Co doping in Ni2Mn1.4In0.6 leads to an increase of magnetic moment and magnetic entropy change but a decrease of magnetic transition temperature with the increase in the Fe or Co contents. This indicates that the transition temperature and magnetocaloric properties of Ni2Mn1.4In0.6 alloy can be tuned by substituting In atom by Fe or Co with different contents.

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Povitsky, Alexander; Dateo, Christopher; Gokcen, Tahir; Willis, Peter A.; Smalley, Richard E.

2003-01-01

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor.

PubMed

Scott, Carl D; Povitsky, Alexander; Dateo, Christopher; Gökçen, Tahir; Willis, Peter A; Smalley, Richard E

2003-01-01

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Surface structure of MgO underlayer with Ti diffusion for (002) oriented L10 FePt-based heat assisted magnetic recording media

NASA Astrophysics Data System (ADS)

Hinata, Sintaro; Jo, Shin; Saito, Shin

2018-05-01

Surface morphology of the MgO layer and magnetic properties of FePt-C layer deposited on the MgO were investigated for the FePt-based heat assisted magnetic recording media. Stacking structure of the underlayer for the FePt-C layer was MgO (0-5 nm)/Cr80Mn20 (0-30 nm)/Cr50Ti50 (0-50 nm)/glass sub.. Surface observation result for the MgO film by using an atomic force microscope revealed the existence of nodules with a height of about 2 nm and a network-like convex structure with a height difference of about sub nm (boundary wall, BW) on the MgO crystal grain boundary. Density of the nodules largely depends on the surface roughness of the CrTi layer, RaCrTi and it is suppressed from 10 to 2/0.5 μm2 by reducing RaCrTi from 420 to 260 pm. Height of the BW depends on thickness of the MgO layer, tMgO and it can be suppressed by reducing tMgO to less than 4 nm. From the cross-sectional energy dispersive x-ray mapping, it is clarified that the BW is formed by atomic diffusion of Ti atoms from CrTi layer due to the substrate heating process, and a compound consists of Mg, Ti and O atoms. This BW can be used as a template to magnetically isolate the FePt column in the FePt-based granular film, such as FePt-SiO2, if the size of the BW is reduced to less than 10 nm. M-H loop of the FePt-C granular film deposited on the underlayer showed that the nodule and BW induce oxidation of the FePt grains, and reduction of intergranular exchange coupling.

Bayes-Turchin analysis of x-ray absorption data above the Fe L{sub 2,3}-edges

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

Rossner, H. H.; Schmitz, D.; Imperia, P.

2006-10-01

Extended x-ray absorption fine structure (EXAFS) data and magnetic EXAFS (MEXAFS) data were measured at two temperatures (180 and 296 K) in the energy region of the overlapping L-edges of bcc Fe grown on a V(110) crystal surface. In combination with a Bayes-Turchin data analysis procedure these measurements enable the exploration of local crystallographic and magnetic structures. The analysis determined the atomic-like background together with the EXAFS parameters which consisted of ten shell radii, the Debye-Waller parameters, separated into structural and vibrational components, and the third cumulant of the first scattering path. The vibrational components for 97 different scattering pathsmore » were determined by a two parameter force-field model using a priori values adjusted to Born-von Karman parameters of inelastic neutron scattering data. The investigations of the system Fe/V(110) demonstrate that the simultaneous fitting of atomic background parameters and EXAFS parameters can be performed reliably. Using the L{sub 2}- and L{sub 3}-components extracted from the EXAFS analysis and the rigid-band model, the MEXAFS oscillations can only be described when the sign of the exchange energy is changed compared to the predictions of the Hedin Lundquist exchange and correlation functional.« less

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

Swanner, E. D.; Bayer, T.; Wu, W.

In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II) aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Fe ppt), with distinct isotopic fractionation (ε 56Fe) values determined from fitting the δ 56Fe(II) aq (1.79‰ and 2.15‰) and the δ 56Fe ppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II)more » and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ 56Fe compositions than Fe(II) aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II) aq using published fractionation factors, is consistent with our resulting δ 56FeNaAc. The δ 56Fe ppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O 2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.« less

Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates.

PubMed

Gu, Cheng; Jia, Hanzhong; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2010-06-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH(4), resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of approximately 5 A. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the X-ray diffraction (XRD) results since the diameter of elemental Fe is 2.5 A. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene/non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnanoscale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, for example, as components of constructed reactive domains such as reactive caps for contaminated sediments.

Synthesis of Highly Reactive Subnano-sized Zero-valent Iron using Smectite Clay Templates

PubMed Central

Gu, Cheng; Jia, Hanzhang; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.

2010-01-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH4, resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of discrete regions of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of ~ 5 Å. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the XRD results since the diameter of elemental Fe is 2.5 Å. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene:non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, e.g. as components of constructed reactive domains such as reactive caps for contaminated sediments. PMID:20446730

Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite

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

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-03-26

Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occursmore » near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.« less

Investigation of electronic and magnetic properties of FeS: First principle and Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Bouachraoui, Rachid; El Hachimi, Abdel Ghafour; Ziat, Younes; Bahmad, Lahoucine; Tahiri, Najim

2018-06-01

Electronic and magnetic properties of hexagonal Iron (II) Sulfide (hexagonal FeS) have been investigated by combining the Density functional theory (DFT) and Monte Carlo simulations (MCS). This compound is constituted by magnetic hexagonal lattice occupied by Fe2+ with spin state (S = 2). Based on ab initio method, we calculated the exchange coupling JFe-Fe between two magnetic atoms Fe-Fe in different directions. Also phase transitions, magnetic stability and magnetizations have been investigated in the framework of Monte Carlo simulations. Within this method, a second phase transition is observed at the Néel temperature TN = 450 K. This finding in good agreement with the reported data in the literature. The effect of the applied different parameters showed how can these parameters affect the critical temperature of this system. Moreover, we studied the density of states and found that the hexagonal FeS will be a promoting material for spintronic applications.

The fabrication of ordered arrays of exchange biased Ni/FeF2 nanostructures.

PubMed

Kovylina, M; Erekhinsky, M; Morales, R; Schuller, I K; Labarta, A; Batlle, X

2010-04-30

The fabrication of ordered arrays of exchange biased Ni/FeF(2) nanostructures by focused ion beam lithography is reported. High quality nano-elements, with controlled removal depth and no significant re-deposition, were carved using small ion beam currents (30 pA), moderate dwell times (1 micros) and repeated passages over the same area. Two types of nanostructures were fabricated: square arrays of circular dots with diameters from 125 +/- 8 to 500 +/- 12 nm and periodicities ranging from 200 +/- 8 to 1000 +/- 12 nm, and square arrays of square antidots (207 +/- 8 nm in edge length) with periodicities ranging from 300 +/- 8 to 1200 +/- 12 nm. The arrays were characterized using scanning ion and electron microscopy, and atomic force microscopy. The effect of the patterning on the exchange bias field (i.e., the shift in the hysteresis loop of ferromagnetic Ni due to proximity to antiferromagnetic FeF(2)) was studied using magneto-transport measurements. These high quality nanostructures offer a unique method to address some of the open questions regarding the microscopic origin of exchange bias. This is not only of major relevance in the fabrication and miniaturization of magnetic devices but it is also one of the important proximity phenomena in nanoscience and materials science.

Oscillations in exchange coupling across a nonmagnetic metallic layer

NASA Astrophysics Data System (ADS)

Edwards, D. M.; Mathon, J.

1991-02-01

The exchange coupling between two strong itinerant ferromagnets separated by N atomic planes of a nonmagnetic metal is calculated using a Hubbard-type model. It is shown that for certain positions of the Fermi level the variation of the exchange coupling with N exhibits oscillations of long period. The amplitude of the oscillations falls of as 1/ N2 and agrees in order of magnitude with the exchange coupling observed by Parkin et al. in Co/Ru and Fe/Cr multilayers. Further agreement is the finding that antiparallel alignment of the ferromagnetic layers is favoured for small N. The relationship between the coupling found here and one of RKKY type is discussed.

Tunable magnetic properties by interfacial manipulation of L1(0)-FePt perpendicular ultrathin film with island-like structures.

PubMed

Feng, C; Wang, S G; Yang, M Y; Zhang, E; Zhan, Q; Jiang, Y; Li, B H; Yu, G H

2012-02-01

Based on interfacial manipulation of the MgO single crystal substrate and non-magnetic AIN compound, a L1(0)-FePt perpendicular ultrathin film with the structure of MgO/FePt-AIN/Ta was designed, prepared, and investigated. The film is comprised of L1(0)-FePt "magnetic islands," which exhibits a perpendicular magnetic anisotropy (PMA), tunable coercivity (Hc), and interparticle exchange coupling (IEC). The MgO substrate promotes PMA of the film because of interfacial control of the FePt lattice orientation. The AIN compound is doped to increase the difference of surface energy between FePt layer and MgO substrate and to suppress the growth of FePt grains, which takes control of island growth mode of FePt atoms. The AIN compound also acts as isolator of L1(0)-FePt islands to pin the sites of FePt domains, resulting in the tunability of Hc and IEC of the films.

First-principles study of electronic properties of Si doped FeSe{sub 0.9} alloys

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

Kumar, Sandeep, E-mail: sandeep@phy.iitb.ac.in; Singh, Prabhakar P.

2016-05-23

We have performed first-principles study of electronic and superconducting properties of FeSe{sub 0.9-x}Si{sub x} (x = 0.0, 0.05) alloys using Korringa-Kohn-Rostoker Atomic Sphere Approximation within the coherent potential approximation (KKR-ASA-CPA). In our calculations, we used the local density approximation (LDA) for the exchange correlation potential. Our calculations show that these alloys are nonmagnetic in nature. We found that the substitution of Si at Se site into FeSe{sub 0.9} made subtle affects in the electronic structure with respect to the parent FeSe. The results have been analyzed in terms of changes in the density of states (DOS), band structures, Fermi surfacesmore » and the superconducting transition temperature of FeSe{sub 0.9} and FeSe{sub 0.85}Si{sub 0.05} alloys.« less

Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

PubMed

Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

2016-06-20

Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

Modelling the cis-oxo-labile binding site motif of non-heme iron oxygenases. Water exchange and remarkable oxidation reactivity of a novel non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand

PubMed Central

Company, Anna; Prat, Irene; Frisch, Jonathan R.; Ballesté, Ruben Mas; Güell, Mireia; Juhász, Gergely; Ribas, Xavi; Münck, Eckard; Luis, Josep M.; Que, Lawrence

2011-01-01

The spectroscopic and chemical characterization of a new synthetic non-heme iron(IV)-oxo species [FeIV(O)(Me,HPytacn)(S)]2+ (2, Me,HPytacn = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, S = CH3CN or H2O) is described. 2 has been prepared by reaction of [FeII(CF3SO3)2(Me,HPytacn)] (1) with peracetic acid. Complex 2 bears a tetradentate N4 ligand that leaves two cis- sites available for binding an oxo group and a second external ligand but, unlike related iron(IV)-oxo of tetradentate ligands, it is remarkably stable at room temperature (t1/2 > 2h at 288 K). Its ability to exchange the oxygen atom of the oxo ligand with water has been analyzed in detail by means of kinetic studies, and a mechanism has been proposed on the basis of DFT calculations. Hydrogen-atom abstraction from C-H bonds and oxygen atom transfer to sulfides by 2 have also been studied. Despite its thermal stability, 2 proves to be a very powerful oxidant that is capable of breaking the strong C-H bond of cyclohexane (BDE = 99.3 kcal·mol−1). PMID:21268165

Magnetic properties of Mg12O12 nanocage doped with transition metal atoms (Mn, Fe, Co and Ni): DFT study

NASA Astrophysics Data System (ADS)

Javan, Masoud Bezi

2015-07-01

Binding energy of the Mg12O12 nanocage doped with transition metals (TM=Mn, Fe, Co and Ni) in endohedrally, exohedrally and substitutionally forms were studied using density functional theory with the generalized gradient approximation exchange-correlation functional along 6 different paths inside and outside of the Mg12O12 nanocage. The most stable structures were determined with full geometry optimization near the minimum of the binding energy curves of all the examined paths inside and outside of the Mg12O12 nanocage. The results reveal that for all stable structures, the Ni atom has a larger binding energy than the other TM atoms. It is also found that for all complexes additional peaks contributed by TM-3d, 4s and 4p states appear in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gap of the host MgO cluster. The mid-gap states are mainly due to the hybridization between TM-3d, 4s and 4p orbitals and the cage π orbitals. The magnetic moment of the endohedrally doped TM atoms in the Mg12O12 are preserved to some extent due to the interaction between the TM and Mg12O12 nanocage, in contrast to the completely quenched magnetic moment of the Fe and Ni atoms in the Mg11(TM)O12 complexes. Furthermore, charge population analysis shows that charge transfer occurs from TM atom to the cage for endohedrally and substitutionally doping.

First-principles study on the ferrimagnetic half-metallic Mn{sub 2}FeAs alloy

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

Qi, Santao; Zhang, Chuan-Hui, E-mail: zhangch@ustb.edu.cn; Chen, Bao

2015-05-15

Mn-based full-Heusler alloys are kinds of promising candidates for new half-metallic materials. Basing on first principles, the electronic structures and magnetic properties of the Mn{sub 2}FeAs full-Heusler alloy have been investigated in detail. The Hg{sub 2}CuTi-type Mn{sub 2}FeAs compound obeys the Slater-Pauling rule, while the anti-parallel alignment atomic magnetic moments of Mn locating at different sites indicate it a ferrimagnetic alloy. The calculated spin-down bands behave half-metallic character, exhibiting a direct gap of 0.46 eV with a 100% spin polarization at the Fermi level. More studies show the compound would maintain half-metallic nature in a large range of variational latticemore » constants. We expect that our calculated results may trigger Mn{sub 2}FeAs applying in the future spintronics field. - Graphical abstract: The d orbitals of Mn and Fe atoms split into multi-degenerated levels which create new bonding and nonbonding states. These exchange splitting shift the Fermi level to origin band gap.▪ - Highlights: • The electronic structure and magnetic properties of Mn{sub 2}FeAs full-Heusler alloy were studied. • A total magnetic moment of 3μ{sub B} was obtained for Mn{sub 2}FeAs alloy, following the SP rule M{sub t}=Z{sub t}−24. • The origin of ferrimagnetism and half-metallic character in Mn{sub 2}FeAs were discussed.« less

Controllable exchange bias in Fe/metamagnetic FeRh bilayers

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

Suzuki, Ippei; Hamasaki, Yosuke; Itoh, Mitsuru

2014-10-27

We report the studies of tuning the exchange bias at ferromagnetic Fe/metamagnetic FeRh bilayer interfaces. Fe/FeRh(111) bilayers show exchange bias in the antiferromagnetic state of FeRh while no exchange bias occurs at Fe/FeRh(001) interface. The contrasting results are attributed to the spin configurations of FeRh at the interface, i.e., the uncompensated ferromagnetic spin configuration of FeRh appears exclusively for (111) orientation. The exchange bias disappears as the bilayers are warmed above the antiferromagnetic-ferromagnetic transition temperature. The direction of the exchange bias for Fe/FeRh(111) is also found to be perpendicular to the cooling-field direction, in contrast to the commonly observed directionmore » of exchange bias for ferromagnetic/antiferromagnetic interfaces. In view of these results, the exchange bias in Fe/FeRh bilayers with the (111) crystallographic orientation should be useful for the design of rapid writing technology for magnetic information devices.« less

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

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

Scherer, Michelle M.; Rosso, Kevin M.

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally,more » structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe 2O 3) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of 57Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects 57Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the Mössbauer spectroscopy and stable isotopes measurements, we have been able to simultaneously track the oxidation state and isotope concentration of the bulk Fe oxide and aqueous Fe. One of our most compelling findings is that despite the apparent stability of the Fe(II)-goethite system, there is actually a tremendous amount of Fe atom cycling occurring between the aqueous phase and the bulk goethite as indicated by the isotopic composition of both phases approaching the mass balance average (Handler et al., 2009). How such extensive re-crystallization and Fe atom exchange can occur with no significant morphological change is a fascinating question. Based on previous work from PI Rosso’s group showing that a potential gradient across hematite crystal faces leads to conduction through hematite and growth and dissolution at separate crystal faces we proposed that a redox-driven recrystallization could be occurring that would explain the extensive mixing observed with the isotope data. From our previous studies utilizing Mössbauer spectroscopy, we know that sorption of Fe(II) onto goethite results in electron transfer between the sorbed Fe(II) and the structural Fe(III) in goethite. Oxidation of the sorbed Fe(II) produces growth of goethite on goethite (i.e., homoepitaxy), as well as injection of an electron into goethite. It is possible that electron transfer from sorbed Fe(II) occurs across a potential gradient, and that Fe(II) atoms are dissolved at a different location on the goethite surface. These newly-reduced Fe(II) atoms could then dissolve into the aqueous phase, exposing fresh Fe(III) goethite to the aqueous phase. Through a repeated series of these five steps of sorption–electron transfer–crystal growth–conduction– dissolution, a redox-driven conveyor belt, could be established that would allow all of the goethite to be eventually exposed to the aqueous phase and exchanged. This surface-mediated recrystallization process would result in similar Fe isotope distributions in the aqueous phase and goethite particle, as we have observed here. It would also result in a stable aqueous Fe(II) concentration, if there were equal rates of goethite growth and dissolution.« less

Role of magnetic exchange interaction due to magnetic anisotropy on inverse spin Hall voltage at FeSi3%/Pt thin film bilayer interface

NASA Astrophysics Data System (ADS)

Shah, Jyoti; Ahmad, Saood; Chaujar, Rishu; Puri, Nitin K.; Negi, P. S.; Kotnala, R. K.

2017-12-01

In our recent studies inverse spin Hall voltage (ISHE) was investigated by ferromagnetic resonance (FMR) using bilayer FeSi3%/Pt thin film prepared by pulsed laser deposition (PLD) technique. In ISHE measurement microwave signal was applied on FeSi3% film along with DC magnetic field. Higher magnetization value along the film-plane was measured by magnetic hysteresis (M-H) loop. Presence of magnetic anisotropy has been obtained by M-H loop which showed easy direction of magnetization when applied magnetic field is parallel to the film plane. The main result of this study is that FMR induced inverse spin Hall voltage 12.6 μV at 1.0 GHz was obtained across Pt layer. Magnetic exchange field at bilayer interface responsible for field torque was measured 6 × 1014 Ω-1 m-2 by spin Hall magnetoresistance. The damping torque and spin Hall angle have been evaluated as 0.084 and 0.071 respectively. Presence of Si atom in FeSi3% inhomogenize the magnetic exchange field among accumulated spins at bilayer interface and feebly influenced by spin torque of FeSi3% layer. Weak field torque suppresses the spin pumping to Pt layer thus low value of inverse spin Hall voltage is obtained. This study provides an excellent opportunity to investigate spin transfer torque effect, thus motivating a more intensive experimental effort for its utilization at maximum potential. The improvement in spin transfer torque may be useful in spin valve, spin battery and spin transistor application.

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework.

PubMed

Berger, Daniel; Logsdail, Andrew J; Oberhofer, Harald; Farrow, Matthew R; Catlow, C Richard A; Sherwood, Paul; Sokol, Alexey A; Blum, Volker; Reuter, Karsten

2014-07-14

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capability by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO2(110).

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework

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

Berger, Daniel, E-mail: daniel.berger@ch.tum.de; Oberhofer, Harald; Reuter, Karsten

2014-07-14

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capabilitymore » by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO{sub 2}(110)« less

ThMn12-type phases for magnets with low rare-earth content: Crystal-field analysis of the full magnetization process.

PubMed

Tereshina, I S; Kostyuchenko, N V; Tereshina-Chitrova, E A; Skourski, Y; Doerr, M; Pelevin, I A; Zvezdin, A K; Paukov, M; Havela, L; Drulis, H

2018-02-26

Rare-earth (R)-iron alloys are a backbone of permanent magnets. Recent increase in price of rare earths has pushed the industry to seek ways to reduce the R-content in the hard magnetic materials. For this reason strong magnets with the ThMn 12  type of structure came into focus. Functional properties of R(Fe,T) 12 (T-element stabilizes the structure) compounds or their interstitially modified derivatives, R(Fe,T) 12 -X (X is an atom of hydrogen or nitrogen) are determined by the crystal-electric-field (CEF) and exchange interaction (EI) parameters. We have calculated the parameters using high-field magnetization data. We choose the ferrimagnetic Tm-containing compounds, which are most sensitive to magnetic field and demonstrate that TmFe 11 Ti-H reaches the ferromagnetic state in the magnetic field of 52 T. Knowledge of exact CEF and EI parameters and their variation in the compounds modified by the interstitial atoms is a cornerstone of the quest for hard magnetic materials with low rare-earth content.

BH-DFTB/DFT calculations for iron clusters

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

Aktürk, Abdurrahman; Sebetci, Ali, E-mail: asebetci@mevlana.edu.tr

2016-05-15

We present a study on the structural, electronic, and magnetic properties of Fe{sub n}(n  =  2  −  20) clusters by performing density functional tight binding (DFTB) calculations within a basin hopping (BH) global optimization search followed by density functional theory (DFT) investigations. The structures, total energies and total spin magnetic moments are calculated and compared with previously reported theoretical and experimental results. Two basis sets SDD with ECP and 6-31G** are employed in the DFT calculations together with BLYP GGA exchange-correlation functional. The results indicate that the offered BH-DFTB/DFT strategy collects all the global minima of which different minima havemore » been reported in the previous studies by different groups. Small Fe clusters have three kinds of packing; icosahedral (Fe{sub 9−13}), centered hexagonal antiprism (Fe{sub 14−17}, Fe{sub 20}), and truncated decahedral (Fe{sub 17(2)}, Fe{sub 18−19}). It is obtained in a qualitative agreement with the time of flight mass spectra that the magic numbers for the small Fe clusters are 7, 13, 15, and 19 and with the collision induced dissociation experiments that the sizes 6, 7, 13, 15, and 19 are thermodynamically more stable than their neighboring sizes. The spin magnetic moment per atom of Fe{sub n}(n = 2 − 20) clusters is between 2.4 and 3.6 μ{sub B} for the most of the sizes. The antiferromagnetic coupling between the central and the surface atoms of the Fe{sub 13} icosahedron, which have already been reported by experimental and theoretical studies, is verified by our calculations as well. The quantitative disagreements between the calculations and measurements of the magnetic moments of the individual sizes are still to be resolved.« less

Exchange-coupling of hard and soft magnetic sublattices and magnetic anomalies in mixed spinel NiFe0.75Cr1.25O4 nanoparticles

NASA Astrophysics Data System (ADS)

Lyubutin, I. S.; Starchikov, S. S.; Baskakov, A. O.; Gervits, N. E.; Lin, Chun-Rong; Tseng, Yaw-Teng; Lee, Wen-Jen; Shih, Kun-Yauh

2018-04-01

A set of single-crystalline nanoparticles (NPs) of nickel-chromium ferrite NiFe0.75Cr1.25O4 with a cubic spinel structure were synthesized and investigated. The NPs size can be varied from about 5 to 50 nm by the final annealing of the precursor at different temperatures. The distribution of cations over the tetrahedral (A) and the octahedral [B] sites (Fe0.75 Ni0.25) [Ni0.75 Cr1.25] O4 was established from the magnetic and Mössbauer measurements. In large NPs, the magnetic structure at low temperatures is close to the collinear antiferromagnetic (AFM) structure of the Neel type; and the total magnetic moment Mtot of the ferrite coincides with the direction of the B-sublattice moment. Several size-dependent magnetic anomalies were revealed. Three types of magnetic ions present in the A- and B- sublattices cause the competition of AFM and FM exchange interactions resulting in the highly frustrated magnetic ordering and the occurrence of canted magnetic structure in the octahedral B-sublattice. The frustrated structure is very flexible and significantly subjected to temperature and applied field. It results in several magnetic anomalies observed, including the occurrence of magnetic compensation, abnormal behavior of ZFC and FC magnetization curves and hysteresis loops. It was shown that magnetic anomalies can be explained in terms of exchange coupling of "soft" and "hard" magnetic B- and A-sublattices. This effect in the (Fe0.75 Ni0.25) [Ni0.75Cr1.25] O4 NPs can be considered as an atomic-scale analog of a similar effect observed in two-phase exchange-coupled alloys developed for permanent magnets and for the perpendicular recoding media.

Cooling field and ion-beam bombardment effects on exchange bias behavior in NiFe/(Ni,Fe)O bilayers.

PubMed

Lin, K W; Wei, M R; Guo, J Y

2009-03-01

The dependence of the cooling field and the ion-beam bombardment on the exchange bias effects in NiFe/(Ni,Fe)O bilayers were investigated. The positive exchange bias was found in the zero-field-cooled (ZFC) process whereas a negative exchange bias occurred in the FC process. The increased exchange field, H(ex) with increasing (Ni,Fe)O thicknesses indicates the thicker the AF (Ni,Fe)O, the stronger the exchange coupling between the NiFe layer and the (Ni,Fe)O layer. In addition, the dependence of the H(ex) (ZFC vs. FC) on the (Ni,Fe)O thicknesses reflects the competition between the applied magnetic field and the (Ni,Fe)O surface layer exchange coupled to the NiFe layer. Further, an unusual oscillating exchange bias was observed in NiFe/(Ni,Fe)O bilayers that results from the surface of the (Ni,Fe)O layer being bombarded with different Ar-ion energies using End-Hall deposition voltages (V(EH)) from 0 to 150 V. The behavior of the H(ex) and the H(c) with the V(EH) is attributed to the surface spin reorientation that is due to moderate ion-beam bombardment effects on the surface of the (Ni,Fe)O layer. Whether the (Ni,Fe)O antiferromagnetic spins are coupled to the NiFe moments antiferromagnetically or ferromagnetically changes the sign of the exchange bias.

Effect of adatom deposition on surface magnetism and exchange coupling parameter in (0001) SmCo{sub 5} slabs

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

Selva Chandrasekaran, S.; Murugan, P., E-mail: murugan@cecri.res.in; Saravanan, P.

2015-04-07

First principles calculations are performed on 3d-transition metal atom deposited (0001) surface of SmCo{sub 5} to understand the magnetic properties and the improvement of Curie temperature (T{sub c}). Various atomic sites are examined to identify the energetically feasible adsorption of adatom and it is found that the void site of Co-rich (0001) SmCo{sub 5} surface is the most favourable one to deposit. The surface magnetic moments of various adatom deposited SmCo{sub 5} surfaces are larger than the clean surface except for Cu and Zn. Eventually, the surface exchange coupling of clean and adatom deposited surface is found to increase formore » Mn, Fe, Co, Ni, and Cu deposited surfaces and this improvement results in the increase in T{sub c} of SmCo{sub 5} slab.« less

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

PubMed

Chen, Ying; Bylaska, Eric J; Weare, John H

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe-OH 2 distances in the DFT calculations it was proposed that the surface Fe 3+ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination. Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe 3+ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe 3+ is coordinated with only 5 neighbors.

Epitaxial Fe{sub 3}Pt/FePt nanocomposites on MgO and SrTiO{sub 3}

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

Casoli, F., E-mail: casoli@imem.cnr.it; Nasi, L.; Cabassi, R.

We have exploited the pseudomorphic growth of the magnetically soft Fe{sub 3}Pt phase on top of L1{sub 0}-FePt to obtain fully epitaxial soft/hard nanocomposites on both MgO(100) and SrTiO{sub 3}(100). The magnetic properties of this new nanocomposite system, driven by the soft/hard exchange-coupling, can be tailored by varying soft phase thickness, soft phase magnetic anisotropy and substrate. Coercivity is strongly reduced by the addition of the soft phase, a reduction which is definitely affected by the nominal composition of the soft phase and by the substrate choice; similarly is the magnetic phase diagram of the composite system. Coercive field decreasesmore » down to 21% of the hard layer value for Fe{sub 3}Pt(5 nm)/FePt(3.55 nm) nanocomposites on SrTiO{sub 3}; this maximum coercivity reduction was obtained with a nominal atomic content of Fe in the soft phase of 80%.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that ismore » determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.« less

[Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: synthesis, crystal structures, and magnetic properties of cyano-bridged Fe(III)-Ni(II) complexes [(bpb)(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate].

PubMed

Ni, Zhong-Hai; Kou, Hui-Zhong; Zhao, Yi-Hua; Zheng, Lei; Wang, Ru-Ji; Cui, Ai-Li; Sato, Osamu

2005-03-21

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.

Hole localization in Fe2O3 from density functional theory and wave-function-based methods

NASA Astrophysics Data System (ADS)

Ansari, Narjes; Ulman, Kanchan; Camellone, Matteo Farnesi; Seriani, Nicola; Gebauer, Ralph; Piccinin, Simone

2017-08-01

Hematite (α -Fe2O3 ) is a promising photocatalyst material for water splitting, where photoinduced holes lead to the oxidation of water and the release of molecular oxygen. In this work, we investigate the properties of holes in hematite using density functional theory (DFT) calculations with hybrid functionals. We find that holes form small polarons and, depending on the fraction of exact exchange included in the PBE0 functional, the site where the holes localize changes from Fe to O. We find this result to be independent of the size and structure of the system: small Fe2O3 clusters with tetrahedral coordination, larger clusters with octahedral coordination, Fe2O3 (001) surfaces in contact with water, and bulk Fe2O3 display a very similar behavior in terms of hole localization as a function of the fraction of exact exchange. We then use wave-function-based methods such as coupled cluster with single and double excitations and Møller-Plesset second-order perturbation theory applied on a cluster model of Fe2O3 to shed light on which of the two solutions is correct. We find that these high-level quantum chemistry methods suggest holes in hematite are localized on oxygen atoms. We also explore the use of the DFT +U approach as a computationally convenient way to overcome the known limitations of generalized gradient approximation functionals and recover a gap in line with experiments and hole localization on oxygen in agreement with quantum chemistry methods.

Double perovskite Sr2FeMoO6-xNx (x=0.3, 1.0) oxynitrides with anionic ordering

NASA Astrophysics Data System (ADS)

Retuerto, M.; de la Calle, C.; Martínez-Lope, M. J.; Porcher, F.; Krezhov, K.; Menéndez, N.; Alonso, J. A.

2012-01-01

Two new oxynitride double perovskites of composition Sr2FeMoO6-xNx (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 °C and 650 °C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Mössbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) Å, c=7.9024(2) Å, V=247.46(2) Å3 for Sr2FeMoO5.7N0.3; and a=5.6202(2) Å, c=7.9102(4) Å, V=249.85(2) Å3 for Sr2FeMoO5N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 °C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the and distances suggests a shift towards a configuration close to Fe4+(3d4, S=2):Mo5+(4d1, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr2FeMoO6, due to the different nature of the magnetic double exchange interactions through Fe-N-Mo-N-Fe paths in contrast to the stronger Fe-O-Mo-O-Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization.

First-principles study of magnetism, lattice dynamics, and superconductivity in LaFeSiHx

NASA Astrophysics Data System (ADS)

Hung, Linda; Yildirim, Taner

2018-06-01

The structural, electronic, magnetic, and vibrational properties of LaFeSiHx for x between 0 and 1 are investigated using density functional theory calculations. We find that the electronic and magnetic properties are strongly controlled by the hydrogen concentration x in LaFeSiHx. While fully hydrogenated LaFeSiH has a striped antiferromagnetic ground state, the underdoped LaFeSiHx for x ≤0.75 is not magnetic within the virtual crystal approximation or with explicit doping of supercells. The antiferromagnetic configuration breaks the symmetry of Fe d orbitals and increases electron-phonon coupling up to 50 % , especially for modes in the 20-50 meV range that are associated with Fe atomic movement. We find competing nearest and next-nearest-neighbor exchange interactions and significant spin-phonon coupling, qualitatively similar but smaller in magnitude compared those found in LaOFeAs superconductors. Hence, it is likely that the mechanism of superconductivity for LaFeSiHx is, like that of LaOFeAs, also unconventional. We furthermore suggest that LaFeSiHx could be a good proton conductor due to phase stability with a wide range of hydrogen concentrations x <1 .

The structural, electronic, magnetic, and mechanical properties of perovskite oxides PbM1/2Nb1/2O3 (M = Fe, Co and Ni)

NASA Astrophysics Data System (ADS)

Erkisi, A.; Surucu, G.; Deligoz, E.

2018-03-01

In this study, the structural, electronic, magnetic, and mechanical properties of perovskite oxides PbM1/2Nb1/2O3 (M = Fe, Co and Ni) are investigated. The systems are treated in ferromagnetic order. The calculations are carried out in the framework of density functional theory (DFT) within the plane-wave pseudopotential method. The exchange-correlation potential is approximated by generalized-gradient spin approach (GGA). The intra-atomic Coulomb repulsion is also taken into account in calculations (GGA + U). We have considered two generalized-gradient spin approximation functionals, which are Perdew-Burke-Ernzerhof (PBE) and PBE for solids (PBEsol) for structural parameter calculations when it included Hubbard potential. Although the spin-polarized electronic band structures of PbCo1/2Nb1/2O3 and PbNi1/2Nb1/2O3 systems exhibit metallic property in ferromagnetic phase, a bandgap is observed in spin-down states of PbFe1/2Nb1/2O3 resulting in half-metallic behavior. The main reason for this behavior is attributed to the hybridization between d-states of transition metal atoms and p-states of oxygen atoms. The stability mechanically and the calculated mechanical properties by using elastic constants show that these compounds are mechanically stable in tetragonal phase and have anisotropic character mechanically.

Spin structure, magnetism, and cation distributions of NiFe2-xAlxO4 solid solutions

NASA Astrophysics Data System (ADS)

Kamali, Saeed

2017-07-01

Low temperature Mössbauer spectroscopy together with isothermal magnetization and zero-field-cooled and field-cooled measurements have been used to perform a systematic investigation of the cation distributions and magnetic properties of solid solutions of NiFe2-xAlxO4 with x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2.0. Mössbauer spectroscopy for the starting member of the series, NiFe2O4, shows that nickel atoms occupy the octahedral sites and are in 2+ oxidation state, while iron atoms, all in 3+ oxidation state, occupy equally the tetrahedral and the octahedral sites. When low concentration of aluminum, x = 0.4, is incorporated into the system, they substitute preferentially iron atoms in the octahedral sites. As the concentration of aluminum is increased, there are distributions of them in both the tetrahedral and octahedral sites leading to complex cation distributions. The magnetic characters of iron and nickel atoms and the diamagnetic nature of aluminum atoms and the complex cation distributions result in interesting magnetic properties for this class of materials. As the concentration of aluminum increases, the saturation magnetization decreases drastically and then gradually increases. In the end member of the series, NiAl2O4, the absent of any super-exchange interaction between the A-sites and the B-sites due to presence of Ni ions as the only magnetic atoms in the B-sites results in a paramagnetic structure and a magnetization close to zero although the nickel atoms have a spin moment of 2μB . This paramagnetic feature makes this compound to be considered as a magnetic resonant imaging agent. Another very interesting feature is the back and forth switching of the dominance of the magnetic moments in the tetrahedral sites and the octahedral sites as aluminum concentration increases.

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

NASA Astrophysics Data System (ADS)

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.

Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper).

PubMed

Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

2017-04-01

In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300°C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300°C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L 3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents. Copyright © 2016 Elsevier Inc. All rights reserved.

Self-learning kinetic Monte Carlo simulations of diffusion in ferromagnetic α-Fe-Si alloys

NASA Astrophysics Data System (ADS)

Nandipati, Giridhar; Jiang, Xiujuan; Vemuri, Rama S.; Mathaudhu, Suveen; Rohatgi, Aashish

2018-01-01

Diffusion of Si atom and vacancy in the A2-phase of α-Fe-Si alloys in the ferromagnetic state, with and without magnetic order and in various temperature ranges, are studied using AKSOME, an on-lattice self-learning KMC code. Diffusion of the Si atom and the vacancy are studied in the dilute limit and up to 12 at.% Si, respectively, in the temperature range 350-700 K. Local Si neighborhood dependent activation energies for vacancy hops were calculated on-the-fly using a broken-bond model based on pairwise interaction. The migration barrier and prefactor for the Si diffusion in the dilute limit were obtained and found to agree with published data within the limits of uncertainty. Simulations results show that the prefactor and the migration barrier for the Si diffusion are approximately an order of magnitude higher, and a tenth of an electron-volt higher, respectively, in the magnetic disordered state than in the fully ordered state. However, the net result is that magnetic disorder does not have a significant effect on Si diffusivity within the range of parameters studied in this work. Nevertheless, with increasing temperature, the magnetic disorder increases and its effect on the Si diffusivity also increases. In the case of vacancy diffusion, with increasing Si concentration, its diffusion prefactor decreases while the migration barrier more or less remained constant and the effect of magnetic disorder increases with Si concentration. Important vacancy-Si/Fe atom exchange processes and their activation barriers were identified, and the effect of energetics on ordered phase formation in Fe-Si alloys are discussed.

Electronic and magnetic structures of Fe3O4 ferrimagnetic investigated by first principle, mean field and series expansions calculations

NASA Astrophysics Data System (ADS)

Masrour, R.; Hlil, E. K.; Hamedoun, M.; Benyoussef, A.; Mounkachi, O.; El Moussaoui, H.

2015-03-01

Self-consistent ab initio calculations, based on density functional theory (DFT) approach and using a full potential linear augmented plane wave (FLAPW) method, are performed to investigate both electronic and magnetic properties of the Fe3O4. Polarized spin and spin-orbit coupling are included in calculations within the framework of the antiferromagnetic state between two adjacent Fe plans. Magnetic moment considered to lie along (010) axes are computed. Obtained data from ab initio calculations are used as input for the high temperature series expansions (HTSEs) calculations to compute other magnetic parameters. The exchange interactions between the magnetic atoms Fe-Fe in Fe3O4 are given using the mean field theory. The high temperature series expansions (HTSEs) of the magnetic susceptibility of with the magnetic moments, mFe in Fe3O4 is given up to seventh order series in (1/kBT). The Néel temperature TN is obtained by HTSEs of the magnetic susceptibility series combined with the Padé approximant method. The critical exponent γ associated with the magnetic susceptibility is deduced as well.

Model many-body Stoner Hamiltonian for binary FeCr alloys

NASA Astrophysics Data System (ADS)

Nguyen-Manh, D.; Dudarev, S. L.

2009-09-01

We derive a model tight-binding many-body d -electron Stoner Hamiltonian for FeCr binary alloys and investigate the sensitivity of its mean-field solutions to the choice of hopping integrals and the Stoner exchange parameters. By applying the local charge-neutrality condition within a self-consistent treatment we show that the negative enthalpy-of-mixing anomaly characterizing the alloy in the low chromium concentration limit is due entirely to the presence of the on-site exchange Stoner terms and that the occurrence of this anomaly is not specifically related to the choice of hopping integrals describing conventional chemical bonding between atoms in the alloy. The Bain transformation pathway computed, using the proposed model Hamiltonian, for the Fe15Cr alloy configuration is in excellent agreement with ab initio total-energy calculations. Our investigation also shows how the parameters of a tight-binding many-body model Hamiltonian for a magnetic alloy can be derived from the comparison of its mean-field solutions with other, more accurate, mean-field approximations (e.g., density-functional calculations), hence stimulating the development of large-scale computational algorithms for modeling radiation damage effects in magnetic alloys and steels.

Formation of Environmentally Persistent Free Radical (EPFR) in Iron(III) Cation-Exchanged Smectite Clay

PubMed Central

Nwosu, Ugwumsinachi G.; Roy, Amitava; dela Cruz, Albert Leo N.; Dellinger, Barry; Cook, Robert

2016-01-01

Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm−1 and 1595 cm−1, and at lower frequencies between 694 cm−1 and 806 cm−1, as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHp-p of 6.1 G at an average concentration of 7.5 × 1017 spins/g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10−2 spins/Fe(II) atom. PMID:26647158

Formation of environmentally persistent free radical (EPFR) in iron(III) cation-exchanged smectite clay.

PubMed

Nwosu, Ugwumsinachi G; Roy, Amitava; dela Cruz, Albert Leo N; Dellinger, Barry; Cook, Robert

2016-01-01

Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm(-1) and 1595 cm(-1), and at lower frequencies between 694 cm(-1) and 806 cm(-1), as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHP-P of 6.1 G at an average concentration of 7.5 × 10(17) spins per g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10(-2) spins per Fe(II) atom.

Kambersky Damping in L10 Magnetic Materials of Ordered and Disordered States with Substitutional Defects

NASA Astrophysics Data System (ADS)

Qu, Tao; Victora, Randall

2015-03-01

L10 phase alloys with high magnetic anisotropy play a key role in spintronic devices. The damping constant α represents the elimination of the magnetic energy and affects the efficiency of devices. However, the intrinsic Kambersky damping reported experimentally differs among investigators and the effect of defects on α is never investigated. Here, we apply Kambersky's torque correlation technique, within the tight-binding method, to L10 ordered and disordered alloys FePt, FePd,CoPt and CoPd. In the ordered phase, CoPt has the largest damping of 0.067 while FePd has the minimum value of 0.009 at room temperature. The calculated damping value of FePt and FePd agrees well with experiment. Artificially shifting Ef, as might be accomplished by doping with impurity atoms, shows that α follows the density of states (DOS) at Ef in these four L10 alloys. We introduce lattice defects through exchanging the positions of 3d and non-3d transition elements in 36 atom supercells. The damping increases with reduced degree of chemical order, owing to the enhanced spin-flip channel allowed by the broken symmetry. This prediction is confirmed by measurements in FePt. It is demonstrated that this corresponds to an enhanced DOS at the Fermi level, owing to the rounding of the DOS with loss of long-range order. This work was supported primarily by C-SPIN (one of the six SRC STAR-net Centers) and partly by the MRSEC Program under Contract No. DMR-0819885.

Self-learning kinetic Monte Carlo simulations of diffusion in ferromagnetic α -Fe–Si alloys

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

Nandipati, Giridhar; Jiang, Xiujuan; Vemuri, Rama S.

Diffusion in α-Fe-Si alloys is studied using AKSOME, an on-lattice self-learning KMC code, in the ferromagnetic state. Si diffusivity in the α-Fe matrix were obtained with and without the magnetic disorder in various temperature ranges. In addition we studied vacancy diffusivity in ferromagnetic α-Fe at various Si concentrations up to 12.5at.% in the temperature range of 350–550 K. The results were compared with available experimental and theoretical values in the literature. Local Si-atom dependent activation energies for vacancy hops were calculated using a broken-model and were stored in a database. The migration barrier and prefactors for Si-diffusivity were found tomore » be in reasonable agreement with available modeling results in the literature. Magnetic disorder has a larger effect on the prefactor than on the migration barrier. Prefactor was approximately an order of magnitude and the migration barrier a tenth of an electron-volt higher with magnetic disorder when compared to a fully ferromagnetic ordered state. In addition, the correlation between various have a larger effect on the Si-diffusivity extracted in various temperature range than the magnetic disorder. In the case of vacancy diffusivity, the migration barrier more or less remained constant while the prefactor decreased with increasing Si concentration in the disordered or A2-phase of Fe-Si alloy. Important vacancy-Si/Fe atom exchange processes and their activation barriers were also identified and discuss the effect of energetics on the formation of ordered phases in Fe-Si alloys.« less

Dynamic Stabilization of Metal Oxide–Water Interfaces

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

McBriarty, Martin E.; von Rudorff, Guido Falk; Stubbs, Joanne E.

2017-02-08

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (1102) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locationsmore » and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.« less

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

NASA Astrophysics Data System (ADS)

Hussain, Zaineb; Kumar, Dileep; Reddy, V. Raghavendra; Gupta, Ajay

2017-05-01

Magnetization reversal and magnetic microstructure of top soft magnetic layer (Fe) in exchange spring coupled L10 FePt/Fe is studied using high resolution Kerr microscopy. With remnant state of the hard magnetic layer (L10 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 (HSAT) and also by varying the angle between measuring field and HSAT. 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.

Magnetic properties of TM3[Cr(CN)6]2.n H2O

NASA Astrophysics Data System (ADS)

Zentková, M.; Mihalik, M.; Ková, J.; Zentko, A.; Mitróová, Z.; Lukáová, M.; Kaveanský, V.; Kiss, L. F.

2006-01-01

Magnetization measurements performed on Prussian blue analogs TM2+3[CrIII(CN)6]2.n H2O (TM = Cr, Mn, Fe, Co, Ni, Cu) confirmed the dual character of the exchange interaction (antiferromagnetic AFM and ferromagnetic FM) in this system. AFM interaction dominates for the Cr2+ sample and with rising atomic number Z the FM interaction becomes more important reaching pure FM character for the Cu2+ sample.

Structural and magnetic properties of FeGen-/0 (n = 3-12) clusters: Mass-selected anion photoelectron spectroscopy and density functional theory calculations

NASA Astrophysics Data System (ADS)

Deng, Xiao-Jiao; Kong, Xiang-Yu; Liang, Xiaoqing; Yang, Bin; Xu, Hong-Guang; Xu, Xi-Ling; Feng, Gang; Zheng, Wei-Jun

2017-12-01

The structural, electronic, and magnetic properties of FeGen-/0 (n = 3-12) clusters were investigated by using anion photoelectron spectroscopy in combination with density functional theory calculations. For both anionic and neutral FeGen (n = 3-12) clusters with n ≤ 7, the dominant structures are exohedral. The FeGe8-/0 clusters have half-encapsulated boat-shaped structures, and the opening of the boat-shaped structure is gradually covered by the additional Ge atoms to form Gen cage from n = 9 to 11. The structures of FeGe10-/0 can be viewed as two Ge atoms symmetrically capping the opening of the boat-shaped structure of FeGe8, and those of FeGe12-/0 are distorted hexagonal prisms with the Fe atom at the center. Natural population analysis shows that there is an electron transfer from the Ge atoms to the Fe atom at n = 8-12. The total magnetic moment of FeGen-/0 and local magnetic moment of the Fe atom have not been quenched.

Probing Single Pt Atoms in Complex Intermetallic Al13Fe4.

PubMed

Yamada, Tsunetomo; Kojima, Takayuki; Abe, Eiji; Kameoka, Satoshi; Murakami, Yumi; Gille, Peter; Tsai, An Pang

2018-03-21

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al 13 Fe 4 , was investigated using a single crystal prepared by the Czochralski method. High-angle annular dark-field scanning transmission electron microscopy showed that the Pt atoms were dispersed as single atoms and substituted at Fe sites in Al 13 Fe 4 . Single-crystal X-ray structural analysis revealed that the Pt atoms preferentially substitute at Fe(1). Unlike those that have been reported, Pt single atoms in the surface layers showed lower activity and selectivity than those of Al 2 Pt and bulk Pt for propyne hydrogenation, indicating that the active state of a given single-atom Pt site is strongly dominated by the bonding to surrounding Al atoms.

Molecule-assisted ferromagnetic atomic chain formation

NASA Astrophysics Data System (ADS)

Kumar, Manohar; Sethu, Kiran Kumar Vidya; van Ruitenbeek, Jan M.

2015-06-01

One dimensional systems strongly enhance the quantum character of electron transport. Such systems can be realized in 5 d transition metals Au, Pt, and Ir, in the form of suspended monatomic chains between bulk leads. Atomic chains between ferromagnetic leads would open up many perspectives in the context of spin-dependent transport and spintronics, but the evidence suggests that for pure metals only the mentioned three 5 d metals are susceptible to chain formation. It has been argued that the stability of atomic chains made up from ferromagnetic metals is compromised by the same exchange interaction that produces the local moments. Here we demonstrate that magnetic atomic chains can be induced to form in break junctions under the influence of light molecules. Explicitly, we find deuterium assisted chain formation in the 3 d ferromagnetic transition metals Fe and Ni. Chain lengths up to eight atoms are formed upon stretching the ferromagnetic atomic contact in deuterium atmosphere at cryogenic temperatures. From differential conductance spectra vibronic states of D2 can be identified, confirming the presence of deuterium in the atomic chains. Shot noise spectroscopy indicates the presence of weakly spin polarized transmission channels.

Atomic level structural modulation during the structural relaxation and its effect on magnetic properties of Fe81Si4B10P4Cu1 nanocrystalline alloy

NASA Astrophysics Data System (ADS)

Cao, C. C.; Zhu, L.; Meng, Y.; Zhai, X. B.; Wang, Y. G.

2018-06-01

The evolution of local structure and defects in the Fe81Si4B10P4Cu1 amorphous alloy during the structural relaxation has been investigated by Mössbauer spectroscopy, positron annihilation lifetime spectroscopy and transmission electron microscopy to explore their effects on magnetic properties of the nanocrystalline. The atomic rearrangements at the early stage of the structural relaxation cause the density increase of the amorphous matrix, but the subsequent atomic rearrangements contribute to the transformation of Fe3B-like atomic arrangements to FeB-like ones with the temperature increasing. As the structural relaxation processes, the released Fe atoms both from Fe3B- and Fe3P-like atomic arrangements result in the formation of new Fe clusters and the increase of Fe-Fe coordination number in the existing Fe clusters and the nucleation sites for α-Fe gradually increase, both of which promote the crystallization. However, the homogeneity of amorphous matrix will be finally destroyed under excessive relaxation temperature, which coarsens nanograins during the crystallization instead. Therefore, soft magnetic properties of the Fe81Si4B10P4Cu1 nanocrystalline alloy can be improved by pre-annealing the amorphous precursor at an appropriate temperature due to the atomic level structural optimization.

Nanocomposite Nd-Y-Fe-B-Mo bulk magnets prepared by injection casting technique

NASA Astrophysics Data System (ADS)

Tao, Shan; Ahmad, Zubair; Zhang, Pengyue; Yan, Mi; Zheng, Xiaomei

2017-09-01

The phase composition, magnetic and microstructural properties of Nd2Fe14B/(α-Fe, Fe3B) nanocomposite magnets produced by injection casting technique have been studied. Magnetic hysteresis loop of the Nd7Y6Fe61B22Mo4 permanent magnet demonstrates the coercivity as high as 1289 kA/m. Electron microscopy elucidates a microstructure composed of magnetically soft α-Fe, Fe3B and hard Nd2Fe14B/Y2Fe14B nanograins (20-50 nm) separated by ultra-thin grain boundary layer. The Henkel plot curve of the Nd7Y6Fe61B22Mo4 magnet yields the existence of exchange coupling interactions between soft and hard phases. Macroscopically large size sheet magnet is obtained due to high glass forming ability of the Nd7Y6Fe61B22Mo4 alloy derived from large atomic radius mismatch and negative enthalpy of alloy constituent elements. The high coercivity of the magnet is attributed to the magnetically hard phase increment, nucleation of reverse domains and the presence of thin grain boundary phase. Good magnetic properties such as remanence of 0.51 T, coercivity of 1289 kA/m and maximum energy product of 46.2 kJ/m3 are obtained in directly casted Nd7Y6Fe61B22Mo4 sheet magnets.

Atomic origin of the spin-polarization of the Co2FeAl Heusler compound

NASA Astrophysics Data System (ADS)

Liang, Jaw-Yeu; Lam, Tu-Ngoc; Lin, Yan-Cheng; Chang, Shu-Jui; Lin, Hong-Ji; Tseng, Yuan-Chieh

2016-02-01

Using synchrotron x-ray techniques, we studied the Co2FeAl spin-polarization state that generates the half-metallicity of the compound during an A2 (low-spin)  →  B2 (high-spin) phase transition. Given the advantage of element specificity of x-ray techniques, we could fingerprint the structural and magnetic cross-reactions between Co and Fe within a complex Co2FeAl structure deposited on a MgO (0 0 1) substrate. X-ray diffraction and extended x-ray absorption fine structure investigations determined that the Co atoms preferably populate the (1/4,1/4,1/4) and (3/4,3/4,3/4) sites during the development of the B2 phase. X-ray magnetic spectroscopy showed that although the two magnetic elements were ferromagnetically coupled, they interacted in a competing manner via a charge-transfer effect, which enhanced Co spin polarization at the expense of Fe spin polarization during the phase transition. This means that the spin-polarization of Co2FeAl was electronically dominated by Fe in A2 whereas the charge transfer turned the dominance to Co upon B2 formation. Helicity-dependent x-ray absorption spectra also revealed that only the minority state of Co/Fe was involved in the charge-transfer effect whereas the majority state was independent of it. Despite an overall increase of Co2FeAl magnetization, the charge-transfer effect created an undesired trade-off during the Co-Fe exchange interactions, because of the presence of twice as many X sites (Co) as Y sites (Fe) in the Heusler X 2 YZ formula. This suggests that the spin-polarization of Co2FeAl is unfortunately regulated by compromising the enhanced X (Co) sites and the suppressed Y (Fe) sites, irrespective of the development of the previously known high-spin-polarization phase of B2. This finding provides a possible cause for the limited half-metallicity of Co2FeAl discovered recently. Electronic tuning between the X and Y sites is necessary to further increase the spin-polarization, and likely the half-metallicity as well, of the compound.

Structural and magnetic properties of Nd0.67Ba0.33MnO3 manganites with partial replacement of Fe and Cu at Mn-site

NASA Astrophysics Data System (ADS)

Sudakshina, B.; Arun, B.; Chandrasekhar, K. Devi; Yang, H. D.; Vasundhara, M.

2018-06-01

We have investigated the structural and magnetic properties of Nd0.67Ba0.33MnO3 manganite and partial replacement of Mn with Fe and Cu compounds followed by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and vibrating sample magnetometer (VSM). The Rietveld refinement of XRD indicates orthorhombic crystal structure with I-mma space group for all the compounds and thus obtained lattice parameters confirm the presence of co-operative Jahn-Teller effect. XRD and XAS spectra results suggests the existence of Fe3+ in Fe-substituted compound where as a mixed state of Cu2+ and Cu3+ ions in the Cu-substituted compound. The ferromagnetic (FM) to paramagnetic (PM) transition and magnetic moment is found to decrease upon the substitution of Fe and Cu atoms because of the suppression of double exchange interaction. The theoretically obtained and experimentally determined values of effective PM moment and saturation magnetic moment confirms the presence of inhomogeneous magnetic states containing FM and antiferromagnetic clusters in all the studied compounds.

Effect of film thickness on soft magnetic behavior of Fe2CoSi Heusler alloy for spin transfer torque device applications

NASA Astrophysics Data System (ADS)

Asvini, V.; Saravanan, G.; Kalaiezhily, R. K.; Raja, M. Manivel; Ravichandran, K.

2018-04-01

Fe2CoSi based Heusler alloy thin films were deposited on Si (111) wafer (substrate) of varying thickness using ultra high vacuum DC magnetron sputtering. The structural behavior was observed and found to be hold the L21 structure. The deposited thin films were characterized magnetic properties using vibrating sample magnetometer; the result shows a very high saturated magnetization (Ms), lowest coercivity (Hc), high curie transition temperature (Tc) and low hysteresis loss. Thin film thickness of 75 nm Fe2CoSi sample maintained at substrate temperature 450°C shows the lowest coercivity (Hc=7 Oe). In general, Fe2CoSi Heusler alloys curie transition temperature is very high, due to strong exchange interaction between the Fe and Co atoms. The substrate temperature was kept constant at 450°C for varying thickness (e.g. 5, 20, 50, 75 and 100 nm) of thin film sample. The 75 nm thickness thin film sample shows well crystallanity and good magnetic properties, further squareness ratio in B-H loop increases with the increase in film thickness.

Structural investigation of the (010) surface of the Al13 Fe4 catalyst.

PubMed

Ledieu, J; Gaudry, É; Loli, L N Serkovic; Villaseca, S Alarcón; de Weerd, M-C; Hahne, M; Gille, P; Grin, Y; Dubois, J-M; Fournée, V

2013-02-15

We have investigated the structure of the Al(13)Fe(4)(010) surface using both experimental and ab initio computational methods. The results indicate that the topmost surface layers correspond to incomplete puckered (P) planes present in the bulk crystal structure. The main building block of the corrugated termination consists of two adjacent pentagons of Al atoms, each centered by a protruding Fe atom. These motifs are interconnected via additional Al atoms referred to as "glue" atoms which partially desorb above 873 K. The surface structure of lower atomic density compared to the bulk P plane is explained by a strong Fe-Al-Fe covalent polar interaction that preserves intact clusters at the surface. The proposed surface model with identified Fe-containing atomic ensembles could explain the Al(13)Fe(4) catalytic properties recently reported in line with the site-isolation concept [M. Armbrüster et al., Nat. Mater. 11, 690 (2012)].

Sulfur Adsorption on the Goethite (110) Surface

NASA Astrophysics Data System (ADS)

Simonetti, S.; Damiani, D.; Brizuela, G.; Juan, A.

The electronic structure of S adsorption on goethite (110) surface has been studied by ASED-MO cluster calculations. For S location, the most exposed surface atoms of goethite surface were selected. The calculations show that the surface offers several places for S adsorption. The most energetically stable system corresponds to S location above H atom. We studied in detail the configurations that correspond to the higher OP values. For these configurations, the H-S and Fe-S computed distances are 2.1 and 3.7 Å, respectively. The H-S and Fe-S are mainly bonding interaction with OP values of 0.156 and 0.034, respectively. The Fe-S interaction mainly involves Fe 3dx2-y2 atomic orbitals with lesser participation of Fe 4py and Fe 3dyz atomic orbitals. The O-S interaction shows the same bonding and antibonding contributions giving a small OP value. The O-S interaction involves O 2p orbitals. There is an electron transfer to the Fe atom from the S atom. On the other hand, there is an electron transfer to S atom from the H and O atoms, respectively.

Brillouin Light Scattering study of the rotatable magnetic anisotropy in exchange biased bilayers of Ni81 Fe19 Ir20 Mn80

NASA Astrophysics Data System (ADS)

Rodríguez, Roberto; Oliveira, Alexandre; Estrada, Francisco; Santos, Obed; Azevedo, Antonio; Rezende, Sergio

It is known that when a ferromagnet (FM) is in atomic contact with an antiferromagnet (AF) the exchange coupling between the FM and AF spins at the interface induces a unidirectional anisotropy in the ferromagnetic film. This effect is known as exchange bias (EB). Despite the large amount of research on this topic there are still several aspects of the EB mechanism that are not well understood. One of this aspects is the origin of the rotatable anisotropy in polycrystalline AFs. By means of Brillouin Light Scattering (BLS) measurements, we investigated the dependence of the rotatable anisotropy field HRA and exchange field HE with the magnitude of the external magnetic field (Ho) in FM/AM bilayers of Ni81Fe19(10nm)/Ir20Mn80(tAF) . We developed an algorithm to numerically fit the in-plane angular dependence of the magnon frequency, at a fixed value of Ho measured by BLS. From the fit parameters we were able to investigate HRA and HE dependency on Ho. The results reveal that HRA value depends on Ho, so we argue that AF grain distribution at the interface is partially modified by the applied field strength. Contrary to this, the relation between HE and Ho is not straightforward, remaining constant at high values of Ho.

Snoek Relaxation in Fe-Cr Alloys and Interstitial-Substitutional Interaction

NASA Astrophysics Data System (ADS)

Golovin, I. S.; Blanter, M. S.; Schaller, R.

1997-03-01

The internal friction (IF) spectra of -Fe, Fe-Cr ferritic alloys and Cr have been investigated in a frequency range of 0.01 to 10 Hz. A Snoek-type relaxation was found in all the investigated C doped Fe-Cr alloys, starting from pure Fe and finishing with pure Cr. The temperature location of the Snoek peak (Tmax) in -Fe was found to be 315 K (1 Hz). The activation energy deduced from the T - f shift was 0.81 eV. Tmax in Cr was 433 K with an activation energy of 1.11 eV. The Snoek-type peaks in Fe-Cr alloys are much wider than in pure Fe or pure Cr. The temperature location of the peak versus chromium content curve exhibits a maximum in the vicinity of 35 wt% Cr (Tmax was 573 to 578 K, f 1.2 Hz and the activation energy was about 1.45 eV). It is important that Cr atoms in α-Fe have a more pronounced influence on the temperature location of the peak than Fe atoms have in chromium. A new model based on the atomic interactions is proposed to explain the influence of composition on Snoek peak location. The internal friction has been simulated by a Monte Carlo method, using C-C and C-substitutional atom (s) interaction energies. A model of long-range strain-induced (elastic) interaction supplemented by the chemical interaction in the two nearest coordination shells around an immobile substitutional atom was used for the C-s interaction. The interatomic interaction was supposed to affect IF by changing both the carbon atom arrangement (short-range order) and the energy of C atoms in octahedral interstices, and therefore the activation energy of IF. The peak temperatue calculated coincides well with the experimental ones if the value for the chemical interaction in the first coordination shell (Hchem) for C-Cr in Fe is - 0.15 eV and for C-Fe in Cr +0.15 eV. The difference in the influence of Cr in α-Fe and Fe in Cr is accounted for by a difference in the elastic and chemical interaction both between the carbon atoms and the substitutional atoms. The relaxation process in chromium Fe-based alloys is due to the carbon atom diffusion under stress between octahedral interstices of first and second coordination shells around the Cr atoms, and in Cr-based alloys, between second and third shells around the Fe atoms.

Crystal structure and magnetic properties of FeTe2O5X (X=Cl, Br): a frustrated spin cluster compound with a new Te(IV) coordination polyhedron.

PubMed

Becker, Richard; Johnsson, Mats; Kremer, Reinhard K; Klauss, Hans-Henning; Lemmens, Peter

2006-12-06

A new layered transition metal oxohalide, FeTe2O5ClxBr1-x, has been identified. It crystallizes in the monoclinic space group P21/c. The unit cell for FeTe2O5Br is a = 13.3964(8), b = 6.5966(4), c = 14.2897(6) A, beta=108.118(6) degrees, and Z=8. The layers are built of edge sharing [FeO6] octahedra forming [Fe4O16]20- units that are linked by [Te4O10X2]6- groups. The layers have no net charge and are only weakly connected via van der Waals forces to adjacent layers. There are four crystallographically different Te atoms, and one of them displays a unique [TeO2X] coordination polyhedron (X=Cl, Br). Magnetic susceptibility measurements show a broad maximum typical for 4-spin clusters of coupled Fe(III) ions in the high-spin state. Evidence for magnetic instabilities exists at low temperatures, which have been confirmed with specific heat experiments. A theoretical modeling of the susceptibility concludes a frustration of the intra-tetramer anti-ferromagnetic exchange interaction.

First principle study of the electronic and magnetic properties of a single iron atomic chain encapsulated in boron nitrite nanotubes

NASA Astrophysics Data System (ADS)

Fathalian, Ali; Jalilian, Jaafar; Shahidi, Sahar

2011-11-01

The electronic and magnetic properties for a single Fe atom chain wrapped in armchair (n,n) boron nitride nanotubes (BNNTs) ( 4≤n≤6) are investigated through the density functional theory. By increasing the nanotube diameter, the magnetic moments, total magnetic moments and spin polarization of Fe@(n,n) systems are increased. We have calculated the majority and minority density of states (DOS) of armchair Fe@(6,6) BNNT. Our results show that the magnetic moment of the system come mostly from the Fe atom chain. The magnetic moment on an Fe atom, the total magnetic moment and spin polarization decrease by increasing the axial separation of the Fe atom chain for the Fe@(6,6) system. The Fe@(6,6) BNNT can be used in the magnetic nanodevices because of higher magnetic moment and spin polarization.

Single d-metal atoms on F(s) and F(s+) defects of MgO(001): a theoretical study across the periodic table.

PubMed

Neyman, Konstantin M; Inntam, Chan; Matveev, Alexei V; Nasluzov, Vladimir A; Rösch, Notker

2005-08-24

Single d-metal atoms on oxygen defects F(s) and F(s+) of the MgO(001) surface were studied theoretically. We employed an accurate density functional method combined with cluster models, embedded in an elastic polarizable environment, and we applied two gradient-corrected exchange-correlation functionals. In this way, we quantified how 17 metal atoms from groups 6-11 of the periodic table (Cu, Ag, Au; Ni, Pd, Pt; Co, Rh, Ir; Fe, Ru, Os; Mn, Re; and Cr, Mo, W) interact with terrace sites of MgO. We found bonding with F(s) and F(s+) defects to be in general stronger than that with O2- sites, except for Mn-, Re-, and Fe/F(s) complexes. In M/F(s) systems, electron density is accumulated on the metal center in a notable fashion. The binding energy on both kinds of O defects increases from 3d- to 4d- to 5d-atoms of a given group, at variance with the binding energy trend established earlier for the M/O2- complexes, 4d < 3d < 5d. Regarding the evolution of the binding energy along a period, group 7 atoms are slightly destabilized compared to their group 6 congeners in both the F(s) and F(s+) complexes; for later transition elements, the binding energy increases gradually up to group 10 and finally decreases again in group 11, most strongly on the F(s) site. This trend is governed by the negative charge on the adsorbed atoms. We discuss implications for an experimental detection of metal atoms on oxide supports based on computed core-level energies.

Spectral and magnetic properties of hematite Fe2O3 (001) surface: results from DFT+DMFT

NASA Astrophysics Data System (ADS)

Kabir, Alamgir; Turkowski, Volodymyr; Rahman, Talat S.

2015-03-01

It has been demonstrated that strong correlation effects may significantly modify the spectrum of a system, in particular leading to an increase of the bandgap and to a change in the orbital occupancies, which affects the magnetic properties of the system. With this in mind, we have examined the spectral and magnetic properties of the hematite Fe2O3 film system with (001) surface orientation by using the combined density functional theory (DFT) and dynamical mean-field theory (DMFT) approach. We pay special attention to the surface geometry and electronic structure, magnetization and magnetic anisotropy (MA) of the system by performing calculations at different values of the parameters for the local Coulomb repulsion and exchange energy. To calculate the MA of the system, we propose and apply a combined Bruno model within DMFT, and demonstrate that under-coordinated surface Fe atoms contribute significantly to the MA of the film. We also compare our results with the DFT+U solution and show that the dynamical effects taken into account by the DMFT significantly affect system properties, notably leading to a decrease of the atomic magnetic moments. Work supported in part by DOE Grant No. DOE-DE-FG02-07ER46354.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

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

Yan, Ling -Hao; Wu, Rong -Ting; Bao, De -Liang

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H 2Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H 2Nc molecules and formed Fe-H 2Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H 2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform sizemore » and adsorbed dispersively at the interstitial positions of Fe-H 2Nc complex monolayer. Furthermore, the H 2Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.« less

Intermixing enables strong exchange coupling in nanocomposites: Magnetism through the interfacial ferrite in γ -Fe2O3/NiO

NASA Astrophysics Data System (ADS)

Skoropata, E.; Su, T. T.; Ouyang, H.; Freeland, J. W.; van Lierop, J.

2017-07-01

γ -Fe2O3 particles, surface modified with NiO crystallites, form a unique nanocomposite that points to how to tune strong interfacial exchange coupling. We find that Ni2 + migrates into the octahedral sites of the γ -Fe2O3 nanoparticle surface, and this NiFe2O4 -like layer permits effective magnetic coupling of Ni and Fe sites that strengthens the interface exchange. A large increase in coercivity coinciding with a loss of exchange bias is achieved by this strong interfacial coupling that results in a Ni2 + moment reversal in the NiO with the γ -Fe2O3 . This work reveals the importance of intermixing in, and possibility to use, such an exchange coupling regime to alter substantially the coercivity and hence control an important property of exchange-coupled nanocomposite magnets.

Spontaneous perpendicular exchange bias effect in L10-MnGa/FeMn bilayers grown by molecular-beam epitaxy

NASA Astrophysics Data System (ADS)

Zhao, X. P.; Lu, J.; Mao, S. W.; Yu, Z. F.; Wei, D. H.; Zhao, J. H.

2018-01-01

We report on the spontaneous perpendicular exchange bias effect in as-grown L10-MnGa/FeMn bilayers. An FeMn layer with different thicknesses is introduced as an antiferromagnetic layer to couple with single-crystalline ferromagnetic L10-MnGa, which is epitaxially grown on a GaAs (001) substrate by molecular-beam epitaxy. The perpendicular exchange bias shows a strong dependence on both the thickness of the FeMn layer and the measurement temperature. A large spontaneous perpendicular exchange bias up to 8.9 kOe is achieved in L10-MnGa/FeMn bilayers at 5 K without any external magnetic treatment. The corresponding effective interfacial exchange energy Jeff is estimated to be 1.4 mJ/m2. The spontaneous perpendicular exchange bias effect in the (001) textured L10-MnGa/FeMn bilayers paves the way for spintronic devices based on exchange biased perpendicularly magnetized materials.

Structural Investigation of the (010) Surface of the Al13Fe4 Catalyst

NASA Astrophysics Data System (ADS)

Ledieu, J.; Gaudry, É.; Loli, L. N. Serkovic; Villaseca, S. Alarcón; de Weerd, M.-C.; Hahne, M.; Gille, P.; Grin, Y.; Dubois, J.-M.; Fournée, V.

2013-02-01

We have investigated the structure of the Al13Fe4(010) surface using both experimental and ab initio computational methods. The results indicate that the topmost surface layers correspond to incomplete puckered (P) planes present in the bulk crystal structure. The main building block of the corrugated termination consists of two adjacent pentagons of Al atoms, each centered by a protruding Fe atom. These motifs are interconnected via additional Al atoms referred to as “glue” atoms which partially desorb above 873 K. The surface structure of lower atomic density compared to the bulk P plane is explained by a strong Fe-Al-Fe covalent polar interaction that preserves intact clusters at the surface. The proposed surface model with identified Fe-containing atomic ensembles could explain the Al13Fe4 catalytic properties recently reported in line with the site-isolation concept [M. Armbrüster , Nat. Mater. 11, 690 (2012)NMAACR1476-1122].

Water-Mediated Proton Hopping on an Iron Oxide Surface

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

Merte, L. R.; Peng, Guowen; Bechstein, Ralf

2012-05-18

The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H3O+-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO2(110), where water dissociationmore » is a key step in proton diffusion.« less

Magnetism of metallacrown single-molecule magnets: From a simplest model to realistic systems

NASA Astrophysics Data System (ADS)

Pavlyukh, Y.; Rentschler, E.; Elmers, H. J.; Hübner, W.; Lefkidis, G.

2018-06-01

Electronic and magnetic properties of molecular nanomagnets are determined by competing energy scales due to the crystal field splitting, the exchange interactions between transition metal atoms, and relativistic effects. We present a comprehensive theory embracing all these phenomena based on first-principles calculations. In order to achieve this goal, we start from the FeNi4 cluster as a paradigm. The system can be accurately described on the ab initio level yielding all expected electronic states in a range of multiplicities from 1 to 9, with a ferromagnetic ground state. By adding the spin-orbit coupling between them we obtain the zero-field splitting. This allows to introduce a spin Hamiltonian of a giant spin model, which operates on a smaller energy scale. We compare the computed parameters of this Hamiltonian with the experimental and theoretical magnetic anisotropy energies of the monolayer Ni/Cu(001). In line with them, we find that the anisotropy almost entirely originates from the second-order spin-orbit coupling, the spin-spin coupling constitutes only a small fraction. Finally, we include the ligand atoms in our consideration. This component has a decisive role for the stabilization of molecules in experimental synthesis and characterization, and also substantially complicates the theory by bringing the superexchange mechanisms into play. Since they are higher-order effects involving two hopping matrix elements, not every theory can describe them. Our generalization of the corresponding perturbation theory substantiates the use of complete active space methods for the description of superexchange. At the same time, our numerical results for the {CuFe4} system demonstrate that the Goodenough-Kanamori rules, which are often used to determine the sign of these exchange interactions, cannot deliver quantitative predictions due to the interplay of other mechanisms, e. g., involving multicenter Coulomb integrals. We conclude by comparing ab initio values of the exchange interaction constants for the {CuCu4} and {CuFe4} metallacrown magnetic molecules with experimental values determined by fitting of the magnetic susceptibility curves χMT (T ) , and attribute the remaining discrepancy between them to the role of virtual electron excitations into and out of the active space (dynamical correlations).

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

USGS Publications Warehouse

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. 

Structural and Magnetic Properties of Transition-Metal-Doped Zn 1-x Fe x O.

PubMed

Abdel-Baset, T A; Fang, Yue-Wen; Anis, B; Duan, Chun-Gang; Abdel-Hafiez, Mahmoud

2016-12-01

The ability to produce high-quality single-phase diluted magnetic semiconductors (DMS) is the driving factor to study DMS for spintronics applications. Fe-doped ZnO was synthesized by using a low-temperature co-precipitation technique producing Zn 1-x Fe x O nanoparticles (x= 0, 0.02, 0.04, 0.06, 0.08, and 0.1). Structural, Raman, density functional calculations, and magnetic studies have been carried out in studying the electronic structure and magnetic properties of Fe-doped ZnO. The results show that Fe atoms are substituted by Zn ions successfully. Due to the small ionic radius of Fe ions compared to that of a Zn ions, the crystal size decreases with an increasing dopant concentration. First-principle calculations indicate that the charge state of iron is Fe (2+) and Fe (3+) with a zinc vacancy or an interstitial oxygen anion, respectively. The calculations predict that the exchange interaction between transition metal ions can switch from the antiferromagnetic coupling into its quasi-degenerate ferromagnetic coupling by external perturbations. This is further supported and explains the observed ferromagnetic bahaviour at magnetic measurements. Magnetic measurements reveal that decreasing particle size increases the ferromagnetism volume fraction. Furthermore, introducing Fe into ZnO induces a strong magnetic moment without any distortion in the geometrical symmetry; it also reveals the ferromagnetic coupling.

Physical properties of FePt nanocomposite doped with Ag atoms: First-principles study

NASA Astrophysics Data System (ADS)

Jia, Yong-Fei; Shu, Xiao-Lin; Xie, Yong; Chen, Zi-Yu

2014-07-01

L10 FePt nanocomposite with high magnetocrystalline anisotropy energy has been extensively investigated in the fields of ultra-high density magnetic recording media. However, the order—disorder transition temperature of the nanocomposite is higher than 600 °C, which is a disadvantage for the use of the material due to the sustained growth of FePt grain under the temperature. To address the problem, addition of Ag atoms has been proposed, but the magnetic properties of the doped system are still unclear so far. Here in this paper, we use first-principles method to study the lattice parameters, formation energy, electronic structure, atomic magnetic moment and order—disorder transition temperature of L10 FePt with Ag atom doping. The results show that the formation energy of a Ag atom substituting for a Pt site is 1.309 eV, which is lower than that of substituting for an Fe site 1.346 eV. The formation energy of substituting for the two nearest Pt sites is 2.560 eV lower than that of substituting for the further sites 2.621 eV, which indicates that Ag dopants tend to segregate L10 FePt. The special quasirandom structures (SQSs) for the pure FePt and the FePt doped with two Ag atoms at the stable Pt sites show that the order—disorder transition temperatures are 1377 °C and 600 °C, respectively, suggesting that the transition temperature can be reduced with Ag atom, and therefore the FePt grain growth is suppressed. The saturation magnetizations of the pure FePt and the two Ag atoms doped FePt are 1083 emu/cc and 1062 emu/cc, respectively, indicating that the magnetic property of the doped system is almost unchanged.

The Chemistry of Meteoric Iron

NASA Astrophysics Data System (ADS)

Self, D. E.; Plane, J. M. C.

About 120 tonnes of interplanetary dust enters the earth's atmosphere each day. Iron comprises a large fraction of this dust (12% by mass), and ablation of the particles gives rise to the layer of Fe atoms that occurs globally in the mesosphere around 85 km. Previous work in our laboratory has shown that Fe reacts rapidly with O3 to form FeO, which in turn reacts with O3, O2 and H2O to form FeO2, FeO3 and Fe(OH)2, respectively. The purpose of the present study was to determine which of these com- pounds provide stable reservoirs for iron below the atomic Fe layer, and hence form the "building blocks" of meteoric smoke particles which are implicated in phenomena lower in the atmosphere (e.g., noctilucent clouds and polar stratospheric ozone deple- tion). The reactions of these iron compounds were studied in a fast flow tube using the pulsed laser ablation of a rotating iron rod as the source of Fe atoms in the up- stream section of the tube. Iron compounds were produced by adding reactants further down the tube, and finally atomic O or H was added through a movable injector. At the downstream end of the tube, atomic Fe was detected by laser induced fluorescence at 248 nm. The following reactions were studied: FeO + O, FeO2 + O, FeO3 + O, FeO2 + O3, FeO3 + H2O, FeO3 + H, Fe(OH)2 + H, and FeOH + H. It is clear that the iron reservoir around 80 km is FeO3, which reacts very slowly with atomic O, in agreement with the requirements of a recent atmospheric model. However, Fe(OH)2 and FeO(OH), which are thermodynamically the most stable of these Fe species and eventually form from FeO3, are the likely building blocks of meteoric smoke.

Structural and magnetic characterization of Mn/NiFe bilayers with ion-beam-assisted deposition

NASA Astrophysics Data System (ADS)

Wu, Chun-Hsien; Zheng, Chao; Chiu, Chun-Cheng; Manna, Palash Kumar; van Lierop, Johan; Lin, Ko-Wei; Pong, Philip W. T.

2018-01-01

The exchange bias effect in ferromagnetic (FM)/antiferromagnetic (AF) bilayer structures has been widely investigated because its underlying principle is critical for spintronic applications. In this work, the effect of Ar+ beam bombardment on the microstructural and magnetic properties of the Mn/NiFe thin films was investigated. The in-situ Ar+ bombardment nontrivially promoted the Mn/NiFe intermixing and facilitated the formation of the FeMn phase, accompanied by a remarkable reduction of Mn and NiFe layer thickness. The enhanced Mn/NiFe intermixing greatly disordered the interfacial spins, inhibiting the interfacial exchange coupling and giving rise to a significant decrease of the exchange bias field (H ex). The facilitated Mn/NiFe intermixing effect also dramatically degraded the magnetocrystalline anisotropy of the NiFe crystallites, leading to a notable suppression of the coercivity (H c). These results indicate that both the exchange bias and coercivity of the Mn/NiFe bilayers can be directly affected by the in-situ Ar+ bombardment, offering an effective way to modify the magnetism of the exchange-bias systems.

Modulated exchange bias in NiFe/CoO/α-Fe2O3 trilayers and NiFe/CoO bilayers

NASA Astrophysics Data System (ADS)

Li, X.; Lin, K.-W.; Yeh, W.-C.; Desautels, R. D.; van Lierop, J.; Pong, Philip W. T.

2017-02-01

While the exchange bias in ferromagnetic/antiferromagnetic (FM/AF) bilayer and FM1/AF/FM2 trilayer configurations has been widely investigated, the role of an AF2 layer in FM/AF1/AF2 trilayer configurations is still not well understood. In this work, the magnetic properties of NiFe/CoO, NiFe/α-Fe2O3 bilayers, and NiFe/CoO/α-Fe2O3 trilayer were studied comparatively. The microstructure and chemical composition were characterized. Temperature dependent magnetometry reveals increased irreversibility temperature in NiFe/CoO/α-Fe2O3 trilayer compared with NiFe/CoO bilayer. The magnetic hysteresis loops show that the exchange bias (Hex) and coercivity (Hc) depend strongly on the anisotropy of AF layer (CoO, α-Fe2O3 and CoO/α-Fe2O3). Our work shows that the AF1/AF2 interfacial interactions can be used effectively for tuning the exchange bias in FM/AF1/AF2 trilayers.

Local structure study of (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} thin films using x-ray absorption spectroscopy

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

Ren, Yuan; Xing, Yaya; Ma, Guanxiong

2015-07-15

The (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} (x = 0.06, 0.08, 0.15, and 0.20) films prepared by RF-magnetron sputtering were investigated by the combination of x-ray absorption spectroscopy (XAS) at Fe, Cu, and O K-edge. Although the Fe and O K-edge XAS spectra show that the Fe atoms substitute for the In sites of In{sub 2}O{sub 3} lattice for all the films, the Cu K-edge XAS spectra reveal that the codoped Cu atoms are separated to form the Cu metal clusters. After being annealed in air, the Fe atoms are still substitutionally incorporated into the In{sub 2}O{sub 3} lattice, while the Cumore » atoms form the CuO secondary phases. With the increase of Fe concentration, the bond length R{sub Fe-O} shortens and the Debye–Waller factor σ{sup 2}{sub Fe-O} increases in the first coordination shell of Fe, which are attributed to the relaxation of oxygen environment around the substitutional Fe ions. The forming of Cu relating secondary phases in the films is due to high ionization energy of Cu atoms, leading that the Cu atoms are energetically much harder to be oxidized to substitute for the In sites of In{sub 2}O{sub 3} lattice than Fe atoms. These results provide new experimental guidance in the preparation of the codoped In{sub 2}O{sub 3} based dilute magnetic oxides.« less

Electric field induced reversible 180° magnetization switching through tuning of interfacial exchange bias along magnetic easy-axis in multiferroic laminates

PubMed Central

Xue, Xu; Zhou, Ziyao; Peng, Bin; Zhu, Mingmin; Zhang, Yijun; Ren, Wei; Ren, Tao; Yang, Xi; Nan, Tianxiang; Sun, Nian X.; Liu, Ming

2015-01-01

E-field control of interfacial exchange coupling and deterministic switching of magnetization have been demonstrated in two sets of ferromagnetic(FM)/antiferromagnetic(AFM)/ferroelectric(FE) multiferroic heterostructures, including NiFe/NiCoO/glass/PZN-PT (011) and NiFe/FeMn/glass/PZN-PT (011). We designed this experiment to achieve exchange bias tuning along the magnetic easy axis, which is critical for realizing reversible 180° magnetization deterministic switching at zero or small magnetic bias. Strong exchange coupling were established across AFM-FM interfaces, which plays an important role in voltage control of magnetization switching. Through the competition between the E-field induced uniaxial anisotropy in ferromagnetic layer and unidirectional anisotropy in antiferromagnetic layer, the exchange bias was significantly shifted by up to |∆Hex|/Hex = 8% in NiFe/FeMn/glass/PZN-PT (011) and 13% in NiFe/NiCoO/glass/PZN-PT (011). In addition, the square shape of the hysteresis loop, as well as a strong shape tunability of |∆Hex|/Hc = 67.5 ~ 125% in NiFe/FeMn/glass/PZN-PT and 30 ~ 38% in NiFe/NiCoO/glass/PZN-PT were achieved, which lead to a near 180° magnetization switching. Electrical tuning of interfacial exchange coupling in FM/AFM/FE systems paves a new way for realizing magnetoelectric random access memories and other memory technologies. PMID:26576658

Electric field induced reversible 180° magnetization switching through tuning of interfacial exchange bias along magnetic easy-axis in multiferroic laminates

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

Xue, Xu; Zhou, Ziyao; Peng, Bin

2015-11-18

E-field control of interfacial exchange coupling and deterministic switching of magnetization have been demonstrated in two sets of ferromagnetic(FM)/antiferromagnetic(AFM)/ferroelectric(FE) multiferroic heterostructures, including NiFe/NiCoO/glass/PZN-PT (011) and NiFe/FeMn/glass/PZN-PT (011). We designed this experiment to achieve exchange bias tuning along the magnetic easy axis, which is critical for realizing reversible 180° magnetization deterministic switching at zero or small magnetic bias. Strong exchange coupling were established across AFM-FM interfaces, which plays an important role in voltage control of magnetization switching. Through the competition between the E-field induced uniaxial anisotropy in ferromagnetic layer and unidirectional anisotropy in antiferromagnetic layer, the exchange bias was significantly shiftedmore » by up to |ΔH ex|/H ex=8% in NiFe/FeMn/glass/PZN-PT (011) and 13% in NiFe/NiCoO/glass/PZN-PT (011). In addition, the square shape of the hysteresis loop, as well as a strong shape tunability of |ΔH ex|/H c=67.5~125% in NiFe/FeMn/glass/PZN-PT and 30~38% in NiFe/NiCoO/glass/PZN-PT were achieved, which lead to a near 180° magnetization switching. Lastly, electrical tuning of interfacial exchange coupling in FM/AFM/FE systems paves a new way for realizing magnetoelectric random access memories and other memory technologies.« less

Electric field induced reversible 180° magnetization switching through tuning of interfacial exchange bias along magnetic easy-axis in multiferroic laminates

NASA Astrophysics Data System (ADS)

Xue, Xu; Zhou, Ziyao; Peng, Bin; Zhu, Mingmin; Zhang, Yijun; Ren, Wei; Ren, Tao; Yang, Xi; Nan, Tianxiang; Sun, Nian X.; Liu, Ming

2015-11-01

E-field control of interfacial exchange coupling and deterministic switching of magnetization have been demonstrated in two sets of ferromagnetic(FM)/antiferromagnetic(AFM)/ferroelectric(FE) multiferroic heterostructures, including NiFe/NiCoO/glass/PZN-PT (011) and NiFe/FeMn/glass/PZN-PT (011). We designed this experiment to achieve exchange bias tuning along the magnetic easy axis, which is critical for realizing reversible 180° magnetization deterministic switching at zero or small magnetic bias. Strong exchange coupling were established across AFM-FM interfaces, which plays an important role in voltage control of magnetization switching. Through the competition between the E-field induced uniaxial anisotropy in ferromagnetic layer and unidirectional anisotropy in antiferromagnetic layer, the exchange bias was significantly shifted by up to |ΔHex|/Hex = 8% in NiFe/FeMn/glass/PZN-PT (011) and 13% in NiFe/NiCoO/glass/PZN-PT (011). In addition, the square shape of the hysteresis loop, as well as a strong shape tunability of |ΔHex|/Hc = 67.5 ~ 125% in NiFe/FeMn/glass/PZN-PT and 30 ~ 38% in NiFe/NiCoO/glass/PZN-PT were achieved, which lead to a near 180° magnetization switching. Electrical tuning of interfacial exchange coupling in FM/AFM/FE systems paves a new way for realizing magnetoelectric random access memories and other memory technologies.

Electric field induced reversible 180° magnetization switching through tuning of interfacial exchange bias along magnetic easy-axis in multiferroic laminates.

PubMed

Xue, Xu; Zhou, Ziyao; Peng, Bin; Zhu, Mingmin; Zhang, Yijun; Ren, Wei; Ren, Tao; Yang, Xi; Nan, Tianxiang; Sun, Nian X; Liu, Ming

2015-11-18

E-field control of interfacial exchange coupling and deterministic switching of magnetization have been demonstrated in two sets of ferromagnetic(FM)/antiferromagnetic(AFM)/ferroelectric(FE) multiferroic heterostructures, including NiFe/NiCoO/glass/PZN-PT (011) and NiFe/FeMn/glass/PZN-PT (011). We designed this experiment to achieve exchange bias tuning along the magnetic easy axis, which is critical for realizing reversible 180° magnetization deterministic switching at zero or small magnetic bias. Strong exchange coupling were established across AFM-FM interfaces, which plays an important role in voltage control of magnetization switching. Through the competition between the E-field induced uniaxial anisotropy in ferromagnetic layer and unidirectional anisotropy in antiferromagnetic layer, the exchange bias was significantly shifted by up to |∆Hex|/Hex = 8% in NiFe/FeMn/glass/PZN-PT (011) and 13% in NiFe/NiCoO/glass/PZN-PT (011). In addition, the square shape of the hysteresis loop, as well as a strong shape tunability of |∆Hex|/Hc = 67.5 ~ 125% in NiFe/FeMn/glass/PZN-PT and 30 ~ 38% in NiFe/NiCoO/glass/PZN-PT were achieved, which lead to a near 180° magnetization switching. Electrical tuning of interfacial exchange coupling in FM/AFM/FE systems paves a new way for realizing magnetoelectric random access memories and other memory technologies.

Multiple antiferromagnet/ferromagnet interfaces as a probe of grain-size-dependent exchange bias in polycrystalline Co/Fe 50Mn 50

NASA Astrophysics Data System (ADS)

Bolon, Bruce T.; Haugen, M. A.; Abin-Fuentes, A.; Deneen, J.; Carter, C. B.; Leighton, C.

2007-02-01

We have used ferromagnet/antiferromagnet/ferromagnet trilayers and ferromagnet/antiferromagnet multilayers to probe the grain size dependence of exchange bias in polycrystalline Co/Fe 50Mn 50. X-ray diffraction and transmission electron microscopy show that the Fe 50Mn 50 (FeMn) grain size increases with increasing FeMn thickness in the Co (30 Å)/FeMn system. Hence, in Co(30 Å)/FeMn( tAF Å)/Co(30 Å) trilayers the two Co layers sample different FeMn grain sizes at the two antiferromagnet/ferromagnet interfaces. For FeMn thicknesses above 100 Å, where simple bilayers have a thickness-independent exchange bias, we are therefore able to deduce the influence of FeMn grain size on the exchange bias and coercivity (and their temperature dependence) simply by measuring trilayer and multilayer samples with varying FeMn thicknesses. This can be done while maintaining the (1 1 1) orientation, and with little variation in interface roughness. Increasing the average grain size from 90 to 135 Å results in a fourfold decrease in exchange bias, following an inverse grain size dependence. We interpret the results as being due to a decrease in uncompensated spin density with increasing antiferromagnet grain size, further evidence for the importance of defect-generated uncompensated spins.

Atom probe study of B2 order and A2 disorder of the FeCo matrix in an Fe-Co-Mo-alloy.

PubMed

Turk, C; Leitner, H; Schemmel, I; Clemens, H; Primig, S

2017-07-01

The physical and mechanical properties of intermetallic alloys can be tailored by controlling the degree of order of the solid solution by means of heat treatments. FeCo alloys with an appropriate composition exhibit an A2-disorder↔B2-order transition during continuous cooling from the disordered bcc region. The study of atomic order in intermetallic alloys by diffraction and its influence on the material properties is well established, however, investigating magnetic FeCo-based alloys by conventional methods such as X-ray diffraction is quite challenging. Thus, the imaging of ordered FeCo-nanostructures needs to be done with high resolution techniques. Transmission electron microscopy investigations of ordered FeCo domains are difficult, due to the chemical and physical similarity of Fe and Co atoms and the ferromagnetism of the samples. In this work it will be demonstrated, that the local atomic arrangement of ordered and disordered regions in an industrial Fe-Co-Mo alloy can be successfully imaged by atom probe measurements supported by field ion microscopy and transmission Kikuchi diffraction. Furthermore, a thorough atom probe parameter study will be presented and field evaporation artefacts as a function of crystallographic orientation in Fe-Co-samples will be discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

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

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

Electronic and magnetic properties of Zn1-xFexSe alloys

NASA Astrophysics Data System (ADS)

Khatta, Swati; Tripathi, S. K.; Prakash, Satya

2017-12-01

The spin polarized density functional theory along with self consistent plane wave pseudopotential method is used to investigate electronic and magnetic properties of ternary Zn1-xFexSe alloys with x = 0.125, 0.25, 0.5 and 0.75. The exchange-correlation potential treated within generalized gradient approximation is used. The calculated spin-polarized band structures, partial and total density of states reveal that Zn0.875Fe0.125Se and Zn0.75Fe0.25Se exhibit half metallic ferromagnetic characteristics and Zn0.50Fe0.50Se is nearly half metallic in nature. The half metallic band gaps for x = 0.125 and 0.25 are 0.69 and 0.39 eV respectively, while the corresponding band gaps are 0.86 and 0.81 eV. The p-d hybridization reduces the magnetic moment of Fe atoms from its free space charge value of 4 μB and induces the small magnetic moments on Zn and Se sites. The results are compared with available experimental data.

Magnetic and interface properties of the core-shell Fe3O4/Au nanocomposites

NASA Astrophysics Data System (ADS)

Baskakov, A. O.; Solov'eva, A. Yu.; Ioni, Yu. V.; Starchikov, S. S.; Lyubutin, I. S.; Khodos, I. I.; Avilov, A. S.; Gubin, S. P.

2017-11-01

Core-shell Fe3O4/Au nanostructures were obtained with an advanced method of two step synthesis and several complementary methodics were applied for investigation structural and magnetic properties of the samples. Along with X-ray diffraction and transmission electron microscopy, electron diffraction, optical, Raman and Mössbauer spectroscopy were used for nanoparticle characterization. It was established that the physical and structural properties Fe3O4/Au nanocomposites are specific of intrinsic properties of gold and magnetite. Mössbauer and Raman spectroscopy data indicated that magnetite was in a nonstoichiometric state with an excess of trivalent iron both in the initial Fe3O4 nanoparticles and in the Fe3O4/Au nanocomposites. As follows from the Mössbauer data, magnetic properties of iron ions in the internal area (in core) and in the surface layer of magnetite nanoparticles are different due to the rupture of exchange bonds at the particles surface. This leads to decrease in an effective magnetic moment at the surface. Gold atoms at the interface of the composites interact with dangling bonds of magnetite and stabilize the magnetic properties of the surface layers of magnetite.

Electrical and magnetic properties of spherical SmFeO{sub 3} synthesized by aspartic acid assisted combustion method

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

Yuvaraj, Subramanian; Layek, Samar; Vidyavathy, S. Manisha

2015-12-15

Highlights: • SmFeO{sub 3} is synthesized by simple combustion method using aspartic acid as the fuel. • The particles are spherical in shape with the size ranges between 150 and 300 nm. • Cole–Cole plot infers the bulk conduction mechanism. • Room temperature VSM analysis reveal the weak ferromagnetic behaviour of SmFeO{sub 3}. • Mössbauer analysis elucidates the +3 oxidation state of Fe atoms. - Abstract: Samarium orthoferrite (SmFeO{sub 3}) is synthesized by a simple combustion method using aspartic acid as fuel. Phase purity and functional groups are analyzed via X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis, whichmore » confirms the single phase formation of orthorhombic SmFeO{sub 3}. Approximately spherical particles with size range 150–300 nm is revealed by scanning electron microscope (SEM). The conductivity of the material is identified by the single semicircle obtained in the solid state impedance spectra at elevated temperatures. The calculated electrical conductivity increases with increasing temperature, inferring the semiconducting nature of SmFeO{sub 3}. A magnetic study at room temperature revealed weak ferromagnetic behaviour in SmFeO{sub 3} due to Dzyaloshinsky–Moriya antisymmetric exchange interaction mechanism. Mössbauer analysis confirmed the +3 oxidation state of iron and magnetic ordering of the sample at room temperature.« less

Origins of giant biquadratic coupling in CoFe/Mn/CoFe sandwich structures (abstract)

NASA Astrophysics Data System (ADS)

Koon, Norman C.

1996-04-01

Recently Filipkowski et al. reported extremely strong, near 90 degree coupling of 2.5 erg/cm2 for epitaxial sandwiches of CoFe/Mn/CoFe, where the CoFe composition was chosen to be a good lattice match to Mn. Both CoFe and Mn have the bcc structure, but Mn is antiferromagnetic while CoFe is ferromagnetic. It was found that the data were very well described by a simple model due to Slonczewski, in which the interlayer coupling is given by Fc=C+(φ1-φ2)2+C-(φ1-φ2-π)2. While this model describes the data much better than the usual biquadratic form, it still does not connect directly to the microscopic origins of the effect. In the present work we seek to explain the results in terms of normal bilinear exchange and magnetocrystalline anisotropy, together with reasonable assumptions about the structure of the interfaces. We obtain excellent agreement with both the experimental results and the Slonczewski model under the assumptions that at least one of the two CoFe/Mn interfaces is smooth (i.e., atomically flat) on a length scale comparable to or greater than the thickness of the Mn layer and at least one interface is rough on a scale less than approximately a domain wall thickness.

Polaronic deformation at the Fe2+/3 + impurity site in Fe:LiNbO3 crystals

NASA Astrophysics Data System (ADS)

Sanson, A.; Zaltron, A.; Argiolas, N.; Sada, C.; Bazzan, M.; Schmidt, W. G.; Sanna, S.

2015-03-01

Iron doped LiNbO3 crystals with different iron valence states are investigated. An extended x-ray absorption fine structure (EXAFS) spectroscopy study highlights evident changes in the local structure around iron that can be ascribed to the presence of small polarons. In particular, when a Fe3+ replaced a Li ion, the oxygen octahedron shrinked with respect to the pure material, with an average iron-oxygen bond value very similar to that of Fe2O3 hematite. When adding an electron, it localizes at the Fe site in a configuration very close to the atomic Fe d orbitals, inducing a relaxation of the oxygen cage. The same system was modelled by spin-polarized density functional theory (DFT). Several local as well as hybrid exchange-correlation functionals were probed on the bulk LiNbO3 structural properties. The computation is then extended to the case of hematite and finally to the Fe defect in LiNbO3. The calculations reproduced with good accuracy the large lattice relaxation of the oxygen ligands associated to the electronic capture at the Fe center that can be interpreted as due to the polaron formation. The calculations reproduce satisfactorily the available EXAFS data, and allow for the estimation of the polaron energies and the optical properties of the defect.

Magnetic anisotropy of heteronuclear dimers in the gas phase and supported on graphene: relativistic density-functional calculations.

PubMed

Błoński, Piotr; Hafner, Jürgen

2014-04-09

The structural and magnetic properties of mixed PtCo, PtFe, and IrCo dimers in the gas phase and supported on a free-standing graphene layer have been calculated using density-functional theory, both in the scalar-relativistic limit and self-consistently including spin-orbit coupling. The influence of the strong magnetic moments of the 3d atoms on the spin and orbital moments of the 5d atoms, and the influence of the strong spin-orbit coupling contributed by the 5d atom on the orbital moments of the 3d atoms have been studied in detail. The magnetic anisotropy energy is found to depend very sensitively on the nature of the eigenstates in the vicinity of the Fermi level, as determined by band filling, exchange splitting and spin-orbit coupling. The large magnetic anisotropy energy of free PtCo and IrCo dimers relative to the easy direction parallel to the dimer axis is coupled to a strong anisotropy of the orbital magnetic moments of the Co atom for both dimers, and also on the Ir atom in IrCo. In contrast the PtFe dimer shows a weak perpendicular anisotropy and only small spin and orbital anisotropies of opposite sign on the two atoms. For dimers supported on graphene, the strong binding within the dimer and the stronger interaction of the 3d atom with the substrate stabilizes an upright geometry. Spin and orbital moments on the 3d atom are strongly quenched, but due to the weaker binding within the dimer the properties of the 5d atom are more free-atom-like with increased spin and orbital moments. The changes in the magnetic moment are reflected in the structure of the electronic eigenstates near the Fermi level, for all three dimers the easy magnetic direction is now parallel to the dimer axis and perpendicular to the graphene layer. The already very large magnetic anisotropy energy (MAE) of IrCo is further enhanced by the interaction with the support, the MAE of PtFe changes sign, and that of the PtCo dimer is reduced. These changes are discussed in relation to the relativistic electronic structure of free and supported dimers and it is demonstrated that the existence of a partially occupied quasi-degenerate state at the Fermi level favors the formation of a large magnetic anisotropy.

Enhanced Fe2O3 Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions

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

Hensley, Alyssa; Hong, Yongchun; Zhang, Renqin

2014-10-03

The synergistic catalysis in the hydrodeoxygenation of phenolic compounds over a Pd/Fe bimetallic surface has been well established. However, the nature of this synergy is still in part a mystery. In this work, we used a combined experimental and theoretical approach to understand a potential function of the surface Pd in the reduction of Pd/Fe2O3. This function of Pd was investigated via the comparison of the reduction properties as well as other physicochemical properties of samples synthesized by the reduction of Fe2O3 nanoparticles with and without surface Pd. Temperature-programmed reduction studies demonstrated the remarkable facilitation of reduction by addition ofmore » Pd, evidenced by a 150 degrees C shift toward lower temperature of the reduction peak of Fe3+. From X-ray photoelectron spectroscopy and theoretical calculation results, the interaction between Pd and the Fe2O3 surface occurs through the exchange of electrons with both the surface Fe and O atoms. This bonding between the Pd and surface oxide elements causes the Pd to partially donate electrons to the oxide surface, making the surface electrons more delocalized. This electron delocalization stabilizes the reduced oxide surfaces, as suggested by the TPR results and theoretical prediction. Therefore, the stabilization of the reduced Fe surface as well as the facilitated water formation by introduction of Pd is expected to significantly contribute to the Pd-Fe synergy in hydrodeoxygenation catalysis.« less

Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

PubMed

Joshi, Prachi; Gorski, Christopher A

2016-07-19

When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

Thickness dependence of exchange anisotropy for (0 0 1) oriented Mn 89Pt 11/NiFe and Mn 80Ir 20/NiFe bilayers

NASA Astrophysics Data System (ADS)

Kume, T.; Yamato, T.; Kato, T.; Tsunashima, S.; Iwata, S.

2007-03-01

Antiferromagnetic layer thickness dependences of exchange anisotropy for (0 0 1) oriented Mn 89Pt 11 ( tAF nm)/Ni 80Fe 20 (5 nm) and Mn 80Ir 20 ( tAF nm)/Ni 80Fe 20 (5 nm) were investigated. For Mn 89Pt 11/NiFe, the exchange bias field appeared at tAF⩾5 nm. This critical thickness was found to be thicker than that of Mn 80Ir 20/NiFe ( tAF=3 nm). The thickness dependence of exchange bias field agreed well with that of 1-fold Fourier amplitude estimated from in-plane torque curves. The large coercivity of about 100 Oe was found for Mn 89Pt 11/NiFe at tAF=30 nm compared to that of Mn 80Ir 20/NiFe. The large coercivity in Mn 89Pt 11/NiFe bilayers seems to result from the large 4-fold anisotropy in their torque curve.

Ligand Displacement Reaction Paths in a Diiron Hydrogenase Active Site Model Complex.

PubMed

Blank, Jan H; Moncho, Salvador; Lunsford, Allen M; Brothers, Edward N; Darensbourg, Marcetta Y; Bengali, Ashfaq A

2016-08-26

The mechanism and energetics of CO, 1-hexene, and 1-hexyne substitution from the complexes (SBenz)2 [Fe2 (CO)6 ] (SBenz=SCH2 Ph) (1-CO), (SBenz)2 [Fe2 (CO)5 (η(2) -1-hexene)] (1-(η(2) -1-hexene)), and (SBenz)2 [Fe2 (CO)5 (η(2) -1-hexyne)] (1-(η(2) -1-hexyne)) were studied by using time-resolved infrared spectroscopy. Exchange of both CO and 1-hexyne by P(OEt)3 and pyridine, respectively, proceeds by a bimolecular mechanism. As similar activation enthalpies are obtained for both reactions, the rate-determining step in both cases is assumed to be the rotation of the Fe(CO)2 L (L=CO or 1-hexyne) unit to accommodate the incoming ligand. The kinetic profile for the displacement of 1-hexene is quite different than that for the alkyne and, in this case, both reaction channels, that is, dissociative (SN 1) and associative (SN 2), were found to be competitive. Because DFT calculations predict similar binding enthalpies of alkene and alkyne to the iron center, the results indicate that the bimolecular pathway in the case of the alkyne is lower in free energy than that of the alkene. In complexes of this type, subtle changes in the departing ligand characteristics and the nature of the mercapto bridge can influence the exchange mechanism, such that more than one reaction pathway is available for ligand substitution. The difference between this and the analogous study of (μ-pdt)[Fe(CO)3 ]2 (pdt=S(CH2 )3 S) underscores the unique characteristics of a three-atom S-S linker in the active site of diiron hydrogenases. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric angular dependence of spin-transfer torques in CoFe/Mg-B-O/CoFe magnetic tunnel junctions

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

Tang, Ling, E-mail: lingtang@zjut.edu.cn; Xu, Zhi-Jun, E-mail: xzj@zjut.edu.cn; Zuo, Xian-Jun

Using a first-principles noncollinear wave-function-matching method, we studied the spin-transfer torques (STTs) in CoFe/Mg-B-O/CoFe(001) magnetic tunnel junctions (MTJs), where three different types of B-doped MgO in the spacer are considered, including B atoms replacing Mg atoms (Mg{sub 3}BO{sub 4}), B atoms replacing O atoms (Mg{sub 4}BO{sub 3}), and B atoms occupying interstitial positions (Mg{sub 4}BO{sub 4}) in MgO. A strong asymmetric angular dependence of STT can be obtained both in ballistic CoFe/Mg{sub 3}BO{sub 4} and CoFe/Mg{sub 4}BO{sub 4} based MTJs, whereas a nearly symmetric STT curve is observed in the junctions based on CoFe/Mg{sub 4}BO{sub 3}. Furthermore, the asymmetry ofmore » the angular dependence of STT can be suppressed significantly by the disorder of B distribution. Such skewness of STTs in the CoFe/Mg-B-O/CoFe MTJs could be attributed to the interfacial resonance states induced by the B diffusion into MgO spacer.« less

Database and Related Activities in Japan

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

Murakami, Izumi; Kato, Daiji; Kato, Masatoshi

2011-05-11

We have constructed and made available atomic and molecular (AM) numerical databases on collision processes such as electron-impact excitation and ionization, recombination and charge transfer of atoms and molecules relevant for plasma physics, fusion research, astrophysics, applied-science plasma, and other related areas. The retrievable data is freely accessible via the internet. We also work on atomic data evaluation and constructing collisional-radiative models for spectroscopic plasma diagnostics. Recently we have worked on Fe ions and W ions theoretically and experimentally. The atomic data and collisional-radiative models for these ions are examined and applied to laboratory plasmas. A visible M1 transition ofmore » W{sup 26+} ion is identified at 389.41 nm by EBIT experiments and theoretical calculations. We have small non-retrievable databases in addition to our main database. Recently we evaluated photo-absorption cross sections for 9 atoms and 23 molecules and we present them as a new database. We established a new association ''Forum of Atomic and Molecular Data and Their Applications'' to exchange information among AM data producers, data providers and data users in Japan and we hope this will help to encourage AM data activities in Japan.« less

Database and Related Activities in Japan

NASA Astrophysics Data System (ADS)

Murakami, Izumi; Kato, Daiji; Kato, Masatoshi; Sakaue, Hiroyuki A.; Kato, Takako; Ding, Xiaobin; Morita, Shigeru; Kitajima, Masashi; Koike, Fumihiro; Nakamura, Nobuyuki; Sakamoto, Naoki; Sasaki, Akira; Skobelev, Igor; Tsuchida, Hidetsugu; Ulantsev, Artemiy; Watanabe, Tetsuya; Yamamoto, Norimasa

2011-05-01

We have constructed and made available atomic and molecular (AM) numerical databases on collision processes such as electron-impact excitation and ionization, recombination and charge transfer of atoms and molecules relevant for plasma physics, fusion research, astrophysics, applied-science plasma, and other related areas. The retrievable data is freely accessible via the internet. We also work on atomic data evaluation and constructing collisional-radiative models for spectroscopic plasma diagnostics. Recently we have worked on Fe ions and W ions theoretically and experimentally. The atomic data and collisional-radiative models for these ions are examined and applied to laboratory plasmas. A visible M1 transition of W26+ ion is identified at 389.41 nm by EBIT experiments and theoretical calculations. We have small non-retrievable databases in addition to our main database. Recently we evaluated photo-absorption cross sections for 9 atoms and 23 molecules and we present them as a new database. We established a new association "Forum of Atomic and Molecular Data and Their Applications" to exchange information among AM data producers, data providers and data users in Japan and we hope this will help to encourage AM data activities in Japan.

Thermoelectric properties of the unfilled skutterudite FeSb 3 from first principles and Seebeck local probes

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

Lemal, Sébastien; Nguyen, Ngoc; de Boor, Johannes

2015-11-16

In this paper, using a combination of first-principles calculations and experimental transport measurements, we study the electronic and magnetic structure of the unfilled skutterudite FeSb 3. We employ the hybrid functional approach for exchange correlation. The ground state is determined to be antiferromagnetic with an atomic magnetic moment of 1.6μ B/Fe. The Néel temperature T N is estimated at 6 K, in agreement with experiments which found a paramagnetic state down to 10 K. The ground state is semiconducting, with a small electronic gap of 33meV, also consistent with previous experiments on films. Charge carrier concentrations are estimated from Hallmore » resistance measurements. The Seebeck coefficient is measured and mapped using a scanning probe at room temperature that yields an average value of 38.6μVK -1, slightly lower than the theoretical result. Finally, the theoretical conductivity is analyzed as a function of temperature and concentration of charge carriers.« less

Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Nastar, Maylise

2016-06-01

We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

Interfacial magnetism and exchange coupling in BiFeO3-CuO nanocomposite.

PubMed

Chakrabarti, Kaushik; Sarkar, Babusona; Ashok, Vishal Dev; Das, Kajari; Chaudhuri, Sheli Sinha; De, S K

2013-12-20

Ferromagnetic BiFeO3 nanocrystals of average size 9 nm were used to form a composite with antiferromagnetic CuO nanosheets, with the composition (x)BiFeO3/(100-x)CuO, x = 0, 20, 40, 50, 60, 80 and 100. The dispersion of BiFeO3 nanocrystals into the CuO matrix was confirmed by x-ray diffraction and transmission electron microscopy. The ferromagnetic ordering as observed in pure BiFeO3 occurs mainly due to the reduction in the particle size as compared to the wavelength (62 nm) of the spiral modulated spin structure of the bulk BiFeO3. Surface spin disorder of BiFeO3 nanocrystals gives rise to an exponential behavior of magnetization with temperature. Strong magnetic exchange coupling between the BiFeO3 nanocrystal and the CuO matrix induces an interfacial superparamagnetic phase with a blocking temperature of about 80 K. Zero field and field cooled magnetizations are analyzed by a ferromagnetic core and disordered spin shell model. The temperature dependence of the calculated saturation magnetization exhibits three magnetic contributions in three temperature regimes. The BiFeO3/CuO nanocomposites reveal an exchange bias effect below 170 K. The maximum exchange bias field HEB is 1841 Oe for x = 50 at 5 K under field cooling of 50 kOe. The exchange bias coupling results in an increase of coercivity of 1934 Oe at 5 K. Blocked spins within an interfacial region give rise to a remarkable exchange bias effect in the nanocomposite due to strong magnetic exchange coupling between the BiFeO3 nanocrystals and the CuO nanosheets.

Identification of O-rich structures on platinum(111)-supported ultrathin iron oxide films

DOE PAGES

Merte, Lindsay R.; Bai, Yunhai; Zeuthen, Helene; ...

2016-01-06

Using high-resolution scanning tunneling microscopy (STM) we have studied the oxidation of ultrathin FeO films grown on Pt(111). At the initial stage of the FeO film oxidation by atomic oxygen exposure, we identified three distinct types of line defects, all of which form boundaries between FeO domains of opposite orientation. Two types of line defects appearing bright ( type-i) and dark ( type-ii) in the STM images at typical scanning parameters are “metallic”, whereas the third line defect exhibits nonmetallic behavior ( type-iii). Atomic-scale structure models of these line defects are proposed, with type-i defects exhibiting 4-fold coordinated Fe atoms,more » type-ii exhibiting 2-fold coordinated O atoms, and type-iii exhibiting tetrahedrally-coordinated Fe atoms. In addition, FeO 2 trilayer islands are formed upon oxidation, which appear at FCC-type domains of the moiré structure. At high scanning bias, distinct protrusions on the trilayer islands are observed over surface O ions, which are assigned to H adatoms. The experimental data are supported by density functional theory (DFT) calculations, in which bare and hydroxylated FeO 2 trilayer islands are compared. Finally, we compare the formation of O-rich features on continuous FeO films using atomic oxygen with the oxidation of Pt(111)-supported FeO islands accomplished by O 2 exposure.« less

Observation of hidden atomic order at the interface between Fe and topological insulator Bi2Te3.

PubMed

Sánchez-Barriga, Jaime; Ogorodnikov, Ilya I; Kuznetsov, Mikhail V; Volykhov, Andrey A; Matsui, Fumihiko; Callaert, Carolien; Hadermann, Joke; Verbitskiy, Nikolay I; Koch, Roland J; Varykhalov, Andrei; Rader, Oliver; Yashina, Lada V

2017-11-22

To realize spintronic devices based on topological insulators (TIs), well-defined interfaces between magnetic metals and TIs are required. Here, we characterize atomically precisely the interface between the 3d transition metal Fe and the TI Bi 2 Te 3 at different stages of its formation. Using photoelectron diffraction and holography, we show that after deposition of up to 3 monolayers Fe on Bi 2 Te 3 at room temperature, the Fe atoms are ordered at the interface despite the surface disorder revealed by our scanning-tunneling microscopy images. We find that Fe occupies two different sites: a hollow adatom deeply relaxed into the Bi 2 Te 3 quintuple layers and an interstitial atom between the third (Te) and fourth (Bi) atomic layers. For both sites, our core-level photoemission spectra and density-functional theory calculations demonstrate simultaneous chemical bonding of Fe to both Te and Bi atoms. We further show that upon deposition of Fe up to a thickness of 20 nm, the Fe atoms penetrate deeper into the bulk forming a 2-5 nm interface layer containing FeTe. In addition, excessive Bi is pushed down into the bulk of Bi 2 Te 3 leading to the formation of septuple layers of Bi 3 Te 4 within a distance of ∼25 nm from the interface. Controlling the magnetic properties of the complex interface structures revealed by our work will be of critical importance when optimizing the efficiency of spin injection in TI-based devices.

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

DOE PAGES

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

2017-03-24

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

PubMed

de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

2017-04-18

We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acidity and hydrogen exchange dynamics of iron(II)-bound nitroxyl in aqueous solution.

PubMed

Gao, Yin; Toubaei, Abouzar; Kong, Xianqi; Wu, Gang

2014-10-20

Nitroxyl-iron(II) (HNO-Fe(II)) complexes are often unstable in aqueous solution, thus making them very difficult to study. Consequently, many fundamental chemical properties of Fe(II)-bound HNO have remained unknown. Using a comprehensive multinuclear ((1)H, (15)N, (17)O) NMR approach, the acidity of the Fe(II)-bound HNO in [Fe(CN)5(HNO)](3-) was investigated and its pK(a) value was determined to be greater than 11. Additionally, HNO undergoes rapid hydrogen exchange with water in aqueous solution and this exchange process is catalyzed by both acid and base. The hydrogen exchange dynamics for the Fe(II)-bound HNO have been characterized and the obtained benchmark values, when combined with the literature data on proteins, reveal that the rate of hydrogen exchange for the Fe(II)-bound HNO in the interior of globin proteins is reduced by a factor of 10(6). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ferromagnetic Coupling of Mononuclear Fe Centers in a Self-Assembled Metal-Organic Network on Au(111)

NASA Astrophysics Data System (ADS)

Umbach, T. R.; Bernien, M.; Hermanns, C. F.; Krüger, A.; Sessi, V.; Fernandez-Torrente, I.; Stoll, P.; Pascual, J. I.; Franke, K. J.; Kuch, W.

2012-12-01

The magnetic state and magnetic coupling of individual atoms in nanoscale structures relies on a delicate balance between different interactions with the atomic-scale surroundings. Using scanning tunneling microscopy, we resolve the self-assembled formation of highly ordered bilayer structures of Fe atoms and organic linker molecules (T4PT) when deposited on a Au(111) surface. The Fe atoms are encaged in a three-dimensional coordination motif by three T4PT molecules in the surface plane and an additional T4PT unit on top. Within this crystal field, the Fe atoms retain a magnetic ground state with easy-axis anisotropy, as evidenced by x-ray absorption spectroscopy and x-ray magnetic circular dichroism. The magnetization curves reveal the existence of ferromagnetic coupling between the Fe centers.

Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges

PubMed Central

Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M.; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H.

2014-01-01

Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp2 carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations. PMID:25331874

3D Polymer Hydrogel for High-Performance Atomic Fe and Mn Catalysts for Oxygen Reduction in Challenging Acids

NASA Astrophysics Data System (ADS)

Qiao, Zhi

Current platinum group metal (PGM)-free carbon nanocomposite catalysts for the oxygen reduction reaction (ORR) in acidic electrolyte often suffer from rapid degradation associated with carbon corrosion due to the use of large amount of the amorphoous carbon black supports. Here, we developed a new concept of using freestanding 3D hydrogel to design support-free Fe-N-C catalysts. A 3D polyaniline (PANI)-based hydrogel approach was used for preparing a new type of single atomic iron site-rich catalyst, which has exhibited exceptionally enhanced activity and stability compared to conventional Fe-N-C catalysts supported on amorphous carbon blacks. The achieved performance metric on the hydrogel PANI-Fe catalysts is one of the best ever reported PGM-free catalysts, reaching a half-wave potential up to 0.83 V vs. RHE and only leaving 30 mV gap with Pt/C catalysts (60mugPt/cm 2) in challenging acidic media. Remarkable ORR stability was accomplished as well on the same catalyst evidenced by using harsh potential cycling tests. The well dispersion of atomic iron into partially graphitized carbon, featured with dominance of micropores and porous network structures, is capable of accommodating increased number of active sites, strengthening local bonding among iron, nitrogen and carbon, and facilitating mass transfer. On the other hand, in order to decrease the produced Fenton reagent, which will oxidize the proton exchange membrane and ionomer in membrane electrode assembly (MEA), we produce Mn-based catalysts by this novel hydrogel method. This is the first time that Mn-based catalysts can show such outstanding performance in acid media, whose half-wave potential is up to 0.80 V vs. RHE. The work related to the performance improvement is still in processing. We believe the 3D polymer hydrogel approach would be a new pathway to advance PGM-free catalysts.

Iron cycling under oscillatory redox conditions: from observations to processes

NASA Astrophysics Data System (ADS)

Meile, C. D.; Chen, C.; Barcellos, D.; Wilmoth, J.; Thompson, A.

2017-12-01

Fe oxyhydroxides play a critical role in soils through their role as structural entities, their high sorption capacity, their role as terminal electron acceptors in the respiration of organic matter, as well as their potential to affect the reactivity of that organic matter. In soils that undergo repeated fluctuations in O2 concentrations, soil iron undergoes transformations between reduced and oxidized forms. The rate of Fe(II) oxidation can govern the nature of Fe(III) oxyhydroxides formed, and hence can affect rates of OC mineralization under suboxic conditions. But it remains unclear if this same behavior occurs in soils, where Fe(II) is mainly present as surface complexes. We documented the impact of such redox oscillations on iron cycling through targeted experiments, in which the magnitude and frequency of redox oscillations were varied systematically on soils from the Luquillo Critical Zone Observatory, Puerto Rico. Our observations demonstrated that higher O2 concentrations led to a faster Fe(II) oxidation and resulted in less crystalline Fe(III)-oxyhydroxides than lower O2 concentrations. We further studied the dynamics of iron phases by amending soil slurries with isotopically-labeled 57Fe(II) and developed a numerical model to quantify the individual processes. Our model showed a higher rate of Fe(III) reduction and increased sorption capacity following the oxidation of Fe(II) at high O2 levels than at low O2 levels, and revealed rapid Fe atom exchange between solution and solid phase. Concurrent measurements of CO2 in our oscillation experiments further illustrated the importance O2 fluctuations on coupled Fe-C dynamics.

Tuning the exchange bias in NiFe/Fe-oxide bilayers by way of different Fe-oxide based mixtures made with an ion-beam deposition technique.

PubMed

Lin, K W; Kol, P H; Guo, Z Y; Ouyang, H; van Lierop, J

2007-01-01

We have investigated the structural and magnetic properties of ion-beam deposited polycrystalline NiFe (25 nm)/Fe-oxide (35 nm) bilayers. A film prepared with an assist beam O2 to Ar gas ratio of 0% during deposition had a bottom layer that consisted of pure b.c.c. Fe (a = 2.87 A) whereas films prepared with 19%O2/Ar and 35%O2/Ar had either Fe3O4 (a = 8.47 angstroms) or alpha-Fe2O3 (a = 5.04 angstroms, c = 13.86 angstroms) bottom layers, respectively. Cross-sectional transmission electron microscopy revealed a smooth interface between the top nano-columnar NiFe and bottom nano-columnar Fe-oxide layer for all films. At room temperature, the observed coercivity (Hc approximately 25 Oe) for a film prepared with 19% O2/Ar indicates the existence of a magnetically hard ferrimagnetic Fe3O4 phase that is enhancing the plain NiFe (Hc approximately 2 Oe) by way of exchange coupling. A significant amount of exchange bias is observed below 50 K, and at 10 K the size of exchange bias hysteresis loops shift increases with increasing oxygen in the films. Furthermore, the strongest exchange coupling (H(ex) approximately 135 Oe at 10 K) is with alpha-Fe2O3 (35% O2/Ar) as the bottom film layer. This indicates that the pure antiferromagnetic phases work better than ferrimagnetic phases when in contact with ferromagnetic NiFe. H(ex) (T) is well described by an effective AF domain wall energy that creates an exchange field with a (1 - T/T(crit)) temperature dependence. Hc (T) exhibits three distinct regimes of constant temperature that may indicate the existence of different AF spin populations that couple to the FM layer at different temperatures.

Dirac State in the FeB2 Monolayer with Graphene-Like Boron Sheet.

PubMed

Zhang, Haijun; Li, Yafei; Hou, Jianhou; Du, Aijun; Chen, Zhongfang

2016-10-12

By introducing the commonly utilized Fe atoms into a two-dimensional (2D) honeycomb boron network, we theoretically designed a new Dirac material of FeB 2 monolayer with a Fermi velocity in the same order of graphene. The electron transfer from Fe atoms to B networks not only effectively stabilizes the FeB 2 networks but also leads to the strong interaction between the Fe and B atoms. The Dirac state in FeB 2 system primarily arises from the Fe d orbitals and hybridized orbital from Fe-d and B-p states. The newly predicted FeB 2 monolayer has excellent dynamic and thermal stabilities and is also the global minimum of 2D FeB 2 system, implying its experimental feasibility. Our results are beneficial to further uncovering the mechanism of the Dirac cones and providing a feasible strategy for Dirac materials design.

Helium behavior in oxide dispersion strengthened (ODS) steel: Insights from ab initio modeling

NASA Astrophysics Data System (ADS)

Sun, Dan; Li, Ruihuan; Ding, Jianhua; Huang, Shaosong; Zhang, Pengbo; Lu, Zheng; Zhao, Jijun

2018-02-01

Using first-principles calculations, we systemically investigate the energetics and stability behavior of helium (He) atoms and small Hen (n = 2-4) clusters inside oxide dispersion strengthened (ODS) steel, as well as the incorporation of large amount of He atoms inside Y2O3 crystal. From the energetic point of view, He atom inside Y2O3 cluster is most stable, followed by the interstitial sites at the α-Fe/Y2O3 interface, and the tetrahedral interstitial sites inside α-Fe region. We further consider Hen (n = 2-4) clusters at the tetrahedral interstitial site surrounded by four Y atoms, which is the most stable site in the ODS steel model. The incorporation energies of all these Hen clusters are lower than that of single He atom in α-Fe, while the binding energy between two He atoms is relatively small. With insertion of 15 He atoms into 80-atom unit cell of Y2O3 crystal, the incorporation energy of He atoms is still lower than that of He4 cluster in α-Fe crystal. These theoretical results suggest that He atoms tend to aggregate inside Y2O3 clusters or at the α-Fe/Y2O3 interface, which is beneficial to prevent the He embrittlement in ODS steels.

Exchange Interactions on the Highest-Spin Reported Molecule: the Mixed-Valence Fe42 Complex

NASA Astrophysics Data System (ADS)

Aravena, Daniel; Venegas-Yazigi, Diego; Ruiz, Eliseo

2016-04-01

The finding of high-spin molecules that could behave as conventional magnets has been one of the main challenges in Molecular Magnetism. Here, the exchange interactions, present in the highest-spin molecule published in the literature, Fe42, have been analysed using theoretical methods based on Density Functional Theory. The system with a total spin value S = 45 is formed by 42 iron centres containing 18 high-spin FeIII ferromagnetically coupled and 24 diamagnetic low-spin FeII ions. The bridging ligands between the two paramagnetic centres are two cyanide ligands coordinated to the diamagnetic FeII cations. Calculations were performed using either small Fe4 or Fe3 models or the whole Fe42 complex, showing the presence of two different ferromagnetic couplings between the paramagnetic FeIII centres. Finally, Quantum Monte Carlo simulations for the whole system were carried out in order to compare the experimental and simulated magnetic susceptibility curves from the calculated exchange coupling constants with the experimental one. This comparison allows for the evaluation of the accuracy of different exchange-correlation functionals to reproduce such magnetic properties.

Binding of dinitrogen to an iron-sulfur-carbon site

NASA Astrophysics Data System (ADS)

Čorić, Ilija; Mercado, Brandon Q.; Bill, Eckhard; Vinyard, David J.; Holland, Patrick L.

2015-10-01

Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2-bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site.

Effect of L1{sub 2} ordering in antiferromagnetic Ir-Mn epitaxial layer on exchange bias of FePd films

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

Chang, Y. C.; Duh, J. G., E-mail: pmami.hsiao@gmail.com, E-mail: lin.yg@nsrrc.org.tw, E-mail: jgd@mx.nthu.edu.tw; Hsiao, S. N., E-mail: pmami.hsiao@gmail.com, E-mail: lin.yg@nsrrc.org.tw, E-mail: jgd@mx.nthu.edu.tw

2015-05-07

Two series of samples of single-layer IrMn and IrMn/FePd bilayer films, deposited on a single-crystal MgO substrate at different IrMn deposition temperatures (T{sub s} = 300–700 °C), were investigated using magnetron sputtering. L1{sub 2} ordering was revealed for the 30 nm-thick IrMn epitaxial (001) films with T{sub s} ≥ 400 °C, determined by synchrotron radiation x-ray diffractometry (XRD). XRD results also provide evidence of the epitaxial growth of the IrMn films on MgO substrate. Increasing T{sub s} from 400 to 700 °C monotonically increases the ordering parameter of L1{sub 2} phases from 0.17 to 0.81. An in-plane exchange bias field (H{sub eb}) of 22 Oe is obtained in amore » 10 nm-thick FePd film that is deposited on the disordered IrMn films. As the L1{sub 2} ordering of the IrMn layers increases, the H{sub eb} gradually decreases to 0 Oe, meaning that the exchange bias behavior vanishes. The increased surface roughness, revealed by atomic force microscopy, of the epitaxial IrMn layers with increasing T{sub s} cannot be the main cause of the decrease in H{sub eb} due to the compensated surface spins regardless of the disordered and ordered (001) IrMn layers. The change of antiferromagnetic structure from the A1 to the L1{sub 2} phase was correlated with the evolution of H{sub eb}.« less

Many-particle effects in adsorbed magnetic atoms with easy-axis anisotropy: the case of Fe on the CuN/Cu(100) surface

NASA Astrophysics Data System (ADS)

Žitko, R.; Pruschke, Th

2010-06-01

We study the effects of the exchange interaction between an adsorbed magnetic atom with easy-axis magnetic anisotropy and the conduction-band electrons from the substrate. We model the system using an anisotropic Kondo model and we compute the impurity spectral function, which is related to the differential conductance (dI/dV) spectra measured using a scanning tunneling microscope. To make contact with the known experimental results for iron atoms on the CuN/Cu(100) surface (Hirjibehedin et al 2007 Science 317 1199), we calculated the spectral functions in the presence of an external magnetic field of varying strength applied along all three spatial directions. It is possible to establish an upper bound on the coupling constant J: in the range of the magnetic fields for which the experimental results are currently known (up to 7 T), the low-energy features in the calculated spectra agree well with the measured dI/dV spectra if the exchange coupling constant J is at most half as large as that for cobalt atoms on the same surface. We show that for an even higher magnetic field (between 8 and 9 T) applied along the 'hollow direction', the impurity energy states cross, giving rise to a Kondo effect which takes the form of a zero-bias resonance. The coupling strength J could be determined experimentally by performing tunneling spectroscopy in this range of magnetic fields. On the technical side, the paper introduces an approach for calculating the expectation values of global spin operators and all the components of the impurity magnetic susceptibility tensor (including the out-of-diagonal ones) in numerical renormalization group (NRG) calculations with no spin symmetry. An appendix contains a density functional theory (DFT) study of the Co and Fe adsorbates on the CuN/Cu(100) surface: we compare magnetic moments, as well as orbital energies, occupancies, centers and spreads, by calculating the maximally localized Wannier orbitals of the adsorbates.

H T P21/ c- C2/ c phase transition and kinetics of Fe2+-Mg order-disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

NASA Astrophysics Data System (ADS)

Alvaro, Matteo; Cámara, Fernando; Domeneghetti, M. Chiara; Nestola, Fabrizio; Tazzoli, Vittorio

2011-09-01

A natural Ca-poor pigeonite (Wo6En76Fs18) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P21/ c, was annealed up to 1,093°C to induce a phase transition from P21/ c to C2/ c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections ( h + k = 2 n + 1, present only in the P21/ c phase) showed a displacive phase transition P21/ c to C2/ c at a transition temperature T Tr = 944°C, first order in character. The Fe-Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe-Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k D versus 1/ T yielded the following equation: ln k_{{D}} = - 3717( ± 416)/T(K) + 1.290( ± 0.378);quad (R2 = 0.988) . The closure temperature ( T c) calculated using this equation was ˜740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe-Mg degree of order, performed according to Mueller's model, allowed us to retrieve the disordering rate constants C 0 K {dis/+} for all three temperatures yielding the following Arrhenius relation: ln ( {C0 K_{{dis}}^{ + } } ) = ln K0 - Q/(RT) = 20.99( ± 3.74) - 26406( ± 4165)/T(K);quad (R2 = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe-Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X Fe (in the range of X Fe = 0.20-0.50): ln ( {C0 K_{{dis}}^{ + } } ) = (21.185 - 1.47X_{{Fe}} ) - {{(27267 - 4170X_{{Fe}} )}/T(K)} . The cooling time constant, η = 6 × 10-1 K-1 year-1 calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.

Observation of magnetization and exchange bias reversals in NdFe0.5Cr0.5O3

NASA Astrophysics Data System (ADS)

Sharannia, M. P.; De, Santanu; Singh, Ripandeep; Das, A.; Nirmala, R.; Santhosh, P. N.

2017-05-01

Polycrystalline NdFe0.5Cr0.5O3 has orthorhombic structure with Pnma space group and is magnetically ordered at room temperature as confirmed by neutron diffraction. The magnetic structure involves CxGyFz type ordering of Fe3+/Cr3+ ions. NdFe0.5Cr0.5O3 shows magnetization reversal and sign reversal of exchange bias at 16 K. Nd3+ moments that get induced by the internal field of |Fe+Cr| sublattice couple antiferromagnetically with the ferromagnetic component of |Fe+Cr| sublattice. Nd3+ moments overcome the |Fe+Cr| moments at 16 K below which the material shows negative magnetization and positive exchange bias.

Comparative assessment of the methods for exchangeable acidity measuring

NASA Astrophysics Data System (ADS)

Vanchikova, E. V.; Shamrikova, E. V.; Bespyatykh, N. V.; Zaboeva, G. A.; Bobrova, Yu. I.; Kyz"yurova, E. V.; Grishchenko, N. V.

2016-05-01

A comparative assessment of the results of measuring the exchangeable acidity and its components by different methods was performed for the main mineral genetic horizons of texturally-differentiated gleyed and nongleyed soddy-podzolic and gley-podzolic soils of the Komi Republic. It was shown that the contents of all the components of exchangeable soil acidity determined by the Russian method (with potassium chloride solution as extractant, c(KCl) = 1 mol/dm3) were significantly higher than those obtained by the international method (with barium chloride solution as extractant, c(BaCl2) = 0.1 mol/dm3). The error of the estimate of the concentration of H+ ions extracted with barium chloride solution equaled 100%, and this allowed only qualitative description of this component of the soil acidity. In the case of the extraction with potassium chloride, the error of measurements was 50%. It was also shown that the use of potentiometric titration suggested by the Russian method overestimates the results of soil acidity measurement caused by the exchangeable metal ions (Al(III), Fe(III), and Mn(II)) in comparison with the atomic emission method.

From single magnetic adatoms on superconductors to coupled spin chains

NASA Astrophysics Data System (ADS)

Franke, Katharina J.

Magnetic adsorbates on conventional s-wave superconductors lead to exchange interactions that induce Yu-Shiba-Rusinov (YSR) states inside the superconducting energy gap. Here, we employ tunneling spectroscopy at 1.1 K to investigate magnetic atoms and chains on superconducting Pb surfaces. We show that individual Manganese (Mn) atoms give rise to a distinct number of YSR-states. The single-atom junctions are stable over several orders of magnitude in conductance. We identify single-electron tunneling as well as Andreev processes. When the atoms are brought into sufficiently close distance, the Shiba states hybridize, thus giving rise to states with bonding and anti-bonding character. It has been shown that the Pb(110) surface supports the self-assembly of Fe chains, which exhibit fingerprints of Majorana bound states. Using superconducting tips, we resolve a rich subgap structure including peaks at zero energy and low-energy resonances, which overlap with the putative Majorana states. We gratefully acknowledge funding by the Deutsche Forschungsgemeinschaft through collaborative research Grant Sfb 658, and through Grant FR2726/4, as well by the European Research Council through Consolidator Grant NanoSpin.

Dimensionality effects on magnetic properties of FexCo1-x nanoclusters on Pt(1 1 1)

NASA Astrophysics Data System (ADS)

Miranda, I. P.; Igarashi, R. N.; Klautau, A. B.; Petrilli, H. M.

2017-11-01

The behavior of local magnetic moments and exchange coupling parameters of FexCo1-x nanostructures (nanowires and compact clusters) on the fcc Pt(1 1 1) surface is here investigated using the first-principles real-space RS-LMTO-ASA method, in the framework of the DFT. Different configurations of FexCo1-x trimers and heptamers on Pt(1 1 1) are considered, varying the positions and the concentration of Fe or Co atoms. We discuss the influence of dimensionality and stoichiometry changes on the magnetic properties, specially on the orbital moments, which are very important in establishing a nanoscopic understanding of delocalized electron systems. We demonstrate the existence of a strictly decreasing nonlinear trend of the average orbital moments with the Fe concentration for the compact clusters, different from what was found for FexCo1-x nanowires on Pt(1 1 1) and also for corresponding higher-dimensional systems (FexCo1-x monolayer on Pt(1 1 1) and FexCo1-x bulk). The average spin moments, however, are invariably described by a linear function with respect to stoichiometry. In all studied cases, the nearest neighbors exchange couplings have shown to be strongly ferromagnetic.

Non-Target Effect for Chromosome Aberrations in Human Lymphocytes and Fibroblasts After Exposure to Very Low Doses of High LET Radiation

NASA Technical Reports Server (NTRS)

Hada, Megumi; George, Kerry A.; Cucinotta, F. A.

2011-01-01

The relationship between biological effects and low doses of absorbed radiation is still uncertain, especially for high LET radiation exposure. Estimates of risks from low-dose and low-dose-rates are often extrapolated using data from Japanese atomic bomb survivor with either linear or linear quadratic models of fit. In this study, chromosome aberrations were measured in human peripheral blood lymphocytes and normal skin fibroblasts cells after exposure to very low dose (.01 - 0.2 Gy) of 170 MeV/u Si-28-ions or 600 MeV/u Fe-56-ions. Chromosomes were analyzed using the whole chromosome fluorescence in situ hybridization (FISH) technique during the first cell division after irradiation, and chromosome aberrations were identified as either simple exchanges (translocations and dicentrics) or complex exchanges (involving >2 breaks in 2 or more chromosomes). The curves for doses above 0.1 Gy were more than one ion traverses a cell showed linear dose responses. However, for doses less than 0.1 Gy, Si-28-ions showed no dose response, suggesting a non-targeted effect when less than one ion traversal occurs. Additional findings for Fe-56 will be discussed.

Atomic structures of B20 FeGe thin films grown on the Si(111) surface

NASA Astrophysics Data System (ADS)

Kim, Wondong; Noh, Seungkyun; Yoon, Jisoo; Kim, Young Heon; Lee, Inho; Kim, Jae-Sung; Hwang, Chanyong

We investigated the growth and atomic structures of FeGe thin films on the Si (111) surface by using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). The 2 5nm- thick FeGe thin films were prepared on the clean Si(111) 7x7 surface by co-deposition of Fe and Ge from separated electron-beam evaporators. With direct deposition on the substrate at the temperature above 550 K, the surface of FeGe films was not smooth and consisted of coarse grains. By the combination of room-temperature annealing and post-annealing process around 800 K, the structure of FeGe thin films evolved into the well crystalized structures. Atom-resolved STM images revealed that there are at least four different surface terminations. We constructed atomic models for each surface terminations based on the bulk atomic arrangement of a B20 chiral structure and confirmed that the observed STM images are successfully reproduced by using computational simulations employing Vienna Ab Initio Simulation package (VASP) with a B20 chiral structure model. TEM cross-sectional images also support our atomic models by revealing clearly the characteristic zigzag features of B20 structures of FeGe(111) thin films.

Design and performance of an ultra-high vacuum spin-polarized scanning tunneling microscope operating at 30 mK and in a vector magnetic field

NASA Astrophysics Data System (ADS)

von Allwörden, Henning; Eich, Andreas; Knol, Elze J.; Hermenau, Jan; Sonntag, Andreas; Gerritsen, Jan W.; Wegner, Daniel; Khajetoorians, Alexander A.

2018-03-01

We describe the design and performance of a scanning tunneling microscope (STM) that operates at a base temperature of 30 mK in a vector magnetic field. The cryogenics is based on an ultra-high vacuum (UHV) top-loading wet dilution refrigerator that contains a vector magnet allowing for fields up to 9 T perpendicular and 4 T parallel to the sample. The STM is placed in a multi-chamber UHV system, which allows in situ preparation and exchange of samples and tips. The entire system rests on a 150-ton concrete block suspended by pneumatic isolators, which is housed in an acoustically isolated and electromagnetically shielded laboratory optimized for extremely low noise scanning probe measurements. We demonstrate the overall performance by illustrating atomic resolution and quasiparticle interference imaging and detail the vibrational noise of both the laboratory and microscope. We also determine the electron temperature via measurement of the superconducting gap of Re(0001) and illustrate magnetic field-dependent measurements of the spin excitations of individual Fe atoms on Pt(111). Finally, we demonstrate spin resolution by imaging the magnetic structure of the Fe double layer on W(110).

Design and performance of an ultra-high vacuum spin-polarized scanning tunneling microscope operating at 30 mK and in a vector magnetic field.

PubMed

von Allwörden, Henning; Eich, Andreas; Knol, Elze J; Hermenau, Jan; Sonntag, Andreas; Gerritsen, Jan W; Wegner, Daniel; Khajetoorians, Alexander A

2018-03-01

We describe the design and performance of a scanning tunneling microscope (STM) that operates at a base temperature of 30 mK in a vector magnetic field. The cryogenics is based on an ultra-high vacuum (UHV) top-loading wet dilution refrigerator that contains a vector magnet allowing for fields up to 9 T perpendicular and 4 T parallel to the sample. The STM is placed in a multi-chamber UHV system, which allows in situ preparation and exchange of samples and tips. The entire system rests on a 150-ton concrete block suspended by pneumatic isolators, which is housed in an acoustically isolated and electromagnetically shielded laboratory optimized for extremely low noise scanning probe measurements. We demonstrate the overall performance by illustrating atomic resolution and quasiparticle interference imaging and detail the vibrational noise of both the laboratory and microscope. We also determine the electron temperature via measurement of the superconducting gap of Re(0001) and illustrate magnetic field-dependent measurements of the spin excitations of individual Fe atoms on Pt(111). Finally, we demonstrate spin resolution by imaging the magnetic structure of the Fe double layer on W(110).

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

NASA Astrophysics Data System (ADS)

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-O multilayers. Firstly, the formation energy and the cohesive energy of the multilayers are discussed. For optimised values, the cohesive energy of the multilayers to obtain the lattice parameters at the equilibrium ground state was used, i.e. a new methodology for this calculus was applied. Secondly, the magnetic properties and hyperfine interactions (magnetic field, electric field gradient and the isomer shift) of the iron atoms of the multilayers are discussed.

Origin of high thermoelectric performance of FeNb1−xZr/HfxSb1−ySny alloys: A first-principles study

PubMed Central

Zhang, Xiwen; Wang, Yuanxu; Yan, Yuli; Wang, Chao; Zhang, Guangbiao; Cheng, Zhenxiang; Ren, Fengzhu; Deng, Hao; Zhang, Jihua

2016-01-01

The previous experimental work showed that Hf- or Zr-doping has remarkably improved the thermoelectric performance of FeNbSb. Here, the first-principles method was used to explore the possible reason for such phenomenon. The substitution of X (Zr/Hf) atoms at Nb sites increases effective hole-pockets, total density of states near the Fermi level (EF), and hole mobility to largely enhance electrical conductivity. It is mainly due to the shifting the EF to lower energy and the nearest Fe atoms around X atoms supplying more d-states to hybrid with X d-states at the vicinity of the EF. Moreover, we find that the X atoms indirectly affect the charge distribution around Nb atoms via their nearest Fe atoms, resulting in the reduced energy difference in the valence band edge, contributing to enhanced Seebeck coefficients. In addition, the further Bader charge analysis shows that the reason of more holes by Hf-doping than Zr in the experiment is most likely derived from Hf atoms losing less electrons and the stronger hybridization between Hf atoms and their nearest Fe atoms. Furthermore, we predict that Hf/Sn co-doping may be an effective strategy to further optimize the thermoelectric performance of half-Heusler (HH) compounds. PMID:27604826

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

NASA Astrophysics Data System (ADS)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in low-pH abiologic systems, and such results bear on the search for biosignatures in Mars and Mars-analog settings. [1] Crosby et al., 2007 Geobiol. 5, 169-189 [2] Beard et al., 2010 Earth Planet. Sci. Lett. 295, 241-250 [3] Wu et al., 2011 Environ. Sci. Technol. 45, 1847-1852 [4] Reddy et al., 2015 Chem. Geol. 397, 118-127 [5] Amenabar et al., 2017 Nat. Geosci. In press

Electrical control of antiferromagnetic metal up to 15 nm

NASA Astrophysics Data System (ADS)

Zhang, PengXiang; Yin, GuFan; Wang, YuYan; Cui, Bin; Pan, Feng; Song, Cheng

2016-08-01

Manipulation of antiferromagnetic (AFM) spins by electrical means is on great demand to develop the AFM spintronics with low power consumption. Here we report a reversible electrical control of antiferromagnetic moments of FeMn up to 15 nm, using an ionic liquid to exert a substantial electric-field effect. The manipulation is demonstrated by the modulation of exchange spring in [Co/Pt]/FeMn system, where AFM moments in FeMn pin the magnetization rotation of Co/Pt. By carrier injection or extraction, the magnetic anisotropy of the top layer in FeMn is modulated to influence the whole exchange spring and then passes its influence to the [Co/Pt]/FeMn interface, through a distance up to the length of exchange spring that fully screens electric field. Comparing FeMn to IrMn, despite the opposite dependence of exchange bias on gate voltages, the same correlation between carrier density and exchange spring stiffness is demonstrated. Besides the fundamental significance of modulating the spin structures in metallic AFM via all-electrical fashion, the present finding would advance the development of low-power-consumption AFM spintronics.

Metallic ions in the equatorial ionosphere

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Goldberg, R. A.

1972-01-01

Four positive ion composition measurements of the equatorial E region made at Thumba, India, are presented. During the day, the major ions between 90 and 125 km are NO(+) and O2(+). A metallic ion layer centered at 92 km is observed, and found to contain Mg(+), Fe(+), Ca(+), K(+), Al(+), and Na(+) ions. The layer is explained in terms of a similarly shaped latitude distribution of neutral atoms which are photoionized and charge-exchanged with NO(+) and O2(+). Three body reactions form molecular metallic ions which are rapidly lost by dissociative ion-electron recombination. Nighttime observations show downward drifting of the metallic ion layer caused by equatorial dynamo effects. These ions react and form neutral metals which exchange charges with NO(+) and O2(+) to produce an observed depletion of those ions within the metallic ion region.

First-principles approach to the dynamic magnetoelectric couplings for the non-reciprocal directional dichroism in BiFeO 3

DOE PAGES

Kezsmarki, I.; Fishman, Randy Scott

2016-04-18

Due to the complicated magnetic and crystallographic structures of BiFeO 3, its magnetoelectric (ME) couplings and microscopic model Hamiltonian remain poorly understood. By employing a firstprinciples approach, we uncover all possibleMEcouplings associated with the spin-current (SC) and exchange-striction (ES) polarizations, and construct an appropriate Hamiltonian for the long-range spin-cycloid in BiFeO 3. First-principles calculations are used to understand the microscopic origins of theMEcouplings.Wefind that inversion symmetries broken by ferroelectric and antiferroelectric distortions induce the SC and the ES polarizations, which cooperatively produce the dynamicME effects in BiFeO 3. A model motivated by first principles reproduces the absorption difference of counter-propagatingmore » light beams called non-reciprocal directional dichroism. The current paper focuses on the spin-driven (SD) polarizations produced by a dynamic electric field, i.e. the dynamic MEcouplings. Due to the inertial properties of Fe, the dynamic SD polarizations differ significantly from the static SD polarizations. Our systematic approach can be generally applied to any multiferroic material, laying the foundation for revealing hiddenMEcouplings on the atomic scale and for exploiting opticalMEeffects in the next generation of technological devices such as optical diodes.« less

Spin reorientation and magnetoelastic coupling in Tb 6Fe 1-xCo xBi 2 (x = 0, 0.125, 0.25, 0.375) alloy system

DOE PAGES

Koehler, Michael R.; Garlea, Vasile O.; McGuire, Michael A.; ...

2014-07-05

Tb 6FeBi 2 adopts a noncentrosymmetric crystal structure and orders ferromagnetically at T C1 = 250 K with an additional magnetic transition at T C2 = 60 K. The low temperature magnetoelastic response in this material is strong, and is enhanced by cobalt substitution. In this paper, the temperature dependence of the atomic and magnetic structure of Tb 6Fe 1-xCo xBi 2 (x = 0, 0.125, 0.25, and 0.375) is reported from powder X-ray diffraction (XRD) and powder neutron diffraction (PND) measurements. Below the Néel temperature a ferrimagnetic ordering between the terbium and iron moments exists in all compounds studied.more » Related to the enhanced magnetostructural response, the Co-doped compounds undergo a crystallographic phase transition below about 60 K. This transition also involves a canting of the magnetic moments away from the c-axis. The structural transition is sluggish and not fully completed in the parent Tb 6FeBi 2 compound, where a mixture of monoclinic and hexagonal phases is identified below 60 K. Lastly, the spin reorientation transition is discussed in terms of competing exchange interactions and magnetocrystalline anisotropies of the two Tb sites and Fe/Co sublattices.« less

Meteoric Ions in Planetary Ionospheres

NASA Technical Reports Server (NTRS)

Pesnell, W. D.; Grebowsky, Joseph M.; Vondrak, Richard R. (Technical Monitor)

2001-01-01

Solar system debris, in the form of meteoroids, impacts every planet. The flux, relative composition and speed of the debris at each planet depends on the planet's size and location in the solar system. Ablation in the atmosphere evaporates the meteoric material and leaves behind metal atoms. During the ablation process metallic ions are formed by impact ionization. For small inner solar system planets, including Earth, this source of ionization is typically small compared to either photoionization or charge exchange with ambient molecular ions. For Earth, the atmosphere above the main deposition region absorbs the spectral lines capable of ionizing the major metallic atoms (Fe and Mg) so that charge exchange with ambient ions is the dominant source. Within the carbon dioxide atmosphere of Mars (and possibly Venus), photoionization is important in determining the ion density. For a heavy planet like Jupiter, far from the sun, impact ionization of ablated neutral atoms by impacts with molecules becomes a prominent source of ionization due to the gravitational acceleration to high incident speeds. We will describe the processes and location and extent of metal ion layers for Mars, Earth and Jupiter, concentrating on flagging the uncertainties in the models at the present time. This is an important problem, because low altitude ionosphere layers for the planets, particularly at night, probably consist predominantly of metallic ions. Comparisons with Earth will be used to illustrate the differing processes in the three planetary atmospheres.

Exchange Interactions on the Highest-Spin Reported Molecule: the Mixed-Valence Fe42 Complex

PubMed Central

Aravena, Daniel; Venegas-Yazigi, Diego; Ruiz, Eliseo

2016-01-01

The finding of high-spin molecules that could behave as conventional magnets has been one of the main challenges in Molecular Magnetism. Here, the exchange interactions, present in the highest-spin molecule published in the literature, Fe42, have been analysed using theoretical methods based on Density Functional Theory. The system with a total spin value S = 45 is formed by 42 iron centres containing 18 high-spin FeIII ferromagnetically coupled and 24 diamagnetic low-spin FeII ions. The bridging ligands between the two paramagnetic centres are two cyanide ligands coordinated to the diamagnetic FeII cations. Calculations were performed using either small Fe4 or Fe3 models or the whole Fe42 complex, showing the presence of two different ferromagnetic couplings between the paramagnetic FeIII centres. Finally, Quantum Monte Carlo simulations for the whole system were carried out in order to compare the experimental and simulated magnetic susceptibility curves from the calculated exchange coupling constants with the experimental one. This comparison allows for the evaluation of the accuracy of different exchange-correlation functionals to reproduce such magnetic properties. PMID:27033418

Exchange bias effect in Au-Fe 3O 4 dumbbell nanoparticles induced by the charge transfer from gold

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

Feygenson, Mikhail; Bauer, John C; Gai, Zheng

2015-08-10

We have studied the origin of the exchange bias effect in the Au-Fe 3O 4 dumbbell nanoparticles in two samples with different sizes of the Au seed nanoparticles (4.1 and 2.7 nm) and same size of Fe 3O 4 nanoparticles (9.8 nm). The magnetization, small-angle neutron scattering, synchrotron x-ray diffraction and scanning transmission electron microscope measurements determined the antiferromagnetic FeO wüstite phase within Fe 3O 4 nanoparticles, originating at the interface with the Au nanoparticles. The interface between antiferromagnetic FeO and ferrimagnetic Fe 3O 4 is giving rise to the exchange bias effect. The strength of the exchange bias fieldsmore » depends on the interfacial area and lattice mismatch between both phases. We propose that the charge transfer from the Au nanoparticles is responsible for a partial reduction of the Fe 3O 4 into FeO phase at the interface with Au nanoparticles. The Au-O bonds are formed across the interface to accommodate an excess of oxygen released during the reduction of magnetite.« less

Exchange bias effect in Au-Fe3O4 dumbbell nanoparticles induced by the charge transfer from gold

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

Feygenson, Mikhail; Bauer, John C.; Gai, Zheng

2015-08-10

We have studied the origin of the exchange bias effect in the Au-Fe3O4 dumbbell nanoparticles in two samples with different sizes of the Au seed nanoparticles (4.1 and 2.7 nm) and same size of Fe3O4 nanoparticles (9.8 nm). The magnetization, small-angle neutron-scattering, synchrotron x-ray diffraction, and scanning transmission electron microscope measurements determined the antiferromagnetic FeO wustite phase within Fe3O4 nanoparticles, originating at the interface with the Au nanoparticles. The interface between antiferromagnetic FeO and ferrimagnetic Fe3O4 is giving rise to the exchange bias effect. The strength of the exchange bias fields depends on the interfacial area and lattice mismatch betweenmore » both phases. We propose that the charge transfer from the Au nanoparticles is responsible for a partial reduction of the Fe3O4 into the FeO phase at the interface with Au nanoparticles. The Au-O bonds are formed, presumably across the interface to accommodate an excess of oxygen released during the reduction of magnetite« less

The role of the (111) texture on the exchange bias and interlayer coupling effects observed in sputtered NiFe/IrMn/Co trilayers

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

Castro, I. L.; Nascimento, V. P.; Passamani, E. C.

2013-05-28

Magnetic properties of sputtered NiFe/IrMn/Co trilayers grown on different seed layers (Cu or Ta) deposited on Si (100) substrates were investigated by magnetometry and ferromagnetic resonance measurements. Exchange bias effect and magnetic spring behavior have been studied by changing the IrMn thickness. As shown by X-ray diffraction, Ta and Cu seed layers provoke different degrees of (111) fcc-texture that directly affect the exchange bias and indirectly modify the exchange spring coupling behavior. Increasing the IrMn thickness, it was observed that the coupling angle between the Co and NiFe ferromagnetic layers increases for the Cu seed system, but it reduces formore » the Ta case. The results were explained considering (i) different anisotropies of the Co and IrMn layers induced by the different degree of the (111) texture and (ii) the distinct exchange bias set at the NiFe/IrMn and IrMn/Co interfaces in both systems. The NiFe and Co interlayer coupling angle is strongly correlated with both exchange bias and exchange magnetic spring phenomena. It was also shown that the highest exchange bias field occurs when an unstressed L1{sub 2} IrMn structure is stabilized.« less

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

NASA Astrophysics Data System (ADS)

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.

Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

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

Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

2015-07-01

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸O Gth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II) aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.« less

Local configurations and atomic intermixing in as-quenched and annealed Fe1-xCrx and Fe1-xMox ribbons

NASA Astrophysics Data System (ADS)

Stanciu, A. E.; Greculeasa, S. G.; Bartha, C.; Schinteie, G.; Palade, P.; Kuncser, A.; Leca, A.; Filoti, G.; Birsan, A.; Crisan, O.; Kuncser, V.

2018-04-01

Local atomic configuration, phase composition and atomic intermixing in Fe-rich Fe1-xCrx and Fe1-xMox ribbons (x = 0.05, 0.10, 0.15), of potential interest for high-temperature applications and nuclear devices, are investigated in this study in relation to specific processing and annealing routes. The Fe-based thin ribbons have been prepared by induction melting, followed by melt spinning and further annealed in He at temperatures up to 1250 °C. The complex structural, compositional and atomic configuration characterisation has been performed by means of X-ray diffraction (XRD), transmission Mössbauer spectroscopy and differential scanning calorimetry (TG-DSC). The XRD analysis indicates the formation of the desired solid solutions with body-centred cubic (bcc) structure in the as-quenched state. The Mössbauer spectroscopy results have been analysed in terms of the two-shell model. The distribution of Cr/Mo atoms in the first two coordination spheres is not homogeneous, especially after annealing, as supported by the short-range order parameters. In addition, high-temperature annealing treatments give rise to oxidation of Fe (to haematite, maghemite and magnetite) at the surface of the ribbons. Fe1-xCrx alloys are structurally more stable than the Mo counterpart under annealing at 700 °C. Annealing at 1250 °C in He enhances drastically the Cr clustering around Fe nuclei.

Local ordering and magnetism in Ga{sub 0.9}Fe{sub 3.1}N

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

Burghaus, Jens; Sougrati, Moulay T., E-mail: moulay-tahar.sougrati@univ-montp2.fr; Moechel, Anne

Prior investigations of the ternary nitride series Ga{sub 1-x}Fe{sub 3+x}N (0{<=}x{<=}1) have indicated a transition from ferromagnetic {gamma}'-Fe{sub 4}N to antiferromagnetic 'GaFe{sub 3}N'. The ternary nitride 'GaFe{sub 3}N' has been magnetically and spectroscopically reinvestigated in order to explore the weakening of the ferromagnetic interactions through the gradual incorporation of gallium into {gamma}'-Fe{sub 4}N. A hysteretic loop at RT reveals the presence of a minority phase of only 0.1-0.2 at%, in accord with the sound two-step synthesis. The composition of the gallium-richest phase 'GaFe{sub 3}N' was clarified by Prompt Gamma-ray Activation Analysis and leads to the berthollide formula Ga{sub 0.91(1)}Fe{sub 3.09(10)}N{submore » 1.05(7)}. Magnetic measurements indicate a transition around 8 K, further supported by Moessbauer spectral data. The weakening of the ferromagnetic coupling through an increasing gallium concentration is explained by a simple Stoner argument. In Ga{sub 0.9}Fe{sub 3.1}N, the presence of iron on the gallium site affects the magnetism by the formation of 13-atom iron clusters. - Graphical Abstract: The crystal structure of GaFe{sub 3}N with green nitrogen atoms in the very center, red iron atoms at the face centers, and gray gallium atoms at the corner positions. Highlights: > Almost phase-pure synthesis of Ga{sub 0.9}Fe{sub 3.1}N. > Prompt gamma-ray activation analysis yields precise composition. > Magnetic ordering of the facial Fe atoms at the lowest temperatures. > Moessbauer spectroscopy suggests percolation or RKKY-type interaction. > Fe{sub 13} clusters due to berthollide character.« less

Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity.

PubMed

Jena, Ajit; Nanda, B R K

2016-01-21

Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)(3-). The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

PubMed Central

Jena, Ajit; Nanda, B. R. K.

2016-01-01

Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3−. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

Spin-polarized currents generated by magnetic Fe atomic chains.

PubMed

Lin, Zheng-Zhe; Chen, Xi

2014-06-13

Fe-based devices are widely used in spintronics because of high spin-polarization and magnetism. In this work, freestanding Fe atomic chains, the thinnest wires, were used to generate spin-polarized currents due to the spin-polarized energy bands. By ab initio calculations, the zigzag structure was found to be more stable than the wide-angle zigzag structure and had a higher ratio of spin-up and spin-down currents. By our theoretical prediction, Fe atomic chains have a sufficiently long thermal lifetime only at T ≦̸ 150 K, while C atomic chains are very stable even at T = 1000 K. This means that the spintronic devices based on Fe chains could work only at low temperatures. A system constructed by a short Fe chain sandwiched between two graphene electrodes could be used as a spin-polarized current generator, while a C chain could not be used in this way. The present work may be instructive and meaningful to further practical applications based on recent technical developments on the preparation of metal atomic chains (Proc. Natl. Acad. Sci. USA 107 9055 (2010)).

Magnetism of CrO overlayers on Fe(001)bcc surface: first principles calculations

NASA Astrophysics Data System (ADS)

Félix-Medina, Raúl Enrique; Leyva-Lucero, Manuel Andrés; Meza-Aguilar, Salvador; Demangeat, Claude

2018-04-01

Riva et al. [Surf. Sci. 621, 55 (2014)] as well as Calloni et al. [J. Phys.: Condens. Matter 26, 445001 (2014)] have studied the oxydation of Cr films deposited on Fe(001)bcc through low-energy electron diffraction, Auger electron spectroscopy and scanning tunneling microscopy. In the present work we perform a density functional approach within Quantum Expresso code in order to study structural and magnetic properties of CrO overlayers on Fe(001)bcc. The calculations are performed using DFT+U. The investigated systems include O/Cr/Fe(001)bcc, Cr/O/Fe(001)bcc, Cr0.25O0.75/Fe(001)bcc, as well as the O coverage Ox/Cr/Fe(001)bcc (x = 0.25; 0.50). We have found that the ordered CrO overlayer presents an antiferromagnetic coupling between Cr and Fe atoms. The O atoms are located closer to the Fe atoms of the surface than the Cr atoms. The ground state of the systems O/Cr/Fe(001)bcc and Cr/O/Fe(001)bcc corresponds to the O/Cr/Fe(001)bcc system with a magnetic coupling c(2 × 2). The effect of the O monolayer on Cr/Fe(001)bcc changes the ground state from p(1 × 1) ↓ to c(2 × 2) and produces an enhancement of the magnetic moments. The Ox overlayer on Cr/Fe(001)bcc produces an enhancement of the Cr magnetic moments.

NH 3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

DOE PAGES

Wang, Aiyong; Wang, Yilin; Walter, Eric D.; ...

2017-10-07

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4/Beta, and NH 4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance ( 27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further testedmore » with standard NH 3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3-SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.« less

NH 3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

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

Wang, Aiyong; Wang, Yilin; Walter, Eric D.

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4/Beta, and NH 4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance ( 27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further testedmore » with standard NH 3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3-SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.« less

Effect of Nb doping on the microstructure and magnetic properties of Nd-Ce-Fe-B alloy

NASA Astrophysics Data System (ADS)

Quan, Qichen; Zhang, Lili; Jiang, Qingzheng; Lei, Weikai; Zeng, Qingwen; Hu, Xianjun; Wang, Lei; Yu, Xi; Du, Junfeng; Fu, Gang; Liu, Renhui; Zhong, Minglong; Zhong, Zhenchen

2017-11-01

With the intention to reduce the Nd content in Nd2Fe14B-type alloys, 20 at.% Ce and 0.5 at.% Nb substituting Nd and Fe in the Nd13Fe82B5 alloys were previously employed to improve successfully the coercivity and the thermal stability without the energy product reduction. In this study, a light increase of the remnant polarization Jr was observed in (Nd0.8Ce0.2)13Fe82-xNbxB5 alloy at x = 0.5 and x = 1.0, resulting from the increasing amount of α-Fe phase. The optimum magnetic properties obtained with 0.5 at.% Nb doping are Hcj = 13.1 kOe, Jr = 0.79 T, (BH)max = 13.3 MGOe, respectively. Besides, the coercivity Hcj and maximum energy product (BH)max for the melt-spun ribbons with 0.5 at.% Nb addition are higher than those of the Nb-free ribbons in the temperature range of 300-450 K. Both the variations of Curie temperature Tc and a increase of lattice constants a and c of the hard magnetic phase with Nb addition imply that some of Nb atoms may directly enter into the hard magnetic phase, occupying the Fe sites. With the analysis on the demagnetization curve, Henkel curve and the observation of transmission electron microscope (TEM), the results indicate that a small amount of Nb can enhance the coercivity and exchange coupling though improving the microstructure of alloys.

Reduced-temperature crystallization of thin amorphous Fe80B20 films studied via empirical modeling of extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.

1996-04-01

The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.

The influence of structural fluorine on biotite oxidation in copper-bearing, aqueous solutions at low temperatures and pressures

NASA Astrophysics Data System (ADS)

Earley, Drummond, III; Darby Dyar, M.; Ilton, Eugene S.; Granthem, Allen A.

1995-06-01

High-F (5.4 wt%) and low-F (0.8 wt%) biotites were reacted with aqueous (Cu, Na 2)Cl 2 solutions at ambient conditions to investigate biotite oxidation mechanisms at low temperatures and pressures and at atmospheric pO 2. The exchange of Cu +2 for interlayer cations increases the rate of biotite oxidation under these conditions. Solid reactants and products were characterized by Mössbauer spectroscopy, X-ray diffraction, and comprehensive bulk chemical analyses. Even though both biotites were pretreated with a sodium tetraphenylboron (NaTPB) solution, which rapidly exchanges Na for K, only about 50% of the interlayer K was exchanged during most of these experiments. As a result, the exchange reactions produced variably expanded phases with d(001) ranging from approximately 10 to 14 Å. Octahedral Fe +2 in samples of high- and low-F biotite was oxidized rapidly during Cu exchange. The degree of Fe +2 oxidation amounted to about 50% of the total Fe in most experiments and was nearly independent of the total mass of Cu introduced into the interlayer which ranged from 2.0 to 9.2 wt% CuO. The Mössbauer spectra also show that the Fe +2 in M(1) octahedra of the high-F biotite was oxidized more slowly than Fe +2 in M(2) sites, whereas in the low-F biotite experiments M(1) Fe +2 was oxidized at a slightly faster rate than the Fe +2 in M(2) sites. Our study suggests that the total amount of Fe oxidized was limited by the amount of K exchanged, and that preferred oxidation of Fe +2 at M(2) sites relative to M(1) sites was a function of the F content of these biotites. Charge transfer from octahedral Fe +2 to the interlayer may be facilitated by deprotonation. In exchange experiments conducted on the F-rich biotite, Fe +2 oxidation at M(1) sites was limited indicating that preferential substitution of F for OH might occur at the M(1) site. We used the Fe-F avoidance law to develop an F-OH ordering model that preferentially distributes F on selected trans positions of Fe-filled M(1) octahedra in Fe- and F-rich biotites. If charge transfer is facilitated by the presence of OH then the proposed F-OH ordering model could account for the selective deactivation of the Fe +2 oxidation mechanism at the M(1) site.

Superconducting and Magnetic Properties of Vanadium/iron Superlattices.

NASA Astrophysics Data System (ADS)

Wong, Hong-Kuen

A novel ultrahigh vacuum evaporator was constructed for the preparation of superlattice samples. The thickness control was much better than an atomic plane. With this evaporator we prepared V/Fe superlattice samples on (0001) sapphire substrates with different thicknesses. All samples showed a good bcc(110) structure. Mossbauer experiments showed that the interface mixing extended a distance of about one atomic plane indicating an almost rectangular composition profile. Because of this we were able to prepare samples with layer thickness approaching one atomic plane. Even with ultrathin Fe layers, the samples are ferromagnetic, at least at lower temperatures. Superparamagnetism and spin glass states were not seen. In the absence of an external field, the magnetic moments lie close to the film plane. In addition to this shape anisotropy, there is some uniaxial anisotropy. No magnetic dead layers have been observed. The magnetic moments within the Fe layers vary little with the distance from the interfaces. At the interfaces the Fe moment is reduced and an antiparallel moment is induced on the vanadium atoms. It is observed that ultrathin Fe layers behave in a 2D fashion when isolated by sufficiently thick vanadium layers; however, on thinning the vanadium layers, a magnetic coupling between the Fe layers has been observed. We also studied the superconducting properties of V/Fe sandwiches and superlattices. In both cases, the Fe layer, a strong pair-breaker, suppresses the superconducting transition temperature consistent with the current knowledge of the magnetic proximity effect. For the sandwiches with thin (thick) vanadium layers, the temperature dependence of the upper critical fields is consistent with the simple theory for a 2D (3D) superconductor. For the superlattices, when the vanadium layer is on the order of the BCS coherence length and the Fe layer is only a few atomic planes thick, a 2D-3D crossover has been observed in the temperature dependence of the parallel upper critical field. This implies the coexistence of superconductivity and ferromagnetism. We observe three dimensional behavior for thinner Fe layers ((TURN)1 atomic plane) and two dimensional behavior for thicker Fe layers (greater than 10 atomic planes).

Ferromagnetism of Pd-Fe (abstract)

NASA Astrophysics Data System (ADS)

Griffith, G.; Carnegie, D. W., Jr.; Claus, H.

1984-03-01

We present new low field ac susceptibility measurements on Pd1-xFex alloys (0.002≤X<0.01). The Curie temperature TC, determined from these measurements, are significantly lower than those previously obtained in higher magnetic fields [G. J. Nieuwenhuys, Adv. Phys. 24, 515 (1975)]. We also found that for a given sample, TC depends very sensitively on its heat treatment. As an example, for an alloy with 0.4 at. % Fe, TC can be varied between 4 and 10 K. In other alloys, like PdNi or RhNi similar changes in TC are due to changes in the degree of atomic short-range order [S. Crane, D. W. Carnegie, Jr., and H. Claus, J. Appl. Phys. 53, 2179 (1982)]. However, for PdFe we show evidence that the changes in TC are due to absorption of small amounts of oxygen, the samples with the highest amount of oxygen having the highest TC. It thus seems that oxygen has the opposite effect from hydrogen on the exchange enhanced susceptibility of Pd [J. A. Mydosh, Phys. Rev. Lett. 33, 1562 (1974)].

Fabrication of ordered Fe–Ni nitride film with equiatomic Fe/Ni ratio

NASA Astrophysics Data System (ADS)

Takata, Fumiya; Ito, Keita; Suemasu, Takashi

2018-05-01

We successfully grew a single-phase tetragonal FeNiN film with an equiatomic ratio of Fe, Ni, and N on a MgO(001) substrate by molecular beam epitaxy. We then demonstrated the formation of Fe2Ni2N films by extracting N atoms from the FeNiN film. These results suggested that Fe and Ni atoms in the Fe2Ni2N film were L10-ordered along the film plane direction because of the a-axis orientation growth of the FeNiN film on the MgO(001) substrate.

Local structures in mixed Li{sub x}Fe{sub 1−y}M{sub y}PO{sub 4} (M=Co, Ni) electrode materials

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

Jalkanen, K.; Lindén, J.; Karppinen, M., E-mail: maarit.karppinen@aalto.fi

We employ {sup 57}Fe Mössbauer spectroscopy as a local tool to probe electrical environments of Fe{sup 2+} and Fe{sup 3+} at different lithiation (x) and cation-substitution (y) levels in Li{sub x}Fe{sub 1−y}M{sub y}PO{sub 4}/C (M=Co, Ni) Li-ion battery electrode materials. Upon delithiation the local environment of Fe{sup 3+} remains unaffected for the parent y=0 system due to the LiFePO{sub 4}/FePO{sub 4} phase separation, whereas for y>0 changes in the electrical environment are seen for Fe{sup 3+}. When the Fe{sup 2+}/Fe{sup 3+} redox couple is partially-delithiated, a decreasing quadrupole splitting value is observed for Fe{sup 3+} with increasing y, implying amore » more symmetric electrical environment. The increasing concentration of the Co{sup 2+}/Ni{sup 2+} substituent introduces increasing amounts of Li atoms in the Fe{sup 3+}-containing phase, and these nearest-neighbor Li atoms are suspected to cause the changes seen in the local environment of Fe{sup 3+}. - Graphical abstract: Local environment of iron in Li{sub x}Fe{sub 1−y}(Co/Ni){sub y}PO{sub 4} is studied by {sup 57}Fe Mössbauer spectroscopy at different lithiation (x) and cation-substitution (y) levels. - Highlights: • Local Fe environment in Li{sub x}Fe{sub 1−y}(Co/Ni){sub y}PO{sub 4} is studied by {sup 57}Fe Mössbauer spectroscopy. • Co/Ni-for-Fe substitution results in a more symmetric electrical environment for Fe{sup 3+}. • Due to presence of Co{sup 2+}/Ni{sup 2+}, Li atoms are introduced into the Fe{sup 3+}-containing phase. • These nearest-neighbor Li atoms are suggested to change the local Fe{sup 3+} environment.« less

Electronic structure, magnetism, and optical properties of Fe2SiO4 fayalite at ambient and high pressures: A GGA+U study

NASA Astrophysics Data System (ADS)

Jiang, Xuefan; Guo, G. Y.

2004-04-01

The electronic structure, magnetism, and optical properties of Fe2SiO4 fayalite, the iron-rich end member of the olivine-type silicate, one of the most abundant minerals in Earth’s upper mantle, have been studied by density-functional theory within the generalized gradient approximation (GGA) with the on-site Coulomb energy U=4.5 eV taken into account (GGA+U). The stable insulating antiferromagnetic solution with an energy gap ˜1.49 eV and a spin magnetic moment of 3.65μB and an orbital magnetic moment of 0.044μB per iron atom is obtained. It is found that the gap opening in this fayalite results mainly from the strong on-site Coulomb interaction on the iron atoms. In this band structure, the top of valence bands consists mainly of the 3d orbitals of Fe2 atoms, and the bottom of the conduction bands is mainly composed of the 3d orbitals of Fe1 atoms. Therefore, since the electronic transition from the Fe2 3d to Fe1 3d states is weak, significant electronic transitions would appear only about 1 eV above the absorption edge when Fe-O orbitals are involved in the final states. In addition, our band-structure calculations can explain the observed phenomena including redshift near the absorption edge and the decrease of the electrical resistivity of Fe2SiO4 upon compression. The calculated Fe p partial density of states agree well with Fe K-edge x-ray absorption spectrum. The calculated lattice constants and atomic coordinates for Fe2SiO4 fayalite in orthorhombic structure are in good agreement with experiments.

Introducing Fe2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity.

PubMed

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; Bak, Seongmin; Wu, Yueshen; Wu, Zishan; Tian, Yang; Xiong, Xuya; Li, Yaping; Liu, Wen; Siahrostami, Samira; Kuang, Yun; Yang, Xiao-Qing; Duan, Haohong; Feng, Zhenxing; Wang, Hailiang; Sun, Xiaoming

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel-iron layered double hydroxides (NiFe-LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe-O-Fe moieties. These Fe2+-containing NiFe-LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm2, which is among the best OER catalytic performance reported to date. In-situ X-ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe-O-Fe motifs could stabilize high-valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-optical measurement of interlayer exchange coupling in Fe/Pt/FePt thin films

NASA Astrophysics Data System (ADS)

Berk, C.; Ganss, F.; Jaris, M.; Albrecht, M.; Schmidt, H.

2018-01-01

Time Resolved Magneto Optic Kerr Effect spectroscopy was used to all-optically study the dynamics in exchange coupled Fe(10 nm)/Pt(x = 0-5 nm)/FePt (10 nm) thin films. As the Pt spacer decreases, the effective magnetization of the layers is seen to evolve towards the strong coupling limit where the two films can be described by a single effective magnetization. The coupling begins at x = 1.5 nm and reaches a maximum exchange coupling constant of 2.89 erg/cm2 at x = 0 nm. The films are ferromagnetically coupled at all Pt thicknesses in the exchange coupled regime (x ≤ 1.5 nm). A procedure for extracting the interlayer exchange constant by measuring the magnetic precession frequencies at multiple applied fields and angles is outlined. The dynamics are well reproduced using micromagnetic simulations.

Mechanism of pyridine-ligand exchanges at the different labile sites of 3d heterometallic and mixed valence mu3-oxo trinuclear clusters.

PubMed

Novitchi, Ghenadie; Riblet, Fabrice; Scopelliti, Rosario; Helm, Lothar; Gulea, Aurelian; Merbach, André E

2008-11-17

The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic mu 3-oxo trinuclear cluster with the formula [Fe (III) 2M (II)(mu 3-O)(mu-O 2CCH 3) 6(4-Rpy) 3]. x(4-Rpy). y(CH 3CN) where R = Ph for 1(Fe 2Mn), 2(Fe 2Fe), 3(Fe 2Co), 4(Fe 2Ni) and R = CF 3 for 5(Fe 2Co), are reported. The persistence of the structure for compounds 2- 5 in dichloromethane solution in the temperature range 190-320 K is demonstrated by (1)H and (19)F NMR spectroscopy. Even at the lowest temperature, the electron exchange in the homometallic mixed-valence compound 2(Fe 2Fe) is in the fast regime at the NMR time scale. Variable temperature and pressure NMR line broadening allowed quantifying the fast coordinated/free 4-Rpy exchanges at the two labile metal centers in these clusters: 2: Fe (III)( k (298)/10 (3) s (-1) = 16.6; Delta H (++) = 60.32 kJ mol (-1); Delta S (++) = + 34.8 J K (-1) mol (-1); Delta V (++) = + 12.5 cm (3) mol (-1)); 3: Fe (11.9; 58.92; +30.7; +10.6) and Co (2.8; 68.24; +49.8; +13.9); 4: Fe(12.2; 67.91; +61.0; -) and Ni (0.37; 78.62; +67.8; +12.3); 5: Fe (46; 58.21; +39.3; +14.2) and Co (4.7; 55.37; +11.2; +10.9). A limiting D mechanism is assigned to these exchange reactions. This assignment is based on a first-order rate law, the detection of intermediates, the positive and large entropies and volumes of activation. The order of reactivity k (Co) > k (Ni) is expected for a D mechanism at these metal centers: their low exchange rates are due to their strong binding with the 4-Rpy donor. Surrounded by oxygen donors the d (5) iron(III) usually reacts associatively; however, here due to low affinity of this ion for nitrogen the mechanism is D and the rate of exchange is very fast, even faster than on the divalent ions. There is no significant effect of the divalent ion in cluster 2, 3, and 5 on the exchange rates of 4-Phpy at the iron center, which seems to indicate that the specific electronic interactions between the three ions making the clusters do not influence the Fe (III)-N bond strength.

Distribution of Fe atom density in a dc magnetron sputtering plasma source measured by laser-induced fluorescence imaging spectroscopy

NASA Astrophysics Data System (ADS)

Shibagaki, K.; Nafarizal, N.; Sasaki, K.; Toyoda, H.; Iwata, S.; Kato, T.; Tsunashima, S.; Sugai, H.

2003-10-01

Magnetron sputtering discharge is widely used as an efficient method for thin film fabrication. In order to achieve the optimized fabrication, understanding of the kinetics in plasmas is essential. In the present work, we measured the density distribution of sputtered Fe atoms using laser-induced fluorescence imaging spectroscopy. A dc magnetron plasma source with a Fe target was used. An area of 20 × 2 mm in front of the target was irradiated by a tunable laser beam having a planar shape. The picture of laser-induced fluorescence on the laser beam was taken using an ICCD camera. In this way, we obtained the two-dimensional image of the Fe atom density. As a result, it has been found that the Fe atom density observed at a distance of several centimeters from the target is higher than that adjacent to the target, when the Ar gas pressure was relatively high. It is suggested from this result that some gas-phase production processes of Fe atoms are available in the plasma. This work has been performed under the 21st Century COE Program by the Ministry of Education, Culture, Sports, Science and Technology in Japan.

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

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Ab initio investigation of competing antiferromagnetic structures in low Si-content FeMn(PSi) alloy

NASA Astrophysics Data System (ADS)

Li, Guijiang; Eriksson, Olle; Johansson, Börje; Vitos, Levente

2016-06-01

The antiferromagnetic structures of a low Si-content FeMn(PSi) alloy were investigated by first principles calculations. One possible antiferromagnetic structure in supercell along the c-axis was revealed in FeMnP0.75Si0.25 alloy. It was found that atomic disorder occupation between Fe atom on 3f and Mn atoms on 3g sites is responsible for the formation of antiferromagnetic structures. Furthermore the magnetic competition and the coupling between possible AFM supercells along the c and a-axis can promote a non-collinear antiferromagnetic structure. These theoretical investigations help to deeply understand the magnetic order in FeMn(PSi) alloys and benefit to explore the potential magnetocaloric materials in Fe2P-type alloys.

Periodic table of 3d-metal dimers and their ions.

PubMed

Gutsev, G L; Mochena, M D; Jena, P; Bauschlicher, C W; Partridge, H

2004-10-08

The ground states of the mixed 3d-metal dimers TiV, TiCr, TiMn, TiFe, TiCo, TiNi, TiCu, TiZn, VCr, VMn, VFe, VCo, VNi, VCu, VZn, CrMn, CrFe, CrCo, CrNi, CrCu, CrZn, MnFe, MnCo, MnNi, MnCu, MnZn, FeCo, FeNi, FeCu, FeZn, CoNi, CoCu, CoZn, NiCu, NiZn, and CuZn along with their singly negatively and positively charged ions are assigned based on the results of computations using density functional theory with generalized gradient approximation for the exchange-correlation functional. Except for TiCo and CrMn, our assignment agrees with experiment. Computed spectroscopic constants (r(e),omega(e),D(o)) are in fair agreement with experiment. The ground-state spin multiplicities of all the ions are found to differ from the spin multiplicities of the corresponding neutral parents by +/-1. Except for TiV, MnFe, and MnCu, the number of unpaired electrons, N, in a neutral ground-state dimer is either N(1)+N(2) or mid R:N(1)-N(2)mid R:, where N(1) and N(2) are the numbers of unpaired 3d electrons in the 3d(n)4s(1) occupation of the constituent atoms. Combining the present and previous results obtained at the same level of theory for homonuclear 3d-metal and ScX (X=Ti-Zn) dimers allows one to construct "periodic" tables of all 3d-metal dimers along with their singly charged ions.

X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor.

PubMed

Lancaster, Kyle M; Roemelt, Michael; Ettenhuber, Patrick; Hu, Yilin; Ribbe, Markus W; Neese, Frank; Bergmann, Uwe; DeBeer, Serena

2011-11-18

Nitrogenase is a complex enzyme that catalyzes the reduction of dinitrogen to ammonia. Despite insight from structural and biochemical studies, its structure and mechanism await full characterization. An iron-molybdenum cofactor (FeMoco) is thought to be the site of dinitrogen reduction, but the identity of a central atom in this cofactor remains unknown. Fe Kβ x-ray emission spectroscopy (XES) of intact nitrogenase MoFe protein, isolated FeMoco, and the FeMoco-deficient nifB protein indicates that among the candidate atoms oxygen, nitrogen, and carbon, it is carbon that best fits the XES data. The experimental XES is supported by computational efforts, which show that oxidation and spin states do not affect the assignment of the central atom to C(4-). Identification of the central atom will drive further studies on its role in catalysis.

Finite-size effects and magnetic exchange coupling in thin CoO layers

NASA Astrophysics Data System (ADS)

Ambrose, Thomas Francis

Finite size effects in CoO have been observed in CoO/SiOsb2 multilayers. The Neel temperatures of the CoO layers, as determined by dc susceptibility measurements, follow a finite-size scaling relation with a shift exponent lambda = 1.55 ± 0.05. This determined exponent is close to the theoretical value for finite size scaling in an Ising system. The value of the zero temperature correlation length has also been determined to be 18A, while antiferromagnetic ordering persists down to a CoO layer thickness of 10A. The properties of exchange biasing have been extensively studied in NiFe/CoO bilayers. The effects of the cooling field (Hsb{FC}), up to 50 kOe, on the resultant exchange field (Hsb{E}) and coercivity (Hsb{C}) have been examined. The value of Hsb{E} increases rapidly at low cooling fields (Hsb{FC} < 1kOe) and levels off for Hsb{FC} larger than 4 kOe. The value of Hsb{C} also depends upon Hsb{FC}, but less sensitively. The bilayer thickness also influences exchange biasing. We find that Hsb{E} varies inversely proprotional to both tsb{FM} and tsb{AF} where tsb{FM} and tsb{AF} are the ferromagnetic and antiferromagnetic layer thickness respectively. Because of the 1/tsb{AF}, the simple picture of interfacial coupling between ferromagnet and antiferromagnet spins appears to be inadequate. The assertion of long range coupling between ferromagnetic and antiferromagnetic layers has been verified by the observation of antiferromagnetic exchange coupling across spacer layers in NiFe/NM/CoO trilayers, where NM is a non-magnetic material. Exchange biasing has been observed in trilayers with metallic spacer layers up to 50A thick using Ag, Cu and Au, while no exchange field was observed for insulating spacer layers of any thickness using Alsb2Osb3, SiOsb2 and MgO. The temperature dependence of Hsb{E} and Hsb{C} and the effect of the deposition order have been studied in a series of bilayer (NiFe/CoO and CoO/NiFe) and trilayer (NiFe/CoO/NiFe) films. A profound difference in Hsb{E} was observed in samples with NiFe deposited on top of CoO compared to samples with CoO deposited on top of NiFe. When CoO is on top of NiFe Hsb{E} varies linearly with temperature, while for samples with NiFe on top of CoO Hsb{E} has a plateau followed by a rapid decrease. These distinct temperature dependences have been reproduced in NiFe/CoO/NiFe trilayers which contain both geometries. Structural analysis using Transmission Electron Microscopy indicate no apparent differences in the top and bottom interfaces. The angular dependence of the exchange coupling in a NiFe/CoO bilayer has been measured. Both Hsb{E} and Hsb{C} with unidirectional and uniaxial characteristics, respectively, are integral parts of the exchange coupling. The values of Hsb{E} can be expressed by a series of odd angle cosine terms, while the values of Hsb{C} can be expressed by a series of even angle cosine terms. Finally, exchange biasing has been used to "spin engineer" ferromagnetic layers in NiFe/CoO/NiFe trilayers. Four different spin structures have been observed. A phase diagram, for the four spin structures and the conditions with which each spin structure is obtained, has been determined. (Abstract shortened by UMI.)

Separation and preconcentration of the rare-earth elements and yttrium from geological materials by ion-exchange and sequential acid elution

USGS Publications Warehouse

Crock, J.G.; Lichte, F.E.; Riddle, G.O.; Beech, C.L.

1986-01-01

The abundance of rare-earth elements (REE) and yttrium in geological materials is generally low, and most samples contain elements that interfere in the determination of the REE and Y, so a separation and/or preconcentration step is often necessary. This is often achieved by ion-exchange chromatography with either nitric or hydrochloric acid. It is advantageous, however, to use both acids sequentially. The final solution thus obtained contains only the REE and Y, with minor amounts of Al, Ba, Ca, Sc, Sr and Ti. Elements that potentially interfere, such as Be, Co, Cr, Fe, Mn, Th, U, V and Zr, are virtually eliminated. Inductively-coupled argon plasma atomic-emission spectroscopy can then be used for a final precise and accurate measurement. The method can also be used with other instrumental methods of analysis. ?? 1986.

From Metal-Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media.

PubMed

Jiao, Long; Wan, Gang; Zhang, Rui; Zhou, Hua; Yu, Shu-Hong; Jiang, Hai-Long

2018-05-09

It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal-organic frameworks (MOFs) have been synthesized based on a novel mixed-ligand strategy to afford high-content (1.76 wt %) single-atom (SA) iron-implanted N-doped porous carbon (Fe SA -N-C) via pyrolysis. Thanks to the single-atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized Fe SA -N-C exhibits excellent oxygen reduction activity and stability, surpassing almost all non-noble-metal catalysts and state-of-the-art Pt/C, in both alkaline and more challenging acidic media. More far-reaching, this MOF-based mixed-ligand strategy opens a novel avenue to the precise fabrication of efficient single-atom catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Liu, Xing-Wu; Cao, Zhi; Zhao, Shu

As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2C and ε’-Fe 2.2C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe xC, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectramore » for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2C has six sets of chemically distinct Fe atoms.« less

Exchange field and Hc dependence on the ferromagnetic material in exchange couples with CoO (abstract)

NASA Astrophysics Data System (ADS)

Takano, Kentaro; Berkowitz, A. E.

1997-04-01

As recording density increases, magnetoresistive (MR) sensors are becoming increasingly important in read heads. NixCo(1-x)O is receiving technological attention for biasing magnetoresistive sensors as a robust alternative to FeMn. The interfacial exchange coupling between a ferromagnetic (FM) layer and an antiferromagnetic (AFM) is observed as an exchange field and an enhanced coercive field of the FM layer. The AFM/FM coupling is sensitive to the interfacial structure and the AFM and FM magnetic parameters. In this work, we deposited various FM layers on similar 300 Å CoO base layers to study the dependence of the FM exchange integral parameter J on the exchange HE and coercive HC fields. CoO was selected as the AFM material because (i) its simple spin and crystal structures facilitate the structural characterization and modeling of its magnetic properties, and (ii) it's modest Néel temperature of 300 K facilitates the use of a superconducting quantum interference device for the magnetic measurements at temperatures ranging from 5 to 400 K. The 300 Å CoO films were reactively sputtered on silicon substrates and capped with various 300 Å FM films, Ni, Co, Fe, and permalloy (Ni81Fe19). The 300 Å CoO base layer films were polycrystalline with columnar grains. The CoO deposition conditions were reproduced to ensure similar structural and magnetic interfacial AF environments. The observed HE temperature dependence cannot be explained by current theoretical models. The temperature dependence of the exchange fields have the common features (i) a blocking temperature Tb=300 K, which corresponds to the bulk Néel temperature of CoO, (ii) a rise in the exchange field with decreasing temperature, (iii) an intermediate temperature region of constant HE (plateau value), and (iv) a second region of linearly increasing HE with decreasing temperatures down to 0 K. The plateau value of the HE decreased inversely with increasing FM magnetization as predicted by theory. The low-temperature increase of HE is more significant in the FM with higher exchange integral J values. The crossover temperature from the plateau to the low-temperature rise in HE appears to be dependent on FM's J value. The increase in the interfacial coupling strength could suggest the magnetic ordering of a secondary phase localized at the interfacial atoms. The temperature dependence of HC enhancement does not share the nonlinear temperature behavior of HE. For T<300 K, HC increases linearly with decreasing temperatures down to 10 K. Although the HC enhancement may have magnetoelastic contributions, the disappearance of the linear enhancement at 300 K, the Néel temperature of CoO, indicates that the dominant mechanism is the interfacial magnetic coupling.

Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

PubMed

Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

2018-06-01

Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

NASA Astrophysics Data System (ADS)

Paris, E.; Simonelli, L.; Wakita, T.; Marini, C.; Lee, J.-H.; Olszewski, W.; Terashima, K.; Kakuto, T.; Nishimoto, N.; Kimura, T.; Kudo, K.; Kambe, T.; Nohara, M.; Yokoya, T.; Saini, N. L.

2016-06-01

Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity.

Iron nanoparticles with tunable tetragonal structure and magnetic properties

NASA Astrophysics Data System (ADS)

Liu, Jinming; Schliep, Karl; He, Shi-Hai; Ma, Bin; Jing, Ying; Flannigan, David J.; Wang, Jian-Ping

2018-05-01

Body-centered cubic (bcc) Fe is known as a typical soft magnetic material with high-saturation magnetization (Ms) and low magnetocrystalline anisotropy. However, first-principles calculations demonstrate that body-centered tetragonal (bct) Fe has higher magnetocrystalline anisotropy than bcc Fe and comparable Ms. In this work, bct Fe nanoparticles (NPs) were successfully fabricated by a gas-phase condensation method for the first time. The bct Fe phase is confirmed by the x-ray diffraction pattern and diffraction images of transmission electron microscopy. An increased magnetocrystalline anisotropy of bct Fe, (2.65 ±0.67 ) ×1 05J /m3 [ (21.2 ±5.3 ) μ eV /atom ], is observed, which is around seven times higher than that of bcc Fe 4.8 ×1 04J /m3 (3.5 μ eV /atom ). The bct Fe NPs sample has coercivity of 3.22 ×1 05 A/m at 5 K and 1.0 4 ×1 05 A/m at 300 K, which are much higher than that of bcc Fe NPs. In addition, the saturation magnetization at 5 K is estimated to be (1.6 ±0.4 ) ×1 06 A/m (2.2 ±0.5 μB/atom ), comparable to that of bcc Fe 1.7 ×1 06 A/m (2.2 μB/atom ).

On the mineral core of ferritin-like proteins: structural and magnetic characterization

NASA Astrophysics Data System (ADS)

García-Prieto, A.; Alonso, J.; Muñoz, D.; Marcano, L.; Abad Díaz de Cerio, A.; Fernández de Luis, R.; Orue, I.; Mathon, O.; Muela, A.; Fdez-Gubieda, M. L.

2015-12-01

It is generally accepted that the mineral core synthesized by ferritin-like proteins consists of a ferric oxy-hydroxide mineral similar to ferrihydrite in the case of horse spleen ferritin (HoSF) and an oxy-hydroxide-phosphate phase in plant and prokaryotic ferritins. The structure reflects a dynamic process of deposition and dissolution, influenced by different biological, chemical and physical variables. In this work we shed light on this matter by combining a structural (High Resolution Transmission Electron Microscopy (HRTEM) and Fe K-edge X-ray Absorption Spectroscopy (XAS)) and a magnetic study of the mineral core biomineralized by horse spleen ferritin (HoSF) and three prokaryotic ferritin-like proteins: bacterial ferritin (FtnA) and bacterioferritin (Bfr) from Escherichia coli and archaeal ferritin (PfFtn) from Pyrococcus furiosus. The prokaryotic ferritin-like proteins have been studied under native conditions and inside the cells for the sake of preserving their natural attributes. They share with HoSF a nanocrystalline structure rather than an amorphous one as has been frequently reported. However, the presence of phosphorus changes drastically the short-range order and magnetic response of the prokaryotic cores with respect to HoSF. The superparamagnetism observed in HoSF is absent in the prokaryotic proteins, which show a pure atomic-like paramagnetic behaviour attributed to phosphorus breaking the Fe-Fe exchange interaction.It is generally accepted that the mineral core synthesized by ferritin-like proteins consists of a ferric oxy-hydroxide mineral similar to ferrihydrite in the case of horse spleen ferritin (HoSF) and an oxy-hydroxide-phosphate phase in plant and prokaryotic ferritins. The structure reflects a dynamic process of deposition and dissolution, influenced by different biological, chemical and physical variables. In this work we shed light on this matter by combining a structural (High Resolution Transmission Electron Microscopy (HRTEM) and Fe K-edge X-ray Absorption Spectroscopy (XAS)) and a magnetic study of the mineral core biomineralized by horse spleen ferritin (HoSF) and three prokaryotic ferritin-like proteins: bacterial ferritin (FtnA) and bacterioferritin (Bfr) from Escherichia coli and archaeal ferritin (PfFtn) from Pyrococcus furiosus. The prokaryotic ferritin-like proteins have been studied under native conditions and inside the cells for the sake of preserving their natural attributes. They share with HoSF a nanocrystalline structure rather than an amorphous one as has been frequently reported. However, the presence of phosphorus changes drastically the short-range order and magnetic response of the prokaryotic cores with respect to HoSF. The superparamagnetism observed in HoSF is absent in the prokaryotic proteins, which show a pure atomic-like paramagnetic behaviour attributed to phosphorus breaking the Fe-Fe exchange interaction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04446d

Fe(+) chemical ionization of peptides.

PubMed

Speir, J P; Gorman, G S; Amster, I J

1993-02-01

Laser-desorbed peptide neutral molecules were allowed to react with Fe(+) in a Fourier transform mass spectrometer, using the technique of laser desorption/chemical ionization. The Fe(+) ions are formed by laser ablation of a steel target, as well as by dissociative charge-exchange ionization of ferrocene with Ne(+). Prior to reaction with laser-desorbed peptide molecules, Fe(+) ions undergo 20-100 thermalizin collisions with xenon to reduce the population of excited-state metal ion species. The Fe(+) ions that have not experienced thermalizing collisions undergo charge exchange with peptide molecules. Iron ions that undergo thermalizing collisions before they are allowed to react with peptides are found to undergo charge exchange and to form adduct species [M + Fe(+)] and fragment ions that result from the loss of small, stable molecules, such as H2O, CO, and CO2, from the metal ion-peptide complex.

Self-regulated Gd atom trapping in open Fe nanocorrals

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

Cao, R. X.; Liu, Z.; Miao, B. F.

2014-07-01

Utilizing open Fe nanocorrals built by atom manipulation, we demonstrate self-regulated Gd atom trapping in open quantum corrals. The number of Gd atoms trapped is exactly determined by the diameter of the corral. The quantization can be understood as a self-regulating process, arising from the long-range interaction between Gd atoms and the open corral. We illustrate with arrays of open corrals that such atom trapping can suppress unwanted statistical fluctuations. Our approach opens a potential pathway for nanomaterial design and fabrication with atomic-level precision.

Auger electron diffraction study of V/Fe(100) interface formation

NASA Astrophysics Data System (ADS)

Huttel, Y.; Avila, J.; Asensio, M. C.; Bencok, P.; Richter, C.; Ilakovac, V.; Heckmann, O.; Hricovini, K.

1998-05-01

Vanadium atoms present a magnetic moment different to zero when they are part of a thin film deposited on Fe or as a bimetallic Fe-V alloy. The understanding of this phenomenon can only be achieved with a correct structural description of these types of systems. We report an Auger electron diffraction investigation of V films grown on body cubic centred (b.c.c.) Fe(100) substrates. Angular-scanned Auger electron diffraction (AED) patterns of V L 23M 23M 4 (473 eV) and Fe L 3VV (703 eV) show the formation of a well-ordered V/Fe interface even at room temperature. The AED patterns of V films in the range of vanadium submonolayer provide evidence of an isotropic Auger emission, indicating the absence of interdiffusion of V atoms into the Fe substrate and absence of cluster growth of the V film. The annealing of these films up to 400°C does not activate the substitution of the topmost Fe surface layers by V atoms.

Study the Polyol Process of Preparing the ru Doped FePt Nanoparticles

NASA Astrophysics Data System (ADS)

Lee, Chih-Hao; Hsu, Jen-Ho; Su, Hui-Chia; Huang, Tzu Wen

The structure of Ru doped FePt nanoparticles using polyol process was studied. The particle size grown is around 5 nm, and a shell structure might be formed. By selecting the time and temperature of adding the Ru precursors into solution, three different processes to synthesize the FePtRu particles were studied resulting in different growing mechanics. The possible models during the reaction process are also discussed. The phase transition temperature for the as-grown FCC FePt nanoparticle to transform into L10 FePt nanoparticle is about 823 K which is about the same as the one without doping Ru atoms. From the XAS study of each element, the possible scenario is that: although Ru atoms with the size close to the Pt, they do not totally replace the Pt sites in the FePt alloy. Instead, most of Ru formed a shell outside the FePt nanoparticles and Fe atoms are replaced.

Effects of 3d-4f magnetic exchange interactions on the dynamics of the magnetization of Dy(III)-M(II)-Dy(III) trinuclear clusters.

PubMed

Pointillart, Fabrice; Bernot, Kevin; Sessoli, Roberta; Gatteschi, Dante

2007-01-01

[{Dy(hfac)(3)}(2){Fe(bpca)(2)}] x CHCl(3) ([Dy(2)Fe]) and [{Dy(hfac)(3)}(2){Ni(bpca)(2)}]CHCl(3) ([Dy(2)Ni]) (in which hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate and bpca(-)=bis(2-pyridylcarbonyl)amine anion) were synthesized and characterized. Single-crystal X-ray diffraction shows that [Dy(2)Fe] and [Dy(2)Ni] are linear trinuclear complexes. Static magnetic susceptibility measurements reveal a weak ferromagnetic exchange interaction between Ni(II) and Dy(III) ions in [Dy(2)Ni], whereas the use of the diamagnetic Fe(II) ion leads to the absence of magnetic exchange interaction in [Dy(2)Fe]. Dynamic susceptibility measurements show a thermally activated behavior with the energy barrier of 9.7 and 4.9 K for the [Dy(2)Fe] and [Dy(2)Ni] complexes, respectively. A surprising negative effect of the ferromagnetic exchange interaction has been found and has been attributed to the structural conformation of these trinuclear complexes.

Simultaneous determination of iron, cadmium, zinc, copper, nickel, lead, and uranium in seawater by stable isotope dilution spark source mass spectrometry

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

Mykytiuk, A.P.; Russell, D.S.; Sturgeon, R.E.

Trace concentrations (ng/mL) of Fe, Cd, Zn, Cu, Ni, Pb, U, and Co have been determined in seawater by stable isotope dilution spark source mass spectrometry. The seawater samples were preconcentrated on the ion exchanger Chelex-100 and the concentrate was evaporated on a graphite or silver electrode. The results are compared with those obtained by graphite furnace atomic absorption spectrometry and inductively coupled plasma emission spectrometry. The technique avoids the use of calibration standards and is capable of producing results in cases where the analyte is only partially recovered. 2 tables.

Effect of Fe(II)/Ce(III) dosage ratio on the structure and anion adsorptive removal of hydrothermally precipitated composites: Insights from EXAFS/XANES, XRD and FTIR.

PubMed

Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan; Yablokova, Ganna

2017-02-01

In this work, we present material chemistry in the hydrothermal synthesis of new complex structure materials based on various dosage ratios of Fe and Ce (1:0, 2:1, 1:1, 1:2, 0:1), characterize them by the relevant methods that allow characterization of both crystalline and amorphous phases and correlate their structure/surface properties with the adsorptive performance of the five toxic anions. The applied synthesis conditions resulted in the formation of different compounds of Fe and Ce components. The Fe-component was dominated by various phases of Fe hydrous oxides, whereas the Ce-component was composed of various phases of Ce carbonates. The presence of two metal salts in raw materials resulted in the formation of a mesoporous structure and averaged the surface area compared to one metal-based material. The surface of all Fe-Ce composites was abundant in Fe component phases. Two-metal systems showed stronger anion removal performance than one-metal materials. The best adsorption was demonstrated by Fe-Ce based materials that had low crystallinity, that were rich in phases and that exhibited surfaces were abundant in greater number of surface functional groups. Notably, Fe extended fine structures simulated by EXAFS in these better adsorbents were rich from oscillations from both heavy and light atoms. This work provides new insights on the structure of composite inorganic materials useful to develop their applications in adsorption and catalysis. It also presents new inorganic anion exchangers with very high removal potential to fluoride and arsenate. Copyright © 2016 Elsevier Inc. All rights reserved.

Fullerene-like boron clusters stabilized by an endohedrally doped iron atom: B(n)Fe with n = 14, 16, 18 and 20.

PubMed

Tam, Nguyen Minh; Pham, Hung Tan; Duong, Long Van; Pham-Ho, My Phuong; Nguyen, Minh Tho

2015-02-07

Stabilized fullerene and tubular forms can be produced in boron clusters Bn in small sizes from n∼ 14 to 20 upon doping by transition metal atoms. B14Fe and B16Fe are stable tubes whereas B18Fe and B20Fe are stable fullerenes. Their formation and stability suggest the use of dopants to induce different growth paths leading to larger cages, fullerenes and tubes of boron.

Magnetic properties of Fe-doped organic-inorganic nanohybrids

NASA Astrophysics Data System (ADS)

Silva, N. J. O.; Amaral, V. S.; Carlos, L. D.; de Zea Bermudez, V.

2003-05-01

We present a magnetic study of Fe-doped diureasils (siloxane-based networks to which poly(ethylene oxide)-based chains are grafted by urea cross linkages doped with Fe(II) or Fe(III) ions. Structural studies show that the Fe(II) ions interact mainly with the organic chain, whereas the incorporation of Fe(III) leads to the formation of iron-based nanoclusters, with radius increasing from 20 to 40 Å. Fe(II)-doped samples behave as simple paramagnets, with μeff=5.32μB. Fe(III)-doped hybrids present antiferromagnetic interactions, with TN increasing with Fe(III) concentration up to 13.6 K for 6% doping. Thermal irreversibility was observed below ˜40 K and is stronger for higher concentrations. The coercive fields (HC) are of the order of 1000 Oe at 5 K. Hysteresis cycles are shifted to negative fields, revealing the presence of exchange anisotropy interactions with exchange fields (HE) of the order of 100 Oe. Both fields decrease rapidly with increasing temperature. We analyze this behavior in terms of the contribution of surface spin disorder to exchange anisotropy.

Effects of hydrogen atom spin exchange collisions on atomic hydrogen maser oscillation frequency

NASA Technical Reports Server (NTRS)

Crampton, S. B.

1979-01-01

Frequency shifts due to collisions between hydrogen atoms in an atomic hydrogen maser frequency standard are studied. Investigations of frequency shifts proportional to the spin exchange frequency shift cross section and those proportional to the duration of exchange collisions are discussed. The feasibility of operating a hydrogen frequency standard at liquid helium temperatures is examined.

Role of iron modifier on boron atomization process using graphite furnace-atomic absorption spectrometry based on speciation of iron using X-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Yamamoto, Yuhei; Tagami, Azusa; Shiarasaki, Toshihiro; Yonetani, Akira; Yamamoto, Takashi; Imai, Shoji

2018-04-01

The role of an Fe modifier on boron atomization process using graphite furnace-atomic absorbance spectrometry was investigated using a spectroscopic approach. The initial state of the Fe modifier in a pyrolytic graphite (PG) furnace was trivalent. With an increase in pyrolysis temperature, the Fe modifier was reduced in a stepwise manner. Fe2O3 and Fe3O4 were dominant at pyrolysis temperatures below 1300 K. From 1300 to 1500 K, FeO was dominant. At temperatures higher than 1700 K, Fe metal was dominant. After a drying step, 17.7% of the initial B remained in the PG furnace. After the pyrolysis step at 773 K, the residual fraction of B was similar to that after the drying step. After the pyrolysis step at a temperature of 1073 K, the residual fraction was 11.7%. At pyrolysis temperatures > 1738 K, the residual fraction was <3.3% (

FeO "Orange Arc" Emission Detected in Optical Spectrum of Leonid Persistent Trains

NASA Technical Reports Server (NTRS)

Jenniskens, Peter; Lacey, Matt; Allan, Beverly J.; Self, Daniel E.; Plane, John M. C.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

We report the detection of a broad continuum emission dominating the visual spectrum of a Leonid persistent train. A comparison with laboratory spectra of FeO 1 "orange arc" emission at I mbar shows a general agreement of the band position and shape. The detection of FeO confirms the classical mechanism of metal atom catalyzed recombination of ozone and oxygen atoms as the driving force behind optical emission from persistent trains. Sodium and iron atoms are now confirmed catalysts.

In situ observation of atomic movement in a ferroelectric film under an external electric field and stress

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

Lee, Hyeon Jun; Guo, Er-Jia; Min, Taewon

Atomic movement under application of external stimuli (i.e., electric field or mechanical stress) in oxide materials has not been observed due to a lack of experimental methods but has been well known to determine the electric polarization. Here, we investigated atomic movement arising from the ferroelectric response of BiFeO 3 thin films under the effect of an electric field and stress in real time using a combination of switching spectroscopy, time-resolved X-ray microdiffraction, and in situ stress engineering. Under an electric field applied to a BiFeO 3 film, the hysteresis loop of the reflected X-ray intensity was found to resultmore » from the opposing directions of displaced atoms between the up and down polarization states. An additional shift of atoms arising from the linearly increased dielectric component of the polarization in BiFeO 3 was confirmed through gradual reduction of the diffracted X-ray intensity. The electric-fieldinduced displacement of oxygen atoms was found to be larger than that of Fe atom for both ferroelectric switching and increase of the polarization. In conclusion, the effect of external stress on the BiFeO 3 thin film, which was controlled by applying an electric field to the highly piezoelectric substrate, showed smaller atomic shifts than for the case of applying an electric field to the film, despite the similar tetragonality.« less

In situ observation of atomic movement in a ferroelectric film under an external electric field and stress

DOE PAGES

Lee, Hyeon Jun; Guo, Er-Jia; Min, Taewon; ...

2017-12-28

Atomic movement under application of external stimuli (i.e., electric field or mechanical stress) in oxide materials has not been observed due to a lack of experimental methods but has been well known to determine the electric polarization. Here, we investigated atomic movement arising from the ferroelectric response of BiFeO 3 thin films under the effect of an electric field and stress in real time using a combination of switching spectroscopy, time-resolved X-ray microdiffraction, and in situ stress engineering. Under an electric field applied to a BiFeO 3 film, the hysteresis loop of the reflected X-ray intensity was found to resultmore » from the opposing directions of displaced atoms between the up and down polarization states. An additional shift of atoms arising from the linearly increased dielectric component of the polarization in BiFeO 3 was confirmed through gradual reduction of the diffracted X-ray intensity. The electric-fieldinduced displacement of oxygen atoms was found to be larger than that of Fe atom for both ferroelectric switching and increase of the polarization. In conclusion, the effect of external stress on the BiFeO 3 thin film, which was controlled by applying an electric field to the highly piezoelectric substrate, showed smaller atomic shifts than for the case of applying an electric field to the film, despite the similar tetragonality.« less

Graphene as a flexible template for controlling magnetic interactions between metal atoms.

PubMed

Lee, Sungwoo; Kim, Dongwook; Robertson, Alex W; Yoon, Euijoon; Hong, Suklyun; Ihm, Jisoon; Yu, Jaejun; Warner, Jamie H; Lee, Gun-Do

2017-03-01

Metal-doped graphene produces magnetic moments that have potential application in spintronics. Here we use density function theory computational methods to show how the magnetic interaction between metal atoms doped in graphene can be controlled by the degree of flexure in a graphene membrane. Bending graphene by flexing causes the distance between two substitutional Fe atoms covalently bonded in graphene to gradually increase and these results in the magnetic moment disappearing at a critical strain value. At the critical strain, a carbon atom can enter between the two Fe atoms and blocks the interaction between relevant orbitals of Fe atoms to quench the magnetic moment. The control of interactions between doped atoms by exploiting the mechanical flexibility of graphene is a unique approach to manipulating the magnetic properties and opens up new opportunities for mechanical-magnetic 2D device systems.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

PubMed

Laguna-Marco, M A; Piquer, C; Roca, A G; Boada, R; Andrés-Vergés, M; Veintemillas-Verdaguer, S; Serna, C J; Iadecola, A; Chaboy, J

2014-09-14

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles. The XAS spectra show that, in the samples synthesized by precipitation in aqueous media and laser pyrolysis, the Bi atoms neither enter into the iron oxide spinel lattice nor form any other mixed Bi-Fe oxides. No modification of the local structure around the Fe atoms induced by the Bi atoms is observed at the Fe K edge. In addition, contrary to expectations, our results indicate that the Bi atoms do not form a well-defined Bi oxide structure. The XAS study at the Bi L3 edge indicates that the environment around Bi atoms is highly disordered and only a first oxygen coordination shell is observed. Indefinite [BiO6-x(OH)x] units (isolated or aggregated forming tiny amorphous clusters) bonded through hydroxyl bridges to the nanoparticle, rather than a well defined Bi2O3 shell, surround the nanoparticle. On the other hand, the XAS study indicates that, in the samples synthesized by thermal decomposition, the Bi atoms are embedded in a longer range ordered structure showing the first and second neighbors.

Resolving the Origin of the Diffuse Soft X-ray Background

NASA Technical Reports Server (NTRS)

Smith, Randall K.; Foster, Adam R.; Edgar, Ricard J.; Brickhouse, Nancy S.; Sanders, Wilton T.

2012-01-01

In January 1993, the Diffuse X-ray Spectrometer (DXS) measured the first high-resolution spectrum of the diffuse soft X-ray background between 44-80A. A line-dominated spectrum characteristic of a 10(exp 6)K collisionally ionized plasma' was expected but while the observed spectrum was clearly line-dominated, no model would fit. Then in 2003 the Cosmic Hot Interstellar Plasma Spectrometer (CHIPS) launched and observed the diffuse extreme-ultraviolet (EUV) spectrum between 90- 265A. Although many emission lines were again expected; only Fe IX at 171.1A was detected. The discovery of X-rays from comets led to the realization that heavy ions (Z=6-28) in the solar wind will emit soft X-rays as the ions interact via charge exchange with neutral atoms in the heliosphere and geocorona. Using a new model for solar wind charge exchange (SWCX) emission, we show that the diffuse soft X-ray background can be understood as a combination of emission from charge exchange onto the slow and fast solar wind together with a more distant and diffuse hot (10(exp 6)K) plasma.

Density functional theory study of small X-doped Mg(n) (X = Fe, Co, Ni, n = 1-9) bimetallic clusters: equilibrium structures, stabilities, electronic and magnetic properties.

PubMed

Kong, Fanjie; Hu, Yanfei

2014-03-01

The geometries, stabilities, and electronic and magnetic properties of Mg(n) X (X = Fe, Co, Ni, n = 1-9) clusters were investigated systematically within the framework of the gradient-corrected density functional theory. The results show that the Mg(n)Fe, Mg(n)Co, and Mg(n)Ni clusters have similar geometric structures and that the X atom in Mg(n)X clusters prefers to be endohedrally doped. The average atomic binding energies, fragmentation energies, second-order differences in energy, and HOMO-LUMO gaps show that Mg₄X (X = Fe, Co, Ni) clusters possess relatively high stability. Natural population analysis was performed and the results showed that the 3s and 4s electrons always transfer to the 3d and 4p orbitals in the bonding atoms, and that electrons also transfer from the Mg atoms to the doped atoms (Fe, Co, Ni). In addition, the spin magnetic moments were analyzed and compared. Several clusters, such as Mg₁,₂,₃,₄,₅,₆,₈,₉Fe, Mg₁,₂,₄,₅,₆,₈,₉Co, and Mg₁,₂,₅,₆,₇,₉Ni, present high magnetic moments (4 μ(B), 3 μ(B), and 2 μ(B), respectively).

Enhanced exchange bias and improved ferromagnetic properties in Permalloy-BiFe0.95Co0.05O3 core-shell nanostructures.

PubMed

Javed, K; Li, W J; Ali, S S; Shi, D W; Khan, U; Riaz, S; Han, X F

2015-12-14

Hybrid core-shell nanostructures consisting of permalloy (Ni80Fe20) and multiferroic(BiFeO3, BFO/BiFe0.95Co0.05O3, BFC) materials were synthesized by a two-step method, based on wet chemical impregnation and subsequent electrodeposition within porous alumina membranes. Structural and magnetic characterizations have been done to investigate doping effect on magnetic properties and exchange bias. The magnetometry analysis revealed significant enhancements of the exchange bias and coercivity in NiFe-BFC core-shell nanostructures as compared with NiFe-BFO core-shell nanostructures. The enhancements can be attributed to the effective reduction of ferromagnet domain sizes between adjacent layers of core-shell structure. It indicates that it is possible to improve properties of multiferroic composites by site-engineering method. Our approach opens a pathway to obtain optimized nanostructured multiferroic composites exhibiting tunable magnetic properties.

Enhanced exchange bias and improved ferromagnetic properties in Permalloy–BiFe0.95Co0.05O3 core–shell nanostructures

PubMed Central

Javed, K.; Li, W. J.; Ali, S. S.; Shi, D. W.; Khan, U.; Riaz, S.; Han, X. F.

2015-01-01

Hybrid core–shell nanostructures consisting of permalloy (Ni80Fe20) and multiferroic(BiFeO3, BFO/BiFe0.95Co0.05O3, BFC) materials were synthesized by a two-step method, based on wet chemical impregnation and subsequent electrodeposition within porous alumina membranes. Structural and magnetic characterizations have been done to investigate doping effect on magnetic properties and exchange bias. The magnetometry analysis revealed significant enhancements of the exchange bias and coercivity in NiFe-BFC core-shell nanostructures as compared with NiFe-BFO core-shell nanostructures. The enhancements can be attributed to the effective reduction of ferromagnet domain sizes between adjacent layers of core-shell structure. It indicates that it is possible to improve properties of multiferroic composites by site-engineering method. Our approach opens a pathway to obtain optimized nanostructured multiferroic composites exhibiting tunable magnetic properties. PMID:26658956

Exchange-mediated spin-lattice relaxation of Fe3+ ions in borate glasses.

PubMed

Misra, Sushil K; Pilbrow, John R

2007-03-01

Spin-lattice relaxation times (T1) of two borate glasses doped with different concentrations of Fe2O3 were measured using the Electron Spin-Echo (ESE) technique at X-band (9.630 GHz) in the temperature range 2-6K. In comparison with a previous investigation of Fe3+-doped silicate glasses, the relaxation rates were comparable and differed by no more than a factor of two. The data presented here extend those previously reported for borate glasses in the 10-250K range but measured using the amplitude-modulation technique. The T1 values were found to depend on temperature (T) as T(n) with n approximately 1 for the 1% and 0.1% Fe2O3-doped glass samples. These results are consistent with spin-lattice relaxation as effected by exchange interaction of a Fe3+ spin exchange-coupled to another Fe3+ spin in an amorphous material.

Exchange-coupled hard magnetic Fe-Co/CoPt nanocomposite films fabricated by electro-infiltration

NASA Astrophysics Data System (ADS)

Wen, Xiao; Andrew, Jennifer S.; Arnold, David P.

2017-05-01

This paper introduces a potentially scalable electro-infiltration process to produce exchange-coupled hard magnetic nanocomposite thin films. Fe-Co/CoPt nanocomposite films are fabricated by deposition of CoFe2O4 nanoparticles onto Si substrate, followed by electroplating of CoPt. Samples are subsequently annealed under H2 to reduce the CoFe2O4 to magnetically soft Fe-Co and also induce L10 ordering in the CoPt. Resultant films exhibit 0.97 T saturation magnetization, 0.70 T remanent magnetization, 127 kA/m coercivity and 21.8 kJ/m3 maximum energy density. First order reversal curve (FORC) analysis and δM plot are used to prove the exchange coupling between soft and hard magnetic phases.

Atomic-Resolution X-ray Energy-Dispersive Spectroscopy Chemical Mapping of Substitutional Dy Atoms in a High-Coercivity Neodymium Magnet

NASA Astrophysics Data System (ADS)

Itakura, Masaru; Watanabe, Natsuki; Nishida, Minoru; Daio, Takeshi; Matsumura, Syo

2013-05-01

We have investigated local element distributions in a Dy-doped Nd2Fe14B hot-deformed magnet by atomic-column resolution chemical mapping using an X-ray energy-dispersive spectrometer (XEDS) attached to an aberration-corrected scanning transmission electron microscope (Cs-corrected STEM). The positions of the Nd and Dy atomic columns were visualized in the XEDS maps. The substitution of Dy was limited to a surface layer 2-3 unit cells thick in the Nd2Fe14B grains, and the Dy atoms preferentially occupied the 4f-Nd sites of Nd2Fe14B. These results provide further insights into the principal mechanism governing the coercivity enhancement due to Dy doping.

Biaxial tensile strain modulates magnetic properties of the 3d transition metal doped stanene

NASA Astrophysics Data System (ADS)

Dai, Xian-Qi; Zhao, Ming-Yu; Zhao, Ru-Meng; Li, Wei

2017-06-01

Utilizing first-principle calculations, the biaxial tensile strain modulating magnetic states and electronic structures of transition metal (TM) (i.e., Mn, Fe, Sc, Ni and Ti) atoms doped in stanene are investigated. It shows that Mn and Fe doped stanene systems are magnetic, while the Sc, Ti and Ni doped stanene systems are nonmagnetic. When the biaxial tensile strain increases, a weaker antiferromagnetic coupling between the nearest neighbor (NN) Sn atoms and Mn (Fe, Ti) atom is observed. For Sc and Ni doped stanene systems, the biaxial strain doesn't introduce spin polarization for the TM atoms. In a word, the TM atoms doped stanene systems may manifest potential applications in nanoelectronics, spintronics and magnetic storage devices.

The role of phase separation for self-organized surface pattern formation by ion beam erosion and metal atom co-deposition

NASA Astrophysics Data System (ADS)

Hofsäss, H.; Zhang, K.; Pape, A.; Bobes, O.; Brötzmann, M.

2013-05-01

We investigate the ripple pattern formation on Si surfaces at room temperature during normal incidence ion beam erosion under simultaneous deposition of different metallic co-deposited surfactant atoms. The co-deposition of small amounts of metallic atoms, in particular Fe and Mo, is known to have a tremendous impact on the evolution of nanoscale surface patterns on Si. In previous work on ion erosion of Si during co-deposition of Fe atoms, we proposed that chemical interactions between Fe and Si atoms of the steady-state mixed Fe x Si surface layer formed during ion beam erosion is a dominant driving force for self-organized pattern formation. In particular, we provided experimental evidence for the formation of amorphous iron disilicide. To confirm and generalize such chemical effects on the pattern formation, in particular the tendency for phase separation, we have now irradiated Si surfaces with normal incidence 5 keV Xe ions under simultaneous gracing incidence co-deposition of Fe, Ni, Cu, Mo, W, Pt, and Au surfactant atoms. The selected metals in the two groups (Fe, Ni, Cu) and (W, Pt, Au) are very similar regarding their collision cascade behavior, but strongly differ regarding their tendency to silicide formation. We find pronounced ripple pattern formation only for those co deposited metals (Fe, Mo, Ni, W, and Pt), which are prone to the formation of mono and disilicides. In contrast, for Cu and Au co-deposition the surface remains very flat, even after irradiation at high ion fluence. Because of the very different behavior of Cu compared to Fe, Ni and Au compared to W, Pt, phase separation toward amorphous metal silicide phases is seen as the relevant process for the pattern formation on Si in the case of Fe, Mo, Ni, W, and Pt co-deposition.

Exchange bias effect in L10-ordered FePt and FeCo-based bilayer structure: effect of increasing applied field

NASA Astrophysics Data System (ADS)

Singh, Sadhana; Kumar, Dileep; Bhagat, Babli; Choudhary, R. J.; Reddy, V. R.; Gupta, Ajay

2018-02-01

The applied magnetic field (H APP) dependence of the exchange bias (EB) is studied in an exchange-coupled thin-film bilayer composed of a hard ferromagnetic FePt layer in the proximity of a soft ferromagnetic FeCo layer. FePt/FeCo structure is deposited in an ultra-high vacuum chamber, where the FePt layer was first annealed at 823 K for 30 min and subsequently cooled to room temperature in the presence of an in-plane magnetic field, H MAX ~ 1.5 kOe to promote L10-ordered hard magnetic phase with magnetic moments aligned in one of the in-plane directions in the FePt layer. In-situ magneto-optical Kerr effect measurements during different stages of bilayer growth and detailed ex-situ superconducting quantum interference device-vibrating sample magnetometer measurements jointly revealed that due to the interplay between exchange coupling at the interface and dipolar energies of the saturated hard FePt layer, a hysteresis loop of FeCo layer shifts along the magnetic field axis. A clear dependence of EB field (H EB) on increasing maximum value of the H APP during the hysteresis loop measurement is understood in terms of the magnetic state of soft and hard magnetic layers, where EB increases with increasing H APP until the hard layer moment remains undisturbed in its remanence state. As soon as the field was sufficient to rotate the spins of the FePt layer, the loop became symmetric with respect to the field axis.

Electronic structure and properties of magnetic defects in Co(1+x)Al(1-x) and Fe(1+x)Al(1-x) alloys. Ph.D. Thesis - Paris Univ.

NASA Technical Reports Server (NTRS)

Abbe, D.

1984-01-01

CoAl and FeAl compounds are developed along two directions. Magnetic susceptibility and specific heat at low temperature on (NiCo)Al and (CoFe)Al ternary alloys are in good agreement with band calculations. Results on magnetization and specific heat under field at low temperature on nonstoichiometric compounds show clearly the importance of the nearest neighbor effects. In the case of CoAl, the isolated cobalt atoms substituting aluminum are characterized by a Kondo behavior, and, for FeAl, the isolated extra iron atoms are magnetic and polarize the matrix. Moreover, for the two compounds, clusters of higher order play a considerable part in the magnetic properties for CoAl, these clusters also seem to be characterized by a Kondo behavior, for FeAl, these clusters whose moment is higher than in the case of isolated atoms, could be constituted of excess parts of iron atoms.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy.

PubMed

Niu, Shuqiang; Huang, Dao-Ling; Dau, Phuong D; Liu, Hong-Tao; Wang, Lai-Sheng; Ichiye, Toshiko

2014-03-11

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH 3 ) 2 ] 1-/0 , [Cu(NCS) 2 ] 1-/0 , [FeCl 4 ] 1-/0 , and [Fe(SCH 3 ) 4 ] 1-/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree-Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC- ω PBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy

PubMed Central

2015-01-01

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH3)2]1–/0, [Cu(NCS)2]1–/0, [FeCl4]1–/0, and [Fe(SCH3)4]1–/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree–Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC-ωPBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes. PMID:24803858

Tris(4,4′-bi-1,3-thia­zole-κ2 N,N′)iron(II) tetra­bromidoferrate(III) bromide

PubMed Central

Abedi, Anita; Amani, Vahid; Safari, Nasser

2011-01-01

In the [Fe(4,4′-bit)3]2+ (4,4′-bit is 4,4′-bi-1,3-thia­zole) cation of the title compound, [Fe(C6H4N2S2)3][FeBr4]Br, the FeII atom (3 symmetry) is six-coordinated in a distorted octa­hedral geometry by six N atoms from three 4,4′-bit ligands. In the [FeBr4]− anion, the FeIII atom (3 symmetry) is four-coordinated in a distorted tetra­hedral geometry. In the crystal, inter­molecular C—H⋯Br hydrogen bonds and Br⋯π inter­actions [Br⋯centroid distances = 3.562 (3) and 3.765 (2) Å] link the cations and anions, stabilizing the structure. PMID:21522247

Enhanced magneto-optical Kerr effect at Fe/insulator interfaces

NASA Astrophysics Data System (ADS)

Gu, Bo; Takahashi, Saburo; Maekawa, Sadamichi

2017-12-01

Using density functional theory calculations, we have found an enhanced magneto-optical Kerr effect in Fe/insulator interfaces. The results of our study indicate that interfacial Fe atoms in the Fe films have a low-dimensional nature, which causes the following two effects: (i) The diagonal component σx x of the optical conductivity decreases dramatically because the hopping integral for electrons between Fe atoms is suppressed by the low dimensionality. (ii) The off-diagonal component σx y of the optical conductivity does not change at low photon energies, but it is enhanced at photon energies around 2 eV, where we obtain enhanced orbital magnetic moments and spin-orbit correlations for the interfacial Fe atoms. A large Kerr angle develops in proportion to the ratio σx y/σx x . Our findings indicate an efficient way to enhance the effect of spin-orbit coupling at metal/insulator interfaces without using heavy elements.

Photoelectron spectroscopic study of the anionic transition metalorganic complexes [Fe(1,2)(COT)](-) and [Co(COT)](-).

PubMed

Li, Xiang; Eustis, Soren N; Bowen, Kit H; Kandalam, Anil

2008-09-28

The gas-phase, iron and cobalt cyclooctatetraene cluster anions, [Fe(1,2)(COT)](-) and [Co(COT)](-), were generated using a laser vaporization source and studied using mass spectrometry and anion photoelectron spectroscopy. Density functional theory was employed to compute the structures and spin multiplicities of these cluster anions as well as those of their corresponding neutrals. Both experimental and theoretically predicted electron affinities and photodetachment transition energies are in good agreement, authenticating the structures and spin multiplicities predicted by theory. The implied spin magnetic moments of these systems suggest that [Fe(COT)], [Fe(2)(COT)], and [Co(COT)] retain the magnetic moments of the Fe atom, the Fe(2) dimer, and the Co atom, respectively. Thus, the interaction of these transition metal, atomic and dimeric moieties with a COT molecule does not quench their magnetic moments, leading to the possibility that these combinations may be useful in forming novel magnetic materials.

Density functional study of double ionization energies

NASA Astrophysics Data System (ADS)

Chong, D. P.

2008-02-01

In this paper, double ionization energies (DIEs) of gas-phase atoms and molecules are calculated by energy difference method with density functional theory. To determine the best functional for double ionization energies, we first study 24 main group atoms in the second, third, and fourth periods. An approximation is used in which the electron density is first obtained from a density functional computation with the exchange-correlation potential Vxc known as statistical average of orbital potentials, after which the energy is computed from that density with 59 different exchange-correlation energy functionals Exc. For the 24 atoms, the two best Exc functional providing DIEs with average absolute deviation (AAD) of only 0.25eV are the Perdew-Burke-Ernzerhof functional modified by Hammer et al. [Phys. Rev. B 59, 6413 (1999)] and one known as the Krieger-Chen-Iafrate-Savin functional modified by Krieger et al. (unpublished). Surprisingly, none of the 20 available hybrid functionals is among the top 15 functionals for the DIEs of the 24 atoms. A similar procedure is then applied to molecules, with opposite results: Only hybrid functionals are among the top 15 functionals for a selection of 29molecules. The best Exc functional for the 29molecules is found to be the Becke 1997 functional modified by Wilson et al. [J. Chem. Phys. 115, 9233 (2001)]. With that functional, the AAD from experiment for DIEs of 29molecules is just under 0.5eV. If the two suspected values for C2H2 and Fe(CO)5 are excluded, the AAD improves to 0.32eV. Many other hybrid functionals perform almost as well.

Atomic layer deposition and properties of ZrO2/Fe2O3 thin films

PubMed Central

Seemen, Helina; Ritslaid, Peeter; Rähn, Mihkel; Tamm, Aile; Kukli, Kaupo; Kasikov, Aarne; Link, Joosep; Stern, Raivo; Dueñas, Salvador; Castán, Helena; García, Héctor

2018-01-01

Thin solid films consisting of ZrO2 and Fe2O3 were grown by atomic layer deposition (ALD) at 400 °C. Metastable phases of ZrO2 were stabilized by Fe2O3 doping. The number of alternating ZrO2 and Fe2O3 deposition cycles were varied in order to achieve films with different cation ratios. The influence of annealing on the composition and structure of the thin films was investigated. Additionally, the influence of composition and structure on electrical and magnetic properties was studied. Several samples exhibited a measurable saturation magnetization and most of the samples exhibited a charge polarization. Both phenomena were observed in the sample with a Zr/Fe atomic ratio of 2.0. PMID:29441257

Near-neighbor mixing and bond dilation in mechanically alloyed Cu-Fe

NASA Astrophysics Data System (ADS)

Harris, V. G.; Kemner, K. M.; Das, B. N.; Koon, N. C.; Ehrlich, A. E.; Kirkland, J. P.; Woicik, J. C.; Crespo, P.; Hernando, A.; Garcia Escorial, A.

1996-09-01

Extended x-ray-absorption fine-structure (EXAFS) measurements were used to obtain element-specific, structural, and chemical information of the local environments around Cu and Fe atoms in high-energy ball-milled CuxFe1-x samples (x=0.50 and 0.70). Analysis of the EXAFS data shows both Fe and Cu atoms reside in face-centered-cubic sites where the first coordination sphere consists of a mixture of Fe and Cu atoms in a ratio which reflects the as-prepared stoichiometry. The measured bond distances indicate a dilation in the bonds between unlike neighbors which accounts for the lattice expansion measured by x-ray diffraction. These results indicate that metastable alloys having a positive heat of mixing can be prepared via the high-energy ball-milling process.

Comparison of colorimetry and electrothermal atomic absorption spectroscopy for the quantification of non-transferrin bound iron in human sera.

PubMed

Jittangprasert, Piyada; Wilairat, Prapin; Pootrakul, Pensri

2004-12-01

This paper describes a comparison of two analytical techniques, one employing bathophenanthrolinedisulfonate (BPT), a most commonly-used reagent for Fe (II) determination, as chromogen and an electrothermal atomic absorption spectroscopy (ETAAS) for the quantification of non-transferrin bound iron (NTBI) in sera from thalassemic patients. Nitrilotriacetic acid (NTA) was employed as the ligand for binding iron from low molecular weight iron complexes present in the serum but without removing iron from the transferrin protein. After ultrafiltration the Fe (III)-NTA complex was then quantified by both methods. Kinetic study of the rate of the Fe (II)-BPT complex formation for various excess amounts of NTA ligand was also carried out. The kinetic data show that a minimum time duration (> 60 minutes) is necessary for complete complex formation when large excess of NTA is used. Calibration curves given by colorimetric and ETAAS methods were linear over the range of 0.15-20 microM iron (III). The colorimetric and ETAAS methods exhibited detection limit (3sigma) of 0.13 and 0.14 microM, respectively. The NTBI concentrations from 55 thalassemic serum samples measured employing BPT as chromogen were statistically compared with the results determined by ETAAS. No significant disagreement at 95% confidence level was observed. It is, therefore, possible to select any one of these two techniques for determination of NTBI in serum samples of thalassemic patients. However, the colorimetric procedure requires a longer analysis time because of a slow rate of exchange of NTA ligand with BPT, leading to the slow rate of formation of the colored complex.

Proton environment of reduced Rieske iron-sulfur cluster probed by two-dimensional ESEEM spectroscopy

PubMed Central

Kolling, Derrick R. J.; Samoilova, Rimma I.; Shubin, Alexander A.; Crofts, Antony R.; Dikanov, Sergei A.

2008-01-01

The proton environment of the reduced [2Fe-2S] cluster in the water-soluble head domain of the Rieske iron—sulfur protein (ISF) from the cytochrome bc1 complex of Rhodobacter sphaeroides has been studied by orientation-selected X-band 2D ESEEM. The 2D spectra show multiple cross-peaks from protons, with considerable overlap. Samples in which 1H2O water was replaced by 2H2O were used to determine which of the observed peaks belong to exchangeable protons, likely involved in hydrogen bonds in the neighborhood of the cluster. By correlating the cross-peaks from 2D spectra recorded at different parts of the EPR spectrum, lines from nine distinct proton signals were identified. Assignment of the proton signals was based on a point-dipole model for interaction with electrons of Fe(III) and Fe(II) ions, using the high-resolution structure of ISF from Rb. sphaeroides. Analysis of experimental and calculated tensors has led us to conclude that even 2D spectra do not completely resolve all contributions from nearby protons. Particularly, the seven resolved signals from non-exchangeable protons could be produced by at least thirteen protons. The contributions from exchangeable protons were resolved by difference spectra (1H2O minus 2H2O), and assigned to two groups of protons with distinct anisotropic hyperfine values. The largest measured coupling exceeded any calculated value. This discrepancy could result from limitations of the point dipole approximation in dealing with the distribution of spin density over the sulfur atoms of the cluster and the cysteine ligands, or from differences between the structure in solution and the crystallographic structure. The approach demonstrated here provides a paradigm for a wide range of studies in which hydrogen-bonding interactions with metallic centers has a crucial role in understanding of function. PMID:19099453

Inverse spin Hall and spin rectification effects in NiFe/FeMn exchange-biased thin films

NASA Astrophysics Data System (ADS)

Garcia, W. J. S.; Seeger, R. L.; da Silva, R. B.; Harres, A.

2017-11-01

Materials presenting high spin-orbit coupling are able to convert spin currents in charge currents. The phenomenon, known as inverse spin Hall effect, promises to revolutionize spintronic technology enabling the electrical detection of spin currents. It has been observed in a variety of systems, usually non-magnetic metals. We study the voltage emerging in exchange biased Ta/NiFe/FeMn/Ta thin films near the ferromagnetic resonance. Measured signals are related to both inverse spin Hall and spin rectification effects, and two distinct protocols were employed to separate their contributions.The curve shift due to the exchange bias effect may enable high frequency applications without an external applied magnetic field.

Adsorption of CO2 on Fe-doped graphene nano-ribbons: Investigation of transport properties

NASA Astrophysics Data System (ADS)

Othman, W.; Fahed, M.; Hatim, S.; Sherazi, A.; Berdiyorov, G.; Tit, N.

2017-07-01

Density functional theory combined with the non-equilibrium Green’s function formalism is used to study the conductance response of Fe-doped graphene nano-ribbons (GNRs) to CO2 gas adsorption. A single Fe atom is either adsorbed on GNR’s surface (aFe-graphene) or it substitutes the carbon atom (sFe-graphene). Metal atom doping reduces the electronic transmission of pristine graphene due to the localization of electronic states near the impurity site. Moreover, the aFe-graphene is found to be less sensitive to the CO2 molecule attachment as compared to the sFe-graphene system. These behaviours are not only consolidated but rather confirmed by calculating the IV characteristics from which both surface resistance and its sensitivity to the gas are estimated. Since the change in the conductivity is one of the main outputs of sensors, our findings will be useful in developing efficient graphene-based solid-state gas sensors.

Iron Carbides in Fischer–Tropsch Synthesis: Theoretical and Experimental Understanding in Epsilon-Iron Carbide Phase Assignment

DOE PAGES

Liu, Xing-Wu; Cao, Zhi; Zhao, Shu; ...

2017-09-11

As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2C and ε’-Fe 2.2C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe xC, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectramore » for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2C has six sets of chemically distinct Fe atoms.« less

Effect of Ir-Mn composition on exchange bias and thermal stability of spin valves with nano-oxide layers

NASA Astrophysics Data System (ADS)

Liu, Y. F.; Cai, J. W.; Lai, W. Y.; Yu, G. H.

2008-05-01

The Ir-Mn bottom-pinned spin valves with nano-oxide layers (NOLs), Ta /Ni81Fe19/Ir-Mn/Co90Fe10/NOL/Co90Fe10/Cu/Co90Fe10/NOL/Ta, were fabricated by dc magnetron sputtering. The magnetoresistance (MR), magnetization, and exchange bias have been studied as a function of Ir-Mn composition and annealing temperature. It was observed that the spin valves with the Ir-Mn layer containing relatively low Mn content (58.9-72.4at.% Mn) show the best thermal endurance. For these samples, the Mn diffusion is effectively hampered by the NOL with a large MR value of about 12.5% even after annealing at 300°C. On the other hand, the exchange bias field of the pinned CoFe layer shows a maximum at Mn content of about 72.4at.%, which is different from the widely adopted composition, Ir-80at.% Mn, optimized from the top-pinned NiFe /Ir-Mn system. Moreover, the blocking temperature of the Ir -Mn/CoFe system with 72.4at.% Mn is higher than that with 80.6at.% Mn. The present results suggest that the Ir -Mn/CoFe pinning system with Mn content at about 72% renders the most favorable exchange bias and the best thermal stability for the bottom-pinned specular spin valves.

Role of the antiferromagnetic pinning layer on spin wave properties in IrMn/NiFe based spin-valves

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

Gubbiotti, G., E-mail: gubbiotti@fisica.unipg.it; Tacchi, S.; Del Bianco, L.

2015-05-07

Brillouin light scattering (BLS) was exploited to study the spin wave properties of spin-valve (SV) type samples basically consisting of two 5 nm-thick NiFe layers (separated by a Cu spacer of 5 nm), differently biased through the interface exchange coupling with an antiferromagnetic IrMn layer. Three samples were investigated: a reference SV sample, without IrMn (reference); one sample with an IrMn underlayer (10 nm thick) coupled to the bottom NiFe film; one sample with IrMn underlayer and overlayer of different thickness (10 nm and 6 nm), coupled to the bottom and top NiFe film, respectively. The exchange coupling with the IrMn, causing the insurgence ofmore » the exchange bias effect, allowed the relative orientation of the NiFe magnetization vectors to be controlled by an external magnetic field, as assessed through hysteresis loop measurements by magneto-optic magnetometry. Thus, BLS spectra were acquired by sweeping the magnetic field so as to encompass both the parallel and antiparallel alignment of the NiFe layers. The BLS results, well reproduced by the presented theoretical model, clearly revealed the combined effects on the spin dynamic properties of the dipolar interaction between the two NiFe films and of the interface IrMn/NiFe exchange coupling.« less

Estimate of the frequency of true incomplete exchanges in human lymphocytes exposed to 1 GeV/u Fe ions in vitro

NASA Technical Reports Server (NTRS)

Wu, H.; George, K.; Yang, T. C.

1999-01-01

PURPOSE: To study the frequency of true incomplete exchanges induced by high-LET radiation. MATERIALS AND METHODS: Human lymphocytes were exposed to 1 GeV/u Fe ions (LET = 140 keV/microm). Chromosome aberrations were analysed by a fluorescence in situ hybridization using a combination of whole-chromosome-specific probes and human telomere probes. Chromosomes 1, 3 and 4 were investigated. RESULTS: The percentage of incomplete exchanges was between 23 and 29% if telomere signals were not considered. The percentage decreased to approximately 10% after ruling out false incomplete exchanges containing telomere signals. The final estimation of true incomplete exchanges was <10%. CONCLUSION: Within a degree of uncertainty, the percentage of true incomplete exchanges in 1 GeV/u Fe ion-irradiated human lymphocytes was similar to that induced by gamma rays.

Study of ion beam sputtered Fe/Si interfaces as a function of Si layer thickness

NASA Astrophysics Data System (ADS)

Kumar, Anil; Brajpuriya, Ranjeet; Singh, Priti

2018-01-01

The exchange interaction in metal/semiconductor interfaces is far from being completely understood. Therefore, in this paper, we have investigated the nature of silicon on the Fe interface in the ion beam deposited Fe/Si/Fe trilayers keeping the thickness of the Fe layers fixed at 3 nm and varying the thickness of the silicon sandwich layer from 1.5 nm to 4 nm. Grazing incidence x-ray diffraction and atomic force microscopy techniques were used, respectively, to study the structural and morphological changes in the deposited films as a function of layer thickness. The structural studies show silicide formation at the interfaces during deposition and better crystalline structure of Fe layers at a lower spacer layer thickness. The magnetization behavior was investigated using magneto-optical Kerr effect, which clearly shows that coupling between the ferromagnetic layers is highly influenced by the semiconductor spacer layer thickness. A strong antiferromagnetic coupling was observed for a value of tSi = 2.5 nm but above this value an unexpected behavior of hysteresis loop (step like) with two coercivity values is recorded. For spacer layer thickness greater than 2.5 nm, an elemental amorphous Si layer starts to appear in the spacer layer in addition to the silicide layer at the interfaces. It is observed that in the trilayer structure, Fe layers consist of various stacks, viz., Si doped Fe layers, ferromagnetic silicide layer, and nonmagnetic silicide layer at the interfaces. The two phase hysteresis loop is explained on the basis of magnetization reversal of two ferromagnetic layers, independent of each other, with different coercivities. X-ray photo electron spectroscopy technique was also used to study interfaces characteristics as a function of tSi.

First-principles investigation of graphitic carbon nitride monolayer with embedded Fe atom

NASA Astrophysics Data System (ADS)

Abdullahi, Yusuf Zuntu; Yoon, Tiem Leong; Halim, Mohd Mahadi; Hashim, Md. Roslan; Lim, Thong Leng

2018-01-01

Density-functional theory (DFT) calculations with spin-polarized generalized gradient approximation and Hubbard U correction are carried out to investigate the mechanical, structural, electronic and magnetic properties of graphitic heptazine with embedded Fe atom under bi-axial tensile strain and applied perpendicular electric field. It was found that the binding energy of heptazine with embedded Fe atom system decreases as larger tensile strain is applied, while it increases as larger electric field strength is applied. Our calculations also predict a band gap at a peak value of 5% tensile strain but at expense of the structural stability of the system. The band gap open up at 5% tensile strain is due to distortion in the structure caused by the repulsive effect in the cavity between the lone pairs of the edge nitrogen atoms and dxy /dx2 -y2 orbital of Fe atom, forcing the unoccupied pz- orbital is forced to shift toward higher energy. The electronic and magnetic properties of the heptazine with embedded Fe system under perpendicular electric field up to a peak value of 8 V/nm is also well preserved despite an obvious buckled structure. Such properties are desirable for diluted magnetic semiconductors, spintronics, and sensing devices.

Structural characterization of Co100-xFex nano-oxide layer

NASA Astrophysics Data System (ADS)

Endo, Hiroaki; Doi, Masaaki; Hasegawa, Naoya; Sahashi, Masashi

2006-04-01

For the structural characterization of a Co100-xFex nano-oxide layer (NOL), the exchange bias properties of the Co100-xFex-natural oxidized NOL in the specular spin-valve (SPSV) system were investigated. The exchange bias energy (Jex) increased monotonically with the increasing Fe content for the Co100-xFex-NOL. The enhancement of both the magnetoresistance ratio and the exchange bias field (Hex) was realized by increasing the Fe content in the Co100-xFex-NOL. It should be mentioned that Hex more than 800 Oe is obtained by the insertion of Co30Fe70-NOL, even in NOL-SPSV, which is a remarkably higher pinning field than that ever reported on IrMn-SV. This high exchange bias field is considered to be realized by the formation of an Fe-rich fcc phase at the interface of IrMn.

Interplay between out-of-plane anisotropic L1{sub 1}-type CoPt and in-plane anisotropic NiFe layers in CoPt/NiFe exchange springs

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

Saravanan, P.; Defence Metallurgical Research Laboratory, Hyderabad 500058; Hsu, Jen-Hwa, E-mail: jhhsu@phys.ntu.edu.tw

2014-06-28

Films of L1{sub 1}-type CoPt/NiFe exchange springs were grown with different NiFe (Permalloy) layer thickness (t{sub NiFe} = 0–10 nm). X-ray diffraction analysis reveals that the characteristic peak position of NiFe(111) is not affected by the CoPt-layer—confirming the absence of any inter-diffusion between the CoPt and NiFe layers. Magnetic studies indicate that the magnetization orientation of NiFe layer can be tuned through varying t{sub NiFe} and the perpendicular magnetic anisotropy of L1{sub 1}-type CoPt/NiFe films cannot sustain for t{sub NiFe} larger than 3.0 nm due to the existence of exchange interaction at the interface of L1{sub 1}-CoPt and NiFe layers. Magnetic force microscopy analysismore » on the as-grown samples shows the changes in morphology from maze-like domains with good contrast to hazy domains when t{sub NiFe} ≥ 3.0 nm. The three-dimensional micro-magnetic simulation results demonstrate that the magnetization orientation in NiFe layer is not uniform, which continuously increases from the interface to the top of NiFe layer. Furthermore, the tilt angle of the topmost NiFe layers can be changed over a very wide range from a small number to about 75° by varying t{sub NiFe} from 1 to 10 nm. It is worth noting that there is an abrupt change in the magnetization direction at the interface, for all the t{sub NiFe} investigated. The results of present study demonstrate that the tunable tilted exchange springs can be realized with L1{sub 1}-type CoPt/NiFe bilayers for future applications in three-axis magnetic sensors or advanced spintronic devices demanding inclined magnetic anisotropy.« less

A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable

USGS Publications Warehouse

Landwehr, J.M.; Meier-Augenstein, W.; Kemp, H.F.

2011-01-01

Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of standards.

Structure and magnetic properties of oxychalcogenides A2F2Fe2OQ2 (A = Sr, Ba; Q = S, Se) with Fe2O square planar layers representing an antiferromagnetic checkerboard spin lattice.

PubMed

Kabbour, Houria; Janod, Etienne; Corraze, Benoît; Danot, Michel; Lee, Changhoon; Whangbo, Myung-Hwan; Cario, Laurent

2008-07-02

The oxychalcogenides A2F2Fe2OQ2 (A = Sr, Ba; Q = S, Se), which contain Fe2O square planar layers of the anti-CuO2 type, were predicted using a modular assembly of layered secondary building units and subsequently synthesized. The physical properties of these compounds were characterized using magnetic susceptibility, electrical resistivity, specific heat, (57)Fe Mossbauer, and powder neutron diffraction measurements and also by estimating their exchange interactions on the basis of first-principles density functional theory electronic structure calculations. These compounds are magnetic semiconductors that undergo a long-range antiferromagnetic ordering below 83.6-106.2 K, and their magnetic properties are well-described by a two-dimensional Ising model. The dominant antiferromagnetic spin exchange interaction between S = 2 Fe(2+) ions occurs through corner-sharing Fe-O-Fe bridges. Moreover, the calculated spin exchange interactions show that the A2F2Fe2OQ2 (A = Sr, Ba; Q = S, Se) compounds represent a rare example of a frustrated antiferromagnetic checkerboard lattice.

A new ion-exchange adsorbent with paramagnetic properties for the separation of genomic DNA.

PubMed

Feng, Guodong; Jiang, Luan; Wen, Puhong; Cui, Yali; Li, Hong; Hu, Daodao

2011-11-21

A new ion-exchange adsorbent (IEA) derived from Fe(3)O(4)/SiO(2)-GPTMS-DEAE with paramagnetic properties was prepared. Fe(3)O(4) nanoparticles were firstly prepared in water-in-oil microemulsion. The magnetic Fe(3)O(4) particles were modified in situ by hydrolysis and condensation reactions with tetraethoxysilane (TEOS) to form the core-shell Fe(3)O(4)/SiO(2). The modified particles were further treated by 3-glycidoxypropyltrimethoxysilane (GPTMS) to form Fe(3)O(4)/SiO(2)-GPTMS nanoparticles. Fe(3)O(4)/SiO(2)-GPTMS-DEAE nanoparticles (IEA) were finally obtained through the condensation reaction between the Cl of diethylaminoethyl chloride-HCl (DEAE) and the epoxy groups of GPTMS in the Fe(3)O(4)/SiO(2)-GPTMS. The obtained IEA has features of paramagnetic and ion exchange properties because of the Fe(3)O(4) nanoparticles and protonated organic amine in the sample. The intermediates and final product obtained in the synthesis process were characterized. The separation result of genomic DNA from blood indicated that Fe(3)O(4)/SiO(2)-GPTMS-DEAE nanoparticles have outstanding advantages in operation, selectivity, and capacity.

Modeling Solar Atmospheric Phenomena with AtomDB and PyAtomDB

NASA Astrophysics Data System (ADS)

Dupont, Marcus; Foster, Adam

2018-01-01

Taking advantage of the modeling tools made available by PyAtomDB (Foster 2015), we evaluated the impact of changing atomic data on solar phenomena, in particular their effects on models of coronal mass ejections (CME). Intitially, we perform modifications to the canonical SunNEI code (Murphy et al. 2011) in order to include non-equilibrium ionization (NEI) processes that occur in the CME modeled in SunNEI. The methods used involve the consideration of radiaitive cooling as well as ion balance calculations. These calculations were subsequently implemented within the SunNEI simulation. The insertion of aforementioned processes and parameter customizaton produced quite similar results of the original except for the case of iron. These differences were traced to inconsistencies in the recombination rates for Argon-like iron ions between the CHIANTI and AtomDB databases, even though they in theory use the same data. The key finding was that theoretical models are greatly impacted by the relative atomic database update cycles.Following the SunNEI comparison, we then use the AtomDB database to model the time depedencies of intensity flux spikes produced by a coronal shock wave (Ma et al. 2011). We produced a theretical representation for an ionizing plasma that interpolated over the intensity in four Astronomical Imaging Assembly (AIA) filters. Specifically, the 171 A (Fe IX) ,193 A (Fe XII, FeXXIV),211 A (Fe XIV),and 335 A (Fe XVI) wavelengths in order to assess the comparative spectral emissions between AtomDB and the observed data. The results of the theoretical model, in principle, shine light on both the equilibrium conditions before the shock and the non-equilibrium response to the shock front, as well as discrepancies introduced by changing the atomic data.

Exchange bias in zinc ferrite-FeNiMoB based metallic glass composite thin films

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

R, Lisha; P, Geetha; B, Aravind P.

2015-06-24

The Exchange bias phenomenon and methods to manipulate the bias field in a controlled manner are thrust areas in magnetism due to its sophisticated theoretical concepts as well as advanced technological utility in the field of spintronics. The Exchange bias effect is observed as a result of ferromagnetic-antiferromagnetic (FM-AFM) exchange interaction, usually observed as a loop shift on field cooling below the Neel temperature of AFM. In the present study, we have chosen zinc ferrite which is a well known antiferromagnet, and FeNiMoB based metallic glass as the ferromagnet. The films were prepared by RF sputtering technique. The thickness andmore » composition was obtained by RBS. The magnetic studies using SQUID VSM indicate exchange bias effect in the system. The effect of thermal annealing on exchange bias effect was studied. The observed exchange bias in the zinc ferrite-FeNiMoB system is not due to FM-AFM coupling but due to spin glass-ferromagnetic interaction.« less

Exchange bias in zinc ferrite-FeNiMoB based metallic glass composite thin films

NASA Astrophysics Data System (ADS)

R, Lisha; T, Hysen; P, Geetha; B, Aravind P.; Ojha, S.; Avasthi, D. K.; Ramanujan, R. V.; Anantharaman, M. R.

2015-06-01

The Exchange bias phenomenon and methods to manipulate the bias field in a controlled manner are thrust areas in magnetism due to its sophisticated theoretical concepts as well as advanced technological utility in the field of spintronics. The Exchange bias effect is observed as a result of ferromagnetic-antiferromagnetic (FM-AFM) exchange interaction, usually observed as a loop shift on field cooling below the Neel temperature of AFM. In the present study, we have chosen zinc ferrite which is a well known antiferromagnet, and FeNiMoB based metallic glass as the ferromagnet. The films were prepared by RF sputtering technique. The thickness and composition was obtained by RBS. The magnetic studies using SQUID VSM indicate exchange bias effect in the system. The effect of thermal annealing on exchange bias effect was studied. The observed exchange bias in the zinc ferrite-FeNiMoB system is not due to FM-AFM coupling but due to spin glass-ferromagnetic interaction.

New Measurement of the 60Fe Half-Life.

PubMed

Rugel, G; Faestermann, T; Knie, K; Korschinek, G; Poutivtsev, M; Schumann, D; Kivel, N; Günther-Leopold, I; Weinreich, R; Wohlmuther, M

2009-08-14

We have made a new determination of the half-life of the radioactive isotope 60Fe using high precision measurements of the number of 60Fe atoms and their activity in a sample containing over 10(15) 60Fe atoms. Our new value for the half-life of 60Fe is (2.62+/-0.04) x 10(6) yr, significantly above the previously reported value of (1.49+/-0.27) x 10(6) yr. Our new measurement for the lifetime of 60Fe has significant implications for interpretations of galactic nucleosynthesis, for determinations of formation time scales of solids in the early Solar System, and for the interpretation of live 60Fe measurements from supernova-ejecta deposits on Earth.

Oxygen evolution on a SrFeO3 anode - Mechanistic considerations from molecular orbital theory

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, Alfred B.

1989-01-01

Various pathways proposed in the literature for the evolution of O2 in electrochemical oxidations are explored using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory and the cluster models of the SrFeO3 surface as a prototype material. Calculations indicate that oxygen atoms can be easily formed on the (100) surface as well as on the edge cation sites of a SrFeO3 anode by the discharge of OH(-), followed by its deprotonation and electron transfer to the electrode. The O atoms can form O2 on the edge and corner sites, where the Fe(4+) is coordinated to four and three bulk oxygen anions, respectively. The calculations strongly disfavor mechanisms involving coupling of oxygen atoms adsorbed on different cations as well as a mechanism featuring an ozone intermediate.

A neutral molecular-based layered magnet [Fe(C2O4)(CH3OH)]n exhibiting magnetic ordering at TN approximately 23 K.

PubMed

Zhang, Bin; Zhang, Yan; Zhang, Jinbiao; Li, Junchao; Zhu, Daoben

2008-10-07

Solvothermal synthesis of FeCl(2).4H2O and H2C2O(4).2H2O in methanol at 120 degrees C yielded yellow plate-like crystals of [Fe(C2O4)(CH3OH)]n. Each iron atom is in a distorted octahedral environment, being bonded to four oxygen atoms from two bisbidentate oxalate anions, one O atom of a chelating oxalate anion and one O atom from a methanol molecule as an oxalate group bridging ligand in a five-coordination mode. The neutral layer of [Fe(C2O4)(CH3OH)]n with a [4,4] net along the ac plane. There is no interaction between layers. A long range magnetic ordering with spin canting at TN approximately 23 K was observed and confirmed by AC susceptibility measurements.

Composition formulas of Fe-based transition metals-metalloid bulk metallic glasses derived from dual-cluster model of binary eutectics.

PubMed

Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang

2017-08-22

It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3  + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.

KMg0.09Fe1.91(PO4)2

PubMed Central

Yatskin, Michael M.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Ogorodnyk, Ivan V.; Slobodyanik, Nikolay S.

2012-01-01

KMg0.09Fe1.91(PO4)2, potassium [iron(II)/magnesium] iron(III) bis(orthophosphate), is a solid solution derived from compounds with general formula KM IIFe(PO4)2 (M II = Fe, Cu), in which the Mg atoms substitute Fe atoms only in the octa­hedrally surrounded sites. The framework of the structure is built up from [FeO5] trigonal bipyramids and [MO6] (M = (Fe, Mg) octa­hedra sharing corners and edges and connected by two types of bridging PO4 tetra­hedra. The K+ cations are nine-coordinated and are situated in channels running along [101]. PMID:22719280

Atomic scale study of ball milled Ni-Fe{sub 2}O{sub 3} using Mössbauer spectroscopy

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

Yadav, Ravi Kumar; Govindaraj, R., E-mail: govind@igcar.gov.in; Vinod, K.

Evolution of hyperfine fields at Fe atoms has been studied in a detailed manner in a mixture of Ni and α-Fe{sub 2}O{sub 3} subjected to high energy ball milling using Mossbauer spectroscopy. Mossbauer results indicate the dispersion of α-Fe{sub 2}O{sub 3} particles in Ni matrix in the as ball milled condition. Evolution of α-Fe{sub 2}O{sub 3} due to ball milling, reduction of the valence of associated Fe and possible interaction between the oxide particles with Ni in the matrix due to annealing treatments has been elucidated in the present study.

Iron in solution with aluminum matrix after non-equilibrium processing: an atom probe tomography study

NASA Astrophysics Data System (ADS)

Saller, Brandon D.; Sha, Gang; Yang, Li Mei; Liu, Fan; Ringer, Simon P.; Schoenung, Julie M.

2017-03-01

In this paper, we report on the influence of rapid solidification and severe plastic deformation on the solid solubility of Fe in Al. Atom probe tomography, for the first time, was performed on fine (3-4 μm diameter) and coarse ( 100 μm) as-atomised Al-5 at.% Fe powder and cryomilled Al-5 at.% Fe powder. The atomised powders exhibited negligible Fe in solution with Al, whereas the cryomilled powder contained 2 at.% Fe in solution. Moreover, our results suggest that severe plastic deformation is preferable to atomisation/rapid solidification for increasing the non-equilibrium solid solubility of Fe in Al.

Synthesis, Crystal Structure, and Magnetic Properties of the YbFeTi2O7 Compound

NASA Astrophysics Data System (ADS)

Drokina, T. V.; Petrakovskii, G. A.; Molokeev, M. S.; Velikanov, D. A.

2018-03-01

We report on the synthesis conductions and results of experimental investigations of the crystal structure and magnetic properties of a new magnetic compound YbFeTi2O7. According to the X-ray diffractometry data, the crystal structure of the investigated compound is described by the rhombic space group Pcnb with unit cell parameters of a = 9.8115(1) Å, b = 13.5106(2) Å, and c = 7.31302(9) Å and atomic disordering in the distribution of iron ions Fe3+ over five structural sites. The magnetic measurements in the lowtemperature region revealed a kink in the temperature dependence of the magnetic moment and its dependence on the sample magnetic prehistory. The experimental results obtained suggest that with a decrease in temperature the sample passes from the paramagnetic state to the spin-glass-like magnetic state characterized by a freezing temperature of T f = 4.5 K at the preferred antiferromagnetic exchange coupling in the sample spin system. The chemical pressure variation upon replacement of rare-earth ion R by Yb in the RFeTi2O7 system does not change the crystal lattice symmetry and magnetic state.

Magnetism and high magnetic-field-induced stability of alloy carbides in Fe-based materials.

PubMed

Hou, T P; Wu, K M; Liu, W M; Peet, M J; Hulme-Smith, C N; Guo, L; Zhuang, L

2018-02-14

Understanding the nature of the magnetic-field-induced precipitation behaviors represents a major step forward towards unravelling the real nature of interesting phenomena in Fe-based alloys and especially towards solving the key materials problem for the development of fusion energy. Experimental results indicate that the applied high magnetic field effectively promotes the precipitation of M 23 C 6 carbides. We build an integrated method, which breaks through the limitations of zero temperature and zero external field, to concentrate on the dependence of the stability induced by the magnetic effect, excluding the thermal effect. We investigate the intimate relationship between the external field and the origins of various magnetics structural characteristics, which are derived from the interactions among the various Wyckoff sites of iron atoms, antiparallel spin of chromium and Fe-C bond distances. The high-magnetic-field-induced exchange coupling increases with the strength of the external field, which then causes an increase in the parallel magnetic moment. The stability of the alloy carbide M 23 C 6 is more dependent on external field effects than thermal effects, whereas that of M 2 C, M 3 C and M 7 C 3 is mainly determined by thermal effects.

Structure and magnetic properties of Fe12X clusters

NASA Astrophysics Data System (ADS)

Gutsev, G. L.; Johnson, L. E.; Belay, K. G.; Weatherford, C. A.; Gutsev, L. G.; Ramachandran, B. R.

2014-02-01

The electronic and geometrical structures of a Fe12X family of binary clusters Fe12Al, Fe12Sc, Fe12Ti, Fe12V, Fe12Cr, Fe12Mn, Fe12Co, Fe12Ni, Fe12Cu, Fe12Zn, Fe12Y, Fe12Zr, Fe12Nb, Fe12Mo, Fe12Tc, Fe12Ru, Fe12Rh, Fe12Pd, Fe12Ag, Fe12Cd, and Fe12Gd are studied using density functional theory within generalized gradient approximation. It is found that the geometrical structures corresponding to the lowest total energy states found for the Fe12X clusters possess icosahedral shape with the substituent atom occupying the central or a surface site. The only exception presents Fe12Nb where a squeezed cage structure is the energetically most favorable. The substitution of an atom in the Fe13 cluster results in the decrease of its total spin magnetic moment of 44 μB, except for Fe12Mn and Fe12Gd. The Fe12X clusters are more stable than the parent Fe13 cluster when X = Al, Sc, Ti, V, Co, Y, Zr, Nb, Mo, Tc, Ru, and Rh.

Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

PubMed

Villar-Acevedo, Gloria; Lugo-Mas, Priscilla; Blakely, Maike N; Rees, Julian A; Ganas, Abbie S; Hanada, Erin M; Kaminsky, Werner; Kovacs, Julie A

2017-01-11

Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe III (S 2 Me2 N 3 (Pr,Pr))] + (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H 2 O 2 ) to afford a rare example of a singly oxygenated sulfenate, [Fe III (η 2 -S Me2 O)(S Me2 )N 3 (Pr,Pr)] + (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O) Cys114 proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [Fe III S 2 Me2 N Me N 2 amide (Pr,Pr)] - (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands. Density functional theory calculations suggest that the mechanism of S-oxygenation does not proceed via direct attack at the thiolate sulfurs; the average spin-density on the thiolate sulfurs is approximately the same for 2 and 8, and Mulliken charges on the sulfurs of 8 are roughly twice those of 2, implying that 8 should be more susceptible to sulfur oxidation. Carboxamide-ligated 8 is shown to be unreactive towards oxo atom donors, in contrast to imine-ligated 2. Azide (N 3 - ) is shown to inhibit sulfur oxidation with 2, and a green intermediate is observed, which then slowly converts to sulfenate-ligated 5. This suggests that the mechanism of sulfur oxidation involves initial coordination of the oxo atom donor to the metal ion. Whether the green intermediate is an oxo atom donor adduct, Fe-O═I-Ph, or an Fe(V)═O remains to be determined.

Making Mn substitutional impurities in InAs using a scanning tunneling microscope.

PubMed

Song, Young Jae; Erwin, Steven C; Rutter, Gregory M; First, Phillip N; Zhitenev, Nikolai B; Stroscio, Joseph A

2009-12-01

We describe in detail an atom-by-atom exchange manipulation technique using a scanning tunneling microscope probe. As-deposited Mn adatoms (Mn(ad)) are exchanged one-by-one with surface In atoms (In(su)) to create a Mn surface-substitutional (Mn(In)) and an exchanged In adatom (In(ad)) by an electron tunneling induced reaction Mn(ad) + In(su) --> Mn(In) + In(ad) on the InAs(110) surface. In combination with density-functional theory and high resolution scanning tunneling microscopy imaging, we have identified the reaction pathway for the Mn and In atom exchange.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM

NASA Astrophysics Data System (ADS)

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-01

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt1/Fe2O3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water–gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe2O3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H2O molecules to the CO or H2 significantly accelerates the sintering of the Fe2O3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal–support interaction.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM.

PubMed

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-18

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt 1 /Fe 2 O 3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water-gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe 2 O 3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H 2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H 2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H 2 O molecules to the CO or H 2 significantly accelerates the sintering of the Fe 2 O 3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal-support interaction.

Effect of the magnetism of impurities on their diffusion in metals: Bulk diffusion of iron, cobalt, and rhodium in iridium single crystals

NASA Astrophysics Data System (ADS)

Klotsman, S. M.; Tatarinova, G. N.

2008-12-01

The coefficients and parameters of the temperature dependences of the coefficients of bulk diffusion of Fe, Co, Rh, and Au atomic probes (APs) in iridium single crystals (mono-Ir) have been determined from the diffusion profiles obtained using secondary-ion mass spectrometry of the diffusion zones. The enthalpies of activation of diffusion of Fe, Co, and Rh APs are considerably lower than the enthalpy of activation of selfdiffusion in mono-Ir. This is caused by the negative contributions of the intraatomic exchange energy and energy of relaxation of the environment of the d transition APs to the enthalpy of interaction of magnetically active APs with the vacancies in the iridium lattice. The interaction energy of partners in such complexes and the relationships between the magnetic moments of d transition APs in complexes with vacancies have been estimated. The Rh APs in complexes with vacancies in iridium possess stable magnetic moments.

Sign reversal of Hall signals in Tm3Fe5O12 /Pt with perpendicular magnetic anisotropy

NASA Astrophysics Data System (ADS)

Liu, Yawen; Tang, Chi; Xu, Yadong; Shi, Zhong; Shi, Jing

Robust interface strain-induced perpendicular magnetic anisotropy is produced in atomically flat ferromagnetic insulator Tm3Fe5O12 (TIG) films grown with pulsed laser deposition on both substituted-Gd3Ga5O12 and Nd3Ga5O12 (NGG). In TIG/Pt bilayers, we observe large hysteresis loops over a wide range of Pt thicknesses and temperatures. Both the ordinary Hall effect and anomalous Hall effect undergo a sign reversal as the temperature is lowered. The temperature dependence of the Hall signals in bilayers with different thickness of Pt indicates the existence of exchange interaction at the interface. Our results provide a clue to further understand the origin of the anomalous Hall effect in ferromagnetic insulator/normal metal bilayer systems. The work was supported as part of the SHINES, an Energy Frontier Research Center funded by the US Department of Energy, BES under Award No. SC0012670.

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Fe implantation effect in the 6H-SiC semiconductor investigated by Mössbauer spectrometry

NASA Astrophysics Data System (ADS)

Diallo, M. L.; Diallo, L.; Fnidiki, A.; Lechevallier, L.; Cuvilly, F.; Blum, I.; Viret, M.; Marteau, M.; Eyidi, D.; Juraszek, J.; Declémy, A.

2017-08-01

P-doped 6H-SiC substrates were implanted with 57Fe ions at 380 °C or 550 °C to produce a diluted magnetic semiconductor with an Fe homogeneous concentration of about 100 nm thickness. The magnetic properties were studied with 57Fe Conversion Electron Mössbauer Spectrometry at room temperature (RT). Results obtained by this technique on annealed samples prove that ferromagnetism in 57Fe-implanted SiC for Fe concentrations close to 2% and 4% is mostly due to Fe atoms diluted in the matrix. In contrast, for Fe concentrations close to 6%, it also comes from Fe in magnetic phase nano-clusters. This study allows quantifying the Fe amount in the interstitial and substitutional sites and the nanoparticles and shows that the majority of the diluted Fe atoms are substituted on Si sites inducing ferromagnetism up to RT.

Interstitial Fe in MgO

NASA Astrophysics Data System (ADS)

Mølholt, T. E.; Mantovan, R.; 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 57Fe atoms were studied in MgO single-crystals by emission Mössbauer spectroscopy following implantation of 57Mn decaying to 57Fe. Four Mössbauer 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.

Effect of 0.25 and 2.0 MeV He-Ion Irradiation on Short-Range Ordering in Model (EFDA) Fe-Cr Alloys

NASA Astrophysics Data System (ADS)

Dubiel, Stanisław M.; Żukrowski, Jan; Serruys, Yves

2018-05-01

The effects of He+ irradiation on a distribution of Cr atoms in Fe100-x Cr x (x = 5.8, 10.75, 15.15) alloys were studied by 57Fe Conversion Electron Mössbauer Spectroscopy (CEMS). The alloys were irradiated with doses up to 12 × 1016 ions/cm2 with 0.25 and 2.0 MeV He+ ions. The distribution of Cr atoms within the first two coordination shells around Fe atoms was expressed with short-range order parameters α 1 (first-neighbor shell, 1NN), α 2 (second-neighbor shell, 2NN), and α 12 (1NN + 2NN). In non-irradiated alloys, α 1 >0 and α 2 <0 was revealed for all three samples. The value of α 12 ≈0, i.e., the distribution of Cr atoms averaged over 1NN and 2NN, was random. The effect of the irradiation of the Fe94.2Cr5.8 alloy was similar for the two energies of He+, viz., increase of number of Cr atoms in 1NN and decrease in 2NN. Consequently, the degree of ordering increased. For the other two samples, the effect of the irradiation depends on the composition, and is stronger for the less energetic ions where, for Fe89.25Cr10.75 alloy, the disordering disappeared and some traces of Cr clustering appeared. In Fe84.85Cr15.15 alloy, the clustering was clear. In the samples irradiated with 2. 0 MeV He+ ions, the ordering also survived in the samples with x = 10.75 and 15.15, yet its degree became smaller than in the Fe94.2Cr5.8 alloy.

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar experiments were performed with bacterial nitric oxide reductase from Paracoccus denitrificans (cNOR). In this case both Nα and Nβ exhibited inverse isotope effects, while O had a normal isotope effect. Together, these data highlight the utility in using stable isotopes as both tracers and mechanistic probes when studying metabolic processes.

Sulfidation behavior of ZnFe2O4 roasted with pyrite: Sulfur inducing and sulfur-oxygen interface exchange mechanism

NASA Astrophysics Data System (ADS)

Min, Xiaobo; Zhou, Bosheng; Ke, Yong; Chai, Liyuan; Xue, Ke; Zhang, Chun; Zhao, Zongwen; Shen, Chen

2016-05-01

The sulfidation roasting behavior was analyzed in detail to reveal the reaction mechanism. Information about the sulfidation reaction, including phase transformation, ionic migration behavior and morphological change, were obtained by XRD, 57Fe Mossbauer spectroscopy, XPS and SEM analysis. The results showed that the sulfidation of zinc ferrite is a process of sulfur inducing and sulfur-oxygen interface exchange. This process can be divided into six stages: decomposition of FeS2, formation of the oxygen-deficient environment, migration of O2- induced by S2(g), formation of ZnFe2O4-δ, migration of Fe2+ accompanied by the precipitation of ZnO, and the sulfur-oxygen interface exchange reaction. The sulfidation products were zinc blende, wurtzite, magnetite and a fraction of zinc-bearing magnetite. These findings can provide theoretical support for controlling the process during which the recovery of Zn and Fe is achieved through the combined flotation-magnetic separation process.

Important role of the non-uniform Fe distribution for the ferromagnetism in group-IV-based ferromagnetic semiconductor GeFe

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

Wakabayashi, Yuki K.; Ohya, Shinobu; Ban, Yoshisuke

2014-11-07

We investigate the growth-temperature dependence of the properties of the group-IV-based ferromagnetic semiconductor Ge{sub 1−x}Fe{sub x} films (x = 6.5% and 10.5%), and reveal the correlation of the magnetic properties with the lattice constant, Curie temperature (T{sub C}), non-uniformity of Fe atoms, stacking-fault defects, and Fe-atom locations. While T{sub C} strongly depends on the growth temperature, we find a universal relationship between T{sub C} and the lattice constant, which does not depend on the Fe content x. By using the spatially resolved transmission-electron diffractions combined with the energy-dispersive X-ray spectroscopy, we find that the density of the stacking-fault defects and the non-uniformitymore » of the Fe concentration are correlated with T{sub C}. Meanwhile, by using the channeling Rutherford backscattering and particle-induced X-ray emission measurements, we clarify that about 15% of the Fe atoms exist on the tetrahedral interstitial sites in the Ge{sub 0.935}Fe{sub 0.065} lattice and that the substitutional Fe concentration is not correlated with T{sub C}. Considering these results, we conclude that the non-uniformity of the Fe concentration plays an important role in determining the ferromagnetic properties of GeFe.« less

Effect of the spin-twist structure on the spin-wave dynamics in Fe{sub 55}Pt{sub 45}/Ni{sub 80}Fe{sub 20} exchange coupled bi-layers with varying Ni{sub 80}Fe{sub 20} thickness

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

Pal, Semanti; Barman, Saswati, E-mail: saswati@bose.res.in; Barman, Anjan, E-mail: abarman@bose.res.in

2014-05-07

We have investigated optically induced ultrafast magnetization dynamics of a series of Fe{sub 55}Pt{sub 45}/Ni{sub 80}Fe{sub 20} exchange spring bi-layers with varying Ni{sub 80}Fe{sub 20} thickness. Rich spin-wave spectra are observed; whose frequency shows a strong dependence on the Ni{sub 80}Fe{sub 20} layer thickness. Micromagnetic simulations based on a simplified magnetic microstructure were able to reproduce the experimental data qualitatively. The spin twist structure introduced in the Ni{sub 80}Fe{sub 20} layer gives rise to new modes in the composite system as opposed to the bare Ni{sub 80}Fe{sub 20} films.

Preparation and biodistribution of 59Fe-radiolabelled iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Pospisilova, Martina; Zapotocky, Vojtech; Nesporova, Kristina; Laznicek, Milan; Laznickova, Alice; Zidek, Ondrej; Cepa, Martin; Vagnerova, Hana; Velebny, Vladimir

2017-02-01

We report on the 59Fe radiolabelling of iron oxide nanoparticle cores through post-synthetic isotope exchange (59Fe-IONPex) and precursor labelling (59Fe-IONPpre). Scanning electron microscopy and dynamic light scattering measurements showed no impact of radiolabelling on nanoparticle size or morphology. While incorporation efficiencies of these methods are comparable—83 and 90% for precursor labelling and post-synthetic isotope exchange, respectively—59Fe-IONPpre exhibited much higher radiochemical stability in citrated human plasma. Quantitative ex vivo biodistribution study of 59Fe-IONPpre coated with triethylene glycol was performed in Wistar rats. Following the intravenous administration, high 59Fe concentration was observed in the lung and the organs of the reticuloendothelial system such as the liver, the spleen and the femur.

The Effect of Interface Texture on Exchange Biasing in Ni(80)Fe(20)/Ir(20)Mn(80) System.

PubMed

Chen, Yuan-Tsung

2009-01-01

Exchange-biasing phenomenon can induce an evident unidirectional hysteresis loop shift by spin coupling effect in the ferromagnetic (FM)/antiferromagnetic (AFM) interface which can be applied in magnetoresistance random access memory (MRAM) and recording-head applications. However, magnetic properties are the most important to AFM texturing. In this work, top-configuration exchange-biasing NiFe/IrMn(x A) systems have been investigated with three different conditions. From the high-resolution cross-sectional transmission electron microscopy (HR X-TEM) and X-ray diffraction results, we conclude that the IrMn (111) texture plays an important role in exchange-biasing field (H(ex)) and interfacial exchange energy (J(k)). H(ex) and J(k) tend to saturate when the IrMn thickness increases. Moreover, the coercivity (H(c)) dependence on IrMn thickness is explained based on the coupling or decoupling effect between the spins of the NiFe and IrMn layers near the NiFe/IrMn interface. In this work, the optimal values for H(ex) and J(k) are 115 Oe and 0.062 erg/cm(2), respectively.

Structure and function of photosystem I–[FeFe] hydrogenase protein fusions: An all-atom molecular dynamics study

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

Harris, Bradley J.; Cheng, Xiaolin; Frymier, Paul

2015-12-15

All-atom molecular dynamics (MD) simulation was used to study the solution dynamics and protein protein interactions of protein fusions of photosystem I (PSI) from Thermosynechococcus elongatus and an [FeFe]-hydrogenase (FeFe H 2ase) from Clostridium pasteurianum, a unique complex capable of photocatalytic hydrogen production. This study involved fusions of these two proteins via dithiol linkers of different length including decanedithiol, octanedithiol, and hexanedithiol, for which experimental data had previously been obtained. Evaluation of root-mean-squared deviations (RMSDs) relative to the respective crystal structures of PSI and the FeFe H 2ase shows that these fusion complexes approach stable equilibrium conformations during the MDmore » simulations. Investigating protein mobility via root-mean-squared fluctuations (RMSFs) reveals that tethering via the shortest hexanedithiol linker results in increased atomic fluctuations of both PSI and the hydrogenase in these fusion complexes. Furthermore, evaluation of the inter- and intraprotein electron transfer distances in these fusion complexes indicates that the structural changes in the FeFe H 2ase arising from ligation to PSI via the shortest hexanedithiol linker may hinder electron transport in the hydrogenase, thus providing a molecular level explanation for the observation that the medium-length octanedithiol linker gives the highest hydrogen production rate.« less

Effect of biaxial strain on the magnetism of Fe16N2: Density-functional investigations

NASA Astrophysics Data System (ADS)

Zhou, Wei; Liu, Lijuan; Wu, Ping

2014-02-01

The effect of biaxial strain on the magnetism of α″-Fe16N2 was investigated by the first principles calculations. The GGA, GGA + U and HSE06 calculations give the same result that the magnetic moments increase with the biaxial strain in the ab plane. All non-equivalent Fe atoms contribute to the increase of magnetic moments, although the variations of inter-atomic distances between non-equivalent Fe and N are different. Additionally, the magnetic anisotropy of Fe16N2 could be controlled by the biaxial strain.

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

Yu, Yongsheng; Sun, Kewei; Tian, Yuan

We report a one-pot synthesis of urchin-like FePd-Fe3O4 nanocomposites, spherical clusters of FePd nanoparticles (NPs) with spikes of Fe3O4 nanorods (NRs), via controlled thermal decomposition of Fe(CO)5 and reduction of Pd(acac)2. The FePd NPs with sizes between 6 and 9 nm self-aggregate into 60 nm superparticles (SPs), and Fe3O4 NRs grow on the surface of these SPs. Reductive annealing at 500 °C converts the FePd-Fe3O4 into exchange-coupled nanocomposites L1(0)-FePd-Fe with their Hc tunable from 0.8 to 2.6 kOe and Ms controlled from 90 to 190 emu/g. The work provides a general approach to L1(0)-FePd-Fe nanocomposite magnets for understanding exchange couplingmore » at the nanoscale. The concept may be extended to other magnetic nanocomposite systems and may help to build superstrong magnets for magnetic applications.« less

Tunability of room-temperature ferromagnetism in spintronic semiconductors through nonmagnetic atoms

NASA Astrophysics Data System (ADS)

Leedahl, Brett; Abooalizadeh, Zahra; LeBlanc, Kyle; Moewes, Alexander

2017-07-01

The implementation and control of room-temperature ferromagnetism (RTFM) by adding magnetic atoms to a semiconductor's lattice has been one of the most important problems in solid-state physics in the last decade. Herein we report on the mechanism that allows RTFM to be tuned by the inclusion of nonmagnetic aluminum in nickel ferrite. This material, NiFe2 -xAlxO4 (x =0 ,0.5 ,1.5 ), has already shown much promise for magnetic semiconductor technologies, and we are able to add to its versatility technological viability with our results. The site occupancies and valencies of Fe atoms (Fe3 +Td , Fe2 +Oh , and Fe3 +Oh ) can be methodically controlled by including aluminum. Using the fact that aluminum strongly prefers a 3+ octahedral environment, we can selectively fill iron sites with aluminum atoms, and hence specifically tune the magnetic contributions for each of the iron sites, and therefore the bulk material as well. Interestingly, the influence of the aluminum is weak on the electronic structure, allowing one to retain the desirable electronic properties while achieving desirable magnetic properties.

Spectroscopy and atomic physics of highly ionized Cr, Fe, and Ni for tokamak plasmas

NASA Technical Reports Server (NTRS)

Feldman, U.; Doschek, G. A.; Cheng, C.-C.; Bhatia, A. K.

1980-01-01

The paper considers the spectroscopy and atomic physics for some highly ionized Cr, Fe, and Ni ions produced in tokamak plasmas. Forbidden and intersystem wavelengths for Cr and Ni ions are extrapolated and interpolated using the known wavelengths for Fe lines identified in solar-flare plasmas. Tables of transition probabilities for the B I, C I, N I, O I, and F I isoelectronic sequences are presented, and collision strengths and transition probabilities for Cr, Fe, and Ni ions of the Be I sequence are given. Similarities of tokamak and solar spectra are discussed, and it is shown how the atomic data presented may be used to determine ion abundances and electron densities in low-density plasmas.

[New iron-porphyrin/vanadium-substituted polyoxometalate catalyst: synthesis, characterization and catalytic activity].

PubMed

Dong, Xiao-li; Zhang, Zhen-cheng; An, Qing-da; Zhang, Shao-yin; Wang, Shao-jun

2007-12-01

A new kind of iron-porphyrin/vanadium-substituted polyoxometalate coordination compound was synthesized by the ion exchange reaction of FeTTMAPPI and H5PMo10V2o40 in solution. The new catalyst was characterized by IR spectrometry and UV-Vis spectrometry. As an excellent catalyst, its effects on benzene hydroxylation and catalytic capabilities were studied with H2O2 solution as the oxidant. The results indicated that the products contained the conjugated structure of porphyrin and the cage structure of polyoxometalate, the V atom in polyoxometalate is the main centre of catalytic activity, meanwhile the presence of iron-porphyrin could increase its catalytic activity greatly.

Recoil hysteresis of Sm -Co/Fe exchange-spring bilayers

NASA Astrophysics Data System (ADS)

Kang, K.; Lewis, L. H.; Jiang, J. S.; Bader, S. D.

2005-12-01

The exchange-spring behavior found in Sm-Co (20nm)/Fe epitaxial bilayer films was investigated by analyzing major hysteresis and recoil curves as a function of anneal conditions. The hard layer consists of nanocrystalline intermetallic Sm-Co hexagonal phases (majority phase Sm2Co7 with SmCo3 and SmCo5). Recoil curves, obtained from the successive removal to remanence and reapplication of an increasingly negative field from the major demagnetization curve, reveal the reversible and irreversible components of the magnetization. The Sm-Co thickness was fixed at 20nm while the Fe thicknesses of 10 and 20nm were studied, with ex situ annealing carried out in evacuated, sealed silica tubes at different temperatures. The peak in the recoil curve area is associated with the coercivity of the hard phase. The development of the soft component magnetization is revealed by the departure of the recoil area from zero with application of a reverse field. These two features together confirm that annealing stabilizes the 10nm Fe bilayer sample against local magnetic reversal while it weakens the 20nm bilayer sample. Furthermore, in both its as-deposited and annealed states the Sm -Co/Fe bilayer of 10nm Fe thickness always displays a higher exchange field and smaller recoil loop areas than the bilayer of 20nm Fe thickness, consistent with a stronger exchange response and more reversible magnetization in the former.

Fe-Cluster Compounds of Chalcogenides: Candidates for Rare-Earth-Free Permanent Magnet and Magnetic Nodal-Line Topological Material.

PubMed

Zhao, Xin; Wang, Cai-Zhuang; Kim, Minsung; Ho, Kai-Ming

2017-12-04

Fe-cluster-based crystal structures are predicted for chalcogenides Fe 3 X 4 (X = S, Se, Te) using an adaptive genetic algorithm. Topologically different from the well-studied layered structures of iron chalcogenides, the newly predicted structures consist of Fe clusters that are either separated by the chalcogen atoms or connected via sharing of the vertex Fe atoms. Using first-principles calculations, we demonstrate that these structures have competitive or even lower formation energies than the experimentally synthesized Fe 3 X 4 compounds and exhibit interesting magnetic and electronic properties. In particular, we show that Fe 3 Te 4 can be a good candidate as a rare-earth-free permanent magnet and Fe 3 S 4 can be a magnetic nodal-line topological material.

Modulation of magnetism in transition-metal-doped two-dimensional GeS

NASA Astrophysics Data System (ADS)

Zhang, Chunxiao; Yang, Baoyong; Tang, Chao; He, Chaoyu; Li, Jin; Ouyang, Tao; Zhong, Jianxin

2018-06-01

Two-dimensional (2D) germanium monosulfide (GeS) is a promising nanoelectronic material with a desirable band gap, high carrier mobility, and anisotropic structures. In this work, we present a density functional theory study on the magnetism of 3d TM (TM  =  Fe, Co and Ni)-doped 2D GeS. We find that the TM atoms strongly bond to the GeS sheet with quite sizable binding energies due to the sp 3-like hybridization of 2D GeS. The Fe- and Co-doped GeS show nonzero magnetic ground states. Hubbard parameter U hardly affects the magnetic moment when U is no more than 6 eV. In particular, substitutional Fe (Fe@GeS) and substitutional Co (Co@GeS) present high-spin states with 4 μ B and 3 μ B. The magnetism of TM-doped 2D GeS mainly arises from the crystal field splitting and spin exchange splitting of TM-3d orbitals. The magnetic and electronic properties of the Fe@GeS and Co@GeS systems can be easily controlled in a small vertical external electric field (E ext). The underlying mechanism of spin crossover is that E ext affects the crystal field splitting and then shifts the relative positions of 3d orbitals, which tunes the spin configurations. These results render monolayer GeS a promising 2D material for applications in future spintronics.

Photoemission and Auger-electron spectroscopic study of the Chevrel-phase compound FexMo6S8

NASA Astrophysics Data System (ADS)

Fujimori, A.; Sekita, M.; Wada, H.

1986-05-01

The electronic structure of the Chevrel-phase compound FexMo6S8 has been studied by photoemission and Auger-electron spectroscopy. Core-level shifts suggest a large charge transfer from the Fe atoms to the Mo6S8 clusters and a small Mo-to-S charge transfer within the cluster. Line-shape asymmetry in the core levels indicates that the density of states (DOS) at the Fermi level has a finite S 3p component as well as the dominant Mo 3d character. Satellite structure and exchange splitting in the Fe core levels point to weak Fe 3d-S 3p hybridization in spite of the short Fe-S distances comparable to that in FeS. The x-ray and ultraviolet valence-band photoemission spectra and the Mo 4d partial DOS obtained by deconvoluting the Mo M4,5VV Auger spectrum are compared with existing band-structure calculations, and the Mo 4d-S 3p bonding character, the structure of the Mo 4d-derived conduction band etc., are discussed. In particular, it is shown that the conduction-band structure is sensitive to the noncubic distortion of the crystal through changes in the intercluster Mo 4d-S 3p hybridization. A pronounced final-state effect is found in the Mo M4,5N2,3V Auger spectrum and is attributed to strong 4p-4d intershell coupling.

Interaction-Free Effects Between Distant Atoms

NASA Astrophysics Data System (ADS)

Aharonov, Yakir; Cohen, Eliahu; Elitzur, Avshalom C.; Smolin, Lee

2018-01-01

A Gedanken experiment is presented where an excited and a ground-state atom are positioned such that, within the former's half-life time, they exchange a photon with 50% probability. A measurement of their energy state will therefore indicate in 50% of the cases that no photon was exchanged. Yet other measurements would reveal that, by the mere possibility of exchange, the two atoms have become entangled. Consequently, the "no exchange" result, apparently precluding entanglement, is non-locally established between the atoms by this very entanglement. This quantum-mechanical version of the ancient Liar Paradox can be realized with already existing transmission schemes, with the addition of Bell's theorem applied to the no-exchange cases. Under appropriate probabilities, the initially-excited atom, still excited, can be entangled with additional atoms time and again, or alternatively, exert multipartite nonlocal correlations in an interaction free manner. When densely repeated several times, this result also gives rise to the Quantum Zeno effect, again exerted between distant atoms without photon exchange. We discuss these experiments as variants of interaction-free-measurement, now generalized for both spatial and temporal uncertainties. We next employ weak measurements for elucidating the paradox. Interpretational issues are discussed in the conclusion, and a resolution is offered within the Two-State Vector Formalism and its new Heisenberg framework.

Interaction-Free Effects Between Distant Atoms

NASA Astrophysics Data System (ADS)

Aharonov, Yakir; Cohen, Eliahu; Elitzur, Avshalom C.; Smolin, Lee

2017-12-01

A Gedanken experiment is presented where an excited and a ground-state atom are positioned such that, within the former's half-life time, they exchange a photon with 50% probability. A measurement of their energy state will therefore indicate in 50% of the cases that no photon was exchanged. Yet other measurements would reveal that, by the mere possibility of exchange, the two atoms have become entangled. Consequently, the "no exchange" result, apparently precluding entanglement, is non-locally established between the atoms by this very entanglement. This quantum-mechanical version of the ancient Liar Paradox can be realized with already existing transmission schemes, with the addition of Bell's theorem applied to the no-exchange cases. Under appropriate probabilities, the initially-excited atom, still excited, can be entangled with additional atoms time and again, or alternatively, exert multipartite nonlocal correlations in an interaction free manner. When densely repeated several times, this result also gives rise to the Quantum Zeno effect, again exerted between distant atoms without photon exchange. We discuss these experiments as variants of interaction-free-measurement, now generalized for both spatial and temporal uncertainties. We next employ weak measurements for elucidating the paradox. Interpretational issues are discussed in the conclusion, and a resolution is offered within the Two-State Vector Formalism and its new Heisenberg framework.

Requirements for functional models of the iron hydrogenase active site: D2/H2O exchange activity in ((mu-SMe)(mu-pdt)[Fe(CO)2(PMe3)]2+)[BF4-].

PubMed

Georgakaki, Irene P; Miller, Matthew L; Darensbourg, Marcetta Y

2003-04-21

Hydrogen uptake in hydrogenase enzymes can be assayed by H/D exchange reactivity in H(2)/D(2)O or H(2)/D(2)/H(2)O mixtures. Diiron(I) complexes that serve as structural models for the active site of iron hydrogenase are not active in such isotope scrambling but serve as precursors to Fe(II)Fe(II) complexes that are functional models of [Fe]H(2)ase. Using the same experimental protocol as used previously for ((mu-H)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)(+)), 1-H(+) (Zhao et al. J. Am. Chem. Soc. 2001, 123, 9710), we now report the results of studies of ((mu-SMe)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)(+)), 1-SMe(+), toward H/D exchange. The 1-SMe(+) complex can take up H(2) and catalyze the H/D exchange reaction in D(2)/H(2)O mixtures under photolytic, CO-loss conditions. Unlike 1-H(+), it does not catalyze H(2)/D(2) scrambling under anhydrous conditions. The molecular structure of 1-SMe(+) involves an elongated Fe.Fe separation, 3.11 A, relative to 2.58 A in 1-H(+). It is proposed that the strong SMe(-) bridging ligand results in catalytic activity localized on a single Fe(II) center, a scenario that is also a prominent possibility for the enzyme active site. The single requirement is an open site on Fe(II) available for binding of D(2) (or H(2)), followed by deprotonation by the external base H(2)O (or D(2)O).

Identifying and Quantifying Chemical Forms of Sediment-Bound Ferrous Iron.

NASA Astrophysics Data System (ADS)

Kohler, M.; Kent, D. B.; Bekins, B. A.; Cozzarelli, I.; Ng, G. H. C.

2015-12-01

Aqueous Fe(II) produced by dissimilatory iron reduction comprises only a small fraction of total biogenic Fe(II) within an aquifer. Most biogenic Fe(II) is bound to sediments on ion exchange sites; as surface complexes and, possibly, surface precipitates; or incorporated into solid phases (e.g., siderite, magnetite). Different chemical forms of sediment-bound Fe(II) have different reactivities (e.g., with dissolved oxygen) and their formation or destruction by sorption/desorption and precipitation/dissolution is coupled to different solutes (e.g., major cations, H+, carbonate). We are quantifying chemical forms of sediment-bound Fe(II) using previously published extractions, novel extractions, and experimental studies (e.g., Fe isotopic exchange). Sediments are from Bemidji, Minnesota, where biodegradation of hydrocarbons from a burst oil pipeline has driven extensive dissimilatory Fe(III) reduction, and sites potentially impacted by unconventional oil and gas development. Generally, minimal Fe(II) was mobilized from ion exchange sites (batch desorption with MgCl2 and repeated desorption with NH4Cl). A < 2mm sediment fraction from the iron-reducing zone at Bemidji had 1.8umol/g Fe(II) as surface complexes or carbonate phases (sodium acetate at pH 5) of which ca. 13% was present as surface complexes (FerroZine extractions). Total bioavailable Fe(III) and biogenic Fe(II) (HCl extractions) was 40-50 umole/g on both background and iron-reducing zone sediments . Approximately half of the HCl-extractable Fe from Fe-reducing zone sediments was Fe(II) whereas 12 - 15% of Fe extracted from background sediments was present as Fe(II). One-third to one-half of the total biogenic Fe(II) extracted from sediments collected from a Montana prairie pothole located downgradient from a produced-water disposal pit was present as surface-complexed Fe(II).

Fe doped Magnetic Nanodiamonds made by Ion Implantation.

PubMed

Chen, ChienHsu; Cho, I C; Jian, Hui-Shan; Niu, H

2017-02-09

Here we present a simple physical method to prepare magnetic nanodiamonds (NDs) using high dose Fe ion-implantation. The Fe atoms are embedded into NDs through Fe ion-implantation and the crystal structure of NDs are recovered by thermal annealing. The results of TEM and Raman examinations indicated the crystal structure of the Fe implanted NDs is recovered completely. The SQUID-VSM measurement shows the Fe-NDs possess room temperature ferromagnetism. That means the Fe atoms are distributed inside the NDs without affecting NDs crystal structure, so the NDs can preserve the original physical and chemical properties of the NDs. In addition, the ion-implantation-introduced magnetic property might make the NDs to become suitable for variety of medical applications.

Fe doped Magnetic Nanodiamonds made by Ion Implantation

NASA Astrophysics Data System (ADS)

Chen, Chienhsu; Cho, I. C.; Jian, Hui-Shan; Niu, H.

2017-02-01

Here we present a simple physical method to prepare magnetic nanodiamonds (NDs) using high dose Fe ion-implantation. The Fe atoms are embedded into NDs through Fe ion-implantation and the crystal structure of NDs are recovered by thermal annealing. The results of TEM and Raman examinations indicated the crystal structure of the Fe implanted NDs is recovered completely. The SQUID-VSM measurement shows the Fe-NDs possess room temperature ferromagnetism. That means the Fe atoms are distributed inside the NDs without affecting NDs crystal structure, so the NDs can preserve the original physical and chemical properties of the NDs. In addition, the ion-implantation-introduced magnetic property might make the NDs to become suitable for variety of medical applications.

High temperature extended x-ray absorption fine structure study of multiferroic BiFeO3

NASA Astrophysics Data System (ADS)

Raghavendra Reddy, V.; Meneghini, Carlo; Kothari, Deepti; Gupta, Ajay; Aquilanti, Giuliana

2012-08-01

Local atomic structure modifications around Fe atoms in polycrystalline multiferroic BiFeO3 are studied by Fe K edge x-ray absorption spectroscopy as a function of temperature across the Néel temperature (TN = 643 K) in order to reveal local structure modifications related to the magnetic transition. This work demonstrates that on crossing TN the local structure around Fe shows peculiar changes: the Fe-O bond lengths get shorter, the ligand symmetry increases and the Fe-O bond length disorder (σ2) deviates from Debye behaviour. These results suggest that the structural transition at the ferroelectric Curie temperature (TC = 1103 K) is anticipated by early local rearrangement of the structure starting already at TN.

Shape-dependent surface magnetism of Co-Pt and Fe-Pt nanoparticles from first principles

NASA Astrophysics Data System (ADS)

Liu, Zhenyu; Wang, Guofeng

2017-12-01

In this paper, we have performed the first-principles density functional theory calculations to predict the magnetic properties of the CoPt and FePt nanoparticles in cuboctahedral, decahedral, and icosahedral shapes. The modeled alloy nanoparticles have a diameter of 1.1 nm and consist of 31 5 d Pt atoms and 24 3 d Co (or Fe) atoms. For both CoPt and FePt, we found that the decahedral nanoparticles had appreciably lower surface magnetic moments than the cuboctahedral and icosahedral nanoparticles. Our analysis indicated that this reduction in the surface magnetism was related to a large contraction of atomic spacing and high local Co (or Fe) concentration in the surface of the decahedral nanoparticles. More interestingly, we predicted that the CoPt and FePt cuboctahedral nanoparticles exhibited dramatically different surface spin structures when noncollinear magnetism was taken into account. Our calculation results revealed that surface anisotropy energy decided the fashion of surface spin canting in the CoPt and FePt nanoparticles, confirming previous predictions from atomistic Monte Carlo simulations.

Spontaneous exchange bias formation driven by a structural phase transition in the antiferromagnetic material.

PubMed

Migliorini, A; Kuerbanjiang, B; Huminiuc, T; Kepaptsoglou, D; Muñoz, M; Cuñado, J L F; Camarero, J; Aroca, C; Vallejo-Fernández, G; Lazarov, V K; Prieto, J L

2018-01-01

Most of the magnetic devices in advanced electronics rely on the exchange bias effect, a magnetic interaction that couples a ferromagnetic and an antiferromagnetic material, resulting in a unidirectional displacement of the ferromagnetic hysteresis loop by an amount called the 'exchange bias field'. Setting and optimizing exchange bias involves cooling through the Néel temperature of the antiferromagnetic material in the presence of a magnetic field. Here we demonstrate an alternative process for the generation of exchange bias. In IrMn/FeCo bilayers, a structural phase transition in the IrMn layer develops at room temperature, exchange biasing the FeCo layer as it propagates. Once the process is completed, the IrMn layer contains very large single-crystal grains, with a large density of structural defects within each grain, which are promoted by the FeCo layer. The magnetic characterization indicates that these structural defects in the antiferromagnetic layer are behind the resulting large value of the exchange bias field and its good thermal stability. This mechanism for establishing the exchange bias in such a system can contribute towards the clarification of fundamental aspects of this exchange interaction.

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

2016-01-01

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe3O4 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. The ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

Realisation of magnetically and atomically abrupt half-metal/semiconductor interface: Co2FeSi0.5Al0.5/Ge(111)

PubMed Central

Nedelkoski, Zlatko; Kuerbanjiang, Balati; Glover, Stephanie E.; Sanchez, Ana M.; Kepaptsoglou, Demie; Ghasemi, Arsham; Burrows, Christopher W.; Yamada, Shinya; Hamaya, Kohei; Ramasse, Quentin M.; Hasnip, Philip J.; Hase, Thomas; Bell, Gavin R.; Hirohata, Atsufumi; Lazarov, Vlado K.

2016-01-01

Halfmetal-semiconductor interfaces are crucial for hybrid spintronic devices. Atomically sharp interfaces with high spin polarisation are required for efficient spin injection. In this work we show that thin film of half-metallic full Heusler alloy Co2FeSi0.5Al0.5 with uniform thickness and B2 ordering can form structurally abrupt interface with Ge(111). Atomic resolution energy dispersive X-ray spectroscopy reveals that there is a small outdiffusion of Ge into specific atomic planes of the Co2FeSi0.5Al0.5 film, limited to a very narrow 1 nm interface region. First-principles calculations show that this selective outdiffusion along the Fe-Si/Al atomic planes does not change the magnetic moment of the film up to the very interface. Polarized neutron reflectivity, x-ray reflectivity and aberration-corrected electron microscopy confirm that this interface is both magnetically and structurally abrupt. Finally, using first-principles calculations we show that this experimentally realised interface structure, terminated by Co-Ge bonds, preserves the high spin polarization at the Co2FeSi0.5Al0.5/Ge interface, hence can be used as a model to study spin injection from half-metals into semiconductors. PMID:27869132

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

DOE PAGES

Zhang, Chenhao; Yang, Shize; Wu, Jingjie; ...

2018-03-25

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

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

Zhang, Chenhao; Yang, Shize; Wu, Jingjie

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Polarization effects in silver delafossite systems

NASA Astrophysics Data System (ADS)

Panapitiya, Gihan; Lewis, James P.

Delafossites are a promising class of materials which has applications in catalysis and optoelectronic devices. Even though much work has been carried out on the cuprate family of delafossites, little is known about the structural and electronic properties of it's silver counterpart. In this work, we present a computational study for two delafossite oxides of the form AgB1 - x FexO2 (For B = Al,Ga). A large number of structures are studied by varying the Fe alloying percentage(x) from 0 to 5 and by choosing the impurity sites randomly. We find that the local structural changes occurring at the vicinity of Fe atoms in these two systems have opposite trends with regard to the O-O distance. The reason for this difference in the trends is identified as the polarization effects on the inter-atomic distances caused by the displacements in O atoms resulting from the incorporation of Fe in sites, previously occupied by either Al or Ga. We believe that these effects are mediated by the differences in the atomic radii of Fe, Al and Ga. Higher alloying levels coupled with nearest neighbor Fe atoms can intensify these distortions in the structure creating deformations in the O-Ag-O bonds, which are directly related to the formation of the conduction band edge in these systems.

New structures of Fe3S for rare-earth-free permanent magnets

NASA Astrophysics Data System (ADS)

Yu, Shu; Zhao, Xin; Wu, Shunqing; Nguyen, Manh Cuong; Zhu, Zi-zhong; Wang, Cai-Zhuang; Ho, Kai-Ming

2018-02-01

We applied an adaptive genetic algorithm (AGA) to search for low-energy crystal structures of Fe3S. A number of structures with energies lower than that of the experimentally reported Pnma and I-4 structures have been obtained from our AGA searches. These low-energy structures can be classified as layer-motif and column-motif structures. In the column-motif structures, Fe atoms self-assemble into rods with a bcc type of underlying lattice, which are separated by the holes terminated by S atoms. In the layer-motif structures, the bulk Fe is broken into slabs of several layers passivated by S atoms. Magnetic property calculations showed that the column-motif structures exhibit reasonably high uniaxial magnetic anisotropy. In addition, we examined the effect of Co doping to Fe3S and found that magnetic anisotropy can be enhanced through Co doping.

New structures of Fe3S for rare-earth-free permanent magnets

DOE PAGES

Yu, Shu; Zhao, Xin; Wu, Shunqing; ...

2018-02-25

We applied adaptive genetic algorithm (AGA) to search for low-energy crystal structures of Fe 3S. A number of structures with energies lower than that of the experimentally reported Pnma and I-4 structures have been obtained from our AGA searches. These low-energy structures can be classified as layer-motif and column-motif structures. In the column-motif structures, Fe atoms self-assemble into rods with bcc type of underlying lattice, which are separated by the holes terminated by S atoms. In the layer-motif structures, the bulk Fe is broken into slabs of several layers passivated by S atoms. Magnetic properties calculations showed that the column-motifmore » structures exhibit reasonably high uniaxial magnetic anisotropy. In addition, we examined the effect of Co doping to Fe 3S and found magnetic anisotropy can be enhanced through Co doping.« less

(Cryptand-222)potassium(+) (hydrogensulfido)[5,10,15,20-tetra-kis(2-pival-amido-phen-yl)porphyrinato]ferrate(II).

PubMed

Dhifet, Mondher; Belkhiria, Mohamed Salah; Daran, Jean-Claude; Nasri, Habib

2009-07-22

As part of a systematic investigation for a number of Fe(II) porphyrin complexes used as biomimetic models for cytochrome P450, crystals of the title compound, [K(C(18)H(36)N(2)O(6))][Fe(II)(C(64)H(64)N(8)O(4))(HS)], were prepared. The compound exhibits a non-planar conformation with major ruffling and saddling distortions. The average equatorial iron-pyrrole N atom [Fe-N(p) = 2.102 (2) Å] bond length and the distance between the Fe(II) atom and the 24-atom core of the porphyrin ring (Fe-P(C)= 0.558 Å) are typical for high-spin iron(II) penta-coordinate porphyrinates. One of the tert-butyl groups in the structure is disordered over two sets with occupancies of 0.84 and 0.16.

Information Exchange of the Atomic Energy Society of Japan with Nuclear Societies Worldwide

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

Masao Hori; Yasushi Tomita

2000-06-04

This paper describes committees of the Atomic Energy Society of Japan (AESJ) related to information exchange, AESJ publications, AESJ Internet applications, and means for future information exchange between nuclear societies.

A comprehensive study of magnetic exchanges in the layered oxychalcogenides Sr 3 Fe 2 O 5 Cu 2 Q 2 ( Q = S, Se)

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

Lü, Minfeng; Mentré, Olivier; Gordon, Elijah E.

2017-12-01

The layered oxysulfide Sr3Fe2O5Cu2S2 was prepared, and its crystal structure and magnetic properties were characterized by synchrotron X-ray diffraction (XRD), powder neutron diffraction (PND), Mössbauer spectroscopy measurements and by density functional theory (DFT) calculations. In addition, the spin exchange interactions leading to the ordered magnetic structure of Sr3Fe2O5Cu2S2 were compared with those of its selenium analogue Sr3Fe2O5Cu2Se2. The oxysulfide Sr3Fe2O5Cu2S2 adopts a G-type antiferromagnetic (AFM) structure at a temperature in the range 485–512 K, which is comparable with the three-dimensional (3D) AFM ordering temperature, TN ≈ 490 K, found for Sr3Fe2O5Cu2Se2. Consistent with this observation, the spin exchange interactions ofmore » the magnetic (Sr3Fe2O5)2+ layers are slightly greater (but comparable) for oxysulfide than for the oxyselenide. Attempts to reduce or oxidize Sr3Fe2O5Cu2S2 using topochemical routes yield metallic Fe.« less

Ni doped Fe3O4 magnetic nanoparticles.

PubMed

Larumbe, S; Gómez-Polo, C; Pérez-Landazábal, J I; García-Prieto, A; Alonso, J; Fdez-Gubieda, M L; Cordero, D; Gómez, J

2012-03-01

In this work, the effect of nickel doping on the structural and magnetic properties of Fe3O4 nanoparticles is analysed. Ni(x)Fe(3-x)O4 nanoparticles (x = 0, 0.04, 0.06 and 0.11) were obtained by chemical co-precipitation method, starting from a mixture of FeCl2 x 4H2O and Ni(AcO)2 x 4H2O salts. The analysis of the structure and composition of the synthesized nanoparticles confirms their nanometer size (main sizes around 10 nm) and the inclusion of the Ni atoms in the characteristic spinel structure of the magnetite Fe3O4 phase. In order to characterize in detail the structure of the samples, X-ray absorption (XANES) measurements were performed on the Ni and Fe K-edges. The results indicate the oxidation of the Ni atoms to the 2+ state and the location of the Ni2+ cations in the Fe2+ octahedral sites. With respect to the magnetic properties, the samples display the characteristic superparamagnetic behaviour, with anhysteretic magnetic response at room temperature. The estimated magnetic moment confirms the partial substitution of the Fe2+ cations by Ni2+ atoms in the octahedral sites of the spinel structure.

Giant interfacial perpendicular magnetic anisotropy in Fe/CuIn 1 -xGaxSe2 beyond Fe/MgO

NASA Astrophysics Data System (ADS)

Masuda, Keisuke; Kasai, Shinya; Miura, Yoshio; Hono, Kazuhiro

2017-11-01

We study interfacial magnetocrystalline anisotropies in various Fe/semiconductor heterostructures by means of first-principles calculations. We find that many of those systems show perpendicular magnetic anisotropy (PMA) with a positive value of the interfacial anisotropy constant Ki. In particular, the Fe/CuInSe 2 interface has a large Ki of ˜2.3 mJ /m2 , which is about 1.6 times larger than that of Fe/MgO known as a typical system with relatively large PMA. We also find that the values of Ki in almost all the systems studied in this work follow the well-known Bruno's relation, which indicates that minority-spin states around the Fermi level provide dominant contributions to the interfacial magnetocrystalline anisotropies. Detailed analyses of the local density of states and wave-vector-resolved anisotropy energy clarify that the large Ki in Fe/CuInSe 2 is attributed to the preferable 3 d -orbital configurations around the Fermi level in the minority-spin states of the interfacial Fe atoms. Moreover, we have shown that the locations of interfacial Se atoms are the key for such orbital configurations of the interfacial Fe atoms.

Site preference and magnetic properties of Ga/In-substituted strontium hexaferrite: An ab initio study

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

Dixit, Vivek; Nandadasa, Chandani N.; Kim, Seong-Gon, E-mail: kimsg@ccs.msstate.edu

2015-11-28

The first-principles density functional theory has been used to study Ga/In-substituted strontium hexaferrite (SrFe{sub 12}O{sub 19}). Based on the calculation of the substitution energy of Ga and In in SrFe{sub 12}O{sub 19} and the formation probability analysis, we conclude that in SrFe{sub 12−x}Ga{sub x}O{sub 19} the substituted Ga atoms prefer to occupy the 12k, 2a, and 4f{sub 1} sites, while In atoms in SrFe{sub 12−x}In{sub x}O{sub 19} occupy the 12k, 4f{sub 2}, and 4f{sub 1} sites. We used the site occupation probabilities to calculate the magnetic properties of the substituted SrFe{sub 12}O{sub 19}. It was found that as the fractionmore » of Ga atoms in SrFe{sub 12−x}Ga{sub x}O{sub 19} increases, the saturation magnetization (M{sub s}) as well as magnetic anisotropy energy (MAE) decrease, while the anisotropy field (H{sub a}) increases. In the case of SrFe{sub 12−x}In{sub x}O{sub 19}, M{sub s}, MAE, and H{sub a} decrease with an increase of the concentration of In atoms.« less

Theoretical study of negatively charged Fe(-)-(H2O)(n ≤ 6) clusters.

PubMed

Castro, Miguel

2012-06-14

Interactions of a singly negatively charged iron atom with water molecules, Fe(-)-(H(2)O)(n≤6), in the gas phase were studied by means of density functional theory. All-electron calculations were performed using the B3LYP functional and the 6-311++G(2d,2p) basis set for the Fe, O, and H atoms. In the lowest total energy states of Fe(-)-(H(2)O)(n), the metal-hydrogen bonding is stronger than the metal-oxygen one, producing low-symmetry structures because the water molecules are directly attached to the metal by basically one of their hydrogen atoms, whereas the other ones are involved in a network of hydrogen bonds, which together with the Fe(δ-)-H(δ+) bonding accounts for the nascent hydration of the Fe(-) anion. For Fe(-)-(H(2)O)(3≤n), three-, four-, five-, and six-membered rings of water molecules are bonded to the metal, which is located at the surface of the cluster in such a way as to reduce the repulsion with the oxygen atoms. Nevertheless, internal isomers appear also, lying less than 3 or 5 kcal/mol for n = 2-3 or n = 4-6. These results are in contrast with those of classical TM(+)-(H(2)O)(n) complexes, where the direct TM(+)-O bonding usually produces high symmetry structures with the metal defining the center of the complex. They show also that the Fe(-) anions, as the TM(+) ions, have great capability for the adsorption of water molecules, forming Fe(-)-(H(2)O)(n) structures stabilized by Fe(δ-)-H(δ+) and H-bond interactions.

ANISOTROPY DETERMINATIONS IN EXCHANGE SPRING MAGNETS.

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

LEWIS,L.H.; HARLAND,C.L.

2002-08-18

Ferromagnetic nanocomposites, or ''exchange spring'' magnets, possess a nanoscaled microstructure that allows intergrain magnetic exchange forces to couple the constituent grains and alter the system's effective magnetic anisotropies. While the effects of the anisotropy alterations are clearly seen in macroscopic magnetic measurement, it is extremely difficult to determine the detailed effects of the system's exchange coupling, such as the interphase exchange length, the inherent domain wall widths or the effective anisotropies of the system. Clarification of these materials parameters may be obtained from the ''micromagnetic'' phenomenological model, where the assumption of magnetic reversal initiating in the magnetically-soft regions of themore » exchange-spring maqet is explicitly included. This approach differs from that typically applied by other researchers and allows a quantitative estimate of the effective anisotropies of an exchange spring system. Hysteresis loops measured on well-characterized nanocomposite alloys based on the composition Nd{sub 2}Fe{sub 14}B + {alpha}-Fe at temperatures above the spin reorientation temperature were analyzed within the framework of the micromagnetic phenomenological model. Preliminary results indicate that the effective anisotropy constant in the material is intermediate to that of bulk {alpha}-Fe and bulk Nd{sub 2}Fe{sub 14}B and increases with decreasing temperature. These results strongly support the idea that magnetic reversal in nanocomposite systems initiates in the lower-anisotropy regions of the system, and that the soft-phase regions become exchange-hardened by virtue of their proximity to the magnetically-hard regions.« less

Tuning the Magnetic Properties of Metal Oxide Nanocrystal Heterostructures by Cation Exchange

PubMed Central

2013-01-01

For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal’s magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe2+ to Co2+ cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co2+ is demonstrated. By applying the cation exchange to FeO/CoFe2O4 core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system. PMID:23362940

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Bernstein, M. P.; Allamandola, L. J.; Gillette, J. S.; Zare, R. N.

2000-01-01

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

Iron-embedded C2N monolayer: a promising low-cost and high-activity single-atom catalyst for CO oxidation.

PubMed

He, B L; Shen, J S; Tian, Z X

2016-09-21

An Fe-embedded C2N monolayer as a promising single-atom catalyst for CO oxidation by O2 has been investigated based on first-principles calculations. It is found that the single Fe atom can be strongly trapped in the cavity of the C2N monolayer with a large adsorption energy of 4.55 eV and a high diffusion barrier of at least 3.00 eV to leave the cavity, indicating that Fe should exist in the isolated single-atom form. Due to the localized metal 3d orbitals near the Fermi level, the embedded Fe single-atom catalyst has a high chemical activity for the adsorption of CO and O2 molecules. CO oxidation by O2 on the catalyst would proceed via a two-step mechanism. The first step of the CO oxidation reaction has been studied via the Langmuir-Hinshelwood and Eley-Rideal mechanisms with energy barriers of 0.46 and 0.65 eV, respectively. The second step of the CO oxidation reaction follows the Eley-Rideal mechanism with a much smaller energy barrier of 0.24 eV. For both the steps, the CO2 molecules produced are weakly adsorbed on the substrates, suggesting that the proposed catalyst will not be poisoned by the generated CO2. Our results indicate that the Fe-embedded C2N monolayer is a promising single-atom catalyst for CO oxidation by O2 at low temperatures.

Molecular dynamics studies of displacement cascades in Fe-Y{sub 2}TiO{sub 5} system

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

Dholakia, Manan, E-mail: manan@igcar.gov.in; Chandra, Sharat; Jaya, S. Mathi

The effect of displacement cascade on Fe-Y{sub 2}TiO{sub 5} bilayer is studied using classical molecular dynamics simulations. Different PKA species – Fe, Y, Ti and O – with the same PKA energy of 8 keV are used to produce displacement cascades that encompass the interface. It is shown that Ti atom has the highest movement in the ballistic regime of cascades which can lead to Ti atoms moving out of the oxide clusters into the Fe matrix in ODS alloys.

Ternary Pt9RhFex Nanoscale Alloys as Highly Efficient Catalysts with Enhanced Activity and Excellent CO-Poisoning Tolerance for Ethanol Oxidation.

PubMed

Wang, Peng; Yin, Shibin; Wen, Ying; Tian, Zhiqun; Wang, Ningzhang; Key, Julian; Wang, Shuangbao; Shen, Pei Kang

2017-03-22

To address the problems of high cost and poor stability of anode catalysts in direct ethanol fuel cells (DEFCs), ternary nanoparticles Pt 9 RhFe x (x = 1, 3, 5, 7, and 9) supported on carbon powders (XC-72R) have been synthesized via a facile method involving reduction by sodium borohydride followed by thermal annealing in N 2 at ambient pressure. The catalysts are physically characterized by X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy, and their catalytic performance for the ethanol oxidation reaction (EOR) is evaluated by cyclic and linear scan voltammetry, CO-stripping voltammograms, and chronopotentiometry. All the Pt 9 RhFe x /C catalysts of different atomic ratios produce high EOR catalytic activity. The catalyst of atomic ratio composition 9:1:3 (Pt/Rh/Fe) has the highest activity and excellent CO-poisoning tolerance. Moreover, the enhanced EOR catalytic activity on Pt 9 RhFe 3 /C when compared to Pt 9 Rh/C, Pt 3 Fe/C, and Pt/C clearly demonstrates the presence of Fe improves catalytic performance. Notably, the onset potential for CO oxidation on Pt 9 RhFe 3 /C (0.271 V) is ∼55, 75, and 191 mV more negative than on Pt 9 Rh/C (0.326 V), Pt 3 Fe/C (0.346 V), and Pt/C (0.462 V), respectively, which implies the presence of Fe atoms dramatically improves CO-poisoning tolerance. Meanwhile, compared to the commercial PtRu/C catalyst, the peak potential on Pt 9 RhFe 3 /C for CO oxidation was just slightly changed after several thousand cycles, which shows high stability against the potential cycling. The possible mechanism by which Fe and Rh atoms facilitate the observed enhanced performance is also considered herein, and we conclude Pt 9 RhFe 3 /C offers a promising anode catalyst for direct ethanol fuel cells.

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.

2016-12-01

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350-360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α-Fe(Cr), α-Fe(Cu), α-Fe 2O3 and Fe 3O4 compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.

Fe-Cluster Compounds of Chalcogenides: Candidates for Rare-Earth-Free Permanent Magnet and Magnetic Nodal-Line Topological Material

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

Zhao, Xin; Wang, Cai-Zhuang; Kim, Minsung

Here, Fe-cluster-based crystal structures are predicted for chalcogenides Fe 3X 4 (X = S, Se, Te) using an adaptive genetic algorithm. Topologically different from the well-studied layered structures of iron chalcogenides, the newly predicted structures consist of Fe clusters that are either separated by the chalcogen atoms or connected via sharing of the vertex Fe atoms. Additionally, using first-principles calculations, we demonstrate that these structures have competitive or even lower formation energies than the experimentally synthesized Fe 3X 4 compounds and exhibit interesting magnetic and electronic properties. In particular, we show that Fe 3X 4 can be a good candidatemore » as a rare-earth-free permanent magnet and Fe 3X 4 can be a magnetic nodal-line topological material.« less

Fe-Cluster Compounds of Chalcogenides: Candidates for Rare-Earth-Free Permanent Magnet and Magnetic Nodal-Line Topological Material

DOE PAGES

Zhao, Xin; Wang, Cai-Zhuang; Kim, Minsung; ...

2017-11-13

Here, Fe-cluster-based crystal structures are predicted for chalcogenides Fe 3X 4 (X = S, Se, Te) using an adaptive genetic algorithm. Topologically different from the well-studied layered structures of iron chalcogenides, the newly predicted structures consist of Fe clusters that are either separated by the chalcogen atoms or connected via sharing of the vertex Fe atoms. Additionally, using first-principles calculations, we demonstrate that these structures have competitive or even lower formation energies than the experimentally synthesized Fe 3X 4 compounds and exhibit interesting magnetic and electronic properties. In particular, we show that Fe 3X 4 can be a good candidatemore » as a rare-earth-free permanent magnet and Fe 3X 4 can be a magnetic nodal-line topological material.« less

Properties of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions through photoelectron spectroscopy and density functional theory calculations.

PubMed

Yin, Shi; Bernstein, Elliot R

2016-10-21

A new magnetic-bottle time-of-flight photoelectron spectroscopy (PES) apparatus is constructed in our laboratory. The PES spectra of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide [FeS m (SH) n - ; m, n = 0-3, 0 < (m + n) ≤ 3] cluster anions, obtained at 2.331 eV (532 nm) and 3.492 eV (355 nm) photon energies, are reported. The electronic structure and bonding properties of these clusters are additionally investigated at different levels of density functional theory. The most probable structures and ground state spin multiplicity for these cluster anions are tentatively assigned by comparing their theoretical first vertical detachment energies (VDEs) with their respective experiment values. The behavior of S and (SH) as ligands in these iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions is investigated and compared. The experimental first VDEs for Fe(SH) 1-3 - cluster anions are lower than those found for their respective FeS 1-3 - cluster anions. The experimental first VDEs for FeS 1-3 - clusters are observed to increase for the first two S atoms bound to Fe - ; however, due to the formation of an S-S bond for the FeS 3 - cluster, its first VDE is found to be ∼0.41 eV lower than the first VDE for the FeS 2 - cluster. The first VDEs of Fe(SH) 1-3 - cluster anions are observed to increase with the increasing numbers of SH groups. The calculated partial charges of the Fe atom for ground state FeS 1-3 - and Fe(SH) 1-3 - clusters are apparently related to and correlated with their determined first VDEs. The higher first VDE is correlated with a higher, more positive partial charge for the Fe atom of these cluster anions. Iron sulfide/hydrosulfide mixed cluster anions are also explored in this work: the first VDE for FeS(SH) - is lower than that for FeS 2 - , but higher than that for Fe(SH) 2 - ; the first VDEs for FeS 2 (SH) - and FeS(SH) 2 - are close to that for FeS 3 - , but higher than that for Fe(SH) 3 - . The first VDEs of general iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide clusters [FeS m (SH) n - ; m, n = 0-3, 0 < (m + n) ≤ 3] are dependent on three properties of these anions: 1. the partial charge on the Fe atom, 2. disulfide bond formation (S-S) in the cluster, and 3. the number of hydrosulfide ligands in the cluster. The higher the partial charge on the Fe atom of these clusters, the larger the first VDE; however, cluster S-S bonding and more (SH) ligands in the cluster lower the cluster anion first VDE.

Properties of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions through photoelectron spectroscopy and density functional theory calculations

NASA Astrophysics Data System (ADS)

Yin, Shi; Bernstein, Elliot R.

2016-10-01

A new magnetic-bottle time-of-flight photoelectron spectroscopy (PES) apparatus is constructed in our laboratory. The PES spectra of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide [FeSm(SH)n-; m, n = 0-3, 0 < (m + n) ≤ 3] cluster anions, obtained at 2.331 eV (532 nm) and 3.492 eV (355 nm) photon energies, are reported. The electronic structure and bonding properties of these clusters are additionally investigated at different levels of density functional theory. The most probable structures and ground state spin multiplicity for these cluster anions are tentatively assigned by comparing their theoretical first vertical detachment energies (VDEs) with their respective experiment values. The behavior of S and (SH) as ligands in these iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions is investigated and compared. The experimental first VDEs for Fe(SH)1-3- cluster anions are lower than those found for their respective FeS1-3- cluster anions. The experimental first VDEs for FeS1-3- clusters are observed to increase for the first two S atoms bound to Fe-; however, due to the formation of an S-S bond for the FeS3- cluster, its first VDE is found to be ˜0.41 eV lower than the first VDE for the FeS2- cluster. The first VDEs of Fe(SH)1-3- cluster anions are observed to increase with the increasing numbers of SH groups. The calculated partial charges of the Fe atom for ground state FeS1-3- and Fe(SH)1-3- clusters are apparently related to and correlated with their determined first VDEs. The higher first VDE is correlated with a higher, more positive partial charge for the Fe atom of these cluster anions. Iron sulfide/hydrosulfide mixed cluster anions are also explored in this work: the first VDE for FeS(SH)- is lower than that for FeS2-, but higher than that for Fe(SH)2-; the first VDEs for FeS2(SH)- and FeS(SH)2- are close to that for FeS3-, but higher than that for Fe(SH)3-. The first VDEs of general iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide clusters [FeSm(SH)n-; m, n = 0-3, 0 < (m + n) ≤ 3] are dependent on three properties of these anions: 1. the partial charge on the Fe atom, 2. disulfide bond formation (S-S) in the cluster, and 3. the number of hydrosulfide ligands in the cluster. The higher the partial charge on the Fe atom of these clusters, the larger the first VDE; however, cluster S-S bonding and more (SH) ligands in the cluster lower the cluster anion first VDE.

Fine structure of Fe-Co-Ga and Fe-Cr-Ga alloys with low Ga content

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

Kleinerman, Nadezhda M., E-mail: kleinerman@imp.uran.ru; Serikov, Vadim V., E-mail: kleinerman@imp.uran.ru; Vershinin, Aleksandr V., E-mail: kleinerman@imp.uran.ru

2014-10-27

Investigation of Ga influence on the structure of Fe-Cr and Fe-Co alloys was performed with the use of {sup 57}Fe Mössbauer spectroscopy and X-ray diffraction methods. In the alloys of the Fe-Cr system, doping with Ga handicaps the decomposition of solid solutions, observed in the binary alloys, and increases its stability. In the alloys with Co, Ga also favors the uniformity of solid solutions. The analysis of Mössbauer experiments gives some grounds to conclude that if, owing to liquation, clusterization, or initial stages of phase separation, there exist regions enriched in iron, some amount of Ga atoms prefer to entermore » the nearest surroundings of iron atoms, thus forming binary Fe-Ga regions (or phases)« less

Effect of nickel on point defects diffusion in Fe – Ni alloys

DOE PAGES

Anento, Napoleon; Serra, Anna; Osetsky, Yury N.

2017-05-05

Iron-Nickel alloys are perspective alloys as nuclear energy structural materials because of their good radiation damage tolerance and mechanical properties. Understanding of experimentally observed features such as the effect of Ni content to radiation defects evolution is essential for developing predictive models of radiation. Recently an atomic-scale modelling study has revealed one particular mechanism of Ni effect related to the reduced mobility of clusters of interstitial atoms in Fe-Ni alloys. In this paper we present results of the microsecond-scale molecular dynamics study of point defects, i.e. vacancies and self-interstitial atoms, diffusion in Fe-Ni alloys. It is found that the additionmore » of Ni atoms affects diffusion processes: diffusion of vacancies is enhanced in the presence of Ni, whereas diffusion of interstitials is reduced and these effects increase at high Ni concentration and low temperature. As a result, the role of Ni solutes in radiation damage evolution in Fe-Ni alloys is discussed.« less

The Role of Iron In Sporadic E Layers

NASA Astrophysics Data System (ADS)

Vondrak, T.; Woodcock, K. R. I.; Plane, J. M. C.

Sporadic E layers in the lower thermosphere are mostly composed of metallic ions, of which Fe+ is the most abundant. Because dielectric recombination (Fe+ + elec- tron) is very slow, the lifetime of Fe+ above about 100 km is at least several days. However, below this height molecular ions such as FeO+, FeO2+ and FeN2+ form in- creasingly rapidly through reactions with O3, O2 and N2, respectively. These undergo rapid dissociative recombination with electrons, causing Fe+ to be neutralised increas- ingly rapidly as a sporadic E layer descends. Indeed, this is the most likely mechanism for the formation of the sporadic neutral Fe layers that are observed by lidar. However, atomic O plays a very important role in reducing these molecular ions back to Fe+, competing with dissociative recombination and thus slowing the rate at which Fe+ is neutralised and a sporadic E layer dissipates. This paper will discuss a laboratory and modelling study of the reactions of FeO+, FeO2+ and FeN2+ with atomic O. These reactions were studied (for the first time) in a fast flow tube, using the pulsed laser ablation of a rotating iron rod as the source of Fe+ ions in the upstream section of the tube. Reactants were then added to produce molecular ions, and atomic O further downstream through a movable injector. Fe+ and the molecular ions were detected at the downstream end of the tube using a two-stage quadrupole mass spectrometer. The spectroscopy of the FeO+ ion, observed by laser induced fluorescence, will also be discussed as a candidate for future ground-based lidar studies of the ion chemistry of the lower thermosphere.

Interfacial Microstructure and Its Influence on Resistivity of Thin Layers Copper Cladding Steel Wires

NASA Astrophysics Data System (ADS)

Li, Hongjuan; Ding, Zhimin; Zhao, Ruirong

2018-04-01

The interfacial microstructure and resistivity of cold-drawn and annealed thin layers copper cladding steel (CCS) wires have been systematically investigated by the methods of scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and resistivity testing. The results showed that the Cu and Fe atoms near interface diffused into each other matrixes. The Fe atoms diffused into Cu matrixes and formed a solid solution. The mechanism of solid solution is of substitution type. When the quantity of Fe atoms exceeds the maximum solubility, the supersaturated solid solution would form Fe clusters and decompose into base Cu and α-Fe precipitated phases under certain conditions. A few of α-Fe precipitates was observed in the copper near Cu/Fe interfaces of cold-drawn CCS wires, with 1-5 nm in size. A number of α-Fe precipitates of 1-20 nm in size can be detected in copper near Cu/Fe interfaces of CCS wires annealed at 850°C. When annealing temperature was less than 750°C, the resistivity of CCS wires annealed was lower than that of cold-drawn CCS wires. However, when annealing temperature was above 750°C, the resistivity of CCS wires was greater than that of cold-drawn CCS wires and increased with rising the annealing temperature. The relationship between nanoscale α-Fe precipitation and resistivity of CCS wires has been well discussed.

Hydrogenases and H(+)-reduction in primary energy conservation.

PubMed

Vignais, Paulette M

2008-01-01

Hydrogenases are metalloenzymes subdivided into two classes that contain iron-sulfur clusters and catalyze the reversible oxidation of hydrogen gas (H(2)[Symbol: see text]left arrow over right arrow[Symbol: see text]2H(+)[Symbol: see text]+[Symbol: see text]2e(-)). Two metal atoms are present at their active center: either a Ni and an Fe atom in the [NiFe]hydrogenases, or two Fe atoms in the [FeFe]hydrogenases. They are phylogenetically distinct classes of proteins. The catalytic core of [NiFe]hydrogenases is a heterodimeric protein associated with additional subunits in many of these enzymes. The catalytic core of [FeFe]hydrogenases is a domain of about 350 residues that accommodates the active site (H cluster). Many [FeFe]hydrogenases are monomeric but possess additional domains that contain redox centers, mostly Fe-S clusters. A third class of hydrogenase, characterized by a specific iron-containing cofactor and by the absence of Fe-S cluster, is found in some methanogenic archaea; this Hmd hydrogenase has catalytic properties different from those of [NiFe]- and [FeFe]hydrogenases. The [NiFe]hydrogenases can be subdivided into four subgroups: (1) the H(2) uptake [NiFe]hydrogenases (group 1); (2) the cyanobacterial uptake hydrogenases and the cytoplasmic H(2) sensors (group 2); (3) the bidirectional cytoplasmic hydrogenases able to bind soluble cofactors (group 3); and (4) the membrane-associated, energy-converting, H(2) evolving hydrogenases (group 4). Unlike the [NiFe]hydrogenases, the [FeFe]hydrogenases form a homogeneous group and are primarily involved in H(2) evolution. This review recapitulates the classification of hydrogenases based on phylogenetic analysis and the correlation with hydrogenase function of the different phylogenetic groupings, discusses the possible role of the [FeFe]hydrogenases in the genesis of the eukaryotic cell, and emphasizes the structural and functional relationships of hydrogenase subunits with those of complex I of the respiratory electron transport chain.

The EUV Emission in Comet-Solar Corona Interactions

NASA Technical Reports Server (NTRS)

Bryans, Paul; Pesnell, William Dean; Schrijver, Carolus J.; Brown, John C.; Battams, Karl; Saint-Hilaire, Pasal; Liu, Wei; Hudson, Hugh S.

2011-01-01

The Atmospheric Imaging Assembly (AlA) on the Solar Dynamics Observatory (SDO) viewed a comet as it passed through the solar corona on 2011 July 5. This was the first sighting of a comet by a EUV telescope. For 20 minutes, enhanced emission in several of the AlA wavelength bands marked the path of the comet. We explain this EUV emission by considering the evolution of the cometary atmosphere as it interacts with the ambient solar atmosphere. Water ice in the comet rapidly sublimates as it approaches the Sun. This water vapor is then photodissociated, primarily by Ly-alpha, by the solar radiation field to create atomic Hand O. Other molecules present in the comet also evaporate and dissociate to give atomic Fe and other metals. Subsequent ionization of these atoms can be achieved by a number of means, including photoionization, electron impact, and charge exchange with coronal protons and other highly-charged species. Finally, particles from the cometary atmosphere are thermalized to the background temperature of the corona. Each step could cause emission in the AlA bandpasses. We will report here on their relative contribution to the emission seen in the AlA telescopes.

Structural, magnetic and Mossbauer studies of TI doped Gd2Fe17-xTix and Gd2Fe16Ga1-xTix (0≤x≤1)

NASA Astrophysics Data System (ADS)

Pokharel, G.; Syed Ali, K. S.; Mishra, S. R.

2015-05-01

Magnetic compounds of the type Gd2Fe17-xTix and Gd2Fe16Ga1-xTix (x=0.0-1.0) were prepared by arc melting and their structural and magnetic properties were studied by X-ray diffraction (XRD), magnetometery and Mossbauer spectroscopy. The Rietveld analysis of X-ray data shows that these α-Fe free solid-solutions crystallize with Th2Ni17-type structure as main phase along with GdFe2 and TiFe2 as additional phases at higher, x≥0.5 contents. The unit cell volume expands with Ga and Ti content. The Rietveld analysis indicate that both Ti and Ga atoms prefer 12j and 12k sites in both compounds. The effect of Ti and co-substituted Ga-Ti on the bond length are quite different. The saturation magnetization Ms, at 300 K for Gd2Fe17-xTix and Gd2Fe16Ga1-xTix was found to decrease linearly with increasing Ti content. The Ms in both compounds at x=1 reduced by 9% as compared to their parent compounds at x=0. The Curie temperature, Tc, for Gd2Fe17-xTix increased from 513 K (x=0) to 544 K (x=1) while Tc for Gd2Fe16Ga1-xTix reduced from 560 (x=0) to 544 K (x=1) with increase in Ti content. Thus the observed variation in Tc follows Gd2Fe17

Local order study of YFe 2D x (0⩽ x⩽3.5) compounds by X-ray absorption and Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Paul-Boncour, V.; Wiesinger, G.; Reichl, Ch.; Latroche, M.; Percheron-Guégan, A.; Cortes, R.

2001-12-01

The local order in YFe 2D x deuterides has been characterized by EXAFS and 57Fe Mössbauer spectroscopy. For all the deuterides several Fe sites and a large distribution of Fe-Fe distances are observed. The Y-Fe and Y-Y distances are close to those calculated for a cubic C15 type structure, but with significant static disorder. These large distance distributions are related to the influence of hydrogen atoms which induce local distortions of the interstitial sites with a displacement of Y and Fe atoms. However, the bulk and mean local magnetic properties remain sensitive to the long range order structure of the deuterides.

Decisive role of magnetism in the interaction of chromium and nickel solute atoms with 1/2$$\\langle$$111$$\\rangle$$-screw dislocation core in body-centered cubic iron

DOE PAGES

Odbadrakh, Kh.; Samolyuk, G.; Nicholson, D.; ...

2016-09-13

Resistance to swelling under irradiation and a low rate of corrosion in high temperature environments make Fe-Cr and Fe-Cr-Ni alloys promising structural materials for energy technologies. In this paper we report the results obtained using a combination of density functional theory (DFT) techniques: plane wave basis set solutions for pseudo-potentials and multiple scattering solutions for all electron potentials. We have found a very strong role of magnetism in the stability of screw dislocation cores in pure Fe and their interaction with Cr and Ni magnetic impurities. In particular, the screw dislocation quadrupole in Fe is stabilized only in the presencemore » of ferromagnetism. In addition, Ni atoms, who's magnetic moment is oriented along the magnetization direction of the Fe matrix, prefer to occupy in core positions whereas Cr atoms, which couple anti-ferromagnetically with the Fe matrix, prefer out of the dislocation core positions. In effect, Ni impurities are attracted to, while Cr impurities are repelled by the dislocation core. Moreover, we demonstrate that this contrasting behavior can be explained only by the nature of magnetic coupling of the impurities to the Fe matrix. In addition, Cr interaction with the dislocation core mirrors that of Ni if the Cr magnetic moment is constrained to be along the direction of Fe matrix magnetization. In addition, we have shown that the magnetic contribution can affect the impurity-impurity interaction at distances up to a few Burgers vectors. In particular, the distance between Cr atoms in Fe matrix should be at least 3–4 lattice parameters in order to eliminate finite size effects.« less

Disparate ultrafast dynamics of itinerant and localized magnetic moments in gadolinium metal

PubMed Central

Frietsch, B.; Bowlan, J.; Carley, R.; Teichmann, M.; Wienholdt, S.; Hinzke, D.; Nowak, U.; Carva, K.; Oppeneer, P. M.; Weinelt, M.

2015-01-01

The Heisenberg–Dirac intra-atomic exchange coupling is responsible for the formation of the atomic spin moment and thus the strongest interaction in magnetism. Therefore, it is generally assumed that intra-atomic exchange leads to a quasi-instantaneous aligning process in the magnetic moment dynamics of spins in separate, on-site atomic orbitals. Following ultrashort optical excitation of gadolinium metal, we concurrently record in photoemission the 4f magnetic linear dichroism and 5d exchange splitting. Their dynamics differ by one order of magnitude, with decay constants of 14 versus 0.8 ps, respectively. Spin dynamics simulations based on an orbital-resolved Heisenberg Hamiltonian combined with first-principles calculations explain the particular dynamics of 5d and 4f spin moments well, and corroborate that the 5d exchange splitting traces closely the 5d spin-moment dynamics. Thus gadolinium shows disparate dynamics of the localized 4f and the itinerant 5d spin moments, demonstrating a breakdown of their intra-atomic exchange alignment on a picosecond timescale. PMID:26355196

Transition metal intercalated bilayer silicene

NASA Astrophysics Data System (ADS)

Pandey, Dhanshree; Kamal, C.; Chakrabarti, Aparna

2018-04-01

We investigate the electronic and magnetic properties of Mn, Fe and Co-intercalated silicene bilayer with AA and AB stacking by using spin polarized density functional theory. The intercalation of Mn increases the gap between the two layers of silicene due to the larger atomic radii of Mn as compared to Fe and Co. Bader charge analysis has been performed to understand the bonding between the TM and Si atoms. This also helps in explaining the magnetic moment possessed by the composite systems after intercalating TM in between the layers of bilayer silicene system. This study reveals that a significant net magnetic moment is observed in cases of Mn-intercalated silicene bilayers, whereas Fe has a very small moment of 0.78 µB in the case of AA stacking configuration only. Co intercalation leads to net zero magnetic moment. Further, we find that Fe and Co marginally favor the AB stacking whereas Mn has a slight preference of the AA over the AB configuration. The composite systems, specifically when intercalated with Fe and Co atoms, favor a hybridization which is far away from sp3-like hybridization along the plane of Si atoms in bilayer silicene.

Modified magnetism within the coherence volume of superconducting Fe1+δSexTe1-x

NASA Astrophysics Data System (ADS)

Leiner, J.; Thampy, V.; Christianson, A. D.; Abernathy, D. L.; Stone, M. B.; Lumsden, M. D.; Sefat, A. S.; Sales, B. C.; Hu, Jin; Mao, Zhiqiang; Bao, Wei; Broholm, C.

2014-09-01

Neutron scattering is used to probe magnetic interactions as superconductivity develops in optimally doped Fe1+δSexTe1-x. Applying the first moment sum rule to comprehensive neutron scattering data, we extract the change in magnetic exchange energy Δ [JR -R'] in the superconducting state referenced to the normal state. Oscillatory changes are observed for Fe-Fe displacements |ΔR |<ξ, where ξ =1.3(1) nm is the superconducting coherence length. Dominated by a large reduction in the second nearest neighbor exchange energy [-1.2(2) meV/Fe], the overall reduction in magnetic interaction energy is Δ=-0.31(9) meV/Fe. Comparison to the superconducting condensation energy ΔESC=-0.013(1) meV/Fe, which we extract from specific heat data, suggests the modified magnetism we probe drives superconductivity in Fe1+δSexTe1-x.

Characterization of an atomic hydrogen source for charge exchange experiments

DOE PAGES

Leutenegger, M. A.; Beiersdorfer, P.; Betancourt-Martinez, G. L.; ...

2016-07-02

Here, we characterized the dissociation fraction of a thermal dissociation atomic hydrogen source by injecting the mixed atomic and molecular output of the source into an electron beam ion trap containing highly charged ions and recording the x-ray spectrum generated by charge exchange using a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchange state-selective capture cross sections are very different for atomic and molecular hydrogen incident on the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

The thermal stability of magnetically exchange coupled MnBi/FeCo composites at electric motor working temperature

NASA Astrophysics Data System (ADS)

Cheng, Ye; Wang, Hongying; Li, Zhigang; Liu, Wanhui; Bao, Ilian

2018-04-01

The magnetically exchange coupled MnBi/FeCo composites were synthesized through a magnetic self-assembly process. The MnBi/FeCo composites were then hot pressed in a magnetic field to form magnets. The thermal stability of the magnets were tested by annealing at electric motor working temperature of 200 °C for 20, 40 and 60 h, respectively. It was found that after heating for 20 h, there was negligible change in its hysteresis loop. However, when the heating time was increased 40 and 60 h, the magnetic hysteresis loops presented two-phase magnetic behaviors, and the maximum energy products of the magnet were decreased. This research showed that the magnetically exchange coupled MnBi/FeCo composites had low thermal stability at electric motor working temperature.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles

NASA Astrophysics Data System (ADS)

de Julián Fernández, C.; Mattei, G.; Paz, E.; Novak, R. L.; Cavigli, L.; Bogani, L.; Palomares, F. J.; Mazzoldi, P.; Caneschi, A.

2010-04-01

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO2 matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

PubMed

de Julián Fernández, C; Mattei, G; Paz, E; Novak, R L; Cavigli, L; Bogani, L; Palomares, F J; Mazzoldi, P; Caneschi, A

2010-04-23

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Truly Incomplete and Complex Chromosomal Exchanges in Human Fibroblast Cells Exposed In Situ to Energetic Heavy Ions

NASA Technical Reports Server (NTRS)

Wu, Honglu; Durante, marco; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis A.

2003-01-01

Confluent human fibroblast cells (AG 1522) were irradiated with gamma rays, 490 MeV/nucleon Si, or with Fe ions at either 200 or 500 MeV/nucleon. The cells were allowed to repair at 37 C for 24 hours after exposure, and a chemically induced premature chromosome condensation (PCC) technique was used to condense chromosomes in the G2 phase of the cell cycle. Incomplete and complex exchanges were analyzed in the irradiated samples. In order to verify that chromosomal breaks were truly unrejoined, chromosome aberrations were analyzed using a combination of whole chromosome specific probes and probes specific for the telomere region of the chromosome. Results showed that the frequency of unrejoined chromosome breaks was higher after high-LET radiation, and consequently, the ratio of incomplete to complete exchanges increased steadily with LET up to 440 keV/micron, the highest LET value in the present study. For samples exposed to 200 MeV/nucleon Fe ions, chromosome aberrations were analyzed using the multicolor FISH (mFISH) technique that allow identification of both complex and truly incomplete exchanges. Results of the mFISH study showed that 0.7 and 3 Gy dose of the Fe ions produced similar ratios of complex to simple exchanges and incomplete to complete exchanges, values for which were higher than those obtained after a 6 Gy gamma exposure. After 0.7 Gy of Fe ions, most complex aberrations were found to involve three or four chromosomes, which is a likely indication of the maximum number of chromosome domains traversed by a single Fe ion track.

Effect of sputtering condition and heat treatment in Co/Cu/Co/FeMn spin valve

NASA Astrophysics Data System (ADS)

Kim, Hong Jin; Bae, Jun Soo; Lee, Taek Dong; Lee, Hyuck Mo

2002-03-01

The exchange field of Cu(50 Å)/FeMn(50 Å)/Co(50 Å) sputtered on Si substrate was studied in terms of surface roughness and phase formation of γ-FeMn under a variety of Ar pressures and powers in sputtering. It was found that the exchange field is stronger when the surface is smoother and the FeMn layer forms better. The exchange bias field increased by more than three times after heat treatment. The effect of heat treament on magnetoresistance (MR) and resistance of the top spin valve, substrate/Co(30 Å)/Cu(30 Å)/Co(30 Å)/FeMn(150 Å), was studied. It was observed that the MR started to increase with annealing temperature and the effect was significant at 150°C. The heat treatment led to the disappearance of the intermixed layer between Co and Cu, and the concentration profile of Cu became flat and smooth at this temperature.

Exchange coupling interaction in L10-FePd/α-Fe nanocomposite magnets with large maximum energy products.

PubMed

Sakuma, Noritsugu; Ohshima, Tsubasa; Shoji, Tetsuya; Suzuki, Yoshihito; Sato, Ryota; Wachi, Ayako; Kato, Akira; Kawai, Yoichiro; Manabe, Akira; Teranishi, Toshiharu

2011-04-26

Nanocomposite magnets (NCMs) consisting of hard and soft magnetic phases are expected to be instrumental in overcoming the current theoretical limit of magnet performance. In this study, structural analyses were performed on L1(0)-FePd/α-Fe NCMs with various hard/soft volume fractions, which were formed by annealing Pd/γ-Fe(2)O(3) heterostructured nanoparticles and pure Pd nanoparticles. The sample with a hard/soft volume ratio of 82/18 formed by annealing at 773 K had the largest maximum energy product (BH(max) = 10.3 MGOe). In such a sample, the interface between the hard and soft phases was coherent and the phase sizes were optimized, both of which effectively induced exchange coupling. This exchange coupling was directly observed by visualizing the magnetic interaction between the hard and soft phases using a first-order reversal curve diagram, which is a valuable tool to improve the magnetic properties of NCMs.

Tunable magnetism of 3d transition metal doped BiFeO3

NASA Astrophysics Data System (ADS)

Lu, S.; Li, C.; Zhao, Y. F.; Gong, Y. Y.; Niu, L. Y.; Liu, X. J.; Wang, T.

2017-10-01

Electronic polarization or bond relaxation can effectively alter the electronic and magnetic behavior of materials by doping impurity atom. For this aim, the thermodynamic, electronic and magnetic performances of cubic BiFeO3 have been modulated by the 3d transition metal (TM) dopants (Sc, Ti, V, Cr, Mn, Co, Ni, Cu and Zn) based on the density functional theory. Results show that the doped specimen with low impurity concentration is more stable than that with high impurity concentration. The Mulliken charge values and spin magnetic moments of TM element are making major changes, while those of all host atoms are making any major changes. Especially, it is the linear relation between the spin magnetic moments of TM dopants and the total magnetic moment of doped specimens; thus, the variations of total magnetic moment of doped specimens are decided by the spin magnetic moments of TM dopants, thought the total magnetic moments of doped specimens mainly come from Fe atom and TM dopants. Besides, as double TM atoms substitution the Fe atoms, the Sc-, Ti-, Mn-, Co- and Zn-doped specimens show AFM state, while the V-, Cr-, Ni- and Cu-doped specimens show FM state.

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

DOE PAGES

Zhang, Yijun; Liu, Ming; Peng, Bin; ...

2016-01-27

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe 2O 3 and superparamagnetic Fe 2O 3with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe 2O 3 in a reducing atmosphere leads to the formation of the spinel Fe 3O 4 phase which displaysmore » a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. Finally, the ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.« less

Synthesis and controllable oxidation of monodisperse cobalt-doped wüstite nanoparticles and their core-shell stability and exchange-bias stabilization.

PubMed

Chen, Chih-Jung; Chiang, Ray-Kuang; Kamali, Saeed; Wang, Sue-Lein

2015-09-14

Cobalt-doped wüstite (CWT), Co0.33Fe0.67O, nanoparticles were prepared via the thermal decomposition of CoFe2-oleate complexes in organic solvents. A controllable oxidation process was then performed to obtain Co0.33Fe0.67O/CoFe2O4 core-shell structures with different core-to-shell volume ratios and exchange bias properties. The oxidized core-shell samples with a ∼4 nm CoFe2O4 shell showed good resistance to oxygen transmission. Thus, it is inferred that the cobalt ferrite shell provides a better oxidation barrier performance than magnetite in the un-doped case. The hysteresis loops of the oxidized 19 nm samples exhibited a high exchange bias field (H(E)), an enhanced coercivity field (H(C)), and a pronounced vertical shift, thus indicating the presence of a strong exchange bias coupling effect. More importantly, the onset temperature of H(E) was found to be higher than 200 K, which suggests that cobalt doping increases the Néel temperature (T(N)) of the CWT core. In general, the results show that the homogeneous dispersion of Co in iron precursors improves the stability of the final CWT nanoparticles. Moreover, the CoFe2O4 shells formed following oxidation increase the oxidation resistance of the CWT cores and enhance their anisotropy energy.

Photo-excitation of electrons in cytochrome c oxidase as a theory of the mechanism of the increase of ATP production in mitochondria by laser therapy

NASA Astrophysics Data System (ADS)

Zielke, Andrzej

2014-02-01

The hypothesis explains the molecular basis for restoring mitochondrial function by laser therapy. It also explains how laser therapy reverses both excessive oxidation (lack of NADH/FADH2) and excessive reduction (lack of O2) states of cytochrome c oxidase complex. It is proposed that photons interact with heme molecules of cytochrome c oxidase. A molecule of heme contains a porphyrin ring and an atom of iron in the center. The iron atom (Fe) can switch oxidation states back and forth between ferrous (Fe2+) and ferric (Fe3+) by accepting or releasing an electron. The porphyrin ring is a complex aromatic molecule that has 26 pi electrons which are "delocalized", spinning in the carbon rings creating a resonating electromagnetic cloud. Photons with similar wavelengths are absorbed by the cloud increasing its energy. The energy is then passed on to the centrally located atom of iron existing in a reduced state (Fe2+). The electrons on the orbits of the iron atom accept this electromagnetic energy, and change orbitals to a higher energetic level. If the energy is sufficient, electrons leave the atom entirely. If this occurs, Fe2+ become oxidized to Fe3+ releasing electrons, thus restoring electron flow and the production of ATP. At the same time, electrons freed from complex IV may have sufficient energy to be picked by NAD+/FADH and re-enter the chain at the complex I or II amplifying the flow of electrons.

Structure and magnetism of new rare-earth-free intermetallic compounds: Fe 3+xCo 3-xTi 2 (0 ≤ x ≤ 3)

DOE PAGES

Balasubramanian, Balamurugan; Das, Bhaskar; Nguyen, Manh Cuong; ...

2016-11-28

Here, we report the fabrication of a set of new rare-earth-free magnetic compounds, which form the Fe 3Co 3Ti 2-type hexagonal structure with P-6m2 symmetry. Neutron powder diffraction shows a significant Fe/Co anti-site mixing in the Fe 3Co 3Ti 2 structure, which has a strong effect on the magnetocrystalline anisotropy as revealed by first-principle calculations. Increasing substitution of Fe atoms for Co in the Fe 3Co 3Ti 2 lattice leads to the formation of Fe 4Co 2Ti 2, Fe 5CoTi, and Fe 6Ti 2 with significantly improved permanent-magnet properties. A high magnetic anisotropy (13.0 Mergs/cm 3) and saturation magnetic polarizationmore » (11.4 kG) are achieved at 10 K by altering the atomic arrangements and decreasing Fe/Co occupancy disorder.« less

Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3 d -5 d double perovskite Sr2FeOsO6

NASA Astrophysics Data System (ADS)

Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; Souza-Neto, N. M.; Feng, H. L.; Yamaura, K.; Haskel, D.

2015-06-01

The ability to tune exchange (magnetic) interactions between 3 d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3 d -5 d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5 d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr2FeOsO6 drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differences with the more thoroughly studied 3 d -3 d systems.

Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

DOE PAGES

Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; ...

2015-06-19

The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differencesmore » with the more thoroughly studied 3d-3d systems.« less

Synthesis and isolation of [Fe@Ge(10)](3-): a pentagonal prismatic Zintl ion cage encapsulating an interstitial iron atom.

PubMed

Zhou, Binbin; Denning, Mark S; Kays, Deborah L; Goicoechea, Jose M

2009-03-04

Reaction of an ethylenediamine (en) solution of the Zintl phase precursor K(4)Ge(9) with FeAr(2) (Ar = 2,6-Mes(2)C(6)H(3)) in the presence of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) yielded the endohedral Zintl ion [Fe@Ge(10)](3-) (1) which was crystallographically characterized as a [K(2,2,2-crypt)](+) salt in [K(2,2,2-crypt)](3)[Fe@Ge(10)]*2en. This unprecedented Zintl ion exhibits a pentagonal prismatic 10-atom germanium cage with an interstitial iron atom in the central cavity. Confirmation of the existence of the cluster anion in solution was corroborated by positive and negative ion mode electrospray mass spectrometry.

Influences on Distribution of Solute Atoms in Cu-8Fe Alloy Solidification Process Under Rotating Magnetic Field

NASA Astrophysics Data System (ADS)

Zou, Jin; Zhai, Qi-Jie; Liu, Fang-Yu; Liu, Ke-Ming; Lu, De-Ping

2018-05-01

A rotating magnetic field (RMF) was applied in the solidification process of Cu-8Fe alloy. Focus on the mechanism of RMF on the solid solution Fe(Cu) atoms in Cu-8Fe alloy, the influences of RMF on solidification structure, solute distribution, and material properties were discussed. Results show that the solidification behavior of Cu-Fe alloy have influenced through the change of temperature and solute fields in the presence of an applied RMF. The Fe dendrites were refined and transformed to rosettes or spherical grains under forced convection. The solute distribution in Cu-rich phase and Fe-rich phase were changed because of the variation of the supercooling degree and the solidification rate. Further, the variation in solute distribution was impacted the strengthening mechanism and conductive mechanism of the material.

Iron-Rhodium and Iron-Iridium Mixed-Metal Nitrido-Carbonyl Clusters. Synthesis, Characterization, Redox Properties, and Solid-State Structure of the Octahedral Clusters [Fe(5)RhN(CO)(15)](2)(-), [Fe(5)IrN(CO)(15)](2)(-), and [Fe(4)Rh(2)N(CO)(15)](-). Infrared and Nuclear Magnetic Resonance Spectroscopic Studies on the Interstitial Nitride.

PubMed

Della Pergola, Roberto; Cinquantini, Arnaldo; Diana, Eliano; Garlaschelli, Luigi; Laschi, Franco; Luzzini, Paola; Manassero, Mario; Repossi, Andrea; Sansoni, Mirella; Stanghellini, Pier Luigi; Zanello, Piero

1997-08-13

The cluster [Fe(5)RhN(CO)(15)](2)(-) was synthesized in 40% yield from [Fe(4)N(CO)(12)](-) and [Rh(CO)(4)](-) in refluxing tetrahydrofuran, whereas the analogous anion [Fe(5)IrN(CO)(15)](2)(-) was prepared in CH(3)CN at room temperature from [Fe(6)N(CO)(15)](3)(-) and [Ir(C(8)H(14))(2)Cl](2); the yields are higher than 60%. The monoanion [Fe(4)Rh(2)N(CO)(15)](-) was obtained in 70% yield from [Fe(5)RhN(CO)(15)](2)(-) and hydrated RhCl(3). The solid-state structures of the three anions were determined on their [PPh(4)](+) salts: the six metal atoms are arranged in octahedral cages and are coordinated to 3 edge-bridging and 12 terminal carbonyl ligands and to a &mgr;(6)-N ligand. The Rh and Ir atoms have less terminal COs than Fe, in order to equalize the excess electrons at the d(9) metal centers. The two rhodium atoms in [Fe(4)Rh(2)N(CO)(15)](-) are directly bound. The (15)N NMR spectra of the three compounds have been recorded; the signals of the nitride ligands were found at delta = 514 ppm for the dianions and 470 ppm for [Fe(4)Rh(2)N(CO)(15)](-); any group 9 atom shifts the resonance of nitrogen to higher fields. The coupling constants J((15)N-(103)Rh) are 8-9 Hz. The vibrational patterns of the metal cores have been interpreted on the basis of an idealized M(6) octahedral arrangement, subsequently modified by the perturbations given by different atomic masses and M-M stretching force constants. The motions of the nitrogen are related to the idealized symmetry of the cage; the M-N force constant values depend on the type of metal and on the charge of the anion. The dianions [Fe(5)MN(CO)(15)](2)(-) can be electrochemically oxidized at -20 degrees C to their short-lived monoanions, which can be characterized by EPR spectroscopy. In contrast, the cluster [Fe(4)Rh(2)N(CO)(15)](-) undergoes a single-step 2-electron reduction to the partially stable trianion [Fe(4)Rh(2)N(CO)(15)](3)(-), which was also characterized by EPR spectroscopy. The Fe-Rh nitride clusters are active catalysts for the hydroformylation of 1-pentene, but display low selectivity (35-65%) in n-hexanal and are demolished under catalytic conditions.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

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

Cai, Zhao; Zhou, Daojin; Wang, Maoyu

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

Autonomous Repair Mechanism of Creep Damage in Fe-Au and Fe-Au-B-N Alloys

NASA Astrophysics Data System (ADS)

Zhang, S.; Kwakernaak, C.; Tichelaar, F. D.; Sloof, W. G.; Kuzmina, M.; Herbig, M.; Raabe, D.; Brück, E.; van der Zwaag, S.; van Dijk, N. H.

2015-12-01

The autonomous repair mechanism of creep cavitation during high-temperature deformation has been investigated in Fe-Au and Fe-Au-B-N alloys. Combined electron-microscopy techniques and atom probe tomography reveal how the improved creep properties result from Au precipitation within the creep cavities, preferentially formed on grain boundaries oriented perpendicular to the applied stress. The selective precipitation of Au atoms at the free creep cavity surface results in pore filling, and thereby, autonomous repair of the creep damage. The large difference in atomic size between the Au and Fe strongly hampers the nucleation of precipitates in the matrix. As a result, the matrix acts as a reservoir for the supersaturated solute until damage occurs. Grain boundaries and dislocations are found to act as fast transport routes for solute gold from the matrix to the creep cavities. The mechanism responsible for the self-healing can be characterized by a simple model for cavity growth and cavity filling.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE PAGES

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; ...

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

Fenton chemistry at aqueous interfaces

PubMed Central

Enami, Shinichi; Sakamoto, Yosuke; Colussi, Agustín J.

2014-01-01

In a fundamental process throughout nature, reduced iron unleashes the oxidative power of hydrogen peroxide into reactive intermediates. However, notwithstanding much work, the mechanism by which Fe2+ catalyzes H2O2 oxidations and the identity of the participating intermediates remain controversial. Here we report the prompt formation of O=FeIVCl3− and chloride-bridged di-iron O=FeIV·Cl·FeIICl4− and O=FeIV·Cl·FeIIICl5− ferryl species, in addition to FeIIICl4−, on the surface of aqueous FeCl2 microjets exposed to gaseous H2O2 or O3 beams for <50 μs. The unambiguous identification of such species in situ via online electrospray mass spectrometry let us investigate their individual dependences on Fe2+, H2O2, O3, and H+ concentrations, and their responses to tert-butanol (an ·OH scavenger) and DMSO (an O-atom acceptor) cosolutes. We found that (i) mass spectra are not affected by excess tert-butanol, i.e., the detected species are primary products whose formation does not involve ·OH radicals, and (ii) the di-iron ferryls, but not O=FeIVCl3−, can be fully quenched by DMSO under present conditions. We infer that interfacial Fe(H2O)n2+ ions react with H2O2 and O3 >103 times faster than Fe(H2O)62+ in bulk water via a process that favors inner-sphere two-electron O-atom over outer-sphere one-electron transfers. The higher reactivity of di-iron ferryls vs. O=FeIVCl3− as O-atom donors implicates the electronic coupling of mixed-valence iron centers in the weakening of the FeIV–O bond in poly-iron ferryl species. PMID:24379389

Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

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

Sato, Soshi, E-mail: sato.soshi@cies.tohoku.ac.jp; Honjo, Hiroaki; Niwa, Masaaki

2015-04-06

We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer.more » The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.« less

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

NASA Astrophysics Data System (ADS)

Serrano, Susana; O'Day, Peggy A.; Vlassopoulos, Dimitri; García-González, Maria Teresa; Garrido, Fernando

2009-02-01

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X - and Y -), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions. Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.

Stellar and laboratory XUV/EUV line ratios in Fe XVIII and Fe XIX

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

Traebert, E.; Beiersdorfer, P.; Clementson, J.

2012-05-25

A so-called XUV excess has been suspected with the relative fluxes of Fe XVIII and Fe XIX lines observed in the XUV and EUV ranges of the spectrum of the star Capella as observed by the Chandra spacecraft, even after correction for interstellar absorption. This excess becomes apparent in the comparison of the observations with simulations of stellar spectra obtained using collisional-radiative models that employ, for example, the Atomic Plasma Emission Code (APEC) or the Flexible Atomic Code (FAC). We have addressed this problem by laboratory studies using the Livermore electron beam ion trap (EBIT).

Antiferromagnetic structure and electronic properties of BaCr2As2 and BaCrFeAs2

NASA Astrophysics Data System (ADS)

Filsinger, Kai A.; Schnelle, Walter; Adler, Peter; Fecher, Gerhard H.; Reehuis, Manfred; Hoser, Andreas; Hoffmann, Jens-Uwe; Werner, Peter; Greenblatt, Martha; Felser, Claudia

2017-05-01

Recent theoretical studies suggest that superconductivity may be found in doped chromium pnictides with crystal structures similar to their iron counterparts. Here, we report a comprehensive study on the magnetic arsenides BaCr2As2 and BaCrFeAs2 (space group I 4 /m m m ), which are possible mother compounds with d4 and d5 electron configurations, respectively. DFT-based calculations of the electronic structure evidence metallic antiferromagnetic ground states for both compounds. By powder neutron diffraction, we confirm for BaCr2As2 a robust ordering in the antiferromagnetic G -type structure at TN=580 K with μCr=1.9 μB . Anomalies in the lattice parameters point to magnetostructural coupling effects. In BaCrFeAs2, the Cr and Fe atoms randomly occupy the transition-metal site and G -type order is found below 265 K with μCr /Fe=1.1 μB . 57Fe Mössbauer spectroscopy demonstrates that only a small ordered moment is associated with the Fe atoms, in agreement with electronic structure calculations leading to μFe˜0 . The temperature dependence of the hyperfine field does not follow that of the total moments. Both compounds are metallic but show large enhancements of the linear specific heat. Electrical transport in BaCrFeAs2 is dominated by the atomic disorder and the partial magnetic disorder of Fe. Our results indicate that Néel-type order is unfavorable for Fe moments and thus it is destabilized with increasing Fe content.

Structure and magnetic behaviors of melt-spun SmFeSiB ribbons and their nitrides

NASA Astrophysics Data System (ADS)

Luo, Y.; Zhang, K.; Li, K. S.; Yu, D. B.; Ling, J. J.; Men, K.; Dou, Q. Y.; Yan, W. L.; Xie, J. J.; Yang, Y. F.

2016-05-01

SmFe9.3+xSi0.2B0.1 (x=0, 0.5, 1.0) ribbons and their nitrides were prepared by melt-spinning, followed by annealing and subsequent nitriding. The structure and magnetic properties have been investigated by means of powder X-ray diffraction, vibrating sample magnetometer and Mossbauer spectroscopy. Rietveld analysis shows that the augment of Fe content gives rise to an increase of the c/a ratio and cell volume. The increasing amount of Fe atoms occupying the 2e sites results in the change of initial structure. It is indicated that the isomer shift of 3g and 6l atom remains quasi-constant while the 2e atom shows a noticeable increase with the increase of iron content, which further conforms the preferential occupation of excessive Fe atoms at this site. Consistent with Tc, the mean hyperfine field 〈Bhf〉 has the highest value of 25.7 T when x=0.5. The hyperfine fields at different Fe sites follow the order H2e>H3g>H6l. The highest curie temperature of 477.68 K and the hyperfine field of 25.7 T in the as-quenched ribbons were obtained when x=0.5. Meanwhile, the highest magnetic properties of Hcj=4.31 kOe, (BH)m=3.5 MGOe in the nitride powders were found.

Bottom-up Approach Design, Band Structure, and Lithium Storage Properties of Atomically Thin γ-FeOOH Nanosheets.

PubMed

Song, Yun; Cao, Yu; Wang, Jing; Zhou, Yong-Ning; Fang, Fang; Li, Yuesheng; Gao, Shang-Peng; Gu, Qin-Fen; Hu, Linfeng; Sun, Dalin

2016-08-24

As a novel class of soft matter, two-dimensional (2D) atomic nanosheet-like crystals have attracted much attention for energy storage devices due to the fact that nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. Herein, atomically thin γ-FeOOH nanosheets with a thickness of ∼1.5 nm are synthesized in a high yield, and the band and electronic structures of the γ-FeOOH nanosheet are revealed using density-functional theory calculations for the first time. The rationally designed γ-FeOOH@rGO composites with a heterostacking structure are used as an anode material for lithium-ion batteries (LIBs). A high reversible capacity over 850 mAh g(-1) after 100 cycles at 200 mA g(-1) is obtained with excellent rate capability. The remarkable performance is attributed to the ultrathin nature of γ-FeOOH nanosheets and 2D heterostacking structure, which provide the minimized Li(+) diffusion length and buffer zone for volume change. Further investigation on the Li storage electrochemical mechanism of γ-FeOOH@rGO indicates that the charge-discharge processes include both conversion reaction and capacitive behavior. This synergistic effect of conversion reaction and capacitive behavior originating from 2D heterostacking structure casts new light on the development of high-energy anode materials.

Phase identification in boron-containing powder metallurgy steel using EBSD in combination with EPMA

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

Wu, Ming-Wei, E-mail: mwwu@ntut.edu.tw; Cai, Wen-Zhang

2016-03-15

Boron (B) is extensively used to induce liquid phase sintering (LPS) in powder metallurgy (PM) steels and thereby increase the densification. The alloying elements in B-containing PM steels affect the boride phase, stability of the boride, the temperature of liquid formation, and the progress of LPS. However, the boride phase has not been systematically identified yet. The main objective of this study was to clarify the influences of alloying elements, including C, Cr, and Ni, on the boride phases using electron backscatter diffraction (EBSD) in combination with electron probe microanalysis (EPMA). Network structures consisting of ferrite, Fe{sub 2}B boride, andmore » Fe{sub 3}C carbide were extensively observed in the Fe–0.4B–0.5C steel. The portions of Fe{sub 2}B were sufficiently larger than those of Fe{sub 3}C, and Fe{sub 3}C was mostly distributed at the interfaces between ferrite and Fe{sub 2}B. Adding 1.5 wt.% Cr or 1.8 wt.% Ni to Fe–0.4B–0.5C steel completely changes the Fe{sub 2}B and Fe{sub 3}C phases to a M{sub 3}(B,C) phase, where M represents the metallic elements, including Fe, Cr, Mo, and Ni. Furthermore, Cr, Mo, B, and C atoms tend to concentrate on the M{sub 3}(B,C) phase, but Ni atoms do not. - Highlights: • Network structures consisting of ferrite, Fe{sub 2}B boride, and Fe{sub 3}C carbide were extensively observed in the Fe–0.4B–0.5C steel. • Adding 1.5 wt.% Cr or 1.8 wt.% Ni to Fe–0.4B–0.5C steel completely transforms the Fe{sub 2}B and Fe{sub 3}C phases to a M{sub 3}(B,C) phase. • Cr, Mo, B, and C atoms tend to concentrate on the M{sub 3}(B,C) phase, but Ni atoms do not.« less

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution.

PubMed

Wernet, Ph; Kunnus, K; Josefsson, I; Rajkovic, I; Quevedo, W; Beye, M; Schreck, S; Grübel, S; Scholz, M; Nordlund, D; Zhang, W; Hartsock, R W; Schlotter, W F; Turner, J J; Kennedy, B; Hennies, F; de Groot, F M F; Gaffney, K J; Techert, S; Odelius, M; Föhlisch, A

2015-04-02

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16 - 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution

NASA Astrophysics Data System (ADS)

Wernet, Ph.; Kunnus, K.; Josefsson, I.; Rajkovic, I.; Quevedo, W.; Beye, M.; Schreck, S.; Grübel, S.; Scholz, M.; Nordlund, D.; Zhang, W.; Hartsock, R. W.; Schlotter, W. F.; Turner, J. J.; Kennedy, B.; Hennies, F.; de Groot, F. M. F.; Gaffney, K. J.; Techert, S.; Odelius, M.; Föhlisch, A.

2015-04-01

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16,17,18,19 and 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

Structural, magnetic and electronic properties of pulsed-laser-deposition grown SrFeO3-δ thin films and SrFeO3-δ /La2/3Ca1/3MnO3 multilayers

NASA Astrophysics Data System (ADS)

Perret, E.; Sen, K.; Khmaladze, J.; Mallett, B. P. P.; Yazdi-Rizi, M.; Marsik, P.; Das, S.; Marozau, I.; Uribe-Laverde, M. A.; de Andrés Prada, R.; Strempfer, J.; Döbeli, M.; Biškup, N.; Varela, M.; Mathis, Y.-L.; Bernhard, C.

2017-12-01

We studied the structural, magnetic and electronic properties of SrFeO3-δ (SFO) thin films and SrFeO3-δ /La2/3 Ca1/3 MnO3 (LCMO) superlattices that have been grown with pulsed laser deposition (PLD) on La0.3 Sr0.7 Al0.65 Ta0.35 O3 (LSAT) substrates. X-ray reflectometry and scanning transmission electron microscopy (STEM) confirm the high structural quality of the films and flat and atomically sharp interfaces of the superlattices. The STEM data also reveal a difference in the interfacial layer stacking with a SrO layer at the LCMO/SFO and a LaO layer at the SFO/LCMO interfaces along the PLD growth direction. The x-ray diffraction (XRD) data suggest that the as grown SFO films and SFO/LCMO superlattices have an oxygen-deficient SrFeO3-δ structure with I4/ mmm space group symmetry (δ≤slant 0.2 ). Subsequent ozone annealed SFO films are consistent with an almost oxygen stoichiometric structure (δ ≈ 0 ). The electronic and magnetic properties of these SFO films are similar to the ones of corresponding single crystals. In particular, the as grown SrFeO3-δ films are insulating whereas the ozone annealed films are metallic. The magneto-resistance effects of the as grown SFO films have a similar magnitude as in the single crystals, but extend over a much wider temperature range. Last but not least, for the SFO/LCMO superlattices we observe a rather large exchange bias effect that varies as a function of the cooling field.

Magnetic response of hybrid ferromagnetic and antiferromagnetic core-shell nanostructures

NASA Astrophysics Data System (ADS)

Khan, U.; Li, W. J.; Adeela, N.; Irfan, M.; Javed, K.; Wan, C. H.; Riaz, S.; Han, X. F.

2016-03-01

The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required.The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07946b

Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in Alkaline Exchange Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Hossen, Md Mosaddek; Artyushkova, Kateryna; Atanassov, Plamen; Serov, Alexey

2018-01-01

In this article, three different Fe-N-C oxygen reduction reaction (ORR) catalysts derived from different organic molecules i.e. Fe-NMG, Fe-NMP, Fe-MBZ have been synthesized, characterized by physical-chemical methods and studied in the reaction of oxygen reduction (ORR). It is found that Fe-NMG shows higher ORR performance than Fe-NMP and Fe-MBZ, by both rotating ring disk electrode (RRDE) and fuel cell tests. From characterization and surface analysis, it can be explained that the presence of higher amount of surface oxides and pyridinic nitrogen is the main reason for better performance towards ORR in alkaline media. To achieve the highest performance in alkaline exchange membrane fuel cell (AEMFC), the optimization of catalyst layer composition using various concentrations of ionomer (Tokuyama, AS4) was performed. At the optimum cathode layer configuration utilizing Fe-NMG produces the peak power density of 218 mWcm-2, which is one of the highest values presented in the open literature.

Characterization of iron ferromagnetism by the local atomic volume: from three-dimensional structures to isolated atoms.

PubMed

Zhang, Lei; Sob, M; Wu, Zhe; Zhang, Ying; Lu, Guang-Hong

2014-02-26

We present a comprehensive study of the relationship between the ferromagnetism and the structural properties of Fe systems from three-dimensional ones to isolated atoms based on the spin-density functional theory. We have found a relation between the magnetic moment and the volume of the Voronoi polyhedron, determining, in most cases, the value of the total magnetic moment as a function of this volume with an average accuracy of ±0.28 μ(B) and of the 3d magnetic moment with an average accuracy of ±0.07 μ(B) when the atomic volume is larger than 22 ų. It is demonstrated that this approach is applicable for many three-dimensional systems, including high-symmetry structures of perfect body-centered cubic (bcc), face-centered cubic (fcc), hexagonal close-packed (hcp), double hexagonal close-packed (dhcp), and simple cubic (sc) crystals, as well as for lower-symmetry ones, for example atoms near a grain boundary (GB) or a surface, around a vacancy or in a linear chain (for low-dimensional cases, we provide a generalized definition of the Voronoi polyhedron). Also, we extend the validity of the Stoner model to low-dimensional structures, such as atomic chains, free-standing monolayers and surfaces, determining the Stoner parameter for these systems. The ratio of the 3d-exchange splitting to the magnetic moment, corresponding to the Stoner parameter, is found to be I(3d) = (0.998 ± 0.006) eV /μ(B) for magnetic moments up to 3.0 μ(B). Further, the 3d exchange splitting changes nearly linearly in the region of higher magnetic moments (3.0-4.0 μ(B)) and the corresponding Stoner exchange parameter equals I(h)(3d) = (0.272 ± 0.006) eV /μ(B). The existence of these two regions reflects the fact that, with increasing Voronoi volume, the 3d bands separate first and, consequently, the 3d magnetic moment increases. When the Voronoi volume is sufficiently large (≥22 ų), the separation of the 3d bands is complete and the magnetic moment reaches a value of 3.0 μ(B). Then, when the volume further increases, the 4s bands start to separate, increasing thus the 4s magnetic moment. Surprisingly, in the region of higher magnetic moments (≥3.0 μ(B)), there is also a linear relationship between the 4s exchange splitting and the total magnetic moment with a slope of I(h)(4s) = (1.053 ± 0.016) eV /μ(B), which is nearly identical to I(3d) for magnetic moments up to 3.0 μB. These linear relations can be considered as an extension of the Stoner model for low-dimensional systems.

The bonding of FeN2, FeCO, and Fe2N2 - Model systems for side-on bonding of CO and N2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.

1987-01-01

Qualitative calculations are performed to elucidate the nature of the side-on interaction of both N2 and CO with a single Fe atom. The systems are found to be quite similar, with bonding leading to an increase in the CO or N2 bond length and a decrease in the vibrational frequency. The CO or N2 stretching modes lead to a large dipole derivative along the metal-ligand bond axis. The populations show an almost identical, large donation from the Fe 3d orbitals into the CO or N2 Pi-asterisk. The larger system Fe2N2 is then considered, with the N2 bridging the Fe2, both parallel and perpendicular to the Fe2 bond axis for two different Fe-Fe distances. For FeN2, the shift in the observed N2 frequency is smaller than observed for the alpha state of N2/Fe(111). The shift in the N2 vibrational frequency increases when the N2 interacts with two Fe atoms, either at the Fe-Fe nearest neighbor distance or at the first layer Fe-Fe distance, when the side-on N2 axis is oriented perpendicular to an Fe-Fe bond.

Ultrafast Photoinduced Multimode Antiferromagnetic Spin Dynamics in Exchange-Coupled Fe/RFeO3 (R = Er or Dy) Heterostructures.

PubMed

Tang, Jin; Ke, Yajiao; He, Wei; Zhang, Xiangqun; Zhang, Wei; Li, Na; Zhang, Yongsheng; Li, Yan; Cheng, Zhaohua

2018-05-25

Antiferromagnetic spin dynamics is important for both fundamental and applied antiferromagnetic spintronic devices; however, it is rarely explored by external fields because of the strong exchange interaction in antiferromagnetic materials. Here, the photoinduced excitation of ultrafast antiferromagnetic spin dynamics is achieved by capping antiferromagnetic RFeO 3 (R = Er or Dy) with an exchange-coupled ferromagnetic Fe film. Compared with antiferromagnetic spin dynamics of bare RFeO 3 orthoferrite single crystals, which can be triggered effectively by ultrafast laser heating just below the phase transition temperature, the ultrafast photoinduced multimode antiferromagnetic spin dynamic modes, for exchange-coupled Fe/RFeO 3 heterostructures, including quasiferromagnetic resonance, impurity, coherent phonon, and quasiantiferromagnetic modes, are observed in a temperature range of 10-300 K. These experimental results not only offer an effective means to trigger ultrafast antiferromagnetic spin dynamics of rare-earth orthoferrites, but also shed light on the ultrafast manipulation of antiferromagnetic magnetization in Fe/RFeO 3 heterostructures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Circuit QED with qutrits: Coupling three or more atoms via virtual-photon exchange

NASA Astrophysics Data System (ADS)

Zhao, Peng; Tan, Xinsheng; Yu, Haifeng; Zhu, Shi-Liang; Yu, Yang

2017-10-01

We present a model to describe a generic circuit QED system which consists of multiple artificial three-level atoms, namely, qutrits, strongly coupled to a cavity mode. When the state transition of the atoms disobeys the selection rules the process that does not conserve the number of excitations can happen determinatively. Therefore, we can realize coherent exchange interaction among three or more atoms mediated by the exchange of virtual photons. In addition, we generalize the one-cavity-mode mediated interactions to the multicavity situation, providing a method to entangle atoms located in different cavities. Using experimentally feasible parameters, we investigate the dynamics of the model including three cyclic-transition three-level atoms, for which the two lowest energy levels can be treated as qubits. Hence, we have found that two qubits can jointly exchange excitation with one qubit in a coherent and reversible way. In the whole process, the population in the third level of atoms is negligible and the cavity photon number is far smaller than 1. Our model provides a feasible scheme to couple multiple distant atoms together, which may find applications in quantum information processing.

Back-clocking of Fe2+/Fe1+ spin states in a H2-producing catalyst by advanced EPR

NASA Astrophysics Data System (ADS)

Stathi, Panagiota; Mitrikas, George; Sanakis, Yiannis; Louloudi, Maria; Deligiannakis, Yiannis

2013-10-01

A mononuclear Fe-(P(PPh2)3) ((P(PPh2)3) = tris[2-diphenylphospino)ethyl]phosphine) catalyst was studied in situ under catalytic conditions using advanced electron paramagnetic resonance (EPR) techniques. Fe-(P(PPh2)3) efficiently catalyses H2 production using HCOOH as substrate. Dual-mode continuous-wave (CW) EPR, used to study the initial Fe2+(S = 2) state, shows that the complex is characterised by a - rather small - zero field splitting parameter Δ = 0.45 cm-1 and geff = 8.0. In the presence of HCOOH substrate the complex evolves and a unique Fe1+(S = 1/2) state is trapped. The Fe1+ atom is coordinated by four 31P nuclei in a pseudo-C3 symmetry. Only a small fraction of the Fe1+ spin density is delocalised onto the 31P atoms. Four-pulse electron spin echo envelope modulation (ESEEM) and two-dimensional hyperfine sublevel correlation spectroscopy (2D-HYSCORE) data reveal the existence of two types of 1H couplings. One corresponds to weak, purely dipolar coupling, tentatively assigned to phenyl protons. The most important is a - rather unusual - 1H coupling with negative Aiso (-2.75 MHz) and strong dipolar part (T = 5.5 MHz). This 1H is located on the pseudo-C3 symmetry axis of the Fe1+-(P(PPh2)3-HCOO- complex where one substrate molecule, formate anion, is coordinated on the Fe1+ atom.

Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

NASA Astrophysics Data System (ADS)

Presniakov, I. A.; Sobolev, A. V.; Rusakov, V. S.; Moskvin, A. S.; Baranov, A. V.

2018-06-01

The objective of this study is to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskite La2Li0.5Cu0.5O4 containing transition metal in unusual formal oxidation states "+3". An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d9L configuration ("Cu2+-O-" state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3+ + O-(L) → Fe4+ + O2-, which transforms "Fe3+" into "Fe4+" state. The experimental spectra in the entire temperature range 77-300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe3+↔Fe4+ valence states related to the iron atom in the [Fe(1)O4]4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO4]5- clusters in the layered perovskite.

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

DOE PAGES

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun; ...

2017-04-27

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

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

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

Properties of Exchange Coupled All-garnet Magneto-Optic Thin Film Multilayer Structures

PubMed Central

Nur-E-Alam, Mohammad; Vasiliev, Mikhail; Kotov, Viacheslav A.; Balabanov, Dmitry; Akimov, Ilya; Alameh, Kamal

2015-01-01

The effects of exchange coupling on magnetic switching properties of all-garnet multilayer thin film structures are investigated. All-garnet structures are fabricated by sandwiching a magneto-soft material of composition type Bi1.8Lu1.2Fe3.6Al1.4O12 or Bi3Fe5O12:Dy2O3 in between two magneto-hard garnet material layers of composition type Bi2Dy1Fe4Ga1O12 or Bi2Dy1Fe4Ga1O12:Bi2O3. The fabricated RF magnetron sputtered exchange-coupled all-garnet multilayers demonstrate a very attractive combination of magnetic properties, and are of interest for emerging applications in optical sensors and isolators, ultrafast nanophotonics and magneto-plasmonics. An unconventional type of magnetic hysteresis behavior not observed previously in magnetic garnet thin films is reported and discussed. PMID:28788043

Iron's Role in Aluminum: A Powder Metallurgy and Sustainability Approach

NASA Astrophysics Data System (ADS)

Saller, Brandon Dale

The family of Al-Fe alloys is both scientifically and technologically interesting for several reasons. First, the low equilibrium solid solubility (0.03 at.%) and diffusivity of Fe in Al suggest that the alloys containing these two elements should be thermally stable. Many studies have tried to extend this low solubility value via non-equilibrium processing routes. Second, published results suggest that there is a range of intermetallic phases, including the metastable orthorhombic Al6Fe and the equilibrium monoclinic Al13Fe4, for example, the formation of which depends on solidification and subsequent processing conditions. Third, from a sustainability standpoint, both Al and Fe are present in bauxite (aluminum ore), however up to 40 wt.% Fe-oxide present in bauxite is discarded as a waste product, creating red mud pits. In order to understand the multiple facets and implications of iron's role in aluminum, a systematic investigation was performed into the precipitates that form as a function of thermal exposure and their subsequent effect on the tensile behavior of the alloy. In this study, Al-2at.% Fe and Al-5at.% Fe powders were synthesized via helium gas atomization and argon gas atomization, respectively. Cooling rates upwards of 106 K/s were achieved resulting in an intermetallic-free starting structure. Powders were subsequently severely plastically deformed via either cryomilling or high-pressure torsion to obtain nanostructured/ultrafine-grained powder or a consolidated specimen, respectively. Characterization via electron microscopy established a map of the powder microstructure as a function of atomization cooling rate. In addition, electron backscatter diffraction revealed a large number of low-angle grain boundaries, which influenced nucleation and precipitation of the metastable Al6Fe phase. X-ray diffraction and atom probe tomography results provide the most comprehensive evidence to date of forcing of 2at.% Fe into solution with the Al matrix via cryomilling. With respect to the powder, a differential scanning calorimetry and activation energy analysis elucidated the formation and phase transformation temperatures of the relevant intermetallic phases, and the microstructural factors that influenced them. With an understanding of the fundamental science behind the intermetallic formation in the Al-Fe system, the composition of helium atomized Al-2at.% Fe was chosen combined with high-pressure torsion processing to yield a bulk alloy that demonstrated an ultimate tensile strength of 488 MPa. This strength was achieved via a combination of two mechanisms: grain refinement (Hall-Petch) and dislocation-Al6Fe interactions (Orowan strengthening), with notable thermal stability present up until 450°C. Finally, the potential for Al-Fe as a sustainable alloy was studied and a link established between current environmental literature and metallurgy literature on the potential for incorporation of Fe into Al to create a structural alloy.

Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

PubMed

Wang, Biwei; Wang, Xinxia; Zou, Jinxiang; Yan, Yancui; Xie, Songhai; Hu, Guangzhi; Li, Yanguang; Dong, Angang

2017-03-08

Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe 3 O 4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.

Manipulation of competing ferromagnetic and antiferromagnetic domains in exchange-biased nanostructures

DOE PAGES

Fraile Rodríguez, Arantxa; Basaran, Ali C.; Morales, Rafael; ...

2015-11-20

In this work, using photoemission electron microscopy combined with x-ray magnetic circular dichroism we show that a progressive spatial confinement of a ferromagnet (FM), either through thickness variation or laterally via patterning, actively controls the domains of uncompensated spins in the antiferromagnet (AF) in exchange-biased systems. Direct observations of the spin structure in both sides of the FM/AF interface in a model system, Ni/FeF 2, show that the spin structure is determined by the balance between the competing FM and AF magnetic energies. Coexistence of exchange bias domains, with opposite directions, can be established in Ni/FeF 2 bilayers for Nimore » thicknesses below 10 nm. Patterning the Ni/FeF 2 heterostructures with antidots destabilizes the FM state, enhancing the formation of opposite exchange bias domains below a critical antidot separation of the order of a few FeF 2 crystal domains. The results suggest that dimensional confinement of the FM may be used to manipulate the AF spin structure in spintronic devices and ultrahigh-density information storage media. Lastly, the underlying mechanism of the uncompensated AF domain formation in Ni/FeF 2 may be generic to other magnetic systems with complex noncollinear FM/AF spin structures.« less

Effect of Fe3O4 addition on removal of ammonium by zeolite NaA.

PubMed

Liu, Haibo; Peng, Shuchuan; Shu, Lin; Chen, Tianhu; Bao, Teng; Frost, Ray L

2013-01-15

Magnetic zeolite NaA with different Fe(3)O(4) loadings was prepared by hydrothermal synthesis based on metakaolin and Fe(3)O(4). The effect of added Fe(3)O(4) on the removal of ammonium by zeolite NaA was investigated by varying the Fe(3)O(4) loading, pH, adsorption temperature, initial concentration, adsorption time. Langmuir, Freundlich, and pseudo-second-order modeling were used to describe the nature and mechanism of ammonium ion exchange using both zeolite and magnetic zeolite. Thermodynamic parameters such as change in Gibbs free energy, enthalpy and entropy were calculated. The results show that all the selected factors affect the ammonium ion exchange by zeolite and magnetic zeolite, however, the added Fe(3)O(4) apparently does not affect the ion exchange performance of zeolite to the ammonium ion. Freundlich model provides a better description of the adsorption process than Langmuir model. Moreover, kinetic analysis indicates the exchange of ammonium on the two materials follows a pseudo-second-order model. Thermodynamic analysis makes it clear that the adsorption process of ammonium is spontaneous and exothermic. Regardless of kinetic or thermodynamic analysis, all the results suggest that no considerable effect on the adsorption of the ammonium ion by zeolite is found after the addition of Fe(3)O(4). According to the results, magnetic zeolite NaA can be used for the removal of ammonium due to the good adsorption performance and easy separation method from aqueous solution. Copyright © 2012 Elsevier Inc. All rights reserved.

Ledge-type Co/L1{sub 0}-FePt exchange-coupled composites

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

Speliotis, Th.; Giannopoulos, G.; Niarchos, D.

2016-06-21

FePt-based exchange-coupled composites consisting of a magnetically hard L1{sub 0}-FePt phase exchange-coupled with a soft ferromagnetic material are promising candidates for future ultra-high density (>1 Tbit/in{sup 2}) perpendicular magnetic recording media, also being of interest for other applications including spin torque oscillators and micro-electro-mechanical systems, among others. In this paper, the effect of the thickness of a soft Co layer (3 < th{sub Co} < 20 nm) on the magnetic behavior of ledge-type fcc(100)-Co/L1{sub 0}(001)-FePt composites deposited on an MgO (100) substrate is systematically studied by combining morpho-structural analyses and angular magnetization measurements. Starting from a film consisting of isolated L1{submore » 0}(001)–FePt islands, the ledge-type structure was obtained by depositing a Co layer that either covered the FePt islands or filled-up the inter-island region, gradually forming a continuous layer with increasing Co thickness. A perpendicular anisotropy was maintained up to th{sub Co} ∼ 9.5 nm and a significant reduction in the coercivity (about 50% for th{sub Co} ∼ 3 nm) with the increase in th{sub Co} was observed, indicating that, by coupling hard FePt and soft Co phases in a ledge-type configuration, the writability can be greatly improved. Recoil loops' measurements confirmed the exchange-coupled behavior, reinforcing a potential interest in these systems for future magnetic recording media.« less

Influence of ball milling on atomic structure and magnetic properties of Co{sub 40}Fe{sub 22}Ta{sub 8}B{sub 30} glassy alloy

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

Taghvaei, Amir Hossein, E-mail: Amirtaghvaei@gmail.com; Department of Materials Science and Engineering, Shiraz University of Technology, Shiraz; Stoica, Mihai

2014-06-01

The influence of ball milling on the atomic structure and magnetic properties of the Co{sub 40}Fe{sub 22}Ta{sub 8}B{sub 30} metallic glass with a high thermal stability and excellent soft magnetic properties has been investigated. After 14 h of milling, the obtained powders were found to consist mainly of an amorphous phase and a small fraction of the (Co,Fe){sub 21}Ta{sub 2}B{sub 6} nanocrystals. The changes in the reduced pair correlation functions suggest noticeable changes in the atomic structure of the amorphous upon ball milling. Furthermore, it has been shown that milling is accompanied by introduction of compressive and dilatational sites inmore » the glassy phase and increasing the fluctuation of the atomic-level hydrostatic stress without affecting the coordination number of the nearest neighbors. Ball milling has decreased the thermal stability and significantly affected the magnetic properties through increasing the saturation magnetization, Curie temperature of the amorphous phase and coercivity. - Highlights: • Ball milling affected the atomic structure of Co{sub 40}Fe{sub 22}Ta{sub 8}B{sub 30} metallic glass. • Mechanically-induced crystallization started after 4 h milling. • Milling increased the fluctuation of the atomic-level hydrostatic stress in glass. • Ball milling influenced the thermal stability and magnetic properties.« less

Peculiarities of FeSi phonon spectrum induced by a change of atomic volume

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

Parshin, P. P., E-mail: Parshin-PP@nrcki.ru, E-mail: neupar45@yandex.ru; Chumakov, A. I.; Alekseev, P. A.

2016-12-15

We analyze in detail the results of experimental investigations of the evolution of the thermal vibration spectra for iron atoms in iron monosilicide FeSi depending on two external parameters, viz., temperature T (in the range 46–297 K at pressure P = 0.1 MPa) and pressure P (in the range 0.1 MPa–43 GPa at temperature T = 297 K), obtained by nuclear inelastic scattering of synchrotron radiation. The decrease of the atomic volume is accompanied by a rearrangement of the phonon spectrum, which is manifested, in particular, in the splitting of the low-energy peak in the spectrum and in an increasemore » of the energy for all phonons. The changes of the average energy of the iron atom vibrational spectrum and of the Debye energy with decreasing atomic volume are analyzed. Different versions of FeSi electron spectrum variation, which can be used to explain the observed phonon anomalies, are considered.« less

Temperature and Time Constraints on Dissolution, Fe-Mg Exchange and Zoning between Relict Forsterite and Chondrule Melt - Implications for Thermal History of Chondrules

NASA Astrophysics Data System (ADS)

Ustunisik, G. K.; Ebel, D. S. S.; Walker, D.

2016-12-01

The chemical and textural characteristics of different generations of relict olivine grains in chondrules record the fact that chondrules were re-melted. Mineral dissolution, Fe-Mg exchange, and zoning within the relict crystals constrain the T-t aspects of this re-melting process. Here, we performed isothermal and dynamic cooling experiments at LDEO of Columbia University. For each run, a cubic crystal of known dimensions of Mogok forsterite (Fo99) was placed in synthetic Type IIA chondrule mesostasis with 4.92 wt% FeO (TLiq 1315ºC). Pressed pellets of this mixture were hung on Pt-wire loops and inserted in vertical Deltech furnace where CO-CO2 gas mixtures kept fO2 IW-1. For isothermal experiments, each charge was heated to 1428ºC, 1350ºC, 1250ºC, and 1150ºC and was held there from 20 mins to several days (>3 days) before drop-quenching into cold water. The dynamic crystallization experiments were held at 1428ºC for 20 mins, cooled at rates of 75ºC, 722ºC, and 1444ºC/hr to 1000ºC and then water quenched. X-ray-CT and EMPA at AMNH were used to image the partially resorbed/zoned olivines in 3-D before and after each run to observe textural evolution of the crystal shapes and volumes and to determine chemical changes. The isothermal experiments at 1150 and 1250ºC for 20 mins, produced no bulk FeO diffusion into the Mogok forsterite. Very minor Fe-Mg exchange at the crystal rims gives slight MgO zoning within the nearby melt. With increasing duration (1 hr and 22 hrs), at 1250ºC, embayments of melt form into the rims of the crystal (amplified at 22 hrs) with significant Fe-Mg exchange. FeO content of Mogok increased with major MgO zonation within nearby melt. At 1150ºC, the same increase in FeO in Mogok and zonation in nearby glass could only be achieved in >3 days experiment. At high Ts (1428ºC) in 20 min run, 75 volume % of Mogok forsterite has been dissolved into the melt. Resorption erodes the Fe-Mg exchange at the rims of the crystal. At longer duration experiments (1250ºC, 22 hrs and 1150ºC, >3days) quench olivine crystals and silica (cristobalite) have been observed within the melt along with low-Ca pyroxene along the edges of the Mogok forsterite. The metastable pyroxene acts as a protective cover thwarting Fe-Mg exchange between Mogok and Fe-bearing melt. The cristobalite occurred as a result of melt fractionation.

Studies of the reactivity of the ferrihydrite surface by iron isotopic exchange and Mossbauer spectroscopy

USGS Publications Warehouse

Rea, Brigid A.; Davis, James A.; Waychunas , Glenn A.

1994-01-01

Two-line ferrihydrite is an important adsorbent of many toxics in natural and anthropogenic systems; however, the specific structural sites responsible for the high adsorption capacity are not well understood. A combination of chemical and spectroscopic techniques have been employed in this study to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59Fe-NTA solutions, while the second population of sites, referred to as non-labile, exhibited a much slower rate of isotopic exchange. Adsorbed arsenate reduced the degree of exchange by labile sites, indicating that the anion blocked or greatly inhibited the rate of exchange of these sites. Mössbauer spectra were collected from a variety of samples including 56Fe-ferrihydrite samples with 57Fe in labile sites, samples containing 57Fe throughout the structure, and samples with 57Fe in non-labile sites. The spectra showed characteristic broad doublets signifying poor structural order. Refined fits of the spectra indicated that labile sites have larger quadrupole splitting, hence more local distortion, than non-labile sites. In all cases, the spectra demonstrated some degree of asymmetry, indicating a distribution of Fe environments in ferrihydrite. Overall spectral findings, combined with recent EXAFS results (Waychunas et al., 1993), indicate that labile sites likely are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population of surface sites. Mössbauer spectra of samples containing adsorbed arsenate indicated that the anion may slightly decrease the distortion of labile sites and stabilized the structure as a whole by bidentate bonding.

Tetra-butyl-ammonium tetra-kis-(trimethyl-silanolato-κO)ferrate(III).

PubMed

Hay, Michael; Staples, Richard; Lee, Andre

2012-09-01

In the title salt, (C(16)H(36)N)[Fe(C(3)H(9)OSi)(4)], the cation contains a central N atom bonded to four n-butyl alkyl groups in a tetra-hedral arrangement, while the anion contains a central Fe(III) atom tetra-hedrally coordinated by four trimethyl-silanolate ligands.

Exchange coupled CoPt/FePtC media for heat assisted magnetic recording

NASA Astrophysics Data System (ADS)

Dutta, Tanmay; Piramanayagam, S. N.; Ru, Tan Hui; Saifullah, M. S. M.; Bhatia, C. S.; Yang, Hyunsoo

2018-04-01

L10 FePtC granular media are being studied as potential future magnetic recording media and are set to be used in conjunction with heat assisted magnetic recording (HAMR) to enable recording at write fields within the range of current day recording heads. Media structures based on a FePtC storage layer and a capping layer can alleviate the switching field distribution (SFD) requirements of HAMR and reduce the noise originating from the writing process. However, the current designs suffer from SFD issues due to high temperature writing. To overcome this problem, we study a CoPt/FePtC exchange coupled composite structure, where FePtC serves as the storage layer and CoPt (with higher Curie temperature, Tc) as the capping layer. CoPt remains ferromagnetic at near Tc of FePtC. Consequently, the counter exchange energy from CoPt would reduce the noise resulting from the adjacent grain interactions during the writing process. CoPt/FePtC bilayer samples with different thicknesses of CoPt were investigated. Our studies found that CoPt forms a continuous layer at a thickness of 6 nm and leads to considerable reduction in the saturation field and its distribution.

Microplasma Jet Synthesis of Ni-Fe Oxide Films for Magnetic Exchange Bias and Electrocatalytic Studies

NASA Astrophysics Data System (ADS)

Pebley, Andrew Christian

Ni-Fe oxides have received significant interest from the scientific community because they have attractive magnetic and electrochemical properties for use in next generation data storage and energy conversion technologies. For example, the NiFe2O4/NiO nanogranular system exhibits the exchange bias effect, a magnetic phenomenon occurring at the interface of a ferro- or ferrimagnet (FM or FiM) and an antiferromagnet (AFM), where the AFM acts to increase the magnetic hardness of the corresponding FM or FiM. Additionally, doping of NiO with Fe has resulted in remarkably high catalytic activities for water splitting, a potential clean energy alternative to fossil fuels. A key challenge in implementing these Ni-Fe oxides for magnetic and electrocatalytic applications is the ability to control film morphology, crystallinity, composition, chemical phase, and doping during synthesis. Moreover, how these physiochemical properties effect magnetic and electrochemical behavior in the Ni-Fe oxide system is not fully understood. This dissertation focuses on the development and use of a novel synthesis technique, known as microplasma (MP) jet-based deposition, for the fabrication of biphasic NiFe2O4 (FiM)/NiO (AFM) and Fe-doped NiO nanostructured films for fundamental studies of exchange bias and electrocatalysis, respectively. The goal of this work was to understand how MP operation and deposition conditions (e.g., precursor composition, flux, substrate temperature, and post-deposition heat treatment) influence Ni-Fe oxide growth and film microstructure. Specifically, the role of composition, phase fraction, grain size, temperature, and interfacial density on exchange bias phenomena in NiFe 2O4/NiO nanogranular films was investigated. MP jets were also used to realize metastable Fe-doped NiO films with high surface area to assess how doping affects the electrochemical properties of NiO for the oxygen evolution reaction (OER). Biphasic NiFe2O4/NiO films of different composition were synthesized using MP jets and post-deposition annealing. The exchange bias effect (HE) and enhanced coercivity (HC) were seen at 300 K, which was the first time that HE has been reported at room temperature in the NiFe2O4/NiO nanogranular system. These values increased with Ni incorporation, and were rationalized as due to increased NiFe2O4/NiO interfacial density. Moreover, MP jet deposition of NiFe2O4/NiO films on heated substrates was explored to realize higher interfacial densities. HE was observed at low temperatures in these films, but not at room temperature, which was attributed to spin glass coupling arising from structurally disordered interfaces. Through systematic post-deposition heat treatments, it was found that spin glass-like phases disappeared after annealing, and the observed HE was due to direct exchange coupling between the NiO and NiFe2O 4 phases. MP jets were also used to deposit high-surface area, metastable Fe-doped NiO films of different composition (up to 20% Fe on a metals basis) at room temperature on indium tin oxide (ITO) substrates for OER catalysis. It was seen that Fe fully incorporated into the NiO rocksalt lattice, decreasing the overpotential for OER (i.e., 360 to 310 mV at 10 mA/cm2 for NiO and Ni0.95Fe0.05O, respectively). Turnover frequency (TOF) calculations demonstrated an improvement in the catalytic activity of the NiO surface with Fe doping, and chronopotentiometry measurements verified that Fe-doped NiO films were mechanically and chemically robust during extended operation under OER conditions. Overall, this work demonstrates the potential of MP jet deposition as a versatile, one-step approach to realize multi-phase and doped nanostructured oxide films with high interfacial densities and surface areas for a variety of magnetic and energy conversion applications.

Effects of trace elements on the crystal field parameters of Nd ions at the surface of Nd{sub 2}Fe{sub 14}B grains

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

Toga, Yuta; Suzuki, Tsuneaki; Sakuma, Akimasa, E-mail: sakuma@solid.apph.tohoku.ac.jp

2015-06-14

Using first-principles calculations, we investigate the positional dependence of trace elements such as O and Cu on the crystal field parameter A{sub 2}{sup 0}, proportional to the magnetic anisotropy constant K{sub u} of Nd ions placed at the surface of Nd{sub 2}Fe{sub 14}B grains. The results suggest the possibility that the A{sub 2}{sup 0} parameter of Nd ions at the (001) surface of Nd{sub 2}Fe{sub 14}B grains exhibits a negative value when the O or Cu atom is located near the surface, closer than its equilibrium position. At the (110) surface, however, O atoms located at the equilibrium position providemore » a negative A{sub 2}{sup 0}, while for Cu additions A{sub 2}{sup 0} remains positive regardless of Cu's position. Thus, Cu atoms are expected to maintain a positive local K{sub u} of surface Nd ions more frequently than O atoms when they approach the grain surfaces in the Nd-Fe-B grains.« less

Fe embedded in ice: The impacts of sublimation and energetic particle bombardment

NASA Astrophysics Data System (ADS)

Frankland, Victoria L.; Plane, John M. C.

2015-05-01

Icy particles containing a variety of Fe compounds are present in the upper atmospheres of planets such as the Earth and Saturn. In order to explore the role of ice sublimation and energetic ion bombardment in releasing Fe species into the gas phase, Fe-dosed ice films were prepared under UHV conditions in the laboratory. Temperature-programmed desorption studies of Fe/H2O films revealed that no Fe atoms or Fe-containing species co-desorbed along with the H2O molecules. This implies that when noctilucent ice cloud particles sublimate in the terrestrial mesosphere, the metallic species embedded in them will coalesce to form residual particles. Sputtering of the Fe-ice films by energetic Ar+ ions was shown to be an efficient mechanism for releasing Fe into the gas phase, with a yield of 0.08 (Ar+ energy=600 eV). Extrapolating with a semi-empirical sputtering model to the conditions of a proton aurora indicates that sputtering by energetic protons (>100 keV) should also be efficient. However, the proton flux in even an intense aurora will be too low for the resulting injection of Fe species into the gas phase to compete with that from meteoric ablation. In contrast, sputtering of the icy particles in the main rings of Saturn by energetic O+ ions may be the source of recently observed Fe+ in the Saturnian magnetosphere. Electron sputtering (9.5 keV) produced no detectable Fe atoms or Fe-containing species. Finally, it was observed that Fe(OH)2 was produced when Fe was dosed onto an ice film at 140 K (but not at 95 K). Electronic structure theory shows that the reaction which forms this hydroxide from adsorbed Fe has a large barrier of about 0.7 eV, from which we conclude that the reaction requires both translationally hot Fe atoms and mobile H2O molecules on the ice surface.

Role of chalcogen vapor annealing in inducing bulk superconductivity in Fe1 +yTe1 -xSex

NASA Astrophysics Data System (ADS)

Lin, Wenzhi; Ganesh, P.; Gianfrancesco, Anthony; Wang, Jun; Berlijn, Tom; Maier, Thomas A.; Kalinin, Sergei V.; Sales, Brian C.; Pan, Minghu

2015-02-01

Recent investigations have shown that Fe1 +yTe1 -xSex can be made superconducting by annealing it in Se and O vapors. The current lore is that these chalcogen vapors induce superconductivity by removing the magnetic excess Fe atoms. To investigate this phenomenon, we performed a combination of magnetic susceptibility, specific heat, and transport measurements together with scanning tunneling microscopy and spectroscopy and density functional theory calculations on Fe1 +yTe1 -xSex treated with Te vapor. We conclude that the main role of the Te vapor is to quench the magnetic moments of the excess Fe atoms by forming FeTem (m ≥1 ) complexes. We show that the remaining FeTem complexes are still damaging to the superconductivity and therefore that their removal potentially could further improve superconductive properties in these compounds.

Fabrication of Mg-X-O (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn) barriers for magnetic tunnel junctions

NASA Astrophysics Data System (ADS)

Yakushiji, K.; Kitagawa, E.; Ochiai, T.; Kubota, H.; Shimomura, N.; Ito, J.; Yoda, H.; Yuasa, S.

2018-05-01

We fabricated magnetic tunnel junctions with a 3d-transition material(X)-doped MgO (Mg-X-O) barrier, and evaluated the effect of the doping on magnetoresistance (MR) and microstructure. Among the variations of X (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn), X = Fe and Mn showed a high MR ratio of more than 100%, even at a low resistance-area product of 3 Ωμm2. The microstructure analysis revealed that (001) textured orientation formed for X = Fe and Mn despite substantial doping (about 10 at%). The elemental mappings indicated that Fe atoms in the Mg-Fe-O barrier were segregated at the interfaces, while Mn atoms were evenly involved in the Mg-Mn-O barrier. This suggests that MgO has high adaptability for Fe and Mn dopants in terms of high MR ratio.

Modulating the electronic and magnetic properties of bilayer borophene via transition metal atoms intercalation: from metal to half metal and semiconductor

NASA Astrophysics Data System (ADS)

Zhang, Xiuyun; Sun, Yi; Ma, Liang; Zhao, Xinli; Yao, Xiaojing

2018-07-01

Borophene, a two-dimensional monolayer made of boron atoms, has attracted wide attention due to its appealing properties. Great efforts have been devoted to fine tuning its electronic and magnetic properties for desired applications. Herein, we theoretically investigate the versatile electronic and magnetic properties of bilayer borophene (BLB) intercalated by 3d transition metal (TM) atoms, TM@BLBs (TM = Ti-Fe), using ab initio calculations. Four allotropes of AA-stacking (α 1-, β-, β 12- and χ 3-) BLBs with different intercalation concentrations of TM atoms are considered. Our results show that the TM atoms are strongly bonded to the borophene layers with fairly large binding energies, around 6.31 ∼ 15.44 eV per TM atom. The BLBs with Cr and Mn intercalation have robust ferromagnetism, while for the systems decorated with Fe atoms, fruitful magnetic properties, such as nonmagnetic, ferromagnetic or antiferromagnetic, are identified. In particular, the α 1- and β-BLBs intercalated by Mn or Fe atom can be transformed into a semiconductor, half metal or graphene-like semimetal. Moreover, some heavily doped TM@BLBs expose high Curie temperatures above room temperature. The attractive properties of TM@BLBs entail an efficient way to modulate the electronic and magnetic properties of borophene sheets for advanced applications.

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

PubMed

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.

Challenges in computational evaluation of redox and magnetic properties of Fe-based sulfate cathode materials of Li- and Na-ion batteries

NASA Astrophysics Data System (ADS)

Shishkin, Maxim; Sato, Hirofumi

2017-06-01

Several Fe-based sulfates have been proposed recently as cathode materials characterized by a high average operating voltage (i.e. Li2Fe(SO4)2 and Na2Fe2(SO4)3) or low fabrication temperature (e.g. Na2Fe(SO4)2·2H2O)). In this work, we apply three methods to evaluate the redox potentials and magnetic properties of these materials: (1) local density functional theory (DFT) in Perdew-Burke-Ernzerhof parametrization; (2) rotationally invariant DFT  +  U and (3) DFT  +  U with magnetic exchange, suggested herein. The U parameters used for DFT  +  U calculations have been evaluated by using a linear response method (this applies to DFT  +  U as well as DFT  +  U calculations with a magnetic exchange term). Moreover, we have performed adjustments of U and, for the case of magnetic exchange, J parameters, to find better agreement with experimental measurements of redox and magnetic properties. We find that a self-consistent DFT  +  U/linear response approach yields quite overestimated redox potentials as compared to experiment. On the other hand, we also show that DFT  +  U calculations are not capable of providing a reasonably accurate description of both redox and magnetic properties for the case of Li2Fe(SO4)2, even when adjusted U parameters are employed. As a solution, we demonstrate that a DFT  +  U methodology augmented by a magnetic exchange term potentially provides more precise values for both the redox potentials and the magnetic moments of the Fe ions in the studied materials. Thus our work shows that for a more accurate description of redox and magnetic properties, further extensions of the DFT  +  U method, such as inclusion of the contribution of magnetic exchange, should be considered.

NH3 molecule adsorption on spinel-type ZnFe2O4 surface: A DFT and experimental comparison study

NASA Astrophysics Data System (ADS)

Zou, Cong-yang; Ji, Wenchao; Shen, Zhemin; Tang, Qingli; Fan, Maohong

2018-06-01

Ammonia (NH3) is a caustic environment pollutant which contributes to haze formation and water pollution. Zinc ferrite (ZnFe2O4) exhibits good catalytic activity in NH3 removal. The density functional theory (DFT) was applied to explore the interaction mechanism of NH3 molecule adsorption on spinel-type ZnFe2O4 (1 1 0) surface with GGA-PW91 method in atomic and electronic level. The results indicated that NH3 molecule preferred to adsorb on surface Zn atom with the formation of H3Nsbnd Zn coordinate bond over ZnFe2O4 (1 1 0) surface. The H3Nsbnd Zn state was exothermic process with adsorption energy of -203.125 kJ/mol. About 0.157e were transferred from NH3 molecule to the surface which resulted in strong interaction. Higher activation degree occurred in H3Nsbnd Zn configuration with two Nsbnd H bonds elongated and NH3 structure became more flat on the surface. The PDOS change of NH3 molecule was consistent with the result of adsorption energy. It was concluded that s orbital of NH3 (N) and s, p orbitals of Zn atom overlapped at -0.619 Ha. The p orbital of NH3 (N) has interaction with d orbital of Zn atom suggesting the hybridization between them. Based on NH3 removal experimental and XPS spectra results, NH3sbnd ZnFe2O4 interaction was mainly depended on the coordination between Zn atom and NH3 molecule. The DFT calculations have deepened our understanding on NH3sbnd ZnFe2O4 interaction system.

Iron hydrides formation in interstellar clouds

NASA Astrophysics Data System (ADS)

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

1980-07-01

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

Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

PubMed

Chen, Yiling; Zhang, Huichun

2013-10-01

Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

Iron rich low cost superalloys. Ph.D. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Wayne, S. F.

1985-01-01

An iron-rich low-cost superalloy was developed. The alloy, when processed by conventional chill casting, has physical and mechanical properties that compare favorably with existing nickel and cobalt based superalloys while containing significantly lower amounts of strategic elements. Studies were also made on the properties of Cr(20)-Mn(10)-C(3.4)-Fe(bal.), a eutectic alloy processed by chill casting and directional solidification which produced an aligned microstructure consisting of M7C3 fibers in a gamma-Fe matrix. Thermal expansion of the M7C3 (M = Fe, Cr, Mn) carbide lattice was measured up to 800 C and found to be highly anisotropic, with the a-axis being the predominant mode of expansion. Repetitive impact sliding wear experiments performed with the Fe rich eutectic alloy showed that the directionally solidified microstructure greatly improved the alloy's wear resistance as compared to the chill cast microstructure and conventional nickel base superalloys. Studies on the molybdenum cementite phase prove that the crystal structure of the xi phase is not orthorhombic. The crystal structure of the xi phase is made up of octahedra building elements consisting of four Mo and two Fe atoms and trigonal prisms consisting of four Fe and two Mo atoms. The voids are occupied by carbon atoms. The previous chemical formula for the molybdenum cementite MoFe2C is now clearly seen to be Mo12Fe22C10.

From solid solution to cluster formation of Fe and Cr in α-Zr

NASA Astrophysics Data System (ADS)

Burr, P. A.; Wenman, M. R.; Gault, B.; Moody, M. P.; Ivermark, M.; Rushton, M. J. D.; Preuss, M.; Edwards, L.; Grimes, R. W.

2015-12-01

To understand the mechanisms by which the re-solution of Fe and Cr additions increase the corrosion rate of irradiated Zr alloys, the solubility and clustering of Fe and Cr in model binary Zr alloys was investigated using a combination of experimental and modelling techniques - atom probe tomography (APT), x-ray diffraction (XRD), thermoelectric power (TEP) and density functional theory (DFT). Cr occupies both interstitial and substitutional sites in the α-Zr lattice; Fe favours interstitial sites, and a low-symmetry site that was not previously modelled is found to be the most favourable for Fe. Lattice expansion as a function of Fe and Cr content in the α-Zr matrix deviates from Vegard's law and is strongly anisotropic for Fe additions, expanding the c-axis while contracting the a-axis. Matrix content of solutes cannot be reliably estimated from lattice parameter measurements, instead a combination of TEP and APT was employed. Defect clusters form at higher solution concentrations, which induce a smaller lattice strain compared to the dilute defects. In the presence of a Zr vacancy, all two-atom clusters are more soluble than individual point defects and as many as four Fe or three Cr atoms could be accommodated in a single Zr vacancy. The Zr vacancy is critical for the increased apparent solubility of defect clusters; the implications for irradiation induced microstructure changes in Zr alloys are discussed.

Magnetic and hyperthermia properties of CoxFe3-xO4 nanoparticles synthesized via cation exchange

NASA Astrophysics Data System (ADS)

Mohapatra, Jeotikanta; Xing, Meiying; Liu, J. Ping

2018-05-01

We demonstrate magnetic and hyperthermia properties of CoxFe3-xO4 (x = 0, 0.1, 0.3 and 0.5) nanoparticles synthesized via a simple cation exchange reaction of ˜12 nm Fe3O4 nanoparticles. The substitution of Fe cations with Co2+ ions leads to enhanced magnetocrystalline anisotropy and coercivity of the pristine superparamagnetic Fe3O4 nanoparticles. Hyperthermia measurement shows that by controlling the Co content (x = 0 to 0.5) in CoxFe3-xO4 nanoparticles, their specific absorption rate (SAR) can be greatly improved from 132 to 534 W/g. The strong enhancement in SAR value is attributed to the increased anisotropy and coercivity. Moreover, with the increase of ac magnetic field from 184 to 491 Oe, the SAR values of Fe3O4 and Co0.5Fe2.5O4 nanoparticles increase from 81 to 132 W/g and 220 to 534 W/g, respectively.

In situ TEM study of electron-beam radiation induced boron diffusion and effects on phase and microstructure evolution in nanostructured CoFeB/SiO2 thin film

NASA Astrophysics Data System (ADS)

Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.

2017-01-01

Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.

Thermodynamic stability of stoichiometric LaFeO3 and BiFeO3: a hybrid DFT study.

PubMed

Heifets, Eugene; Kotomin, Eugene A; Bagaturyants, Alexander A; Maier, Joachim

2017-02-01

BiFeO 3 perovskite attracts great attention due to its multiferroic properties and potential use as a parent material for Bi 1-x Sr x FeO 3-δ and Bi 1-x Sr x Fe 1-y Co y O 3-δ solid solutions in intermediate temperature cathodes of oxide fuel cells. Another iron-based LaFeO 3 perovskite is the end member for well-known solid solutions (La 1-x Sr x Fe 1-y Co y O 3-δ ) used for oxide fuel cells and other electrochemical devices. In this study an ab initio hybrid functional approach was used for the study of the thermodynamic stability of both LaFeO 3 and BiFeO 3 with respect to decompositions to binary oxides and to elements, as a function of temperature and oxygen pressure. The localized (LCAO) basis sets describing the crystalline electron wave functions were carefully re-optimized within the CRYSTAL09 computer code. The results obtained by considering Fe as an all-electron atom and within the effective core potential technique are compared in detail. Based on our calculations, the phase diagrams were constructed allowing us to predict the stability region of stoichiometric materials in terms of atomic chemical potentials. This permits determining the environmental conditions for the existence of stable BiFeO 3 and LaFeO 3 . These conditions were presented as contour maps of oxygen atoms' chemical potential as a function of temperature and partial pressure of oxygen gas. A similar analysis was also performed using the experimental Gibbs energies of formation. The obtained phase diagrams and contour maps are compared with the calculated ones.

Near surface silicide formation after off-normal Fe-implantation of Si(001) surfaces

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

Khanbabaee, B., E-mail: khanbabaee@physik.uni-siegen.de; Pietsch, U.; Lützenkirchen-Hecht, D.

We report on formation of non-crystalline Fe-silicides of various stoichiometries below the amorphized surface of crystalline Si(001) after irradiation with 5 keV Fe{sup +} ions under off-normal incidence. We examined samples prepared with ion fluences of 0.1 × 10{sup 17} and 5 × 10{sup 17} ions cm{sup −2} exhibiting a flat and patterned surface morphology, respectively. Whereas the iron silicides are found across the whole surface of the flat sample, they are concentrated at the top of ridges at the rippled surface. A depth resolved analysis of the chemical states of Si and Fe atoms in the near surface region was performed by combining X-raymore » photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) using synchrotron radiation. The chemical shift and the line shape of the Si 2p core levels and valence bands were measured and associated with the formation of silicide bonds of different stoichiometric composition changing from an Fe-rich silicides (Fe{sub 3}Si) close to the surface into a Si-rich silicide (FeSi{sub 2}) towards the inner interface to the Si(001) substrate. This finding is supported by XAS analysis at the Fe K-edge which shows changes of the chemical environment and the near order atomic coordination of the Fe atoms in the region close to surface. Because a similar Fe depth profile has been found for samples co-sputtered with Fe during Kr{sup +} ion irradiation, our results suggest the importance of chemically bonded Fe in the surface region for the process of ripple formation.« less

Research Update: Spatially resolved mapping of electronic structure on atomic level by multivariate statistical analysis

NASA Astrophysics Data System (ADS)

Belianinov, Alex; Ganesh, Panchapakesan; Lin, Wenzhi; Sales, Brian C.; Sefat, Athena S.; Jesse, Stephen; Pan, Minghu; Kalinin, Sergei V.

2014-12-01

Atomic level spatial variability of electronic structure in Fe-based superconductor FeTe0.55Se0.45 (Tc = 15 K) is explored using current-imaging tunneling-spectroscopy. Multivariate statistical analysis of the data differentiates regions of dissimilar electronic behavior that can be identified with the segregation of chalcogen atoms, as well as boundaries between terminations and near neighbor interactions. Subsequent clustering analysis allows identification of the spatial localization of these dissimilar regions. Similar statistical analysis of modeled calculated density of states of chemically inhomogeneous FeTe1-xSex structures further confirms that the two types of chalcogens, i.e., Te and Se, can be identified by their electronic signature and differentiated by their local chemical environment. This approach allows detailed chemical discrimination of the scanning tunneling microscopy data including separation of atomic identities, proximity, and local configuration effects and can be universally applicable to chemically and electronically inhomogeneous surfaces.

Extrinsic labeling method may not accurately measure Fe absorption from cooked pinto beans (Phaseolus vulgaris): comparison of extrinsic and intrinsic labeling of beans.

PubMed

Jin, Fuxia; Cheng, Zhiqiang; Rutzke, Michael A; Welch, Ross M; Glahn, Raymond P

2008-08-27

Isotopic labeling of food has been widely used for the measurement of Fe absorption in determining requirements and evaluating the factors involved in Fe bioavailability. An extrinsic labeling technique will not accurately predict the total Fe absorption from foods unless complete isotopic exchange takes place between an extrinsically added isotope label and the intrinsic Fe of the food. We examined isotopic exchange in the case of both white beans and colored beans (Phaseolus vulgaris) with an in vitro digestion model. There are significant differences in (58)Fe/(56)Fe ratios between the sample digest supernatant and the pellet of extrinsically labeled pinto bean. The white bean digest shows significantly better equilibration of the extrinsic (58)Fe with the intrinsic (56)Fe. In contrast to the extrinsically labeled samples, both white and red beans labeled intrinsically with (58)Fe demonstrated consistent ratios of (58)Fe/(56)Fe in the bean meal, digest, supernatant, and pellet. It is possible that the polyphenolics in the bean seed coat may bind Fe and thus interfere with extrinsic labeling of the bean meals. These observations raise questions on the accuracy of studies that used extrinsic tags to measure Fe absorption from beans. Intrinsic labeling appears necessary to accurately measure Fe bioavailability from beans.

Structure of the orthorhombic form of Mn(2)Al(7), Fe(2)Al(7), and (Mn(0.7)Fe(0.3))(2)Al(7) that by twinning produces grains with decagonal point-group symmetry.

PubMed

Pauling, L

1988-04-01

Analysis of electron diffraction photographs of grains of Mn(2)Al(7), Fe(2)Al(7), and (Mn(0.7)Fe(0.3))(2)Al(7) leads to the conclusion that they are 5-fold twins of a 1664-atom orthorhombic crystal with a = 32.86 A, b = 31.23 A, and c = 24.80 A and with 16 icosahedral clusters of 104 atoms in positions shifted by small amounts from those of the cubic beta-tungsten structure.

Structure of the orthorhombic form of Mn2Al7, Fe2Al7, and (Mn0.7Fe0.3)2Al7 that by twinning produces grains with decagonal point-group symmetry

PubMed Central

Pauling, Linus

1988-01-01

Analysis of electron diffraction photographs of grains of Mn2Al7, Fe2Al7, and (Mn0.7Fe0.3)2Al7 leads to the conclusion that they are 5-fold twins of a 1664-atom orthorhombic crystal with a = 32.86 Å, b = 31.23 Å, and c = 24.80 Å and with 16 icosahedral clusters of 104 atoms in positions shifted by small amounts from those of the cubic β-tungsten structure. PMID:16593921

Exploiting magnetic properties of Fe doping in zirconia. From first-principles simulations to the experimental growth and characterization of thin films

NASA Astrophysics Data System (ADS)

Sangalli, Davide; Cianci, Elena; Lamperti, Alessio; Ciprian, Roberta; Albertini, Franca; Casoli, Francesca; Lupo, Pierpaolo; Nasi, Lucia; Campanini, Marco; Debernardi, Alberto

2013-05-01

In this study we explore, both from theoretical and experimental side, the effect of Fe doping in ZrO2 (ZrO2:Fe). By means of first principles simulation, we study the magnetization density and the magnetic interaction between Fe atoms. We also consider how this is affected by the presence of oxygen vacancies and compare our findings with models based on impurity band [J.M.D. Coey, M. Venkatesan, C.B. Fitzgerald, Nat. Mater. 4, 173 (2005)] and carrier mediated magnetic interaction [T. Dietl, H. Ohno, F. Matsukura, J. Cibert, D. Ferrand, Science 287, 1019 (2000)]. Experimentally, thin films (≈20 nm) of ZrO2:Fe at high doping concentration are grown by atomic layer deposition. We provide experimental evidence that Fe is uniformly distributed in the ZrO2 by transmission electron microscopy and energy dispersive X-ray mapping, while X-ray diffraction evidences the presence of the fluorite crystal structure. Alternating gradient force magnetometer measurements show magnetic signal at room temperature, however, with low magnetic moment per atom. Results from experimental measures and theoretical simulations are compared.

Changes in the state of iron atoms in Zr alloys during corrosion tests in an autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.; Kargin, N. I.; Petrov, V. I.

2014-04-01

Mössbauerinvestigations were carried out on oxide films formed on specimens of zirconium alloys Zr-1.0 %wtFe-1.2 %wtSn-0.5 %wtCr subjected to corrosion in steam-water environment at a temperature of 360 °C and at a pressure of 16.8 MPa with lithium and boron additions, and on Zr-1.4 %wtFe-0.7 %wtCr corroded in steam-water environment at 350 °C and 16.8 MPa as well as in steam-water environment at 500 °C and 10 MPa. In the metal part of the samples, under the oxide film, the iron atoms are in form of intermetallic precipitates of Zr(Fe, Cr)2. The corrosion process decomposes the intermetallic precipitates and particles are formed of metallic iron with inclusions of chromium atoms -Fe(Cr), α-Fe2O3 and Fe3O4 compounds. Part of the iron ions are in divalent and part in trivalent paramagnetic states. It is proposed that some part of the iron containing oxide precipitates in the oxide film may be in the form of nanoparticles which pass from the superparamagnetic to the ferromagnetic state with decreasing temperature.

Atomic scale study of grain boundary segregation before carbide nucleation in Ni-Cr-Fe Alloys

NASA Astrophysics Data System (ADS)

Li, Hui; Xia, Shuang; Liu, Wenqing; Liu, Tingguang; Zhou, Bangxin

2013-08-01

Three dimensional chemical information concerning grain boundary segregation before carbide nucleation was characterized by atom probe tomography in two Ni-Cr-Fe alloys which were aged at 500 °C for 0.5 h after homogenizing treatment. B, C and Si atoms segregation at grain boundary in Alloy 690 was observed. B, C, N and P atoms segregation at grain boundary in 304 austenitic stainless steel was observed. C atoms co-segregation with Cr atoms at the grain boundaries both in Alloy 690 and 304 austenitic stainless steel was found, and its effect on the carbide nucleation was discussed. The amount of each segregated element at grain boundaries in the two Ni-Cr-Fe alloys were analyzed quantitatively. Comparison of the grain boundary segregation features of the two Ni-Cr-Fe alloys were carried out based on the experimental results. The impurity and solute atoms segregate inhomogeneously in the same grain boundary both in 304 SS and Alloy 690. The grain boundary segregation tendencies (Sav) are B (11.8 ± 1.4) > P (5.4 ± 1.4) > N (4.7 ± 0.3) > C (3.7 ± 0.4) in 304 SS, and B (6.9 ± 0.9) > C (6.7 ± 0.4) > Si (1.5 ± 0.2) in Alloy 690. Cr atoms may co-segregate with C atoms at grain boundaries before carbide nucleation at the grain boundaries both in 304 SS and Alloy 690. Ni atoms generally deplete at grain boundary both in 304 SS and Alloy 690. The literature shows that the Ni atoms may co-segregate with P atoms at grain boundaries [28], but the P atoms segregation do not leads to Ni segregation in the current study. In the current study, Fe atoms may segregate or deplete at grain boundary in Alloy 690. But Fe atoms generally deplete at grain boundary in 304 SS. B atoms have the strongest grain boundary segregation tendency both in 304 SS and Alloy 690. The grain boundary segregation tendency and Gibbs free energy of B in 304 SS is higher than in Alloy 690. C atoms are easy to segregate at grain boundaries both in 304 SS and Alloy 690. The grain boundary segregation tendency and Gibbs free energy of C in Alloy 690 is higher than in 304 SS, due to the higher bulk C concentration and the site competition of P atoms which segregate at grain boundary [29,30]. It is imply that the segregation tendency is influenced by the bulk concentration of the segregates. Si atoms slightly segregate at grain boundaries in Alloy 690, but do not segregate at grain boundaries in 304 SS. N and P atoms segregate at grain boundary in 304 SS, and their segregation Gibbs free energy are similar. N atoms may be exhausted by the TiN precipitated in the matrix and can not be observed in the grain boundary of Alloy 690 [19]. Mn atoms deplete at grain boundary in 304 SS. This phenomenon is similar to that of proton irradiation induced segregation in 304 SS [32]. B, C, N, P segregation Gibbs energies are similar both in 304 SS and Alloy 690. B and C atoms segregate at grain boundary both in Alloy 690 and 304 SS, P and N segregate at grain boundary in 304 SS. Si atoms segregate at grain boundary in Alloy 690, but do not segregate at grain boundary in 304 SS. Cr enriches at grain boundary both in Alloy 690 and 304 SS, although carbide does not nucleate. Ni and Fe may segregate, deplete or homogeneously distribute at grain boundary in Alloy 690, but they deplete at grain boundary in 304 SS. C and Cr atoms co-segregate at grain boundaries before carbide nucleation in Alloy 690 and 304 SS. Combination with other results in literatures, the evolution of Cr concentration at grain boundary should be enrichment at grain boundary before carbide nucleation, depletion at grain boundary after carbide precipitation, and healing after obvious growth of carbide. After aging treatment at 500 °C for 0.5 h, the total reduction of grain boundary free energy due to segregation is 27.489 kJ/mol for Alloy 690 and 45.207 kJ/mol for 304.

Orbital occupancy evolution across spin- and charge-ordering transitions in YBaFe2O5

NASA Astrophysics Data System (ADS)

Lindén, J.; Lindroos, F.; Karen, P.

2017-08-01

Thermal evolution of the Fe2+-Fe3+ valence mixing in YBaFe2O5 is investigated using Mössbauer spectroscopy. In this high-spin double-cell perovskite, the d6 and d5 Fe states differ by the single minority-spin electron which then controls all the spin- and charge-ordering transitions. Orbital occupancies can be extracted from the spectra in terms of the dxz , dz2 and either dx2-y2 (Main Article) or dxy (Supplement) populations of this electron upon conserving its angular momentum. At low temperatures, the minority-spin electrons fill up the ordered dxz orbitals of Fe2+, in agreement with the considerable orthorhombic distortion of the structure. Heating through the Verwey transition supplies 93% of the mixing entropy, at which point the predominantly mixing electron occupies mainly the dx2-y2 /dxy orbitals weakly bonding the two Fe atoms that face each other across the bases of their coordination pyramids. This might stabilize a weak coulombic checkerboard order suggested by McQueeney et alii in Phys. Rev. B 87(2013)045127. When the remaining 7% of entropy is supplied at a subsequent transition, the mixing electron couples the two Fe atoms predominantly via their dz2 orbitals. The valence mixing concerns more than 95% of the Fe atoms present in the crystalline solid; the rest is semi-quantitatively interpreted as domain walls and antiphase boundaries formed upon cooling through the Néel and Verwey-transition temperatures, respectively.

Role of chalcogen vapor annealing in inducing bulk superconductivity in Fe 1+yTe 1-xSe x [How does annealing in chalcogen vapor induce superconductivity in Fe 1+yTe -xSe x?

DOE PAGES

Lin, Wenzhi; Ganesh, P.; Gianfrancesco, Anthony; ...

2015-02-27

Recent investigations have shown that Fe 1+yTe 1-xSe x can be made superconducting by annealing it in Se and O vapors. The current lore is that these chalcogen vapors induce superconductivity by removing the magnetic excess Fe atoms. To investigate this phenomenon we performed a combination of magnetic susceptibility, specific heat and transport measurements together with scanning tunneling microscopy and spectroscopy and density functional theory calculations on Fe 1+yTe 1-xSe x treated with Te vapor. We conclude that the main role of the Te vapor is to quench the magnetic moments of the excess Fe atoms by forming FeTe mmore » (m ≥ 1) complexes. We show that the remaining FeTe m complexes are still damaging to the superconductivity and therefore that their removal potentially could further improve superconductive properties in these compounds.« less

Magnetic and electrical characterization of nickel-rich NiFe thin films synthesized by atomic layer deposition and subsequent thermal reduction.

PubMed

Espejo, A P; Zierold, R; Gooth, J; Dendooven, J; Detavernier, C; Escrig, J; Nielsch, K

2016-08-26

Nickel-rich NiFe thin films (Ni92Fe8, Ni89Fe11 and Ni83Fe17) were prepared by combining atomic layer deposition (ALD) with a subsequent thermal reduction process. In order to obtain Ni x Fe1-x O y films, one ALD supercycle was performed according to the following sequence: m NiCp2/O3, with m = 1, 2 or 3, followed by one FeCp2/O3 cycle. The supercycle was repeated n times. The thermal reduction process in hydrogen atmosphere was investigated by in situ x-ray diffraction studies as a function of temperature. The metallic nickel iron alloy thin films were investigated and characterized with respect to crystallinity, morphology, resistivity, and magnetism. As proof-of-concept magnetic properties of an array of Ni83Fe17, close to the perfect Permalloy stoichiometry, nanotubes and an isolated tube were investigated.

Magnetic and electrical characterization of nickel-rich NiFe thin films synthesized by atomic layer deposition and subsequent thermal reduction

NASA Astrophysics Data System (ADS)

Espejo, A. P.; Zierold, R.; Gooth, J.; Dendooven, J.; Detavernier, C.; Escrig, J.; Nielsch, K.

2016-08-01

Nickel-rich NiFe thin films (Ni92Fe8, Ni89Fe11 and Ni83Fe17) were prepared by combining atomic layer deposition (ALD) with a subsequent thermal reduction process. In order to obtain Ni x Fe1-x O y films, one ALD supercycle was performed according to the following sequence: m NiCp2/O3, with m = 1, 2 or 3, followed by one FeCp2/O3 cycle. The supercycle was repeated n times. The thermal reduction process in hydrogen atmosphere was investigated by in situ x-ray diffraction studies as a function of temperature. The metallic nickel iron alloy thin films were investigated and characterized with respect to crystallinity, morphology, resistivity, and magnetism. As proof-of-concept magnetic properties of an array of Ni83Fe17, close to the perfect Permalloy stoichiometry, nanotubes and an isolated tube were investigated.

Substrate temperature effect on the structural anisotropy in amorphous Tb-Fe films

NASA Astrophysics Data System (ADS)

Harris, V. G.; Hellman, F.; Elam, W. T.; Koon, N. C.

1993-05-01

Using extended x-ray absorption fine structures (EXAFS) measurements we have investigated the atomic environment around the Fe atom in a series of amorphous Tb0.26Fe0.74 films having different magnetic anisotropy energies owing to different deposition temperatures. The polarization properties of synchrotron radiation allowed the separate study of structure parallel and perpendicular to the sample plane. An anisotropy between these two structures was observed. Modeling results indicate this anisotropy is due to anisotropic pair correlations where the Fe-Fe pairs are statistically preferred in-plane and the Fe-Tb pairs out-of-plane. The amplitude of this anisotropy scales with both the substrate temperature and the magnetic anisotropy energy. A ≊1% in-plane compression of the Fe-Fe distance was measured between the in-plane and out-of-plane structure of the sample grown at 77 K. This sample had no detectable local chemical anisotropy suggesting that intrinsic stress plays an important role in determining its magnetic anisotropy.

NASA Astrophysics Data System (ADS)

Yao, Jinhuan; Li, Yanwei; Li, Xuanhai; Le, Shiru

2014-07-01

The geometric structure, electronic structure, and stability of In-substituted ZnFe2O4 (Zn7InFe16O32 and Zn8Fe15InO32) are investigated by the density functional theory at generalized gradient approximation level. Compared with the perfect ZnFe2O4 (Zn8Fe16O32), the unit cell volume of In-substituted ZnFe2O4 increases and the structure deforms slightly. The formation energy of In substitution for Zn is smaller than that of In substitution for Fe, indicating that Zn7InFe16O32 is easier to be formed than Zn8Fe15InO32. In substitution changes the properties of ZnFe2O4 from semiconducting character to metallic character. For ZnFe2O4 and In-substituted ZnFe2O4, the strength of O-Zn bond is stronger than O-Fe bond and both of them have a covalent bond character. The strength of O-In bond is similar to that of O-Zn bond in Zn7InFe16O32, but weaker than O-Fe in Zn8Fe15InO32. In substitution for Zn causes the strength of O-Fe bonds around In atom to weaken. In substitution for Fe causes the strength of O-Zn bonds around In atom to weaken obviously, while the strength of O-Fe bonds strengthen slightly.

Induced dipole-dipole coupling between two atoms at a migration resonance

NASA Astrophysics Data System (ADS)

Kaur, Maninder; Mian, Mahmood

2018-05-01

Results of numerical simulations for the resonant energy exchange phenomenon called Migration reaction between two cold Rydberg atoms are presented. The effect of spatial interatomic distance on the onset of peculiar coherent mechanism is investigated. Observation of Rabi-like population inversion oscillation at the resonance provides a clear signature of dipole induced exchange of electronic excitations between the atoms. Further we present the results for the dependence of expectation value of the interaction hamiltonian on the interatomic distance, which is responsible for energy exchange process. The results of this observation endorse the range of inter atomic distance within which the excitation exchange process occurs completely or partially. Migration process enhance the Rydberg-Rydberg interaction in the absence of an external field, under the condition of the zero permanent dipole moments. Our next observation sheds light on the fundamental mechanism of induced electric fields initiated by the oscillating dipoles in such energy exchange processes. We explore the dependence of induced electric field on the interatomic distance and angle between the dipoles highlighting the inverse power law dependence and anisotropic property of the field. We put forward an idea to utilise the coherent energy exchange process to build efficient and fast energy transfer channels by incorporating more atoms organised at successive distances with decreasing distance gradient.

Nanostructured double-layer FeO as nanotemplate for tuning adsorption of titanyl phthalocyanine molecules

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

Lu, Shuangzan; University of Chinese Academy of Sciences, Beijing 100049; Qin, Zhihui, E-mail: zhqin@wipm.ac.cn

2014-06-23

The growth, structure of Pt(111) supported double-layer FeO and the adsorption of titanyl phthalocyanine (TiOPc) molecules with tunable site and orientation were presented. According to the atomic-resolution STM image, the structure was rationalized as (8√3 × 8√3) R30°/Pt(111) nanostructure constructed by Fe species coordinated with different number of oxygen on top of non-rotated (8 × 8) FeO /Pt(111) structure. Due to the modulation of the stacking of Fe atoms in the second layer relative to the O atoms in the second layer and the underlying layer, the interface and total dipole moment periodically vary within (8√3 × 8√3) R30°/Pt(111) structure. The resulted periodically distributed dipole-dipole interactionmore » benefits the growth of TiOPc molecules with area-selective sites and molecular orientations. Thus, this study provides a reliable method to govern the adsorption process of the polar molecules for potential applications in future functional molecular devices.« less

Magnetization reversal and inverted magnetoresistance of exchange-biased spin valves with a gadolinium layer

NASA Astrophysics Data System (ADS)

Milyaev, M.; Naumova, L.; Chernyshova, T.; Proglyado, V.; Kamensky, I.; Krinitsina, T.; Ryabukhina, M.; Ustinov, V.

2017-03-01

FeMn-based spin valves with a gadolinium layer have been fabricated by magnetron sputtering. The magnetoresistive properties of the spin valves have been investigated at temperatures of 80-293 K. Temperature-induced switching between low- and high-resistance magnetic states has been revealed. Realization of the low- or high-resistance states depends on which magnetic moment dominates in the exchange-coupled Gd/CoFe, of Gd or CoFe. It has been shown that the switching temperature depends on the thickness of the gadolinium layer.

Tuning the surface anisotropy in Fe-doped NiO nanoparticles.

PubMed

Moura, K O; Lima, R J S; Coelho, A A; Souza-Junior, E A; Duque, J G S; Meneses, C T

2014-01-07

Ni(1-x)FexO nanoparticles have been obtained by the co-precipitation chemical route. X-ray diffraction analyses using Rietveld refinement have shown a slight decrease in the microstrain and mean particle size as a function of the Fe content. The zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves show superparamagnetic behavior at high temperatures and a low temperature peak (at T = 11 K), which is enhanced with increasing Fe concentration. Unusual behavior of the coercive field in the low temperature region and an exchange bias behavior were also observed. A decrease in the Fe concentration induces an increase in the exchange bias field. We argue that these behaviors can be linked with the strengthening of surface anisotropy caused by the incorporation of Fe ions.

Effect of surface Fe-S hybrid structure on the activity of the perfect and reduced α-Fe2O3(001) for chemical looping combustion

NASA Astrophysics Data System (ADS)

Xiao, Xianbin; Qin, Wu; Wang, Jianye; Li, Junhao; Dong, Changqing

2018-05-01

Sulfurization of the gradually reduced Fe2O3 surfaces is inevitable while Fe2O3 is used as an oxygen carrier (OC) for coal chemical looping combustion (CLC), which will result in formation of Fe-S hybrid structure on the surfaces. The Fe-S hybrid structure will directly alter the reactivity of the surfaces. Therefore, detailed properties of Fe-S hybrid structure over the perfect and reduced Fe2O3(001) surfaces, and its effect on the interfacial interactions, including CO oxidization and decomposition on the surfaces, were investigated by using density functional theory (DFT) calculations. The S atom prefers to chemically bind to Fe site with electron transfer from the surfaces to the S atom, and a deeper reduction of Fe2O3(001) leads to an increasing interaction between S and Fe. The formation of Fe-S hybrid structure alters the electronic properties of the gradually reduced Fe2O3(001) surfaces, promoting CO oxidation on the surfaces ranging from Fe2O3 to FeO, but depressing carbon deposition on the surfaces ranging from FeO to Fe. The sulfurized FeO acts as a watershed to realize relatively high CO oxidation rate and low carbon deposition. Results provided a fundamental understanding for controlling and optimizing the CLC processes.

Studies on hydrogenase

PubMed Central

YAGI, Tatsuhiko; HIGUCHI, Yoshiki

2013-01-01

Hydrogenases are microbial enzymes which catalyze uptake and production of H2. Hydrogenases are classified into 10 classes based on the electron carrier specificity, or into 3 families, [NiFe]-family (including [NiFeSe]-subfamily), [FeFe]-family and [Fe]-family, based on the metal composition of the active site. H2 is heterolytically cleaved on the enzyme (E) to produce EHaHb, where Ha and Hb have different rate constants for exchange with the medium hydron. X-ray crystallography unveiled the three-dimensional structures of hydrogenases. The simplest [NiFe]-hydrogenase is a heterodimer, in which the large subunit bears the Ni-Fe center buried deep in the protein, and the small subunit bears iron-sulfur clusters, which mediate electron transfer between the Ni-Fe center and the protein surface. Some hydrogenases have additional subunit(s) for interaction with their electron carriers. Various redox states of the enzyme were characterized by EPR, FTIR, etc. Based on the kinetic, structural and spectroscopic studies, the catalytic mechanism of [NiFe]-hydrogenase was proposed to explain H2-uptake, H2-production and isotopic exchange reactions. PMID:23318679

Analysis of Heavy Ion-Induced Chromosome Aberrations in Human Fibroblast Cells Using In Situ Hybridization

NASA Technical Reports Server (NTRS)

Wu, Honglu; Durante, Marco; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis A.

2003-01-01

Confluent human fibroblast cells (AG1522) were irradiated with gamma rays, 490 MeV/nucleon Si, or with Fe ions at either 200 or 500 MeV/nucleon. The cells were allowed to repair at 37 0 C for 24 hours after exposure, and a chemically induced premature chromosome condensation (PCC) technique was used to condense chromosomes in the G2 phase of the cell cycle. Unrejoined chromosomal breaks and complex exchanges were analyzed in the irradiated samples. In order to verify that chromosomal breaks were truly unrejoined, chromosome aberrations were analyzed using a combination of whole chromosome specific probes and probes specific for the telomere region of the chromosome. Results showed that the frequency of unrejoined chromosome breaks was higher after high-LET radiation, and consequently, the ratio of incomplete to complete exchanges increased steadily with LET up to 440 keV/micron, the highest LET value in the present study. For samples exposed to 200 MeV/nucleon Fe ions, chromosome aberrations were analyzed using the multicolor FISH (mFISH) technique that allows identification of both complex and truly incomplete exchanges. Results of the mFISH study showed that 0.7 and 3 Gy dose of the Fe ions produced similar ratios of complex to simple exchanges and incomplete to complete exchanges, values for which were higher than those obtained after a 6 Gy gamma exposure. After 0.7 Gy of Fe ions, most complex aberrations were found to involve three or four chromosomes, indicating the maximum number of chromosome domains traversed by a single Fe ion track. 2

Crystal Structure and Magnetic Properties of New Cubic Quaternary Compounds RT2Sn2Zn18 (R = La, Ce, Pr, and Nd, and T = Co and Fe)

NASA Astrophysics Data System (ADS)

Isikawa, Yosikazu; Mizushima, Toshio; Ejiri, Jun-ichi; Kitayama, Shiori; Kumagai, Keigou; Kuwai, Tomohiko; Bordet, Pierre; Lejay, Pascal

2015-07-01

The new cubic quaternary intermetallic compounds RT2Sn2Zn18 (R = La, Ce, Pr, and Nd, and T = Co and Fe) were synthesized by the mixture-metal flux method using Zn and Sn. The crystal structure was investigated by powder X-ray diffraction and with a four-circle X-ray diffractometer using single crystals. The space group of the compounds is Fdbar{3}m (No. 227). The rare-earth atom is at the cubic site which is the center of a cage composed of Zn and Sn atoms. The crystal structure is the same as the CeCr2Al20-type crystal structure except the atoms at the 16c site, i.e., the Zn atoms at the 16c site are completely replaced by Sn atoms, indicating that the compounds are crystallographically new ordered quaternary compounds. The lattice parameter a and the physical properties of the magnetic susceptibility χ, the magnetization M, and the specific heat C of these cubic caged compounds were investigated. LaCo2Sn2Zn18 and LaFe2Sn2Zn18 are enhanced Pauli paramagnets that originate from the Co and Fe itinerant 3d electrons. CeCo2Sn2Zn18 and CeFe2Sn2Zn18 are also enhanced Pauli paramagnets that originate from both the 3d electrons and Ce 4f electrons. PrCo2Sn2Zn18 and PrFe2Sn2Zn18 are nonmagnetic materials with huge values of C divided by temperature, which indicates that the ground state of Pr ions is a non-Kramers' doublet. NdCo2Sn2Zn18 and NdFe2Sn2Zn18 are magnetic materials with the Néel temperatures of 1.0 and 3.8 K, respectively. All eight compounds have large magnetic moments of Co/Fe in the paramagnetic temperature region, and thus their magnetic moments are inferred to be magnetically frustrating owing to the pyrochlore lattice in the low-temperature region.

Genetics Home Reference: SLC4A1-associated distal renal tubular acidosis

MedlinePlus

... exchanger 1 (AE1) protein, which transports negatively charged atoms (anions) across cell membranes. Specifically, AE1 exchanges negatively charged atoms of chlorine (chloride ions) for negatively charged bicarbonate ...

Magnetization switching behavior with competing anisotropies in epitaxial Co3FeN /MnN exchange-coupled bilayers

NASA Astrophysics Data System (ADS)

Hajiri, T.; Yoshida, T.; Jaiswal, S.; Filianina, M.; Borie, B.; Ando, H.; Asano, H.; Zabel, H.; Kläui, M.

2016-11-01

We report unusual magnetization switching processes and angular-dependent exchange bias effects in fully epitaxial Co3FeN /MnN bilayers, where magnetocrystalline anisotropy and exchange coupling compete, probed by longitudinal and transverse magneto-optic Kerr effect (MOKE) magnetometry. The MOKE loops show multistep jumps corresponding to the nucleation and propagation of 90∘ domain walls in as-grown bilayers. By inducing exchange coupling, we confirm changes of the magnetization switching process due to the unidirectional anisotropy field of the exchange coupling. Taking into account the experimentally obtained values of the fourfold magnetocrystalline anisotropy, the unidirectional anisotropy field, the exchange-coupling constant, and the uniaxial anisotropy including its direction, the calculated angular-dependent exchange bias reproduces the experimental results. These results demonstrate the essential role of the competition between magnetocrystalline anisotropy and exchange coupling for understanding and tailoring exchange-coupling phenomena usable for engineering switching in fully epitaxial bilayers made of tailored materials.

Temperature dependence of exchange anisotropy for (0 0 1) oriented Mn 89Pt 11/ferromagnetic bilayers

NASA Astrophysics Data System (ADS)

Yamato, T.; Kume, T.; Kato, T.; Tsunashima, S.; Iwata, S.

Temperature dependence of the exchange anisotropy was investigated for (0 0 1)-oriented top-type Mn 89Pt 11 ( tAF nm)/Ni 80Fe 20 (5 nm) and bottom-type Ni 80Fe 20 (3 nm)/Mn 89Pt 11 (30 nm) and Co 90Fe 10 (3 nm)/Mn 89Pt 11 (30 nm) bilayers. The top-type MnPt/NiFe bilayers exhibited both 1 and 4-fold anisotropies in their in-plane torque curves at 80 K. For tAF=3 nm, rapid decrease of 1-fold component and gradual decrease of 4-fold component were observed with increasing temperature. While for tAF=30 nm, the 1 and 4-fold anisotropies decreased similarly with temperature. In the bottom-type bilayers, by using CoFe ferromagnetic layer, the 4-fold anisotropy was found to become twice as that of the NiFe/MnPt bilayer.

Syntheses, crystal structures, and magnetic properties of the oxalato-bridged mixed-valence complexes (FeII(bpm)3]2[FeIII2(ox)5].8H2O and FeII(bpm)3Na(H2O)2Fe(ox)(3).4H2O (bpm = 2,2'-bipyrimidine).

PubMed

Armentano, D; De Munno, G; Faus, J; Lloret, F; Julve, M

2001-02-12

The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear high-spin iron(III) [Fe2(ox)5]2- anions, tris-chelated low-spin iron(II) [Fe(bpm)3]2+ cations, and lattice water molecules. The iron atoms are hexacoordinated: six oxygen atoms (iron(III)) from two bidentate and one bisbidentate oxalato ligands and six nitrogen atoms (iron(II)) from three bidentate bpm groups. The Fe(III)-O(ox) and Fe(II)-N(bpm) bond distances vary in the ranges 1.967(3)-2.099(3) and 1.967(4)-1.995(3) A, respectively. The iron(III)-iron(III) separation across the bridging oxalato is 5.449(2) A, whereas the shortest intermolecular iron(III)-iron(II) distance is 6.841(2) A. The structure of complex 2 consists of neutral heterotrinuclear Fe(bpm)2Na(H2O)2Fe(ox)3 units and water molecules of crystallization. The tris-chelated low-spin iron(II) ([Fe(bpm)3]2+) and high-spin iron(III) ([Fe(ox)3]3-) entities act as bidentate ligands (through two bpm-nitrogen and two oxalato-oxygen atoms, respectively) toward the univalent sodium cation, yielding the trinuclear (bpm)2Fe(II)-bpm-Na(I)-ox-Fe(III)(ox)2 complex. Two cis-coordinated water molecules complete the distorted octahedral surrounding of the sodium atom. The ranges of the Fe(II)-N(bpm) and Fe(III)-O(ox) bond distances [1.968(6)-1.993(5) and 1.992(6)-2.024(6) A, respectively] compare well with those observed in 1. The Na-N(bpm) bond lengths (2.548(7) and 2.677(7) A) are longer than those of Na-O(ox) (2.514(7) and 2.380(7) A) and Na-O(water) (2.334(15) and 2.356(12) A). The intramolecular Fe(II)...Fe(III) separation is 6.763(2) A, whereas the shortest intermolecular Fe(II)...Fe(II) and Fe(III)...Fe(III) distances are 8.152(2) and 8.992(2) A, respectively. Magnetic susceptibility measurements in the temperature range 2.0-290 K for 1 reveal that the high-spin iron(III) ions are antiferromagnetically coupled (J = -6.6 cm-1, the Hamiltonian being defined as H = -JS1.S2). The magnitude of the antiferromagnetic coupling through the bridging oxalato in the magneto-structurally characterized family of formula [M2(ox)5](2m-10)+ (M = Fe(III) (1), Cr(III), and Ni(II)) is analyzed and discussed by means of a simple orbital model.

Accurate wavelength measurements and modeling of FeXV to FeXIX spectra recorded in high density plasmas between 13.5 to 17 A.

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

May, M; Beiersdorfer, P; Dunn, J

Iron spectra have been recorded from plasmas created at three different laser plasma facilities, the Tor Vergata University laser in Rome (Italy), the Hercules laser at ENEA in Frascati (Italy), and the Compact Multipulse Terawatt (COMET) laser at LLNL in California (USA). The measurements provide a means of identifying dielectronic satellite lines from FeXVI and FeXV in the vicinity of the strong 2p {yields} 3d transitions of FeXVII. About 80 {Delta}n {ge} 1 lines of FeXV (Mg-like) to FeXIX (O-like) were recorded between 13.8 to 17.1 {angstrom} with a high spectral resolution ({lambda}/{Delta}{lambda} {approx} 4000), about thirty of these linesmore » are from FeXVI and FeXV. The laser produced plasmas had electron temperatures between 100 to 500 eV and electron densities between 10{sup 20} to 10{sup 22} cm{sup -3}. The Hebrew University Lawrence Livermore Atomic Code (HULLAC) was used to calculate the atomic structure and atomic rates for FeXV to FeXIX. HULLAC was used to calculate synthetic line intensities at T{sub e} = 200 eV and n{sub e} = 10{sup 21}cm{sup -3} for three different conditions to illustrate the role of opacity: optically thin plasmas with no excitation-autoionization/dielectronic recombination (EA/DR) contributions to the line intensities, optically thin plasmas that included EA/DR contributions to the line intensities, and optically thick plasmas (optical depth {approx} 200 {micro}m) that included EA/DR contributions to the line intensities. The optically thick simulation best reproduced the recorded spectrum from the Hercules laser. However some discrepancies between the modeling and the recorded spectra remain.« less

DFT calculations of strain and interface effects on electronic structures and magnetic properties of L10-FePt/Ag heterojunction of GMR applications

NASA Astrophysics Data System (ADS)

Pramchu, Sittichain; Jaroenjittichai, Atchara Punya; Laosiritaworn, Yongyut

2018-03-01

In this work, density functional theory (DFT) was employed to investigate the effect of strain and interface on electronic structures and magnetic properties of L10-FePt/Ag heterojunction. Two possible interface structures of L10-FePt(001)/Ag(001), that is, interface between Fe and Ag layers (Fe/Ag) and between Pt and Ag layers (Pt/Ag), were inspected. It was found that Pt/Ag interface is more stable than Fe/Ag interface due to its lower formation energy. Further, under the lattice mismatch induced tensile strain, the enhancement of magnetism for both Fe/Ag and Pt/Ag interface structures has been found to have progressed, though the magnetic moments of "interfacial" Fe and Pt atoms have been found to have decreased. To explain this further, the local density of states (LDOS) analysis suggests that interaction between Fe (Pt) and Ag near Fe/Ag (Pt/Ag) interface leads to spin symmetry breaking of the Ag atom and hence induces magnetism magnitude. In contrast, the magnetic moments of interfacial Fe and Pt atoms reduce because of the increase in the electronic states near the Fermi level of the minority-spin electrons. In addition, the significant enhancements of the LDOS near the Fermi levels of the minority-spin electrons signify the boosting of the transport properties of the minority-spin electrons and hence the spin-dependent electron transport at this ferromagnet/metal interface. From this work, it is expected that this clarification of the interfacial magnetism may inspire new innovation on how to improve spin-dependent electron transport for enhancing the giant magnetoresistance (GMR) ratio of potential GMR-based spintronic devices.

45° sign switching of effective exchange bias due to competing anisotropies in fully epitaxial Co3FeN/MnN bilayers.

PubMed

Hajiri, T; Yoshida, T; Filianina, M; Jaiswal, S; Borie, B; Asano, H; Zabel, H; Kläui, M

2017-12-05

We report an unusual angular-dependent exchange bias effect in ferromagnet/antiferromagnet bilayers, where both ferromagnet and antiferromagnet are epitaxially grown. Numerical model calculations predict an approximately 45° period for the sign switching of the exchange-bias field, depending on the ratio between magnetocrystalline anisotropy and exchange-coupling constant. The switching of the sign is indicative of a competition between a fourfold magnetocrystalline anisotropy of the ferromagnet and a unidirectional anisotropy field of the exchange coupling. This predicted unusual angular-dependent exchange bias and its magnetization switching process are confirmed by measurements on fully epitaxial Co 3 FeN/MnN bilayers by longitudinal and transverse magneto-optic Kerr effect magnetometry. These results provide a deeper understanding of the exchange coupling phenomena in fully epitaxial bilayers with tailored materials and open up a complex switching energy landscape engineering by anisotropies.

45° sign switching of effective exchange bias due to competing anisotropies in fully epitaxial Co3FeN/MnN bilayers

NASA Astrophysics Data System (ADS)

Hajiri, T.; Yoshida, T.; Filianina, M.; Jaiswal, S.; Borie, B.; Asano, H.; Zabel, H.; Kläui, M.

2018-01-01

We report an unusual angular-dependent exchange bias effect in ferromagnet/antiferromagnet bilayers, where both ferromagnet and antiferromagnet are epitaxially grown. Numerical model calculations predict an approximately 45° period for the sign switching of the exchange-bias field, depending on the ratio between magnetocrystalline anisotropy and exchange-coupling constant. The switching of the sign is indicative of a competition between a fourfold magnetocrystalline anisotropy of the ferromagnet and a unidirectional anisotropy field of the exchange coupling. This predicted unusual angular-dependent exchange bias and its magnetization switching process are confirmed by measurements on fully epitaxial Co3FeN/MnN bilayers by longitudinal and transverse magneto-optic Kerr effect magnetometry. These results provide a deeper understanding of the exchange coupling phenomena in fully epitaxial bilayers with tailored materials and open up a complex switching energy landscape engineering by anisotropies.

An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

NASA Astrophysics Data System (ADS)

Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (X_{{{Ni}}}^{{{sulfide}}} 0.4-0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6-0.7) at depths near 80-120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (X_{{{Ni}}}^{{{sulfide}}} 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.

Antiferromagnetic exchange bias of a ferromagnetic semiconductor by a ferromagnetic metal

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

Olejnik, K.; Wadley, P.; Haigh, J.

2009-11-05

We demonstrate an exchange bias in (Ga,Mn)As induced by antiferromagnetic coupling to a thin overlayer of Fe. Bias fields of up to 240 Oe are observed. Using element-specific x-ray magnetic circular dichroism measurements, we distinguish an interface layer that is strongly pinned antiferromagnetically to the Fe. The interface layer remains polarized at room temperature.

17 CFR Appendix C to Part 4 - Form CTA-PR

Code of Federal Regulations, 2014 CFR

2014-04-01

... 17 Commodity and Securities Exchanges 1 2014-04-01 2014-04-01 false Form CTA-PR C Appendix C to Part 4 Commodity and Securities Exchanges COMMODITY FUTURES TRADING COMMISSION COMMODITY POOL OPERATORS AND COMMODITY TRADING ADVISORS Pt. 4, App. C Appendix C to Part 4—Form CTA-PR ER24FE12.052 ER24FE12...

Phenomenological model of spin crossover in molecular crystals as derived from atom-atom potentials.

PubMed

Sinitskiy, Anton V; Tchougréeff, Andrei L; Dronskowski, Richard

2011-08-07

The method of atom-atom potentials, previously applied to the analysis of pure molecular crystals formed by either low-spin (LS) or high-spin (HS) forms (spin isomers) of Fe(II) coordination compounds (Sinitskiy et al., Phys. Chem. Chem. Phys., 2009, 11, 10983), is used to estimate the lattice enthalpies of mixed crystals containing different fractions of the spin isomers. The crystals under study were formed by LS and HS isomers of Fe(phen)(2)(NCS)(2) (phen = 1,10-phenanthroline), Fe(btz)(2)(NCS)(2) (btz = 5,5',6,6'-tetrahydro-4H,4'H-2,2'-bi-1,3-thiazine), and Fe(bpz)(2)(bipy) (bpz = dihydrobis(1-pyrazolil)borate, and bipy = 2,2'-bipyridine). For the first time the phenomenological parameters Γ pertinent to the Slichter-Drickamer model (SDM) of several materials were independently derived from the microscopic model of the crystals with use of atom-atom potentials of intermolecular interaction. The accuracy of the SDM was checked against the numerical data on the enthalpies of mixed crystals. Fair semiquantitative agreement with the experimental dependence of the HS fraction on temperature was achieved with use of these values. Prediction of trends in Γ values as a function of chemical composition and geometry of the crystals is possible with the proposed approach, which opens a way to rational design of spin crossover materials with desired properties. This journal is © the Owner Societies 2011

Triggering of spin-flipping-modulated exchange bias in FeCo nanoparticles by electronic excitation

PubMed Central

Sarker, Debalaya; Bhattacharya, Saswata; Srivastava, Pankaj; Ghosh, Santanu

2016-01-01

The exchange coupling between ferromagnetic (FM)-antiferromagnetic (AF) interfaces is a key element of modern spintronic devices. We here introduce a new way of triggering exchange bias (EB) in swift heavy ion (SHI) irradiated FeCo-SiO2 films, which is a manifestation of spin-flipping at high irradiation fluence. The elongation of FeCo nanoparticles (NPs) in SiO2 matrix gives rise to perpendicular magnetic anisotropy at intermediate fluence. However, a clear shift in hysteresis loop is evident at the highest fluence. This reveals the existence of an AF exchange pinning domain in the NPs, which is identified not to be oxide shell from XANES analysis. Thermal spike calculations along with first-principles based simulations under the framework of density functional theory (DFT) demonstrate that spin flipping of 3d valence electrons is responsible for formation of these AF domains inside the FM NPs. EXAFS experiments at Fe and Co K-edges further unravel that spin-flipping in highest fluence irradiated film results in reduced bond lengths. The results highlight the possibility of miniaturization of magnetic storage devices by using irradiated NPs instead of conventionally used FM-AF multilayers. PMID:27991552

Clusters and holes: Exchange networks in hematite-ilmenite solid solutions

NASA Astrophysics Data System (ADS)

Fabian, K.; McEnroe, S. A.; Robinson, P.

2009-04-01

Holes and clusters of exchange networks dominate the low-temperature, metastable phase diagram of the system (1 - x)Fe2O3 xF eTiO3 (Ilmx ). By our measurements we have probed and extended the phase diagram of Ishikawa et al. (1985) in the light of magnetic influences of the random exchange links, which originate either by replacing random pairs of Fe2+ and Ti4+ ions in the ordered ilmenite lattice by two Fe3+ions (ordered Ilmx phase), or by randomly replacing two Fe3+ ions in the hematite lattice by a pair of Fe2+ and Ti4+ ions (disordered Ilmx phase). Now a large dataset is available from these measurements, and we propose several new ideas to interpret the sometimes unexpected results. By refining a method of Ishikawa (1967), we analyze the PM' region of the phase diagram in terms of a mean field theory of interacting clusters. This allows to determine cluster sizes and interaction field distribution by inverting hysteresis measurements of Ilm92 and Ilm97. To understand the relation between ordered and disordered phases we design a mean field theory to determine Neel and Curie temperatures of both. An especially interesting finding is that the experimentally observed intersection of PM-PM' crossover with the AF phase boundary close to Ilm97 can be explained by analyzing average exchange interaction strengths.

Missing Fe: hydrogenated iron nanoparticles

NASA Astrophysics Data System (ADS)

Bilalbegović, G.; Maksimović, A.; Mohaček-Grošev, V.

2017-03-01

Although it was found that the FeH lines exist in the spectra of some stars, none of the spectral features in the interstellar medium (ISM) have been assigned to this molecule. We suggest that iron atoms interact with hydrogen and produce Fe-H nanoparticles which sometimes contain many H atoms. We calculate infrared spectra of hydrogenated iron nanoparticles using density functional theory methods and find broad, overlapping bands. Desorption of H2 could induce spinning of these small Fe-H dust grains. Some of hydrogenated iron nanoparticles possess magnetic and electric moments and should interact with electromagnetic fields in the ISM. FenHm nanoparticles could contribute to the polarization of the ISM and the anomalous microwave emission. We discuss the conditions required to form FeH and FenHm in the ISM.

NASICON-related Na3.4Mn0.4Fe1.6(PO4)3

PubMed Central

Yatskin, Michael M.; Strutynska, Nataliya Yu.; Baumer, Vyacheslav N.; Ogorodnyk, Ivan V.; Slobodyanik, Nikolay S.

2012-01-01

The solid solution, sodium [iron(III)/manganese(II)] tris­(orthophosphate), Na3.4Mn0.4Fe1.6(PO4)3, was obtained using a flux method. Its crystal structure is related to that of NASICON-type compounds. The [(Mn/Fe)2(PO4)3] framework is built up from an (Mn/Fe)O6 octa­hedron (site symmetry 3.), with a mixed Mn/Fe occupancy, and a PO4 tetra­hedron (site symmetry .2). The Na+ cations are distributed over two partially occupied sites in the cavities of the framework. One Na+ cation (site symmetry -3.) is surrounded by six O atoms, whereas the other Na+ cation (site symmetry .2) is surrounded by eight O atoms. PMID:22807697

Discovery of Suprathermal Fe+ in and near Earth's Magnetosphere

NASA Astrophysics Data System (ADS)

Christon, S. P.; Hamilton, D. C.; Plane, J. M. C.; Mitchell, D. G.; Grebowsky, J. M.; Spjeldvik, W. N.; Nylund, S. R.

2017-12-01

Suprathermal (87-212 keV/e) singly charged iron, Fe+, has been observed in and near Earth's equatorial magnetosphere using long-term ( 21 years) Geotail/STICS ion composition data. Fe+ is rare compared to dominant suprathermal solar wind and ionospheric origin heavy ions. Earth's suprathermal Fe+ appears to be positively associated with both geomagnetic and solar activity. Three candidate lower-energy sources are examined for relevance: ionospheric outflow of Fe+ escaped from ion layers altitude, charge exchange of nominal solar wind Fe+≥7, and/or solar wind transported inner source pickup Fe+ (likely formed by solar wind Fe+≥7 interaction with near sun interplanetary dust particles, IDPs). Semi-permanent ionospheric Fe+ layers form near 100 km altitude from the tons of IDPs entering Earth's atmosphere daily. Fe+ scattered from these layers is observed up to 1000 km altitude, likely escaping in strong ionospheric outflows. Using 26% of STICS's magnetosphere-dominated data at low-to-moderate geomagnetic activity levels, we demonstrate that solar wind Fe charge exchange secondaries are not an obvious Fe+ source then. Earth flyby and cruise data from Cassini/CHEMS, a nearly identical instrument, show that inner source pickup Fe+ is likely not important at suprathermal energies. Therefore, lacking any other candidate sources, it appears that ionospheric Fe+ constitutes at least an important portion of Earth's suprathermal Fe+, comparable to observations at Saturn where ionospheric origin suprathermal Fe+ has also been observed.

Uniform Fe3O4 coating on flower-like ZnO nanostructures by atomic layer deposition for electromagnetic wave absorption.

PubMed

Wan, Gengping; Wang, Guizhen; Huang, Xianqin; Zhao, Haonan; Li, Xinyue; Wang, Kan; Yu, Lei; Peng, Xiange; Qin, Yong

2015-11-21

An elegant atomic layer deposition (ALD) method has been employed for controllable preparation of a uniform Fe3O4-coated ZnO (ZnO@Fe3O4) core-shell flower-like nanostructure. The Fe3O4 coating thickness of the ZnO@Fe3O4 nanostructure can be tuned by varying the cycle number of ALD Fe2O3. When serving as additives for microwave absorption, the ZnO@Fe3O4-paraffin composites exhibit a higher absorption capacity than the ZnO-paraffin composites. For ZnO@500-Fe3O4, the effective absorption bandwidth below -10 dB can reach 5.2 GHz and the RL values below -20 dB also cover a wide frequency range of 11.6-14.2 GHz when the coating thickness is 2.3 mm, suggesting its potential application in the treatment of the electromagnetic pollution problem. On the basis of experimental observations, a mechanism has been proposed to understand the enhanced microwave absorption properties of the ZnO@Fe3O4 composites.

Structural Characterization of CO-Inhibited Mo-Nitrogenase by Combined Application of Nuclear Resonance Vibrational Spectroscopy, Extended X-ray Absorption Fine Structure, and Density Functional Theory: New Insights into the Effects of CO Binding and the Role of the Interstitial Atom

DOE PAGES

Scott, Aubrey D.; Pelmenschikov, Vladimir; Guo, Yisong; ...

2014-10-02

The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N 2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm –1 mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N 2ase variant. In the frequency region above 450 cm –1, additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by 13CO isotope shifts). The EXAFSmore » for wild-type N 2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal ₋CO and a partially reduced ₋CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational “shake” modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. We discuss implications for the CO and N 2 reactivity of N 2ase.« less

Structural characterization of CO-inhibited Mo-nitrogenase by combined application of nuclear resonance vibrational spectroscopy, extended X-ray absorption fine structure, and density functional theory: new insights into the effects of CO binding and the role of the interstitial atom.

PubMed

Scott, Aubrey D; Pelmenschikov, Vladimir; Guo, Yisong; Yan, Lifen; Wang, Hongxin; George, Simon J; Dapper, Christie H; Newton, William E; Yoda, Yoshitaka; Tanaka, Yoshihito; Cramer, Stephen P

2014-11-12

The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm(-1) mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N2ase variant. In the frequency region above 450 cm(-1), additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by (13)CO isotope shifts). The EXAFS for wild-type N2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal -CO and a partially reduced -CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational "shake" modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. Implications for the CO and N2 reactivity of N2ase are discussed.

Magnetism and exchange interaction of small rare-earth clusters; Tb as a representative

PubMed Central

Peters, Lars; Ghosh, Saurabh; Sanyal, Biplab; van Dijk, Chris; Bowlan, John; de Heer, Walt; Delin, Anna; Di Marco, Igor; Eriksson, Olle; Katsnelson, Mikhail I.; Johansson, Börje; Kirilyuk, Andrei

2016-01-01

Here we follow, both experimentally and theoretically, the development of magnetism in Tb clusters from the atomic limit, adding one atom at a time. The exchange interaction is, surprisingly, observed to drastically increase compared to that of bulk, and to exhibit irregular oscillations as a function of the interatomic distance. From electronic structure theory we find that the theoretical magnetic moments oscillate with cluster size in exact agreement with experimental data. Unlike the bulk, the oscillation is not caused by the RKKY mechanism. Instead, the inter-atomic exchange is shown to be driven by a competition between wave-function overlap of the 5d shell and the on-site exchange interaction, which leads to a competition between ferromagnetic double-exchange and antiferromagnetic super-exchange. This understanding opens up new ways to tune the magnetic properties of rare-earth based magnets with nano-sized building blocks. PMID:26795239

Dose Response for Chromosome Aberrations in Human Lymphocytes and Fibroblasts after Exposure to Very Low Doses of High LET Radiation

NASA Technical Reports Server (NTRS)

Hada, M.; George, Kerry; Cucinotta, Francis A.

2011-01-01

The relationship between biological effects and low doses of absorbed radiation is still uncertain, especially for high LET radiation exposure. Estimates of risks from low-dose and low-dose-rates are often extrapolated using data from Japanese atomic bomb survivors with either linear or linear quadratic models of fit. In this study, chromosome aberrations were measured in human peripheral blood lymphocytes and normal skin fibroblasts cells after exposure to very low dose (1-20 cGy) of 170 MeV/u Si-28- ions or 600 MeV/u Fe-56-ions. Chromosomes were analyzed using the whole chromosome fluorescence in situ hybridization (FISH) technique during the first cell division after irradiation, and chromosome aberrations were identified as either simple exchanges (translocations and dicentrics) or complex exchanges (involving greater than 2 breaks in 2 or more chromosomes). The curves for doses above 10 cGy were fitted with linear or linear-quadratic functions. For Si-28- ions no dose response was observed in the 2-10 cGy dose range, suggesting a non-target effect in this range.

Bulk amorphous steels based on Fe alloys

DOEpatents

Lu, ZhaoPing; Liu, Chain T.

2006-05-30

A bulk amorphous alloy has the approximate composition: Fe.sub.(100-a-b-c-d-e)Y.sub.aMn.sub.bT.sub.cM.sub.dX.sub.e wherein: T includes at least one of the group consisting of: Ni, Cu, Cr and Co; M includes at least one of the group consisting of W, Mo, Nb, Ta, Al and Ti; X includes at least one of the group consisting of Co, Ni and Cr; a is an atomic percentage, and a<5; b is an atomic percentage, and b.ltoreq.25; c is an atomic percentage, and c.ltoreq.25; d is an atomic percentage, and d.ltoreq.25; and e is an atomic percentage, and 5.ltoreq.e.ltoreq.30.

Wet-chemical synthesis of nanoscale iron boride, XAFS analysis and crystallisation to α-FeB.

PubMed

Rades, Steffi; Kornowski, Andreas; Weller, Horst; Albert, Barbara

2011-06-20

The reaction of lithium tetrahydridoborate and iron bromide in high boiling ether as reaction medium produces an ultrafine, pyrophoric and magnetic precipitate. X-ray and electron diffraction proved the product to be amorphous. According to X-ray absorption fine structure spectroscopy (XAFS) the precipitate has FeB structure up to nearly two coordination spheres around an iron absorber atom. Transmission electron microscopy (TEM) confirms the ultrafine powder to be nanoscale. Subsequent annealing at 450 °C causes the atoms to arrange in a more distinct FeB structure, and further thermal treatment to 1050 °C extends the local structure to the α-modification of FeB. Between 1050 °C and 1500 °C α-FeB is transformed into β-FeB. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio calculation of electronic structure and magnetic properties of R2Fe14BNx (R = Pr,Nd)

NASA Astrophysics Data System (ADS)

Tian, Guang; Zha, Liang; Yang, Wenyun; Qiao, Guanyi; Wang, Changsheng; Yang, Yingchang; Yang, Jinbo

2018-05-01

The site preference of N atom for R2Fe14BNx (R= Pr, Nd) and the interstitial nitrogen effect on the magnetic properties have been studied by the first-principles method. It was found that the nitrogen is more likely to occupy the 4e site for Pr2Fe14BNx compound, while 4f site for Nd2Fe14BNx. When N atoms entering some specific crystal sites (such as 2a and 4f), the total magnetic moments of these compounds are not reduced, but slightly increased. Although the doping of N may reduce the total magnetic moments of some R2Fe14B compounds in the cases of optimal occupancy, the volumetric effect caused by N doping can still change the electron density distributions of Fe near the Fermi level, improving the magnetic ordering temperature of such compounds.

M-FISH Analysis of Chromosome Aberrations in Human Fibroblast Cells After In Vitro Exposure to Low- and High-LET Radiation

NASA Technical Reports Server (NTRS)

Wu, Honglu; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis

2002-01-01

The recently commercialized multiplex fluorescence in situ hybridization (m-FISH) technique, which allows human chromosomes to be painted in 24 different colors, was used to analyze chromosome aberrations in diploid human fibroblast cells after in vitro radiation exposure. Confluent flasks of a normal primary fibroblast cell line (AG 1522) were irradiated at high dose rates with either gamma rays or 200 MeV/nucleon Fe ions (LET = 440 keV/micron), incubated at 37 C for 24 hours after exposure, and subsequently subcultured. A chemically induced premature chromosome condensation technique was used to collect chromosome samples 32 hours after subculture. Results showed that the fraction of exchanges which were identified as complex, i.e. involving misrejoining of three or more DSB, were higher in the Fe-irradiated samples compared with the gamma-irradiated samples, as has been shown previously using FISH with one or two painted chromosomes . The ratios of complex/simple type exchanges were similar for samples irradiated with 0.7 Gy and 3 Gy of Fe ions, although exchanges involving five or more breaks were found only in 3 Gy irradiated samples. The fraction of incomplete exchanges was also higher in Fe- than gamma-irradiated samples. Data on the distribution of individual chromosome involvement in interchromosomal exchanges will be presented.

Iron(III) carboxylate/aminoalcohol coordination clusters with propeller-shaped Fe8 cores: approaching reasonable exchange energies.

PubMed

Botezat, Olga; van Leusen, Jan; Kravtsov, Victor Ch; Ellern, Arkady; Kögerler, Paul; Baca, Svetlana G

2015-12-21

A series of new octanuclear propeller-like aminoalcohol-supported Fe(III) oxocarboxylate coordination clusters, [Fe8O3(O2CCHMe2)9(tea)(teaH)3]·MeCN·2(H2O) (1), [Fe8O3(O2CCHMe2)6(N3)3(tea)(teaH)3] (2), [Fe8O3(O2CCMe3)6(N3)3(tea)(teaH)3]·0.5(EtOH) (3), and [Fe8O3(O2CCHMe2)6(N3)3(mdea)3(MeO)3] (4) (where teaH3 = triethanolamine; mdeaH2 = N-methyldiethanolamine) has been isolated and magnetochemically analyzed combining the programs wxJFinder and CONDON in an approach to avoid overparameterization issues that are common to larger spin polytopes. Dominant antiferromagnetic exchange interactions exist in all clusters along the edges of the propellers, while moderate ferromagnetic interactions are found along the propeller axes in their {Fe8O3} metallic cores.

Direct assignment of the cysteinyl, the slowly exchangeable, and the aromatic ring H nuclear magnetic resonances in clostridial-type ferredoxins. [Clostridium acidi-urici, C. pasteurianum, C. perfringens, Peptococcus aerogenes

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

Packer, E.L.; Sweeney, W.V.; Rabinowitz, J.C.

1977-04-10

We have directly assigned the /sup 1/H NMR corresponding to the cysteinyl protons, the slowly exchangeable protons, and the aromatic ring protons in the /sup 1/H NMR spectrum of Clostridium acidi-urici ferredoxin by isotopic labeling and /sup 13/C NMR decoupling techniques. We also show that the resonance pattern in the 8- to 20-ppM (from 2,2-dimethyl-2-sialapentanesulfonic acid) region of the /sup 1/H NMR spectra of oxidized Clostridium acidi-urici, Clostridium pasteurianum, Clostridium perfringens, and Peptococcus aerogenes ferredoxins are very similar, and we assign the resonances in this region by analogy with the spectrum of C. acidi-urici ferredoxin. The /sup 1/H NMR spectramore » of the ..beta.. protons of the cysteinyl residues of these ferredoxins differ, however, from the /sup 1/H NMR spectra of equivalent ..beta.. protons of the methylene carbon atoms bonded via a sulfur atom to (4Fe-4S) clusters in synthetic inorganic analogues. In the spectra of the synthetic compounds, the ..beta.. protons appear as a single resonance shifted 10 ppM from its unbonded reference position. In the spectra of oxidized clostridial ferredoxins, the cysteinyl ..beta.. protons appear as a series of at least eight resolved resonances with shifts that range from 6 to 14 ppM, relative to the free amino acid resonance position.« less

Modulating the electronic and magnetic properties of bilayer borophene via transition metal atoms intercalation: from metal to half metal and semiconductor.

PubMed

Zhang, Xiuyun; Sun, Yi; Ma, Liang; Zhao, Xinli; Yao, Xiaojing

2018-07-27

Borophene, a two-dimensional monolayer made of boron atoms, has attracted wide attention due to its appealing properties. Great efforts have been devoted to fine tuning its electronic and magnetic properties for desired applications. Herein, we theoretically investigate the versatile electronic and magnetic properties of bilayer borophene (BLB) intercalated by 3d transition metal (TM) atoms, TM@BLBs (TM = Ti-Fe), using ab initio calculations. Four allotropes of AA-stacking (α 1 -, β-, β 12 - and χ 3 -) BLBs with different intercalation concentrations of TM atoms are considered. Our results show that the TM atoms are strongly bonded to the borophene layers with fairly large binding energies, around 6.31 ∼ 15.44 eV per TM atom. The BLBs with Cr and Mn intercalation have robust ferromagnetism, while for the systems decorated with Fe atoms, fruitful magnetic properties, such as nonmagnetic, ferromagnetic or antiferromagnetic, are identified. In particular, the α 1 - and β-BLBs intercalated by Mn or Fe atom can be transformed into a semiconductor, half metal or graphene-like semimetal. Moreover, some heavily doped TM@BLBs expose high Curie temperatures above room temperature. The attractive properties of TM@BLBs entail an efficient way to modulate the electronic and magnetic properties of borophene sheets for advanced applications.

Recent Developments in the NIST Atomic Databases

NASA Astrophysics Data System (ADS)

Kramida, Alexander

2011-05-01

New versions of the NIST Atomic Spectra Database (ASD, v. 4.0) and three bibliographic databases (Atomic Energy Levels and Spectra, v. 2.0, Atomic Transition Probabilities, v. 9.0, and Atomic Line Broadening and Shapes, v. 3.0) have recently been released. In this contribution I will describe the main changes in the way users get the data through the Web. The contents of ASD have been significantly extended. In particular, the data on highly ionized tungsten (W III-LXXIV) have been added from a recently published NIST compilation. The tables for Fe I and Fe II have been replaced with newer, much more extensive lists (10000 lines for Fe I). The other updated or new spectra include H, D, T, He I-II, Li I-III, Be I-IV, B I-V, C I-II, N I-II, O I-II, Na I-X, K I-XIX, and Hg I. The new version of ASD now incorporates data on isotopes of several elements. I will describe some of the issues the NIST ASD Team faces when updating the data.

Recent Developments in the NIST Atomic Databases

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

Kramida, Alexander

New versions of the NIST Atomic Spectra Database (ASD, v. 4.0) and three bibliographic databases (Atomic Energy Levels and Spectra, v. 2.0, Atomic Transition Probabilities, v. 9.0, and Atomic Line Broadening and Shapes, v. 3.0) have recently been released. In this contribution I will describe the main changes in the way users get the data through the Web. The contents of ASD have been significantly extended. In particular, the data on highly ionized tungsten (W III-LXXIV) have been added from a recently published NIST compilation. The tables for Fe I and Fe II have been replaced with newer, much moremore » extensive lists (10000 lines for Fe I). The other updated or new spectra include H, D, T, He I-II, Li I-III, Be I-IV, B I-V, C I-II, N I-II, O I-II, Na I-X, K I-XIX, and Hg I. The new version of ASD now incorporates data on isotopes of several elements. I will describe some of the issues the NIST ASD Team faces when updating the data.« less

The role of Ag buffer layer in Fe islands growth on Ge (111) surfaces

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

Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw; Wu, Jia-Yuan; Jhou, Ming-Kuan

2015-05-07

Sub-monolayer iron atoms were deposited at room temperature on Ge (111)-c(2 × 8) substrates with and without Ag buffer layers. The behavior of Fe islands growth was investigated by using scanning tunneling microscope (STM) after different annealing temperatures. STM images show that iron atoms will cause defects and holes on substrates at room temperature. As the annealing temperature rises, iron atoms pull out germanium to form various kinds of alloyed islands. However, the silver layer can protect the Ag/Ge(111)-(√3×√3) reconstruction from forming defects. The phase diagram shows that ring, dot, and triangular defects were only found on Ge (111)-c(2 × 8) substrates. The kindsmore » of islands found in Fe/Ge system are similar to Fe/Ag/Ge system. It indicates that Ge atoms were pulled out to form islands at high annealing temperatures whether there was a Ag layer or not. But a few differences in big pyramidal or strip islands show that the silver layer affects the development of islands by changing the surface symmetry and diffusion coefficient. The structure characters of various islands are also discussed.« less

Synthesis and characterization of (cryptand-222)potassium (2-methylimidazolato)(meso-tetraphenylporphinato)ferrate(II)-2-methylimidazole-tetrahydrofuran (1/1/2).

PubMed

Wu, Qi; Yao, Zhen; Li, Jianfeng

2017-09-01

Metalloporphyrin complexes containing an additional imidazole ligand can provide information about the effect of deprotonation or hydrogen bonding on the axial histidine unit in heme proteins. The title high-spin five-coordinate imidazolate-ligated iron(II) porphyrinate, [K(C 18 H 36 N 2 O 6 )][Fe(C 4 H 5 N 2 )(C 44 H 28 N 4 )]·C 4 H 6 N 2 ·2C 4 H 8 O, has been synthesized and investigated. The solvated salt crystallizes with one 2-methylimidazole molecule, two tetrahydrofuran solvent molecules and a potassium cation chelated inside a cryptand-222 (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) molecule. The imidazolate ligand is ordered. The average Fe-Np (Np is a porphyrin N atom) bond length is 2.113 (11) Å and the axial Fe-N Im (N Im is an imidazolate N atom) is 2.0739 (13) Å. The out-of-plane displacement of the Fe II atom from the 24-atom mean plane is 0.6098 (5) Å, indicating an apparent doming of the porphyrin core.

Uncertainties in Atomic Data and Their Propagation Through Spectral Models. I.

NASA Technical Reports Server (NTRS)

Bautista, M. A.; Fivet, V.; Quinet, P.; Dunn, J.; Gull, T. R.; Kallman, T. R.; Mendoza, C.

2013-01-01

We present a method for computing uncertainties in spectral models, i.e., level populations, line emissivities, and emission line ratios, based upon the propagation of uncertainties originating from atomic data.We provide analytic expressions, in the form of linear sets of algebraic equations, for the coupled uncertainties among all levels. These equations can be solved efficiently for any set of physical conditions and uncertainties in the atomic data. We illustrate our method applied to spectral models of Oiii and Fe ii and discuss the impact of the uncertainties on atomic systems under different physical conditions. As to intrinsic uncertainties in theoretical atomic data, we propose that these uncertainties can be estimated from the dispersion in the results from various independent calculations. This technique provides excellent results for the uncertainties in A-values of forbidden transitions in [Fe ii]. Key words: atomic data - atomic processes - line: formation - methods: data analysis - molecular data - molecular processes - techniques: spectroscopic

Specific features of the atomic structure of metallic layers of multilayered (CoFeZr/SiO2)32 and (CoFeZr/ a-Si)40 nanostructures with different interlayers

NASA Astrophysics Data System (ADS)

Domashevskaya, E. P.; Guda, A. A.; Chernyshev, A. V.; Sitnikov, V. G.

2017-02-01

Multilayered nanostructures (MN) were prepared by ion-beam successive sputtering from two targets, one of which was a metallic Co45Fe45Zr10 alloy plate and another target was a quartz (SiO2) or silicon plate on the surface of a rotating glass-ceramic substrate in an argon atmosphere. The Co and Fe K edges X-ray absorption fine structure of XANES in the (CoFeZr/SiO2)32 sample with oxide interlayers was similar to XANES of metallic Fe foil. This indicated the existence in metallic layers of multilayered CoFeZr nanocrystals with a local environment similar to the atomic environment in solid solutions on the base of bcc Fe structure, which is also confirmed by XRD data. XANES near the Co and Fe K edges absorption in another multilayered nanostructure with silicon interlayers (CoFeZr/ a-Si)40 differs from XANES of MN with dielectric SiO2 interlayer, which demonstrates a dominant influence of the Fe-Si and Co-Si bonds in the local environment of 3 d Co and Fe metals when they form CoFeSi-type silicide phases in thinner bilayers of this MN.

Site preference, magnetism and lattice vibrations of intermetallics Lu₂Fe 17–xT x (T=Cr, Mn, Ru)

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

Li, Jin-Chun; Qian, Ping, E-mail: qianpinghu@sohu.com; Zhang, Zhen-Feng

We present an atomistic study on the phase stability, site preference and lattice constants of the rare earth intermetallics Lu₂Fe 17–xT x (T=Cr, Mn, Ru). The calculated preferential occupation site of ternary element T is found to be the 4f site. The order of site preference is given as 4f, 12k, 12j and 6g for Lu₂Fe 17–xT x. The calculated lattice parameters are corresponding to the experimental results. We have calculated the magnetic moments of Lu₂Fe 17–xT x compounds. Results show that the calculated total magnetic moment of Lu₂Fe₁₇ compound is M=37.34 μ B/f.u. In addition, the total and partialmore » phonon densities of states are evaluated first for these complicated structures. - Graphical abstract: The vibrational modes are mostly excited by Fe atoms, Lu contributes to the lower frequencies modes, and the contribution of Ru atoms is the same as Fe atoms. Highlights: • There are no reports on lattice vibrations of Lu₂(Fe, T) 17–x (T=Cr, Mn, Ru) compounds. • The phase stability and site preference are evaluated first for the complex structures of Lu₂(Fe, T) 17–x (T=Cr, Mn, Ru) compounds. • The lattice inversion method to obtain the interatomic pair potential is the unique one.« less

Orbitally dependent kinetic exchange in a heterobimetallic pair: Ferromagnetic spin alignment and magnetic anisotropy in the cyano-bridged Cr(III)Fe(II) dimer

NASA Astrophysics Data System (ADS)

Palii, A. V.; Tsukerblat, B. S.; Verdaguer, M.

2002-11-01

The problem of the kinetic exchange interaction in the cyanide-bridged heterobinuclear dimers involving orbitally degenerate transition metal ions is considered. The developed approach is based on the concept of the effective Hamiltonian of the orbitally dependent kinetic exchange. We deduce this many-electron Hamiltonian on the microscopic background so that all relevant biorbital transfer processes are taken into account as well as the properties of the many-electron states. The bioctahedral cyanide-bridged Cr(III)Fe(II) dimer is considered in detail as an example distinctly exhibiting new quantitative and qualitative features of the orbitally dependent exchange and as a structural unit of three-dimensional ferromagnetic crystals {Fe(II)3)Cr(III)(CN62}[middle dot]13H2O. The proposed mechanism of the kinetic exchange involves the electron transfer from the double occupied t2 orbitals of Fe(II) [ground state 5T2(t2)4e2] to the half occupied t2 orbitals of Cr(III) [ground state 4A2(t2)3] resulting in the charge transfer state 3T1(t2)4Cr(II)- 6A1(t2)3e2 Fe(III) and the transfer between the half-occupied t2 orbitals of the metal ions resulting in the charge transfer state 3T1(t2)4Cr(II)- 4T2(t2)3e2 Fe(III). The effective Hamiltonian of the orbitally dependent exchange for the Cr(III)Fe(II) pair deduced within this theoretical framework describes competitive ferro- and antiferromagnetic contributions arising from these two charge transfer states. This Hamiltonian leads to a complex energy pattern, consisting of two interpenetrating Heisenberg-like schemes, one exhibiting ferromagnetic and another one antiferromagnetic splitting. The condition for the ferromagnetic spin alignment in the ground state is deduced. The orbitally dependent terms of the Hamiltonian are shown to give rise to a strong magnetic anisotropy of the system, this result as well as the condition for the spin alignment in the ground term are shown to be out of the scope of the Goodenough-Kanamori rules. Along with the full spin S the energy levels are labeled by the orbital quantum numbers providing thus the direct information about the magnetic anisotropy of the system. Under a reasonable estimation of the excitation energies based on the optical absorption data we conclude that the kinetic exchange in the cyanide-bridged Cr(III)Fe(II) pair leads to the ferromagnetic spin alignment exhibiting at the same time strong axial magnetic anisotropy with C4 easy axis of magnetization.

Ferrate(VI) oxidation of polychlorinated diphenyl sulfides: Kinetics, degradation, and oxidized products.

PubMed

Chen, Jing; Xu, Xinxin; Zeng, Xiaolan; Feng, Mingbao; Qu, Ruijuan; Wang, Zunyao; Nesnas, Nasri; Sharma, Virender K

2018-06-13

This paper presents oxidation of polychlorinated diphenyl sulfides (PCDPSs), dioxin-like compounds, by ferrate(VI) (Fe VI O 4 2- , Fe(VI)). Kinetics of the reactions of Fe(VI) with seventeen PCDPSs, differ in number and positions of chlorine atoms (from 2 to 7), were investigated at pH 8.0. The second-order rate constants (k, M -1 s -1 ) of the reactions varied with the numbers and positions of chlorine atoms and appeared to be related with standard Gibbs free energy of formation (Δ f G 0 ) of PCDPSs. Degradation experiments in the presence of ions and humic acid demonstrated complete removal of PeCDPS by Fe(VI) in minutes. Pathways of the reaction were investigated by identifying oxidized products (OPs) of the reaction between Fe(VI) and 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) at pH 8.0. Pathways of oxidation involved major pathway of attack on sulfur(II) by Fe(VI) in steps to yield sulfoxide type products, and subsequent breakage of C-S bond with the formation of sulfonic acid-containing trichloro compound. Minor pathways were hydroxylation of benzene ring and substitution of chlorine atom with hydroxyl group. Estimation of toxicity of OPs of the oxidation of PeCDPS by Fe(VI) suggested the decreased toxicity from the parent contaminant. Copyright © 2018. Published by Elsevier Ltd.

Studies of Positrons Trapped at Quantum-Dot Like Particles Embedded in Metal Surfaces

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Nadesalingam, M. P.; Weiss, A. H.

2009-03-01

Experimental studies of the positron annihilation induced Auger electron (PAES) spectra from the Fe-Cu alloy surfaces with quantum-dot like Cu nanoparticles embedded in Fe show that the PAES signal from Cu increase rapidly as the concentration of Cu is enhanced by vacuum annealing. These measurements indicate that almost 75% of positrons that annihilate with core electrons due so with Cu even though the surface concentration of Cu as measured by EAES is only 6%. This result suggests that positrons become localized at sites at the surface containing high concentration of Cu atoms before annihilation. These experimental results are investigated theoretically by performing calculations of the "image-potential" positron surface states and annihilation characteristics of the surface trapped positrons with relevant Fe and Cu core-level electrons for the clean Fe(100) and Cu(100) surfaces and for the Fe(100) surface with quantum-dot like Cu nanoparticles embedded in the top atomic layers of the host substrate. Estimates of the positron binding energy and positron annihilation characteristics reveal their strong sensitivity to the nanoparticle coverage. Computed core annihilation probabilities are compared with experimental ones estimated from the measured Auger peak intensities. The observed behavior of the Fe and Cu PAES signal intensities is explained by theoretical calculations as being due to trapping of positrons in the regions of Cu nanoparticles embedded in the top atomic layers of Fe.

Abnormal variation of magnetic properties with Ce content in (PrNdCe)2Fe14B sintered magnets prepared by dual alloy method

NASA Astrophysics Data System (ADS)

Xue-Feng, Zhang; Jian-Ting, Lan; Zhu-Bai, Li; Yan-Li, Liu; Le-Le, Zhang; Yong-Feng, Li; Qian, Zhao

2016-05-01

Resource-saving (PrNdCe)2Fe14B sintered magnets with nominal composition (PrNd)15-x Ce x Fe77B8 (x = 0-10) were prepared using a dual alloy method by mixing (PrNd)5Ce10Fe77B8 with (PrNd)15Fe77B8 powders. For Ce atomic percent of 1% and 2%, coercivity decreases dramatically. With further increase of Ce atomic percent, the coercivity increases, peaks at 6.38 kOe in (PrNd)11Ce4Fe77B8, and then declines gradually. The abnormal dependence of coercivity is likely related to the inhomogeneity of rare earth chemical composition in the intergranular phase, where PrNd concentration is strongly dependent on the additive amount of (PrNd)5Ce10Fe77B8 powders. In addition, for Ce atomic percent of 8%, 7%, and 6% the coercivity is higher than that of magnets prepared by the conventional method, which shows the advantage of the dual alloy method in preparing high abundant rare earth magnets. Project supported by the National Natural Science Foundation of China (Grant Nos. 51461033, 51571126, 51541105, and 11547032), the Natural Science Foundation of Inner Mongolia, China (Grant No. 2013MS0110), and the Inner Mongolia University of Science and Technology Innovation Fund, China.

Novel Fe-based nanocrystalline powder cores with excellent magnetic properties produced using gas-atomized powder

NASA Astrophysics Data System (ADS)

Chang, Liang; Xie, Lei; Liu, Min; Li, Qiang; Dong, Yaqiang; Chang, Chuntao; Wang, Xin-Min; Inoue, Akihisa

2018-04-01

FeSiBPNbCu nanocrystalline powder cores (NPCs) with excellent magnetic properties were fabricated by cold-compaction of the gas-atomized amorphous powder. Upon annealing at the optimum temperature, the NPCs showed excellent magnetic properties, including high initial permeability of 88, high frequency stability up to 1 MHz with a constant value of 85, low core loss of 265 mW/cm3 at 100 kHz for Bm = 0.05 T, and superior DC-bias permeability of 60% at a bias field of 100 Oe. The excellent magnetic properties of the present NPCs could be attributed to the ultrafine α-Fe(Si) phase precipitated in the amorphous matrix and the use of gas-atomized powder coated with a uniform insulation layer.

Synthesis, characterization and single crystal x-ray analysis of a complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine

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

Kumar, Sandeep; Andotra, Savit; Kaur, Mandeep

2016-09-15

Complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine [((2,4- (CH{sub 3}){sub 2}C{sub 6}H{sub 3}O)2PS2)2Fe(NC{sub 5}H{sub 4}(C{sub 2}H{sub 5})-4){sub 2}] is synthesized and characterized by elemental analysis, magnetic moment, IR spectroscopy and single crystal X-ray analysis. Complex crystallizes in the monoclinic sp. gr. P2{sub 1}/n, Z = 2. Crystal structure consists of mononuclear units with Fe(II) ion chelated by four S atoms of the two diphenyldithiophosphate ligands in bidentate manner. N atoms from two 4-ethylpyridine ligands are axially coordinated to the Fe(II) atom leading to an octahedral geometry.

Ultrafast Magnetism of Multi-component Ferromagnets and Ferrimagnets on the Time Scale of the Exchange Interaction

NASA Astrophysics Data System (ADS)

Radu, Ilie

2012-02-01

Revealing the ultimate speed limit at which magnetic order can be controlled, is a fundamental challenge of modern magnetism having far reaching implications for the magnetic recording industry [1]. Exchange interaction is the strongest force in magnetism, being ultimately responsible for ferromagnetic or antiferromagnetic spin order. How do spins react after being optically excited on a timescale of or even faster than the exchange interaction? Here, we demonstrate that femtosecond (fs) measurements of ferrimagnetic and ferromagnetic alloys using X-ray magnetic circular dichroism provide revolutionary new insights into the problem of ultrafast magnetism on timescales pertinent to the exchange interaction. In particular, we show that upon fs optical excitation the ultrafast spin reversal of GdFeCo - a material with antiferromagnetic coupling of spins - occurs via a transient ferromagnetic state [2]. The latter emerges due to different dynamics of the Gd and Fe magnetic moments: Gd switches within 1.5 ps while it takes only 300 fs for Fe. Thus, by using a single fs laser pulse one can force the spin system to evolve via an energetically unfavorable way and temporarily switch from an antiferromagnetic to a ferromagnetic type of ordering. In order to understand whether the observation of this temporarily decoupled and element-specific dynamics is a general phenomenon or just something strictly related to the case of ferrimagnetic GdFeCo, we have investigated the demagnetization of the archetypal ferromagnetic NiFe alloys. Essentially, we observe the same distinct magnetization dynamics of the constituent magnetic moments: Ni demagnetizes within ˜300 fs being much faster than the demagnetization of Fe of ˜800 fs. This distinct demagnetization behavior leads to an apparent decoupling of the Fe and Ni magnetic moments on a few hundreds of fs time scale, despite the strong exchange interaction of 260meV (˜16 fs) that couples them. These observations supported by atomistic simulations, present a novel concept of manipulating magnetic order on different classes of magnetic materials on timescales of the exchange interaction [3]. [4pt] [1] A. Kirilyuk, A.V. Kimel and Th. Rasing, Rev. Mod. Phys. 82, 2731 (2010). [0pt] [2] I. Radu et al., Nature 472, 205 (2011). [0pt] [3] I. Radu et al., submitted (2011).

Manipulating molecule-substrate exchange interactions via graphene

NASA Astrophysics Data System (ADS)

Bhandary, Sumanta; Eriksson, Olle; Sanyal, Biplab

2013-03-01

Organometallic molecules with a 3d metal center carrying a spin offers many interesting properties, e.g., existence of multiple spin states. A recent interest has been in understanding the magnetic exchange interaction between these organometallic molecules and magnetic substrates both from experiments and theory. In this work, we will show by calculations based on density functional theory how the exchange interaction is mediated via graphene in a geometry containing iron porphyrin(FeP)/graphene/Ni(111). The exchange interaction varies from a ferromagnetic to an antiferromagnetic one depending on the lattice site and type of defect in the graphene lattice along with the switching of spin state of Fe in FeP between S=1 and S=2, which should be detectable by x-ray magnetic circular dichroism experiments. This scenario of complex magnetic couplings with large magnetic moments may offer a unique spintronic logic device. We acknowledge financial support from the Swedish Research Council, KAW foundation and the ERC(project 247062 - ASD).

Iron state in iron nanoparticles with and without zirconium

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Khasanov, A. M.; Lauer, Yu. A.

2017-11-01

Mössbauer and X-ray methods are used for investigations of structure, stability and characteristics of pure-iron grain and two iron-zirconium alloys such as Fe + 5 wt.% Zr and Fe + 10 wt.% Zr. The used powder was ground for 24 h in a SPEX Model 8000 mill shaker. Complex nanoparticles are found, which change their properties under milling. Mössbauer spectral parameters are obtained for investigated materials. Milling results in formation of nanosized particles with two states of iron atoms: one main part is pure α-Fe and another part of iron atoms displaced in grain boundaries or defective zones in which hyperfine magnetic splitting decrease to ˜ 30.0 T. In alloys with Zr three iron states are formed in each alloy, main part of iron is in the form of α-Fe and another two states depend on the concentration of Zr and represent iron in grain boundaries with Zr atoms in nearest neighbor. The changing of iron states is discussed.