Negative Thermal Expansion over a Wide Temperature Range in Fe-doped MnNiGe Composites

NASA Astrophysics Data System (ADS)

Zhao, Wenjun; Sun, Ying; Liu, Yufei; Shi, Kewen; Lu, Huiqing; Song, Ping; Wang, Lei; Han, Huimin; Yuan, Xiuliang; Wang, Cong

2018-02-01

Fe-doped MnNiGe alloys were successfully synthesized by solid-state reaction. Giant negative thermal expansion (NTE) behaviors with the coefficients of thermal expansion (CTE) of -285.23×10-6 K-1 (192-305 K) and -1167.09×10-6 K-1 (246-305 K) have been obtained in Mn0.90Fe0.10NiGe and MnNi0.90Fe0.10Ge, respectively. Furthermore, these materials were combined with Cu in order to control the NTE properties. The results indicate that the absolute value of CTE gradually decreases with increasing Cu contents. In Mn0.92Fe0.08NiGe/x%Cu, the CTE gradually changes from -64.92×10-6 K-1 (125-274 K) to -4.73×10-6 K-1 (173-229 K) with increasing value of x from 15 to 70. The magnetic measurements reveal that the NTE behaviors in this work are strongly correlated with the process of the magnetic phase transition and the introduction of Fe atoms could also change the spiral anti-ferromagnetic (s-AFM) state into ferromagnetic (FM) state at low temperature. Our study launches a new candidate for controlling thermal expansion properties of metal matrix materials which could have potential application in variable temperature environment.

Effect of NiFeCr seed and capping layers on exchange bias and planar Hall voltage response of NiFe/Au/IrMn trilayer structures

NASA Astrophysics Data System (ADS)

Talantsev, Artem; Elzwawy, Amir; Kim, CheolGi

2018-05-01

Thin films and cross junctions, based on NiFe/Au/IrMn structures, were grown on Ta and NiFeCr seed layers by magnetron sputtering. The effects of substitution of Ta with NiFeCr in seed and capping layers on an exchange bias field are studied. A threefold improvement of the exchange bias value in the structures, grown with NiFeCr seed and capping layers, is demonstrated. The reasons for this effect are discussed. Formation of clusters in the NiFeCr capping layer is proved by atomic force microscopy technique. Ta replacement on NiFeCr in the capping layer results in the enhancement of magnetoresistive response and a reduction of noise.

Magnetic properties of the CrMnFeCoNi high-entropy alloy

DOE PAGES

Schneeweiss, Oldřich; Friák, Martin; Dudová, Marie; ...

2017-07-28

In this paper, we present experimental data showing that the equiatomic CrMnFeCoNi high-entropy alloy undergoes two magnetic transformations at temperatures below 100 K while maintaining its fcc structure down to 3 K. The first transition, paramagnetic to spin glass, was detected at 93 K and the second transition of the ferromagnetic type occurred at 38 K. Field-assisted cooling below 38 K resulted in a systematic vertical shift of the hysteresis curves. Strength and direction of the associated magnetization bias was proportional to the strength and direction of the cooling field and shows a linear dependence with a slope of 0.006more » ± 0.001 emu T. The local magnetic moments of individual atoms in the CrMnFeCoNi quinary fcc random solid solution were investigated by ab initio (electronic density functional theory) calculations. Results of the numerical analysis suggest that, irrespective of the initial configuration of local magnetic moments, the magnetic moments associated with Cr atoms align antiferromagnetically with respect to a cumulative magnetic moment of their first coordination shell. The ab initio calculations further showed that the magnetic moments of Fe and Mn atoms remain strong (between 1.5 and 2 μ B), while the local moments of Ni atoms effectively vanish. Finally, these results indicate that interactions of Mn- and/or Fe-located moments with the surrounding magnetic structure account for the observed macroscopic magnetization bias.« less

Microstructure and corrosion properties of CrMnFeCoNi high entropy alloy coating

NASA Astrophysics Data System (ADS)

Ye, Qingfeng; Feng, Kai; Li, Zhuguo; Lu, Fenggui; Li, Ruifeng; Huang, Jian; Wu, Yixiong

2017-02-01

Equimolar CrMnFeCoNi high entropy alloy (HEA) is one of the most notable single phase multi-component alloys up-to-date with promising mechanical properties at cryogenic temperatures. However, the study on the corrosion behavior of CrMnFeCoNi HEA coating has still been lacking. In this paper, HEA coating with a nominal composition of CrMnFeCoNi is fabricated by laser surface alloying and studied in detail. Microstructure and chemical composition are determined by X-ray diffraction (XRD), optical microscope (OM), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) are used to investigate the corrosion behavior. The coating forms a simple FCC phase with an identical dendritic structure composed of Fe/Co/Ni-rich dendrites and Mn/Ni-rich interdendrites. Both in 3.5 wt.% NaCl solution and 0.5 M sulfuric acid the coating exhibits nobler corrosion resistance than A36 steel substrate and even lower icorr than 304 stainless steel (304SS). EIS plots coupled with fitted parameters reveal that a spontaneous protective film is formed and developed during immersion in 0.5 M sulfuric acid. The fitted Rt value reaches its maximum at 24 h during a 48 h' immersion test, indicating the passive film starts to break down after that. EDS analysis conducted on a corroded surface immersed in 0.5 M H2SO4 reveals that corrosion starts from Cr-depleted interdendrites.

Investigation of the mechanical properties of FeNiCrMnSi high entropy alloy wear resistant

NASA Astrophysics Data System (ADS)

Buluc, G.; Florea, I.; Chelariu, R.; Popescu, G.; Carcea, I.

2016-06-01

In this paper we investigated microstructure, hardness and wear resistance for FeNiCrMnAl, high entropy alloy. The FeNiCrMnSi, high entropy alloy was elaborated in a medium induction furnace, by choosing the silicon, as an alliance element within the equi- atomic high entropy alloy, we managed to obtain a dendritic structure, the formation of intermetallic compounds or separated silicon. The medium hardness value of the investigated alloy was 948.33 HV and the medium value of the friction coefficient was 0.6655 in the first 20 seconds and 0.5425 for 1667 seconds. The volume loss of the high entropy alloy FeNiCrMnSi was 0.0557 mm3.

Negative Thermal Expansion over a Wide Temperature Range in Fe-Doped MnNiGe Composites

PubMed Central

Zhao, Wenjun; Sun, Ying; Liu, Yufei; Shi, Kewen; Lu, Huiqing; Song, Ping; Wang, Lei; Han, Huimin; Yuan, Xiuliang; Wang, Cong

2018-01-01

Fe-doped MnNiGe alloys were successfully synthesized by solid-state reaction. Giant negative thermal expansion (NTE) behaviors with the coefficients of thermal expansion (CTE) of −285.23 × 10−6 K−1 (192–305 K) and −1167.09 × 10−6 K−1 (246–305 K) have been obtained in Mn0.90Fe0.10NiGe and MnNi0.90Fe0.10Ge, respectively. Furthermore, these materials were combined with Cu in order to control the NTE properties. The results indicate that the absolute value of CTE gradually decreases with increasing Cu contents. In Mn0.92Fe0.08NiGe/x%Cu, the CTE gradually changes from −64.92 × 10−6 K−1 (125–274 K) to −4.73 × 10−6 K−1 (173–229 K) with increasing value of x from 15 to 70. The magnetic measurements reveal that the NTE behaviors in this work are strongly correlated with the process of the magnetic phase transition and the introduction of Fe atoms could also change the spiral anti-ferromagnetic (s-AFM) state into ferromagnetic (FM) state at low temperature. Our study launches a new candidate for controlling thermal expansion properties of metal matrix materials which could have potential application in variable temperature environment. PMID:29468152

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

DOE PAGES

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia; ...

2017-10-31

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

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

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Elastic moduli and thermal expansion coefficients of medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy

DOE PAGES

Laplanche, Guillaume; Gadaud, P.; Barsch, C.; ...

2018-02-23

Elastic moduli of a set of equiatomic alloys (CrFeCoNi, CrCoNi, CrFeNi, FeCoNi, MnCoNi, MnFeNi, and CoNi), which are medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy were determined as a function of temperature over the range 293 K–1000 K. Thermal expansion coefficients were determined for these alloys over the temperature range 100 K–673 K. All alloys were single-phase and had the face-centered cubic (FCC) crystal structure, except CrFeNi which is a two-phase alloy containing a small amount of body-centered cubic (BCC) precipitates in a FCC matrix. The temperature dependences of thermal expansion coefficients and elastic moduli obtained here are useful formore » quantifying fundamental aspects such as solid solution strengthening, and for structural analysis/design. Furthermore, using the above results, the yield strengths reported in literature for these alloys were normalized by their shear moduli to reveal the influence of shear modulus on solid solution strengthening.« less

Elastic moduli and thermal expansion coefficients of medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy

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

Laplanche, Guillaume; Gadaud, P.; Barsch, C.

Elastic moduli of a set of equiatomic alloys (CrFeCoNi, CrCoNi, CrFeNi, FeCoNi, MnCoNi, MnFeNi, and CoNi), which are medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy were determined as a function of temperature over the range 293 K–1000 K. Thermal expansion coefficients were determined for these alloys over the temperature range 100 K–673 K. All alloys were single-phase and had the face-centered cubic (FCC) crystal structure, except CrFeNi which is a two-phase alloy containing a small amount of body-centered cubic (BCC) precipitates in a FCC matrix. The temperature dependences of thermal expansion coefficients and elastic moduli obtained here are useful for quantifying fundamental aspects suchmore » as solid solution strengthening, and for structural analysis/design. Furthermore, using the above results, the yield strengths reported in literature for these alloys were normalized by their shear moduli to reveal the influence of shear modulus on solid solution strengthening.« less

Electrical conduction mechanism of LaNi{sub x}Me{sub 1−x}O{sub 3−δ} (Me = Fe, Mn)

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

Niwa, Eiki, E-mail: e-niwa@phys.chs.nihon-u.ac.jp; Department of Integrated Sciences in Physics and Biology, College of Humanities and Sciences, Nihon University, Setagaya-ku, Tokyo 156-8550; Maeda, Hiroki

Graphical abstract: Compositional dependence of (a) electrical conductivity and (b) E{sub a} for hopping conduction of LaNi{sub x}Me{sub 1−x}O{sub 3} (Me = Fe, Mn). - Highlights: • Electrical conduction mechanism of LaNi{sub x}Me{sub 1−x}O{sub 3} (Me = Fe, Mn) was investigated. • Hopping conduction model could be applied for conductivity of both specimens. • The difference of E{sub a} due to that of energy level of Fe and Mn was observed. • Hole concentration estimated by iodimetry increases with increasing Ni content. - Abstract: Electrical conduction mechanism of LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} and LaNi{sub x}Mn{sub 1−x}O{sub 3+δ} expected as Sr-freemore » new cathode material for solid oxide fuel cells was analyzed. Electrical conduction behaviors of both specimens could be well fitted by small polaron hopping conduction model. The electrical conductivity of LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} increased with increasing Ni content, showing agreement with decrease of activation energy for hopping conduction. The decrease of electrical conductivity and increase of activation energy of LaNi{sub x}Mn{sub 1−x}O{sub 3+δ} were observed with increasing Ni content for 0.0 ≤ x ≤ 0.4. Further Ni substitution increased electrical conductivity and decreased activation energy for 0.4 ≤ x ≤ 0.6. It was revealed using iodometry that the difference of hole carrier density between LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} and LaNi{sub x}Mn{sub 1−x}O{sub 3+δ} was small. It was suspected that the origin of the difference of electrical conduction behavior of LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} and LaNi{sub x}Mn{sub 1-x}O{sub 3+δ} was difference of energy level of e{sub g} band composed of Fe 3d or Mn 3d orbitals and their overlapping quantity with O 2p and Ni 3d band.« less

Tailoring magnetic behavior of CoFeMnNiX (X = Al, Cr, Ga, and Sn) high entropy alloys by metal doping

DOE PAGES

Zuo, Tingting; Gao, Michael C.; Ouyang, Lizhi; ...

2017-03-07

Magnetic materials with excellent performances are desired for functional applications. Based on the high-entropy effect, a system of CoFeMnNiX (X = Al, Cr, Ga, and Sn) magnetic alloys are designed and investigated. The dramatic change in phase structures from face-centered-cubic (FCC) to ordered body-centered-cubic (BCC) phases, caused by adding Al, Ga, and Sn in CoFeMnNiX alloys, originates from the potent short-range chemical order in the liquid state predicted by ab initio molecular dynamics (AIMD) simulations. This phase transition leads to the significant enhancement of the saturation magnetization (M s), e.g., the CoFeMnNiAl alloy has M s of 147.86 Am 2/kg.more » In conclusion, first-principles density functional theory (DFT) calculations on the electronic and magnetic structures reveal that the anti-ferromagnetism of Mn atoms in CoFeMnNi is suppressed especially in the CoFeMnNiAl HEA because Al changes the Fermi level and itinerant electron-spin coupling that lead to ferromagnetism.« less

Crystallographic, magnetic, and electronic structures of ferromagnetic shape memory alloys Ni2XGa (X=Mn,Fe,Co) from first-principles calculations

NASA Astrophysics Data System (ADS)

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

2011-01-01

The crystallographic, magnetic and electronic structures of the ferromagnetic shape memory alloys Ni2XGa (X=Mn, Fe, and 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 lattice parameters of both austenitic and martensitic phases in Ni2MnGa have been calculated. The formation energies of the cubic phase of Ni2XGa are estimated, and show a destabilization tendency if Mn atom is substituted by Fe or Co. From Ni2MnGa to Ni2CoGa, the down spin total density of states (DOS) at Fermi level is gradually increasing, whereas that of the up spin part remains almost unchanged. This is the main origin of the difference of the magnetic moment in these alloys. The partial DOS is dominated by the Ni and Mn 3d states in the bonding region below EF. There are two bond types existing in Ni2XGa: one is between neighboring Ni atoms in Ni2MnGa; the other is between Ni and X atoms in Ni2FeGa and Ni2CoGa alloys.

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.

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.

Weathering and precipitation after meteorite impact of Ni, Cr, Fe, Ca and Mn in K-T boundary clays from Stevns Klint

NASA Astrophysics Data System (ADS)

Miyano, Yumiko; Yoshiasa, Akira; Tobase, Tsubasa; Isobe, Hiroshi; Hongu, Hidetomo; Okube, Maki; Nakatsuka, Akihiko; Sugiyama, Kazumasa

2016-05-01

Ni, Cr, Fe, Ca and Mn K-edge XANES and EXAFS spectra were measured on K-T boundary clays from Stevns Klint in Denmark. According to XANES spectra and EXAFS analyses, the local structures of Ni, Cr and Fe in K-T boundary clays is similar to Ni(OH)2, Cr2O3 and FeOOH, respectively. It is assumed that the Ni, Cr and Fe elements in impact related glasses is changing into stable hydrate and oxide by the weathering and diagenesis at the surface of the Earth. Ca in K-T boundary clays maintains the diopside-like structure. Local structure of Ca in K-T clays seems to keep information on the condition at meteorite impact. Mn has a local structure like MnCO3 with divalent state. It is assumed that the origin on low abundant of Mn in the Fe-group element in K-T clays was the consumption by life activity and the diffusion to other parts.

Unusual strain glassy phase in Fe doped Ni2Mn1.5In0.5

NASA Astrophysics Data System (ADS)

Nevgi, R.; Priolkar, K. R.

2018-01-01

Fe doped Ni2Mn1.5In0.5, particularly, Ni2Mn1.4Fe0.1In0.5, despite having an incommensurate, modulated 7M martensitic structure at room temperature exhibits frequency dependent behavior of storage modulus and loss which obeys the Vogel-Fulcher law as well as shows ergodicity breaking between zero field cooled and field cooled strain measurements just above the transition temperature. Both frequency dependence and ergodicity breaking are characteristics of a strain glassy phase and occur due to the presence of strain domains which are large enough to present signatures of long range martensitic order in diffraction but are non-interacting with other strain domains due to the presence of Fe impurities.

Magnetoelastic effect in MF2 (M = Mn, Fe, Ni) investigated by neutron powder diffraction

NASA Astrophysics Data System (ADS)

Chatterji, Tapan; Iles, Gail N.; Ouladdiaf, Bachir; Hansen, Thomas C.

2010-08-01

We have investigated the magnetoelastic effects in MF2 (M = Mn, Fe, Ni) associated with the antiferromagnetic phase transition temperature TN by neutron powder diffraction. The temperature variation of the lattice parameters and the unit cell volume has been determined accurately with small temperature steps. From the temperature variation of the lattice parameters a, c and V the lattice strains Δa, Δc and ΔV associated with the antiferromagnetic phase transition have been extracted. Rietveld refinement of the crystal and magnetic structures from the diffraction data at low temperature gave a magnetic moment of 5.12 ± 0.09 μB, 4.05 ± 0.05 μB and 1.99 ± 0.05 μB per Mn, Fe and Ni ions, respectively. The lattice strains Δa, Δc and ΔV couple linearly with the intensity of the 100 magnetic reflection, which is proportional to square of the order parameter of the antiferromagnetic phase transition. The volume strains in MF2 (M = Mn, Fe, Co, Ni) due to the magnetostriction vary smoothly along the transition metal series and seem to be correlated with the strength of the exchange interaction and the moments of the magnetic ions.

Magnetoelastic effect in MF2 (M = Mn, Fe, Ni) investigated by neutron powder diffraction.

PubMed

Chatterji, Tapan; Iles, Gail N; Ouladdiaf, Bachir; Hansen, Thomas C

2010-08-11

We have investigated the magnetoelastic effects in MF(2) (M = Mn, Fe, Ni) associated with the antiferromagnetic phase transition temperature T(N) by neutron powder diffraction. The temperature variation of the lattice parameters and the unit cell volume has been determined accurately with small temperature steps. From the temperature variation of the lattice parameters a, c and V the lattice strains Δa, Δc and ΔV associated with the antiferromagnetic phase transition have been extracted. Rietveld refinement of the crystal and magnetic structures from the diffraction data at low temperature gave a magnetic moment of 5.12 ± 0.09 μ(B), 4.05 ± 0.05 μ(B) and 1.99 ± 0.05 μ(B) per Mn, Fe and Ni ions, respectively. The lattice strains Δa, Δc and ΔV couple linearly with the intensity of the 100 magnetic reflection, which is proportional to square of the order parameter of the antiferromagnetic phase transition. The volume strains in MF(2) (M = Mn, Fe, Co, Ni) due to the magnetostriction vary smoothly along the transition metal series and seem to be correlated with the strength of the exchange interaction and the moments of the magnetic ions.

Estimation of the Temperature-Dependent Nitrogen Solubility in Stainless Fe-Cr-Mn-Ni-Si-C Steel Melts During Processing

NASA Astrophysics Data System (ADS)

Wendler, Marco; Hauser, Michael; Sandig, Eckhard Frank; Volkova, Olena

2018-04-01

The influence of chemical composition, temperature, and pressure on the nitrogen solubility of various high alloy stainless steel grades, namely Fe-14Cr-(0.17-7.77)Mn-6Ni-0.5Si-0.03C [wt pct], Fe-15Cr-3Mn-4Ni-0.5Si-0.1C [wt pct], and Fe-19Cr-3Mn-4Ni-0.5Si-0.15C [wt pct], was studied in the melt. The temperature-dependent N-solubility was determined using an empirical approach proposed by Wada and Pehlke. The thus calculated N-concentrations overestimate the actual N-solubility of all the studied Fe-Cr-Mn-Ni-Si-C steel melts at a given temperature and pressure. Consequently, the calculation model has to be modified by Si and C because both elements are not recognized in the original equation. The addition of the 1st and 2nd order interaction parameters for Si and C to the model by Wada and Pehlke allows a precise estimation of the temperature-dependent nitrogen solubility in the liquid steel bath, and fits very well with the measured nitrogen concentrations during processing of the steels. Moreover, the N-solubility enhancing effect of Cr- and Mn-additions has been demonstrated.

Microstructure and magnetic behavior studies of processing-controlled and composition-modified Fe-Ni and Mn-Al alloys

NASA Astrophysics Data System (ADS)

Geng, Yunlong

L10-type (Space group P4/mmm) magnetic compounds, including FeNi and MnAl, possess promising technical magnetic properties of both high magnetization and large magnetocrystalline anisotropy energy, and thus offer potential in replacing rare earth permanent magnets in some applications. In equiatomic Fe-Ni, the disorder-order transformation from fcc structure to the L10 structure is a diffusional transformation, but is inhibited by the low ordering temperature. The transformation could be enhanced through the creation of vacancies. Thus, mechanical alloying was employed to generate more open-volume defects. A decrease in grain size and concomitant increase in grain boundary area resulted from the mechanical alloying, while an initial increase in internal strain (manifested through an increase in dislocation density) was followed by a subsequent decrease with further alloying. However, a decrease in the net defect concentration was determined by Doppler broadening positron annihilation spectroscopy, as open volume defects utilized dislocations and grain boundaries as sinks. An alloy, Fe32Ni52Zr3B13, formed an amorphous structure after rapid solidification, with a higher defect concentration than crystalline materials. Mechanical milling was utilized in an attempt to generate even more defects. However, it was observed that Fe32Ni52Zr3B13 underwent crystallization during the milling process, which appears to be related to enhanced vacancy-type defect concentrations allowing growth of pre-existing Fe(Ni) nuclei. The milling and enhanced vacancy concentration also de-stabilizes the glass, leading to decreased crystallization temperatures, and ultimately leading to complete crystallization. In Mn-Al, the L10 structure forms from the parent hcp phase. However, this phase is slightly hyperstoichiometric relative to Mn, and the excess Mn occupies Al sites and couples antiparallel to the other Mn atoms. In this study, the Zr substituted preferentially for the Mn atoms in the

Hydrogen vibrations in austenitic fcc Fe-Cr-Mn-Ni steels

NASA Astrophysics Data System (ADS)

Danilkin, S. A.; Fuess, H.; Wipf, H.; Ivanov, A.; Gavriljuk, V. G.; Delafosse, D.; Magnin, T.

2003-07-01

By neutron spectroscopy, we studied vibrations of H interstitials in two austenitic fcc steels (Fe0.55Cr0.20Mn0.10Ni0.15 and Fe0.54Cr0.27Ni0.19) doped with 0.37 and 0.33 at% H. The band modes, in which H vibrates with its metal neighbours, cause a weak intensity in the energy range of the acoustic vibrations of the H-free steels. The energies of the fundamental and the twofold local-mode excitations, in which H vibrates against its metal neighbours, were ~ 130 and ~ 260 meV, respectively. The respective peaks in the spectra were broadened because the metal neighbours of H, and thus its vibrational energies, vary from interstitial site to interstitial site. The above energy values support an H occupation of octahedral interstitial sites.

Microstructures and mechanical properties of compositionally complex Co-free FeNiMnCr 18 FCC solid solution alloy

DOE PAGES

Wu, Z.; Bei, H.

2015-07-01

Recently, a structurally-simple but compositionally-complex FeNiCoMnCr high entropy alloy was found to have excellent mechanical properties (e.g., high strength and ductility). To understand the potential of using high entropy alloys as structural materials for advanced nuclear reactor and power plants, it is necessary to have a thorough understanding of their structural stability and mechanical properties degradation under neutron irradiation. Furthermore, this requires us to develop a similar model alloy without Co because material with Co will make post-neutron-irradiation testing difficult due to the production of the 60Co radioisotope. In order to achieve this goal, a FCC-structured single-phase alloy with amore » composition of FeNiMnCr 18 was successfully developed. This near-equiatomic FeNiMnCr 18 alloy has good malleability and its microstructure can be controlled by thermomechanical processing. By rolling and annealing, the as-cast elongated-grained-microstructure is replaced by homogeneous equiaxed grains. The mechanical properties (e.g., strength and ductility) of the FeNiMnCr 18 alloy are comparable to those of the equiatomic FeNiCoMnCr high entropy alloy. Both strength and ductility increase with decreasing deformation temperature, with the largest difference occurring between 293 and 77 K. Extensive twin-bands which are bundles of numerous individual twins are observed when it is tensile-fractured at 77 K. No twin bands are detected by EBSD for materials deformed at 293 K and higher. Ultimately the unusual temperature-dependencies of UTS and uniform elongation could be caused by the development of the dense twin substructure, twin-dislocation interactions and the interactions between primary and secondary twinning systems which result in a microstructure refinement and hence cause enhanced strain hardening and postponed necking.« less

Hierarchical 3D NiFe2O4@MnO2 core-shell nanosheet arrays on Ni foam for high-performance asymmetric supercapacitors.

PubMed

Zhang, Xinyang; Zhang, Ziqing; Sun, Shuanggan; Sun, Qiushi; Liu, Xiaoyang

2018-02-13

Hierarchical NiFe 2 O 4 @MnO 2 core-shell nanosheet arrays (NSAs) were synthesized on Ni foam as an integrated electrode for supercapacitors, using a facile two-step hydrothermal method followed by calcination treatment. The NiFe 2 O 4 nanosheets were designed as the core and ultrathin MnO 2 nanoflakes as the shell, creating a unique three-dimensional (3D) hierarchical electrode on Ni foam. The composite electrode exhibited remarkable electrochemical performance with a high specific capacitance of 1391 F g -1 at a current density of 2 mA cm -2 and long cycling stability at a high current density of 10 mA cm -2 (only 11.4% loss after 3000 cycles). Additionally, an asymmetric supercapacitor (ASC) device was fabricated with a NiFe 2 O 4 @MnO 2 composite as the positive electrode material and activated carbon (AC) as the negative one. The ASC device exhibited a high energy density (45.2 W h kg -1 ) at a power density of 174 W kg -1 , and an excellent cycling stability over 3000 cycles with 92.5% capacitance retention. The remarkable electrochemical performance demonstrated its great potential as a promising candidate for high-performance supercapacitors.

Antiferromagnetic layer thickness dependence of noncollinear uniaxial and unidirectional anisotropies in NiFe/FeMn/CoFe trilayers

NASA Astrophysics Data System (ADS)

Choi, Hyeok-Cheol; You, Chun-Yeol; Kim, Ki-Yeon; Lee, Jeong-Soo; Shim, Je-Ho; Kim, Dong-Hyun

2010-06-01

We have investigated the dependence of magnetic anisotropies of the exchange-biased NiFe/FeMn/CoFe trilayers on the antiferromagnetic (AF) layer thickness (tAF) by measuring in-plane angular-dependent ferromagnetic resonance fields. The resonance fields of NiFe and CoFe sublayers are shifted to lower and higher values compared to those of single unbiased ferromagnetic (F) layers, respectively, due to the interfacial exchange coupling when tAF≥2nm . In-plane angular dependence of resonance field reveals that uniaxial and unidirectional anisotropies coexist in the film plane, however, they are not collinear with each other. It is found that these peculiar noncollinear anisotropies significantly depend on tAF . The angle of misalignment displays a maximum around tAF=5nm and converges to zero when tAF is thicker than 10 nm. Contributions from thickness-dependent AF anisotropy and spin frustrations at both F/AF interfaces due to the structural imperfections should be accounted in order to understand the AF-layer thickness dependence of noncollinear magnetic anisotropies.

Interface adjustment and exchange coupling in the IrMn/NiFe system

NASA Astrophysics Data System (ADS)

Spizzo, F.; Tamisari, M.; Chinni, F.; Bonfiglioli, E.; Del Bianco, L.

2017-01-01

The exchange bias effect was investigated, in the 5-300 K temperature range, in samples of IrMn [100 Å]/NiFe [50 Å] (set A) and in samples with inverted layer-stacking sequence (set B), produced at room temperature by DC magnetron sputtering in a static magnetic field of 400 Oe. The samples of each set differ for the nominal thickness (tCu) of a Cu spacer, grown at the interface between the antiferromagnetic and ferromagnetic layers, which was varied between 0 and 2 Å. It has been found out that the Cu insertion reduces the values of the exchange field and of the coercivity and can also affect their thermal evolution, depending on the stack configuration. Indeed, the latter also determines a peculiar variation of the exchange bias properties with time, shown and discussed with reference to the samples without Cu of the two sets. The results have been explained considering that, in this system, the exchange coupling mechanism is ruled by the glassy magnetic behavior of the IrMn spins located at the interface with the NiFe layer. Varying the stack configuration and tCu results in a modulation of the structural and magnetic features of the interface, which ultimately affects the spins dynamics of the glassy IrMn interfacial component.

Using granular C0-AI2O3 spacer for optimization of functional parameters of the FeMn/Fe20Ni80 magnetoresistive films

NASA Astrophysics Data System (ADS)

Gorkovenko, A. N.; Lepalovskij, V. N.; Adanakova, O. A.; Vas'kovskiy, V. O.

2016-03-01

In this paper we studied the possibility of tailoring the functional properties of the multilayer magnetoresistive medium with unidirectional anisotropy and the anisotropic magnetoresistance effect (AMR). Objects of the research were composite Co-Al2O3 films and Ta/Fe20Ni80/Fe50Mn50/Fe20Ni80/Co-Al2O3/Fe20Ni80/Ta multilayers structures obtained by magnetron sputtering and selectively subjected vacuum annealing. Structure, magnetic and magnetoresistive properties of the films in the temperature range 77÷440 K were investigated.

First-principles study on the stability and magnetoelectric properties of multiferroic materials XTiO3 (X = Mn, Fe, Co, Ni)

NASA Astrophysics Data System (ADS)

Chen, Xing-Yuan; Lai, Guo-Xia; Gu, Di; Zhu, Wei-Ling; Lai, Tian-Shu; Zhao, Yu-Jun

2018-04-01

The XTiO3 (X = Mn, Fe, Co and Ni) materials with R3c structure could be grown under critical conditions based on first-principles calculations and thermodynamic stability analysis. FeTiO3 and MnTiO3 could be synthesized relatively easily under metal-rich and O-poor conditions, while NiTiO3 could be stable under Ni-rich, O-rich and Ti-poor conditions. The predicted R3c CoTiO3 under thermodynamic equilibrium conditions is suggested to be synthesized under Co-rich, O-rich and Ti-poor conditions, but the calculated phonon dispersion indicates R3c CoTiO3 becomes unstable under the dynamical conditions. The ferroelectric behavior in the XTiO3 (X = Mn, Fe, Co and Ni) system could be dominated by the Ti ion with d0 state and the strong hybridization between Ti and O, while the magnetic property is mainly caused by the contribution of 3d transition metal.

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

Transition-Metal Mixing and Redox Potentials in Li x (M 1–y M' y )PO 4 (M, M' = Mn, Fe, Ni) Olivine Materials from First-Principles Calculations

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

Snydacker, David H.; Wolverton, Chris

The performance of olivine cathode materials can be improved using core/shell structures such as LiMnPO 4/LiFePO 4 and LiMnPO 4/LiNiPO 4. We use density functional theory to calculate the energetics, phase stability, and voltages of transition-metal mixing for a series of olivine phosphate materials. For LiMn 1–yFe yPO 4, LiFe 1–yNi yPO 4, and LiMn 1–yNi yPO 4, we find phase-separating tendencies with (mean-field) maximum miscibility gap temperatures of 120, 320, and 760 K respectively. At room temperature, we find that Mn is completely miscible in LiFePO 4, whereas Mn solubility in LiNiPO 4 is just 0.3%. Therefore, we suggestmore » that core/shell LiMnPO 4/LiNiPO 4 particles could be more effective at containing Mn in the particle core and limiting Mn dissolution into the electrolyte relative to LiMnPO 4/LiFePO 4 particles. We calculate shifts in redox potentials for dilute transition metals, M, substituted into Li xM'PO 4 host materials. Unmixed Li xMnPO 4 exhibits a redox potential of 4.0 V, but we find that dilute Mn in a LiNiPO 4 shell exhibits a redox potential of 4.3 V and therefore remains redox inactive at lower cathode potentials. We find that strain plays a large role in the redox potentials of some mixed systems (Li xMn 1–yFe yPO 4) but not others (Li xMn 1–yNi yPO 4).« less

Magnetic and mechanical properties of Ni-Mn-Ga/Fe-Ga ferromagnetic shape memory composite

NASA Astrophysics Data System (ADS)

Tan, Chang-Long; Zhang, Kun; Tian, Xiao-Hua; Cai, Wei

2015-05-01

A ferromagnetic shape memory composite of Ni-Mn-Ga and Fe-Ga was fabricated by using spark plasma sintering method. The magnetic and mechanical properties of the composite were investigated. Compared to the Ni-Mn-Ga alloy, the threshold field for magnetic-field-induced strain in the composite is clearly reduced owing to the assistance of internal stress generated from Fe-Ga. Meanwhile, the ductility has been significantly improved in the composite. A fracture strain of 26% and a compressive strength of 1600 MPa were achieved. Projects supported by the National Natural Science Foundation of China (Grant Nos. 51271065 and 51301054), the Program for New Century Excellent Talents in Heilongjiang Provincial Education Department, China (Grant No. 1253-NCET-009), the Youth Academic Backbone in Heilongjiang Provincial Education Department, China (Grant No. 1251G022), the Projects of Heilongjiang, China, and China Postdoctoral Science Foundation.

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.

Mechanical properties of Fe -10Ni -7Mn martensitic steel subjected to severe plastic deformation via cold rolling and wire drawing

NASA Astrophysics Data System (ADS)

Ghasemi-Nanesa, H.; Nili-Ahmadabadi, M.; Shirazi, H.

2010-07-01

Fe-Ni-Mn martensitic steels are one of the major groups of ultra-high strength steels that have good mechanical properties and ductility in as annealed condition but they suffer from severe inter-granular embitterment after aging. In this paper, the effect of heavy shaped cold rolling and wire drawing on the mechanical properties of Fe-Ni-Mn steel was investigated. This process could provide a large strain deformation in this alloy. The total strain was epsilon ~7. Aging behavior and tensile properties of Fe-10Ni-7Mn were studied after aging at 753 K. The results showed that the ultimate tensile strength and ductility after cold rolling, wire drawing and aging increased up to 2540 MPa and 7.1 %, respectively, while the conventional steels show a premature fracture stress of 830 MPa with about zero ductility after aging.

Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

2016-03-21

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effects of Ni, Mo, Ti and Si on the mechanical properties of Cr free Mn steel (Fe-25Mn-5Al-2C)

NASA Technical Reports Server (NTRS)

Schuon, S. R.

1982-01-01

The FeMnAlC alloys may hold potential as Cr-free replacements for high strategic material iron base superalloys, but little is known about their intermediate temperature (650 C to 870 C) mechanical properties. The effects of alloying elements on the mechanical properties of model FeMnAlC alloys were studied. Results showed that modified FeMnAlC alloys had promising short term, intermediate temperature properties but had relatively poor stress rupture lives at 172 MPa and 788 C. Room temperature and 788 C tensile strength of FeMnAlC alloys were better than common cast stainless steels. Changes in room temperature tensile and 788 C tensile strength and ductility, and 788 C stress rupture life were correlated with changes in Ni, Mo, Ti, and Si levels due to alloying effects on interstitial carbon levels and carbide morphology. Fe-25Mn-5Al-2C had a very poor stress rupture life at 172 MPa and 788 C. Addition of carbide-forming elements improved the stress rupture life.

High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

DOE PAGES

Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.; ...

2017-05-25

High pressure x-ray diffraction measurements reveal that the face-centered cubic (fcc) high-entropy alloy CrMnFeCoNi transforms martensitically to a hexagonal close-packed (hcp) phase at ~14 GPa. We attribute this to suppression of the local magnetic moments, destabilizing the fcc phase. Similar to fcc-to-hcp transformations in Al and the noble gases, this transformation is sluggish, occurring over a range of >40 GPa. But, the behavior of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures.

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.

Magnetic hysterysis evolution of Ni-Al alloy with Fe and Mn substitution by vacuum arc melting to produce the room temperature magnetocaloric effect material

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

Notonegoro, Hamdan Akbar; Mechanical Engineering Dept., FT-Universitas Sultan Ageng Tirtayasa, Cilegon 42435; Kurniawan, Budhy

The development of magnetocaloric effect (MCE) material is done in order to reduce the damage of the ozone layer caused by the chlorofluorocarbons (CFCs) emitted into the air. The research dealing with synthesis of magnetocaloric materials based of Ni-Al Heusler Alloy structure and by varying substitution some atoms of Ni with Fe and Al with Mn on Ni-Al Heusler Alloy structure to become Ni{sub 44}Fe{sub 6}Mn{sub 32}Al{sub 18}. Vacuum Arc Melting (VAM) equipment is used to form the alloys on vacuum condition and by flowing argon gas atmosphere and then followed by annealing process for 72 hours. X-Ray Diffraction (XRD)more » reveals that crystallite structure of material is observed. We define that Ni{sub 44}Fe{sub 6} as X{sub 2}, Mn{sub 25} as Y, and Al{sub 18}Mn{sub 7} as Z. Based on the XRD result, we observed that the general formula X{sub 2}YZ is not changed. The PERMAGRAF measurement revealed that there exists of magnetic hysterysis. The hysterysis show that the magnetic structures of the system undego evolution from diamagnetic to soft ferromagnetic material which all of the compound have the same crystallite structure. This evolution indicated that the change in the composition has led to changes the magnetic composition. Mn is the major element that gives strong magnetic properties to the sample. When Mn partially replaced position of Al, the sample became dominant to be influenced to improve their magnetic properties. In addition, substitution a part of Ni by Fe in the composition reveals a pinning of the domain walls in the sample.« less

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

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

Zhang, Fuxiang; Tong, Yang; Jin, Ke

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

DOE PAGES

Zhang, Fuxiang; Tong, Yang; Jin, Ke; ...

2018-06-16

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Effect of Fe and Co substitution on the martensitic stability and the elastic, electronic, and magnetic properties of Mn2NiGa : Insights from ab initio calculations

NASA Astrophysics Data System (ADS)

Kundu, Ashis; Ghosh, Sheuly; Ghosh, Subhradip

2017-11-01

We investigate the effects of Fe and Co substitutions on the phase stability of the martensitic phase and mechanical, electronic, and magnetic properties of the magnetic shape memory system Mn2NiGa by first-principles density functional theory calculations. The evolution of these aspects upon substitution of Fe and Co at different crystallographic sites is investigated by computing the electronic structure, mechanical properties (tetragonal shear constant, Pugh ratio, and Cauchy pressure), and magnetic exchange parameters. We find that the austenite phase of Mn2NiGa gradually stabilizes with increase in concentration of Fe/Co due to the weakening of the minority spin hybridization of Ni and Mn atoms occupying crystallographically equivalent sites. The interplay between relative structural stability and the compositional changes is understood from the variations in the elastic moduli and electronic structures. We find that like in the Ni2MnGa -based systems, the elastic shear modulus C' can be considered as a predictor of composition dependence of martensitic transformation temperature Tm in substituted Mn2NiGa , thus singling it out as the universally acceptable predictor for martensitic transformation in Ni-Mn-Ga compounds over a wide composition range. The magnetic properties of Mn2NiGa are found to be greatly improved by the substitutions due to stronger ferromagnetic interactions in the compounds. The gradually weaker (stronger) Jahn-Teller distortion (covalent bonding) in the minority spin densities of states due to substitutions leads to a half-metallic-like gap in these compounds resulting in materials with high spin polarization when the substitutions are complete. The substitutions at the Ga site result in the two compounds Mn2NiFe and Mn2NiCo with very high magnetic moments and Curie temperatures. Thus, our work indicates that although the substitutions destroy the martensitic transformation and thus the possibility of realization of shape memory

Effect of one-step recrystallization on the grain boundary evolution of CoCrFeMnNi high entropy alloy and its subsystems

PubMed Central

Chen, Bo-Ru; Yeh, An-Chou; Yeh, Jien-Wei

2016-01-01

In this study, the grain boundary evolution of equiatomic CoCrFeMnNi, CoCrFeNi, and FeCoNi alloys after one-step recrystallization were investigated. The special boundary fraction and twin density of these alloys were evaluated by electron backscatter diffraction analysis. Among the three alloys tested, FeCoNi exhibited the highest special boundary fraction and twin density after one-step recrystallization. The special boundary increment after one-step recrystallization was mainly affected by grain boundary velocity, while twin density was mainly affected by average grain boundary energy and twin boundary energy. PMID:26923713

Effect of one-step recrystallization on the grain boundary evolution of CoCrFeMnNi high entropy alloy and its subsystems.

PubMed

Chen, Bo-Ru; Yeh, An-Chou; Yeh, Jien-Wei

2016-02-29

In this study, the grain boundary evolution of equiatomic CoCrFeMnNi, CoCrFeNi, and FeCoNi alloys after one-step recrystallization were investigated. The special boundary fraction and twin density of these alloys were evaluated by electron backscatter diffraction analysis. Among the three alloys tested, FeCoNi exhibited the highest special boundary fraction and twin density after one-step recrystallization. The special boundary increment after one-step recrystallization was mainly affected by grain boundary velocity, while twin density was mainly affected by average grain boundary energy and twin boundary energy.

Thermodynamic Stability of Transition Metal Substituted LiMn 2-xMxO 4 (M=Cr, Fe, Co, and Ni) Spinels

NASA Astrophysics Data System (ADS)

Lai, Chenying

The formation enthalpies from binary oxides of LiMn2O 4, LiMn2-xCrxO4 (x = 0.25, 0.5, 0.75 and 1), LiMn2-xFexO4 (x = 0.25 and 0.5), LiMn2-xCoxO4 (x = 0.25, 0.5, and 0.75) and LiMn1.75Ni 0.25O4 at 25 °C have been measured by high-temperature oxide-melt-solution calorimetry and were found to be strongly exothermic. Increasing Cr, Co and Ni content leads to more thermodynamically stable spinels, but increasing Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO 4 (M = Cr, Fe and Co) become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close-to-zero heat of mixing in LiMn2O4 - LiMnMO 4 solid solutions. These data confirm that transition metal doping is beneficial for stabilizing these potential cathode materials for lithium-ion batteries.

Lattice sites of ion-implanted Mn, Fe and Ni in 6H-SiC

NASA Astrophysics Data System (ADS)

Costa, A. R. G.; Wahl, U.; Correia, J. G.; David-Bosne, E.; Amorim, L. M.; Augustyns, V.; Silva, D. J.; da Silva, M. R.; Pereira, L. M. C.

2018-01-01

Using radioactive isotopes produced at the CERN-ISOLDE facility, the lattice location of the implanted transition metal (TM) ions 56Mn, 59Fe and 65Ni in n-type single-crystalline hexagonal 6H-SiC was studied by means of the emission channeling technique. TM probes on carbon coordinated tetrahedral interstitial sites (T C) and on substitutional silicon sites (S Si,h+k ) were identified. We tested for but found no indication that the TM distribution on S Si sites deviates from the statistical mixture of 1/3 hexagonal and 2/3 cubic sites present in the 6H crystal. The TM atoms partially disappear from T C positions during annealing at temperatures between 500 °C and 700 °C which is accompanied by an increase on S Si and random sites. From the temperature associated with these site changes, interstitial migration energies of 1.7-2.7 eV for Mn and Ni, and 2.3-3.2 eV for Fe were estimated. TM lattice locations are compared to previous results obtained in 3C-SiC using the same technique.

Nano-twin Mediated Plasticity in Carbon-containing FeNiCoCrMn High Entropy Alloys

DOE PAGES

Wu, Zhenggang; Bei, Hongbin; Parish, Chad M

2015-06-14

Equiatomic FeNiCoCrMn alloy has been reported to exhibit promising strength and ductility at cryogenic temperature and deformation mediated by nano-twining appeared to be one of the main reasons. We use the FeNiCoCrMn alloy as a base alloy to seek further improvement of its mechanical properties by alloying additional elements, i.e., interstitial carbon. Moreover, the effects of carbon on microstructures, mechanical properties and twinning activities were investigated in two different temperatures (77 and 293 K). With addition of 0.5 at% C, the high entropy alloy still remains entirely single phase face-centered cubic (FCC) crystal structure. We found that these materials canmore » be cold rolled and recrystallized to produce a microstructure with equiaxed grains. Both strain hardening rate and strength are enhanced while high uniform elongations to fracture (~70% at 77 K and ~40% at 293 K) are still maintained. The increased strain hardening and strength could be caused by the promptness of deformation twinning in C-containing high entropy alloys.« less

Coating effect of LiFePO4 and Al2O3 on Li1.2Mn0.54Ni0.13Co0.13O2 cathode surface for lithium ion batteries

NASA Astrophysics Data System (ADS)

Seteni, Bonani; Rapulenyane, Nomasonto; Ngila, Jane Catherine; Mpelane, Siyasanga; Luo, Hongze

2017-06-01

Lithium-manganese-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O2 is prepared by combustion method, and then coated with nano-sized LiFePO4 and nano-sized Al2O3 particles via a wet chemical process. The as-prepared Li1.2Mn0.54Ni0.13Co0.13O2, LiFePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 and Al2O3-coated Li1.2Mn0.54Ni0.13Co0.13O2 are characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The scanning electron microscopy shows the agglomeration of the materials and their nanoparticle size ∼100 nm. The transmission electron microscopy confirms that LiFePO4 forms a rough mat-like surface and Al2O3 remain as islandic particles on the surface of the Li1.2Mn0.54Ni0.13Co0.13O2 material. The Li1.2Mn0.54Ni0.13Co0.13O2 coated with LiFePO4 and Li1.2Mn0.54Ni0.13Co0.13O2 coated with Al2O3 exhibits improved electrochemical performance. The initial discharge capacity is enhanced to 267 mAhg-1 after the LiFePO4 coating and 285 mAhg-1 after the Al2O3 coating compared to the as-prepared Li1.2Mn0.54Ni0.13Co0.13O2 material that has an initial discharge capacity of 243 mAhg-1. Galvanostatic charge-discharge tests at C/10 display longer activation of Li2MnO3 phase and higher capacity retention of 88% after 20 cycles for Li1.2Mn0.54Ni0.13Co0.13O2-LiFePO4 compared to Li1.2Mn0.54Ni0.13Co0.13O2-Al2O3 of 80% after 20 cycles and LMNC of 80% after 20 cycles. Meanwhile Li1.2Mn0.54Ni0.13Co0.13O2-LiFePO4 also shows higher rate capability compared to Li1.2Mn0.54Ni0.13Co0.13O2-Al2O3.

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.

Large enhancement of Blocking temperature by control of interfacial structures in Pt/NiFe/IrMn/MgO/Pt multilayers

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

Chen, Xi; Wang, Shouguo, E-mail: sgwang@ustb.edu.cn; Han, Gang

2015-09-15

The Blocking temperature (T{sub B}) of Pt/NiFe/IrMn/MgO/Pt multilayers was greatly enhanced from far below room temperature (RT) to above RT by inserting 1 nm thick Mg layer at IrMn/MgO interface. Furthermore, the exchange bias field (H{sub eb}) was increased as well by the control of interfacial structures. The evidence for a significant fraction of Mn-O bonding at IrMn/MgO interface without Mg insertion layer was provided by X-ray photoelectron spectroscopy. The bonding between Mn and O can decrease the antiferromagnetism of IrMn film, leading to lower value of T{sub B} in Pt/NiFe/IrMn/MgO/Pt multilayers. Ultrathin Mg film inserted at IrMn/MgO interface actingmore » as an oxygen sinking layer can suppress the oxidation reactions between Mn and O and reduce the formation of Mn-O bonding greatly. The oxidation suppression results in the recovery of the antiferromagnetism of IrMn film, which can enhance T{sub B} and H{sub eb}. Furthermore, the high resolution transmission electron microscopy demonstrates that the Mg insertion layer can efficiently promote a high-quality MgO (200) texture. This study will enhance the understanding of physics in antiferromagnet-based spintronic devices.« less

The effects of annealing on the microstructure and mechanical properties of Fe 28Ni 18Mn 33Al 21

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

Meng, Fanling; Qiu, Jingwen; Baker, Ian

In this paper, As-cast Fe 28Ni 18Mn 33Al 21, which consists of aligned, 50 nm, (Ni, Al)-rich B2, and (Fe, Mn)-rich f.c.c. phases, was annealed at a variety of temperatures up to 1423 K and the microstructure and mechanical properties were examined. It was shown that the as-cast microstructure arises from a eutectoid transformation at ~1300 K. Annealing at temperatures ≤1073 K produces β-Mn-structured precipitates and hardness values up to 816 HV, while annealing at temperatures >1073 K leads to dramatic coarsening of the two-phase B2/f.c.c. microstructure (up to 5.5 µm after 50 h at 1273 K), but does notmore » lead to β-Mn precipitation. Interestingly, annealing at temperatures >1073 K delays the onset of β-Mn precipitation during subsequent anneals at lower temperatures. Coarsening the B2/f.c.c. lamellar structure by annealing at higher temperatures softens it and leads to increases in ductility from fracture before yield to ~8 % elongation. Finally, the presence of β-Mn precipitates makes the very fine, brittle B2/f.c.c. microstructures even more brittle, but significant ductility (8.4 % elongation) is possible even with β-Mn precipitates present if the B2/f.c.c. matrix is coarse and, hence, more ductile.« less

The effects of annealing on the microstructure and mechanical properties of Fe 28Ni 18Mn 33Al 21

DOE PAGES

Meng, Fanling; Qiu, Jingwen; Baker, Ian; ...

2015-08-20

In this paper, As-cast Fe 28Ni 18Mn 33Al 21, which consists of aligned, 50 nm, (Ni, Al)-rich B2, and (Fe, Mn)-rich f.c.c. phases, was annealed at a variety of temperatures up to 1423 K and the microstructure and mechanical properties were examined. It was shown that the as-cast microstructure arises from a eutectoid transformation at ~1300 K. Annealing at temperatures ≤1073 K produces β-Mn-structured precipitates and hardness values up to 816 HV, while annealing at temperatures >1073 K leads to dramatic coarsening of the two-phase B2/f.c.c. microstructure (up to 5.5 µm after 50 h at 1273 K), but does notmore » lead to β-Mn precipitation. Interestingly, annealing at temperatures >1073 K delays the onset of β-Mn precipitation during subsequent anneals at lower temperatures. Coarsening the B2/f.c.c. lamellar structure by annealing at higher temperatures softens it and leads to increases in ductility from fracture before yield to ~8 % elongation. Finally, the presence of β-Mn precipitates makes the very fine, brittle B2/f.c.c. microstructures even more brittle, but significant ductility (8.4 % elongation) is possible even with β-Mn precipitates present if the B2/f.c.c. matrix is coarse and, hence, more ductile.« less

Magnetic characteristics of a high-layer-number NiFe/FeMn multilayer

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

Paterson, G. W., E-mail: gary.paterson@glasgow.ac.uk; Gonçalves, F. J. T.; McFadzean, S.

2015-11-28

We report the static and dynamic magnetic characteristics of a high-layer-number NiFe/FeMn multilayer test structure with potential applications in broadband absorber and filter devices. To allow fine control over the absorption linewidths and to understand the mechanisms governing the resonances in a tailored structure similar to that expected to be used in real world applications, the multilayer was intentionally designed to have layer thickness and interface roughness variations. Magnetometry measurements show that the sample has complex hysteresis loops with features consistent with single ferromagnetic film reversals. Characterisation by transmission electron microscopy allows us to correlate the magnetic properties with structuralmore » features, including the film widths and interface roughnesses. Analysis of resonance frequencies from broadband ferromagnetic resonance measurements as a function of field magnitude and orientation provide values of the local exchange bias, rotatable anisotropy, and uniaxial anisotropy fields for specific layers in the stack and explain the observed mode softening. The linewidths of the multilayer are adjustable around the bias field, approaching twice that seen at larger fields, allowing control over the bandwidth of devices formed from the structure.« less

Room temperature multiferroic properties of (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film

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

Raghavan, C.M.; Kim, H.J.; Kim, J.W.

2013-11-15

Graphical abstract: - Highlights: • Chemical solution deposition of (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}–NiFe{sub 2}O{sub 4} double layered thin film. • Studies on structural, electrical and multiferroic properties. • NiFe{sub 2}O{sub 4} acts as both resistive buffer layer and magnetic source. - Abstract: (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film was prepared on a Pt(111)/Ti/SiO{sub 2}/Si(100) substrate by a chemical solution deposition method. X-ray diffraction and Raman scattering spectroscopy studies confirmed the formation of the distorted rhombohedral perovskite and the inverse spinel cubic structures for the (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4}more » double layered thin film. The (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film exhibited well saturated ferromagnetic (2 M{sub r} of 18.1 emu/cm{sup 3} and 2H{sub c} of 0.32 kOe at 20 kOe) and ferroelectric (2P{sub r} of 60 μC/cm{sup 2} and 2E{sub c} of 813 kV/cm at 866 kV/cm) hysteresis loops with low order of leakage current density (4.5 × 10{sup −6} A/cm{sup 2} at an applied electric field of 100 kV/cm), which suggest the ferroelectric and ferromagnetic multi-layers applications in real devices.« less

Air breathing cathodes for microbial fuel cell using Mn-, Fe-, Co- and Ni-containing platinum group metal-free catalysts

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

Kodali, Mounika; Santoro, Carlo; Serov, Alexey

Here we discuss the oxygen reduction reaction (ORR) is one of the major factors that is limiting the overall performance output of microbial fuel cells (MFC). In this study, Platinum Group Metal-free (PGM-free) ORR catalysts based on Fe, Co, Ni, Mn and the same precursor (Aminoantipyrine, AAPyr) were synthesized using identical sacrificial support method (SSM). The catalysts were investigated for their electrochemical performance, and then integrated into an air-breathing cathode to be tested in “clean” environment and in a working microbial fuel cell (MFC). Their performances were also compared to activated carbon (AC) based cathode under similar conditions. Results showedmore » that the addition of Mn, Fe, Co and Ni to AAPyr increased the performances compared to AC. Fe-AAPyr showed the highest open circuit potential (OCP) that was 0.307 ± 0.001 V (vs. Ag/AgCl) and the highest electrocatalytic activity at pH 7.5. On the contrary, AC had an OCP of 0.203 ± 0.002 V (vs. Ag/AgCl) and had the lowest electrochemical activity. In MFC, Fe-AAPyr also had the highest output of 251 ± 2.3 μWcm –2, followed by Co-AAPyr with 196 ± 1.5 μWcm –2, Ni-AAPyr with 171 ± 3.6 μWcm –2, Mn-AAPyr with 160 ± 2.8 μWcm –2 and AC 129 ± 4.2 μWcm –2. The best performing catalyst (Fe-AAPyr) was then tested in MFC with increasing solution conductivity from 12.4 mScm –1 to 63.1 mScm –1. A maximum power density of 482 ± 5 μWcm –2 was obtained with increasing solution conductivity, which is one of the highest values reported in the field.« less

Air breathing cathodes for microbial fuel cell using Mn-, Fe-, Co- and Ni-containing platinum group metal-free catalysts

DOE PAGES

Kodali, Mounika; Santoro, Carlo; Serov, Alexey; ...

2017-02-07

Here we discuss the oxygen reduction reaction (ORR) is one of the major factors that is limiting the overall performance output of microbial fuel cells (MFC). In this study, Platinum Group Metal-free (PGM-free) ORR catalysts based on Fe, Co, Ni, Mn and the same precursor (Aminoantipyrine, AAPyr) were synthesized using identical sacrificial support method (SSM). The catalysts were investigated for their electrochemical performance, and then integrated into an air-breathing cathode to be tested in “clean” environment and in a working microbial fuel cell (MFC). Their performances were also compared to activated carbon (AC) based cathode under similar conditions. Results showedmore » that the addition of Mn, Fe, Co and Ni to AAPyr increased the performances compared to AC. Fe-AAPyr showed the highest open circuit potential (OCP) that was 0.307 ± 0.001 V (vs. Ag/AgCl) and the highest electrocatalytic activity at pH 7.5. On the contrary, AC had an OCP of 0.203 ± 0.002 V (vs. Ag/AgCl) and had the lowest electrochemical activity. In MFC, Fe-AAPyr also had the highest output of 251 ± 2.3 μWcm –2, followed by Co-AAPyr with 196 ± 1.5 μWcm –2, Ni-AAPyr with 171 ± 3.6 μWcm –2, Mn-AAPyr with 160 ± 2.8 μWcm –2 and AC 129 ± 4.2 μWcm –2. The best performing catalyst (Fe-AAPyr) was then tested in MFC with increasing solution conductivity from 12.4 mScm –1 to 63.1 mScm –1. A maximum power density of 482 ± 5 μWcm –2 was obtained with increasing solution conductivity, which is one of the highest values reported in the field.« less

Weldability of a high entropy CrMnFeCoNi alloy

DOE PAGES

Wu, Zhenggang; David, Stan A.; Feng, Zhili; ...

2016-07-19

We present the high-entropy alloys are unique alloys in which five or more elements are all in high concentrations. In order to determine its potential as a structural alloy, a model face-centered-cubic CrMnFeCoNi alloy was selected to investigate its weldability. Welds produced by electron beam welding show no cracking. The grain structures within the fusion zone (FZ) are controlled by the solidification behavior of the weld pool. The weldment possesses mechanical properties comparable to those of the base metal (BM) at both room and cryogenic temperatures. Finally, compared with the BM, deformation twinning was more pronounced in the FZ ofmore » the tested alloy.« less

Magnetic, optical and phonon properties of novel heterometallic formates [NH3CH2CH2OH][MIIIMII(HCOO)6] (MIII = Fe, Cr; MII = Mn, Ni, Co)

NASA Astrophysics Data System (ADS)

Mączka, Mirosław; Janczak, Jan; Hermanowicz, Krzysztof; Pikul, Adam; Hanuza, Jerzy

2018-04-01

Four novel compounds, [NH3CH2CH2OH][MIIIMII(HCOO)6] with MIII = Fe and MII = Mn (HEAFeMn), MIII = Fe and MII = Ni (HEAFeNi), MIII = Cr and MII = Mn (HEACrMn) and MIII = Cr and MII = Co (HEACrCo), have been synthesized. They crystallize in the trigonal niccolite-type structure (space group P 3 bar 1c). Magnetic studies revealed that HEAFeNi, HEAFeMn and HEACrCo are weak ferromagnets with the ordering temperature of 43, 27 and 11 K, respectively, whereas HEACrMn does not order magnetically at least down to 2 K. A source of the ferromagnetic component is most likely a canting of the antiferromagnetically ordered moments by a small angle resulting from antisymmetric exchange or single-ion anisotropy. Raman and IR data confirm that all obtained samples are isostructural. Optical studies of HEACrMn show that local crystal field around Cr3+ ion is of intermediate strength with the Dq/B value of 2.57. Luminescence studies indicate that HEACrMn exhibits efficient Cr3+-based emission. Below 200 K, the 2E-4A2 phosphorescence observed as two bands at 686 and 696 nm becomes predominate.

Magnetically retrievable nickel hydroxide functionalised AFe2O4 (A = Mn, Ni) spinel nanocatalyst for alcohol oxidation

NASA Astrophysics Data System (ADS)

Bhat, Pooja B.; Bhat, Badekai Ramachandra

2016-03-01

Ultrasmall nickel hydroxide functionalised AFe2O4 (A = Mn, Ni) nanocatalyst was synthesized by traditional co-precipitation method and was examined for oxidation of aromatic alcohols to carbonyls using hydrogen peroxide as terminal oxidant. A very high surface area of 104.55 m2 g-1 was achieved for ferromagnetic MnFe2O4 and 100.50 m2 g-1 for superparamagnetic NiFe2O4, respectively. Efficient oxidation was observed due to the synergized effect of nickel hydroxide (bronsted base) on Lewis center (Fe) of the nanocatalyst. Catalyst recycling experiments revealed that the ultrasmall nanocatalyst can be easily recovered by external magnet and applied for nearly complete oxidation of alcohols for at least five successive cycles. Furthermore, the nickel hydroxide functionalised ultrasmall nanocatalyst exhibited higher efficiency for benzyl alcohol oxidation compared to Ni(OH)2, bare MnFe2O4 and NiFe2O4. Higher conversion rate was observed for nickel hydroxide functionalised NiFe2O4 compared to MnFe2O4. Ultrasmall magnetic nickel hydroxide functionalised nanocatalyst showed environmental friendly, greener route for the oxidation of alcohols without significant loss in activity and selectivity within successive runs.

Magnetic properties of Ni-Cu-Mn ferrite system

NASA Astrophysics Data System (ADS)

Roumaih, Kh.

2011-10-01

Three groups according to the substitution of Cu 2+ and Mn 3+ in the system Ni 1-xCu xFe 2-yMn yO 4 ferrite with x = 0.2, 0.5, 0.8, and y varying from 0.0 to 1.0 in steps of 0.25 are prepared by solid state reactions. The phases of the Ni 1-xCu xFe 2-yMn yO 4 ferrite have been confirmed by X-ray diffraction (XRD). The results demonstrate that all of the synthesized materials are spinel with cubic unit cell and the lattice constant increased with increases of the Cu and Mn ions for all samples. The hyperfine interaction was studied by the Mössbauer spectroscopy at room temperature for all samples. The spectra of all samples show two well-resolved Zeeman patterns corresponding to A- and B-sites. The hyperfine field decreases with increasing Cu and Mn ions concentration. The Curie temperature, TC, was calculated from the temperature dependence of magnetization curves. The hysteresis curve recorded at room temperature shows that the samples are ferrimagnetic materials. The cation distribution was estimated from the results of Mössbauer spectroscopy and magnetic measurements.

Magnetic anisotropies and rotational hysteresis in Ni81Fe19/Fe50Mn50 films: A study by torque magnetometry and anisotropic magnetoresistance

NASA Astrophysics Data System (ADS)

da Silva, O. E.; de Siqueira, J. V.; Kern, P. R.; Garcia, W. J. S.; Beck, F.; Rigue, J. N.; Carara, M.

2018-04-01

Exchange bias properties of NiFe/FeMn thin films have been investigated through X-ray diffraction, hysteresis loops, angular measurements of anisotropic magnetoresistance (AMR) and magnetic torque. As first predicted by Meiklejohn and Bean we found a decrease on the bias field as the NiFe layer thickness increases. However such reduction is not as strong as expected and it was attributed to the increase on the number of uncompensed antiferromagnetic spins resulting from the increase on the number of FeMn grains at the interface as the thickness of the NiFe layer is increased. The angular evolution of AMR and the magnetic torque were calculated and compared to the experimental ones using the minimization of the free magnetic energy and finding the magnetization equilibrium angle. The free energy, for each grain of the polycrystalline sample, is composed by the following terms: Zeeman, uniaxial, unidirectional and the rotatable energies. While from the AMR curves we obtain stable anisotropy fields independently on the measuring fields, from the torque curves we obtain increasing values of the uniaxial and rotatable fields, as the measuring field is increased. These results were attributed to the physical origin and sensitivity of the two different techniques. Magnetoresistance is mainly sensitive to the inner portion of the ferromagnetic layer, and the torque brings out information of the whole ferromagnetic layer including the interface of the layers. In this way, we believe that the increase in the uniaxial and rotatable values were due to an increase on the volume of the ferromagnetic layer, near the interfaces, which is made to rotate with the measuring field. Studying the rotational hysteresis by both techniques allows to separately obtain the contributions coming from the inner portion of ferromagnetic layer and from the interface.

Critical dependence of magnetostructural coupling and magnetocaloric effect on particle size in Mn-Fe-Ni-Ge compounds

PubMed Central

Wu, Rongrong; Shen, Feiran; Hu, Fengxia; Wang, Jing; Bao, Lifu; Zhang, Lei; Liu, Yao; Zhao, Yingying; Liang, Feixiang; Zuo, Wenliang; Sun, Jirong; Shen, Baogen

2016-01-01

Magnetostructural coupling, which is the coincidence of crystallographic and magnetic transition, has obtained intense attention for its abundant magnetoresponse effects and promising technological applications, such as solid-state refrigeration, magnetic actuators and sensors. The hexagonal Ni2In-type compounds have attracted much attraction due to the strong magnetostructural coupling and the resulted giant negative thermal expansion and magnetocaloric effect. However, the as-prepared samples are quite brittle and naturally collapse into powders. Here, we report the effect of particle size on the magnetostructural coupling and magnetocaloric effect in the Ni2In-type Mn-Fe-Ni-Ge compound, which undergoes a large lattice change across the transformation from paramagnetic austenite to ferromagnetic martensite. The disappearance of martensitic transformation in a large amount of austenitic phase with reducing particle size, to our best knowledge, has not been reported up to now. The ratio can be as high as 40.6% when the MnNi0.8Fe0.2Ge bulk was broken into particles in the size range of 5~15 μm. Meanwhile, the remained magnetostructural transition gets wider and the magnetic hysteresis becomes smaller. As a result, the entropy change drops, but the effective cooling power RCeffe increases and attains to the maximum at particles in the range of 20~40 μm. These observations provide constructive information and highly benefit practical applications for this class of novel magnetoresponse materials. PMID:26883719

The corrosion behavior of Fe-Mn-Al weld metals

NASA Astrophysics Data System (ADS)

Aidun, Daryush K.

2001-02-01

The corrosion resistance of a newly developed iron-base, Fe-Mn-Al austenitic, and duplex weld metal has been examined in the NACE solution consisting of 5 wt.% NaCl, 0.5 wt.% acetic acid, and the balance distilled water. The electrochemical techniques such as potentiodynamic polarization, Tafel plots, linear polarization, cyclic polarization, and open-circuit potential versus time were employed. The Fe-Mn-Al weld metals did not passivate and exhibited high corrosion rates. Fe-Cr-Ni (310 and 316) weld and base metals were also examined in the NACE solution at room temperature. The 310 and 316 base metals were more resistant to corrosion than the as-welded 310 and 316 weld metals. Postweld heat treatment (PWHT) improved the corrosion performance of the Fe-Mn-Al weld metals. The corrosion resistance of Fe-Mn-Al weld metals after PWHT was still inferior to that of the 310 and 316 weld and base metals.

Effect of Pre-straining on the Shape Recovery of Fe-Mn-Si-Cr-Ni Shape Memory Alloys

NASA Astrophysics Data System (ADS)

Maji, Bikas C.; Krishnan, Madangopal; Verma, Amit; Basu, R.; Samajdar, I.; Ray, Ranjit K.

2015-02-01

The effect of pre-straining on the shape recovery behavior of Fe-14Mn-6Si-9Cr-5Ni (wt pct) shape memory alloy (SMA) has been studied. The shape recovery associated with the reverse ɛ martensitic transformation, i.e., ɛ → γ, was characterized by dilatometry using specimens which were pre-strained to different extent (0 to 14 pct). Dilatometric studies revealed that in Fe-Mn-Si-Cr-Ni SMA, the shape recovery takes place in two stages: (i) in the first stage, the unpinned fraction of stress-induced ɛ martensite reverts back to parent phase γ in the temperature regime of 353 K to 653 K (80 °C to 380 °C) and (ii) in the second stage the remaining "pinned" ɛ martensite is unpinned by the decomposition of deformation-induced α' martensite in the temperature range of 743 K to 893 K (470 °C to 620 °C). The amount of recovery in the first stage decreases with pre-strain, whereas it increases in the second stage. The ɛ → γ transformation finish temperature, A f, increases with increase in pre-strain amount, though the reverse transformation start temperature, A S, remains unaffected. Microstructural characterization revealed that the amount of deformation-induced α' martensite depends on the mode of straining and the crystallographic texture of the starting material. The reversion of α' martensite is seen to occur by the precipitation of Fe5Ni3Si2-type intermetallic π-phase within these plates.

Giant magnetic coercivity in YNi4B-type SmNi3TB (T=Mn-Cu) solid solutions

NASA Astrophysics Data System (ADS)

Yao, Jinlei; Yan, Chang; Yapaskurt, V. O.; Morozkin, A. V.

2016-12-01

The effects of transition metal substitution for Ni on the magnetic properties of the YNi4B-type SmNi4B via SmNi3TB (T=Mn, Fe, Co, Cu) solid solutions have been investigated. SmNi4B, SmNi3MnB, SmNi3FeB, SmNi3CoB and SmNi3CuB show ferromagnetic ordering at 40 K, 210 K, 322 K, 90 K and 57 K and field sensitive metamagnetic-like transitions at 15 K, 100 K, 185 K, 55 K and 15 K in a magnetic field of 10 kOe, respectively. The magnetocaloric effects of SmNi3TB (T=Mn-Cu) were calculated in terms of isothermal magnetic entropy change (ΔSm). The magnetic entropy ΔSm reaches value of -0.94 J/kg K at 40 K for SmNi4B, -1.5 J/kg K at 205 K for SmNi3MnB, -0.54 J/kg K at 320 K for SmNi3FeB, -0.49 J/kg K at 90 K for SmNi3CoB and -0.54 J/kg K at 60 K for SmNi3CuB in field change of 0-50 kOe around the Curie temperature. They show positive ΔSm of +0.71 J/kg K at ~10 K for SmNi4B, +1.69 J/kg K at 30 K for SmNi3MnB, +0.89 J/kg K at 110 K for SmNi3FeB, +1.08 J/kg K at 25 K for SmNi3CoB and +1.12 J/kg K at 10 K for SmNi3CuB in field change of 0-50 kOe around the low temperature metamagnetic-like transition. Below the field induced transition temperature (change of magnetic structure), SmNi3TB (T=Mn-Cu) exhibits giant magnetic coercivity of 74 kOe at 5 K for SmNi4B, 69 kOe at 20 K (90 kOe at 10 K) for SmNi3MnB, 77 kOe at 60 K for SmNi3FeB, 88 kOe at 20 K for SmNi3CoB and 52 kOe at 5 K for SmNi3CuB.

Evaluation and comparision of dc resistivity of NiZr x Co x Fe2-2x O4, Ni0.5Sn0.5Co x Mn x Fe2-2x O4, Mg1-x Ca x Ni y Fe2-y O4 and Mg1-x Ni x Co y Fe2-y O4 nanocrytalline materials

NASA Astrophysics Data System (ADS)

Ali, Rajjab; Gilani, Zaheer Abbas; Shahzad Shifa, Muhammad; Asghar, H. M. Noor Ul Huda Khan; Azhar Khan, Muhammad; Naeem Anjum, Muhammad; Nauman Usmani, Muhammad; Farooq Warsi, Muhammad; Khawaja, Imtiaz U.

2017-11-01

Four series nanocrystalline ferrites with nominal composition, NiZr x Co x Fe2-2x O4 (x  =  0.0, 0.2, 0.4, 0.6, 0.8) Ni0.5Sn0.5Co x Mn x Fe2-2x O4 (x  =  0.0, 0.2, 0.4, 0.6, 0.8), Mg1-x Ca x Ni y Fe2-y O4 (x  =  0.0, 0.2, 0.4, 0.6, 0.8; y  =  0, 04, 0.8, 1.2, 1.6) and Mg1-x Ni x Co y Fe2-y O4 (x,y  =  0.0, 0.2, 0.4, 0.6, 0.8) have been fabricated using the microemulsion synthesis route. The synthesized materials are investigated for dc electrical resistivity measurements. The variation of dc electrical resistivity of these materials has been explainedon the basis of hopping mechanism of both holes and electrons.

Microstructure and Mechanical Properties Evolution of the Al, C-Containing CoCrFeNiMn-Type High-Entropy Alloy during Cold Rolling.

PubMed

Klimova, Margarita; Stepanov, Nikita; Shaysultanov, Dmitry; Chernichenko, Ruslan; Yurchenko, Nikita; Sanin, Vladimir; Zherebtsov, Sergey

2017-12-29

The effect of cold rolling on the microstructure and mechanical properties of an Al- and C-containing CoCrFeNiMn-type high-entropy alloy was reported. The alloy with a chemical composition (at %) of (20-23) Co, Cr, Fe, and Ni; 8.82 Mn; 3.37 Al; and 0.69 C was produced by self-propagating high-temperature synthesis with subsequent induction. In the initial as-cast condition the alloy had an face centered cubic single-phase coarse-grained structure. Microstructure evolution was mostly associated with either planar dislocation glide at relatively low deformation during rolling (up to 20%) or deformation twinning and shear banding at higher strain. After 80% reduction, a heavily deformed twinned/subgrained structure was observed. A comparison with the equiatomic CoCrFeNiMn alloy revealed higher dislocation density at all stages of cold rolling and later onset of deformation twinning that was attributed to a stacking fault energy increase in the program alloy; this assumption was confirmed by calculations. In the initial as-cast condition the alloy had low yield strength of 210 MPa with yet very high uniform elongation of 74%. After 80% rolling, yield strength approached 1310 MPa while uniform elongation decreased to 1.3%. Substructure strengthening was found to be dominated at low rolling reductions (<40%), while grain (twin) boundary strengthening prevailed at higher strains.

Shape-Memory Effect and Pseudoelasticity in Fe-Mn-Based Alloys

NASA Astrophysics Data System (ADS)

La Roca, P.; Baruj, A.; Sade, M.

2017-03-01

Several Fe-based alloys are being considered as potential candidates for applications which require shape-memory behavior or superelastic properties. The possibility of using fabrication methods which are well known in the steel industry is very attractive and encourages a large amount of research in the field. In the present article, Fe-Mn-based alloys are mainly addressed. On the one hand, attention is paid to the shape-memory effect where the alloys contain (a) a maximum amount of Mn up to around 30 wt%, (b) several possible substitutional elements like Si, Cr, Ni, Co, and Nb and (c) some possible interstitial elements like C. On the other hand, superelastic alloys are analyzed, mainly the Fe-Mn-Al-Ni system discovered a few years ago. The most noticeable properties resulting from the martensitic transformations which are responsible for the mentioned properties, i.e., the fcc-hcp in the first case and the bcc-fcc in the latter are discussed. Selected potential applications are also analyzed.

Mechanisms of radiation-induced segregation in CrFeCoNi-based single-phase concentrated solid solution alloys

DOE PAGES

He, Mo-Rigen; Wang, Shuai; Shi, Shi; ...

2016-12-31

Single-phase concentrated solid solution alloys have attracted wide interest due to their superior mechanical properties and enhanced radiation tolerance, which make them promising candidates for the structural applications in next-generation nuclear reactors. However, little has been understood about the intrinsic stability of their as-synthesized, high-entropy configurations against radiation damage. In this paper, we report the element segregation in CrFeCoNi, CrFeCoNiMn, and CrFeCoNiPd equiatomic alloys when subjected to 1250 kV electron irradiations at 400 °C up to a damage level of 1 displacement per atom. Cr/Fe/Mn/Pd can deplete and Co/Ni can accumulate at radiation-induced dislocation loops, while the actively segregating elementsmore » are alloy-specific. Moreover, electron-irradiated matrix of CrFeCoNiMn and CrFeCoNiPd shows L1 0 (NiMn)-type ordering decomposition and <001>-oriented spinodal decomposition between Co/Ni and Pd, respectively. Finally, these findings are rationalized based on the atomic size difference and enthalpy of mixing between the alloying elements, and identify a new important requirement to the design of radiation-tolerant alloys through modification of the composition.« less

Theory of the magnetism in La2NiMnO6

NASA Astrophysics Data System (ADS)

Sanyal, Prabuddha

2017-12-01

The magnetism of ordered and disordered La2NiMnO6 is explained using a model involving double exchange and superexchange. An important feature of this model is the majority spin hybridization in the large coupling limit, which results in ferromagnetism rather than ferrimagnetism as in Sr2FeMoO6 . The ferromagnetic insulating ground state in the ordered phase is explained. The essential role played by the Ni-Mn superexchange between the Ni eg electron spins and the Mn t2 g core electron spins in realizing this ground state is outlined. In the presence of antisite disorder, the model system is found to exhibit a tendency of becoming a spin glass at low temperatures, while it continues to retain a ferromagnetic transition at higher temperatures, similar to recent experimental observations [D. Choudhury et al., Phys. Rev. Lett. 108, 127201 (2012), 10.1103/PhysRevLett.108.127201]. This reentrant spin glass or reentrant ferromagnetic behavior is explained in terms of the competition of the ferromagnetic double exchange between the Ni eg and the Mn eg electrons, and the ferromagnetic Ni-Mn superexchange, with the antiferromagnetic antisite Mn-Mn superexchange.

Electronic structure and magnetic properties in T 2 AlB 2 ( T = Fe, Mn, Cr, Co, and Ni) and their alloys

DOE PAGES

Ke, Liqin; Harmon, Bruce N.; Kramer, Matthew J.

2017-03-20

In this study, the electronic structure and intrinsic magnetic properties of Fe 2AlB 2-related compounds and their alloys have been investigated using density functional theory. For Fe 2AlB 2, the crystallographic a axis is the easiest axis, which agrees with experiments. The magnetic ground state of Mn 2AlB 2 is found to be ferromagnetic in the basal ab plane, but antiferromagnetic along the c axis. All 3d dopings considered decrease the magnetization and Curie temperature in Fe 2AlB 2. Electron doping with Co or Ni has a stronger effect on the decreasing of Curie temperature in Fe 2AlB 2 thanmore » hole doping with Mn or Cr. However, a larger amount of Mn doping on Fe 2AlB 2 promotes the ferromagnetic to antiferromagnetic transition. A very anisotropic magnetoelastic effect is found in Fe 2AlB 2: the magnetization has a much stronger dependence on the lattice parameter c than on a or b, which is explained by electronic-structure features near the Fermi level. Dopings of other elements on B and Al sites are also discussed.« less

High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.; Zinkle, Steven J.; Bei, Hongbin; Lang, Maik; Ewing, Rodney C.; Mao, Wendy L.

2017-05-01

High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.

Elastic properties of fcc Fe-Mn-X (X = Cr, Co, Ni, Cu) alloys studied by the combinatorial thin film approach and ab initio calculations.

PubMed

Reeh, S; Kasprzak, M; Klusmann, C D; Stalf, F; Music, D; Ekholm, M; Abrikosov, I A; Schneider, J M

2013-06-19

The elastic properties of fcc Fe-Mn-X (X = Cr, Co, Ni, Cu) alloys with additions of up to 8 at.% X were studied by combinatorial thin film growth and characterization and by ab initio calculations using the disordered local moments (DLM) approach. The lattice parameter and Young's modulus values change only marginally with X. The calculations and experiments are in good agreement. We demonstrate that the elastic properties of transition metal alloyed Fe-Mn can be predicted by the DLM model.

Synthesis and electrochemical properties of Na-rich Prussian blue analogues containing Mn, Fe, Co, and Fe for Na-ion batteries

NASA Astrophysics Data System (ADS)

Bie, Xiaofei; Kubota, Kei; Hosaka, Tomooki; Chihara, Kuniko; Komaba, Shinichi

2018-02-01

Electrochemical performance of Prussian blue analogues (PBAs) as positive electrode materials for non-aqueous Na-ion batteries is known to be highly dependent on their synthesis conditions according to the previous researches. Na-rich PBAs, NaxM[Fe(CN)6]·nH2O where M = Mn, Fe, Co, and Ni, are prepared via precipitation method under the same condition. The structure, chemical composition, morphology, valence of the transition metals, and electrochemical property of these samples are comparatively researched. The PBA with Mn shows large reversible capacity of 126 mAh g-1 in 2.0-4.2 V at a current density of 30 mA g-1 and the highest working voltage owning to high redox potential of Mn2+/3+ in MnN6 and Fe2+/3+ in FeC6. While, the PBA with Ni exhibits the best cyclability and rate performance though only 66 mAh g-1 is delivered. The significant differences in electrochemical behaviors of the PBAs originate from the various properties depending on different transition metals.

In Operando XRD and TXM Study on the Metastable Structure Change of NaNi 1/3Fe 1/3Mn 1/3O 2 under Electrochemical Sodium-Ion Intercalation

DOE PAGES

Xie, Yingying; Wang, Hong; Xu, Guiliang; ...

2016-09-02

In operando XRD and TXM-XANES approaches demonstrate that structure evolution in NaNi 1/3Fe 1/3Mn 1/3O 2 during cycling follows a continuous change, and the formation of a nonequilibrium solid solution phase in the existence of two phases. Here, an O3' and P3' monoclinic phase occur, and redox couples of Ni 3+/Ni 4+ and Fe 3+/Fe 4+ are mainly responsible in the charge voltage range from 4.0 to 4.3 V.

Cryogenic strength improvement by utilizing room-temperature deformation twinning in a partially recrystallized VCrMnFeCoNi high-entropy alloy

PubMed Central

Jo, Y. H.; Jung, S.; Choi, W. M.; Sohn, S. S.; Kim, H. S.; Lee, B. J.; Kim, N. J.; Lee, S.

2017-01-01

The excellent cryogenic tensile properties of the CrMnFeCoNi alloy are generally caused by deformation twinning, which is difficult to achieve at room temperature because of insufficient stress for twinning. Here, we induced twinning at room temperature to improve the cryogenic tensile properties of the CrMnFeCoNi alloy. Considering grain size effects on the critical stress for twinning, twins were readily formed in the coarse microstructure by cold rolling without grain refinement by hot rolling. These twins were retained by partial recrystallization and played an important role in improving strength, allowing yield strengths approaching 1 GPa. The persistent elongation up to 46% as well as the tensile strength of 1.3 GPa are attributed to additional twinning in both recrystallized and non-recrystallization regions. Our results demonstrate that non-recrystallized grains, which are generally avoided in conventional alloys because of their deleterious effect on ductility, can be useful in achieving high-strength high-entropy alloys. PMID:28604656

Observation of new neutron-rich Mn, Fe, Co, Ni, and Cu isotopes in the vicinity of 78Ni

NASA Astrophysics Data System (ADS)

Sumikama, T.; Nishimura, S.; Baba, H.; Browne, F.; Doornenbal, P.; Fukuda, N.; Franchoo, S.; Gey, G.; Inabe, N.; Isobe, T.; John, P. R.; Jung, H. S.; Kameda, D.; Kubo, T.; Li, Z.; Lorusso, G.; Matea, I.; Matsui, K.; Morfouace, P.; Mengoni, D.; Napoli, D. R.; Niikura, M.; Nishibata, H.; Odahara, A.; Sahin, E.; Sakurai, H.; Söderström, P.-A.; Stefan, G. I.; Suzuki, D.; Suzuki, H.; Takeda, H.; Taniuchi, R.; Taprogge, J.; Vajta, Zs.; Watanabe, H.; Werner, V.; Wu, J.; Xu, Z. Y.; Yagi, A.; Yoshinaga, K.

2017-05-01

Neutron-rich nuclei in the vicinity of 78Ni were produced using a 238U beam at the RIKEN Radioactive Isotope Beam Factory. The particle-identification plot for the in-flight fission fragments highlights the first observation of eight new isotopes: 73Mn, 76Fe, Co,7877, 80,81,82Ni, and 83Cu. Although the β -decay half-lives of 77Co and 80Ni were recently reported by Xu et al. [Phys. Rev. Lett. 113, 032505 (2014)], 10.1103/PhysRevLett.113.032505 using data from the same experiment, the current work provides the first direct, quantitative evidence for the existence of these isotopes. The experimental production cross sections are reproduced in a satisfactory manner by theoretical predictions. An odd-even staggering of the cross sections was observed, and the effect appears to become more pronounced for the most exotic nuclei that were investigated. The staggering effect was interpreted as an increase of the neutron-evaporation probability for odd-N isotopes, owing to the decrease of the neutron-separation energy, Sn. The predicted cross section for 80Ni is significantly overestimated, which may be related to a weak binding of the neutron pair above the N =50 shell closure.

Critical evaluation of sequential leaching procedures for the determination of Ni and Mn species in welding fumes.

PubMed

Berlinger, B; Náray, M; Sajó, I; Záray, G

2009-06-01

corrosion-resistant steel and unalloyed structural steel, respectively. According to the results of the leaching procedures, GMAW fumes are rich in oxidic Ni (79%), while Ni compounds in welding fumes generated during MMAW are mainly in easily soluble form (44%). The crystalline phases were identified in each welding fume by X-ray powder diffraction (XRPD) technique as well. From the XRPD spectra, it is clear that GMAW fumes contain predominantly magnetite (FeFe(2)O(4)). In case of structural steel welding, there was a little amount of ferrite (alpha-Fe) also found. Welding fume generated during MMAW of structural steel contained a complex alkali-alkali earth fluoride phase (KCaF(3)-CaF(2)) and some magnetite and jakobsite (MnFe(2)O(4)). The XRPD results did not fully confirm the ones obtained from the extraction experiments. However, some results, for example the rate of soluble Ni and Mn compounds compared to the total, can be useful for further investigations of welding fumes.

Microstructure and mechanical properties of friction stir welded and laser welded high entropy alloy CrMnFeCoNi

NASA Astrophysics Data System (ADS)

Jo, Min-Gu; Kim, Han-Jin; Kang, Minjung; Madakashira, Phaniraj P.; Park, Eun Soo; Suh, Jin-Yoo; Kim, Dong-Ik; Hong, Sung-Tae; Han, Heung Nam

2018-01-01

The high entropy alloy CrMnFeCoNi has been shown to have promising structural properties. For a new alloy to be used in a structural application it should be weldable. In the present study, friction stir welding (FSW) and laser welding (LW) techniques were used to butt weld thin plates of CrMnFeCoNi. The microstructure, chemical homogeneity and mechanical behavior of the welds were characterized and compared with the base metal. The tensile stress-strain behavior of the welded specimens were reasonable when compared with that of the base metal. FSW refined the grain size in the weld region by a factor of ˜14 when compared with the base metal. High-angle annular dark field transmission electron microscopy in combination with energy dispersive X-ray spectroscopy showed chemical inhomogeneity between dendritic and interdendritic regions in the fusion zone of LW. Large fluctuations in composition (up to 15 at%) did not change the crystal structure in the fusion zone. Hardness measurements were carried out in the weld cross section and discussed in view of the grain size, low angle grain boundaries and twin boundaries in FSW specimens and the dendritic microstructure in LW specimens.

Dopant driven tunability of dielectric relaxation in MxCo(1-x)Fe2O4 (M: Zn2+, Mn2+, Ni2+) nano-ferrites

NASA Astrophysics Data System (ADS)

Datt, Gopal; Abhyankar, A. C.

2017-07-01

Nano-ferrites with tunable dielectric and magnetic properties are highly desirable in modern electronics industries. This work reports the effect of ferromagnetic (Ni), anti-ferromagnetic (Mn), and non-magnetic (Zn) substitution on cobalt-ferrites' dielectric and magnetic properties. The Rietveld analysis of XRD data and the Raman spectroscopic study reveals that all the samples are crystallized in the Fd-3m space group. The T2g Raman mode was observed to split into branches, which is due to the presence of different cations (with different vibrational frequencies) at crystallographic A and B-sites. The magnetization study shows that the MnCoFe2O4 sample has the highest saturation magnetization of 87 emu/g, which is attributed to the presence of Mn2+ cations at the B-site with a magnetic moment of 5 μB. The dielectric permittivity of these nanoparticles (NPs) obeys the modified Debye model, which is further supported by Cole-Cole plots. The dielectric constant of MnCoFe2O4 ferrite is found to be one order higher than that of the other two ferrites. The increased bond length of the Mn2+-O2- bond along with the enhanced d-d electron transition between Mn 2 +/Co 2 +⇋Fe 3 + cations at the B-site are found to be the main contributing factors for the enhanced dielectric constant of MnCoFe2O4 ferrite. We find evidence of variable-range hopping of localized polarons in these ferrite NPs. The activation energy, hopping range, and density of states N (" separators="|EF ), of these polarons were calculated using Motts' 1/4th law. The estimated activation energies of these polarons at 300 K were found to be 288 meV, 426 meV, and 410 meV, respectively, for the MnCoFe2O4, NiCoFe2O4, and ZnCoFe2O4 ferrite NPs, while the hopping range of these polarons were found to be 27.14 Å, 11.66 Å, and 8.17 Å, respectively. Observation of a low dielectric loss of ˜0.04, in the frequency range of 0.1-1 MHz, in these NPs makes them potential candidates for energy harvesting devices in

Nanostructured LiMPO4 (M = Fe, Mn, Co, Ni) - carbon composites as cathode materials for Li-ion battery

NASA Astrophysics Data System (ADS)

Dimesso, L.; Spanheimer, C.; Nguyen, T. T. D.; Hausbrand, R.; Jaegermann, W.

2012-10-01

Nanostructured materials are considered to be strong candidates for fundamental advances in efficient storage and/or conversion. In nanostructured materials transport kinetics and surface processes play determining roles. This work describes recent developments in the synthesis and characterization of composites which consist of lithium metal phosphates (LiMPO4, M = Fe, Mn, Co, Ni) coated on nanostructured carbon supports (unordered nanofibers, foams). The composites have been prepared by coating the carbon structures in aqueous (or polyols) solutions containing lithium, metal ions and phosphates. After drying out, the composites have been thermally treated at different temperatures (between 600-780°C) for 5-12 hours under nitrogen. The formation of the olivine structured phase was confirmed by the X-ray diffraction analysis on powders prepared under very similar conditions. The surface investigation revealed the formation of an homogeneous coating of the olivine phase on the carbon structures. The electrochemical performance on the composites showed a dramatic improvement of the discharge specific capacity (measured at a discharge rate of C/25 and room temperature) compared to the prepared powders. The delivered values were 105 mAhg-1 for M = Fe, 100 mAhg-1 for M = Co, 70 mAhg-1 for M = Mn and 30 mAhg-1 for M = Ni respectively.

Enhancement of magnetocaloric effect by external hydrostatic pressure in MnNi0.75Fe0.25Ge alloy

NASA Astrophysics Data System (ADS)

Mandal, K.; Dutta, P.; Dasgupta, P.; Pramanick, S.; Chatterjee, S.

2018-06-01

A systematic investigation on the structural and magnetic properties of an Fe-doped MnNiGe alloy with nominal composition MnNi0.75Fe0.25Ge has been performed. Temperature dependent x-ray diffraction studies indicate a clear structural phase transition (martensitic type) from the high temperature hexagonal austenite phase (space group P63/mmc) to the low temperature orthorhombic martensite phase (space group Pnma). Interestingly, about 1.4% of the high temperature hexagonal phase has been observed at 15 K, which is well below the martensitic phase transition (MPT) temperature. The studied alloy is found to be ferromagnetic in nature at the lowest temperature of measurement and the saturation moment increases in the presence of external hydrostatic pressure (P). In addition, it shows a significantly large conventional (negative) magnetocaloric effect with an adiabatic entropy change () of about ‑16.2 J kg‑1 K‑1 around the MPT for a magnetic field changing from 0  →  5 T. The most interesting observation is the  ∼40.1% increase in the peak value of on application of 6 kbar of external P. A considerable increment in the refrigeration capacity has also been noted with the applied P.

Imaging the surface morphology, chemistry and conductivity of LiNi 1/3 Fe 1/3 Mn 4/3 O 4 crystalline facets using scanning transmission X-ray microscopy

DOE PAGES

Zhou, Jigang; Wang, Jian; Cutler, Jeffrey; ...

2016-07-26

We have employed scanning transmission X-ray microscopy (STXM) using the X-ray fluorescence mode in order to elucidate the chemical structures at Ni, Fe, Mn and O sites from the (111) and (100) facets of micron-sized LiNi 1/3Fe 1/3Mn 4/3O 4 energy material particles. Furthermore, STXM imaging using electron yield mode has mapped out the surface conductivity of the crystalline particles. Our study presents a novel approach that visualizes local element segregation, chemistry and conductivity variation among different crystal facets, which will assist further tailoring of the morphology and surface structure of this high voltage spinel lithium ion battery cathode material.

Organic-Acid-Assisted Fabrication of Low-Cost Li-Rich Cathode Material (Li[Li1/6Fe1/6Ni1/6Mn1/2]O-2) for Lithium-Ion Battery

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

Zhao, Taolin; Chen, Shi; Li, Li

2014-12-24

A novel Li-rich cathode Li[Li1/6Fe1/6Ni1/6Mn1/2]O-2 (0.4Li(2)MnO(3-)0.6LiFe(1/3)Ni(1/3)Mn(1/3)O(2)) was synthesized by a solgel method, which uses citric acid (SC), tartaric acid (ST), or adipic acid (SA) as a chelating agent. The structural, morphological, and electrochemical properties of the prepared samples were characterized by various methods. X-ray diffraction showed that single-phase materials are formed mainly with typical alpha-NaFeO2 layered structure (R3 m), and the SC sample has the lowest Li/Ni cation disorder. The morphological study indicated homogeneous primary particles in good distribution size (100 nm) with small aggregates. The Fe, Ni, and Mn valences were determined by X-ray absorption near-edge structure analysis. Inmore » coin cell tests, the initial reversible discharge capacity of an SA electrode was 289.7 mAh g(-1) at the 0.1C rate in the 1.54.8 V voltage range, while an SC electrode showed a better cycling stability with relatively high capacity retention. At the 2C rate, the SC electrode can deliver a discharge capacity of 150 mAh g(-1) after 50 cycles. Differential capacity vs voltage curves were employed to further investigate the electrochemical reactions and the structural change process during cycling. This low-cost, Fe-based compound prepared by the solgel method has the potential to be used as the high capacity cathode material for Liion batteries.« less

Magnetism of hexagonal Mn{sub 1.5}X{sub 0.5}Sn (X = Cr, Mn, Fe, Co) nanomaterials

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

Fuglsby, R.; Kharel, P., E-mail: parashu.kharel@sdstate.edu; Nebraska Center for Materials and Nanoscience, University of Nebraska, Lincoln, Nebraska 68588

2015-05-07

Mn{sub 1.5}X{sub 0.5}Sn (X = Cr, Mn, Fe, Co) nanomaterials in the hexagonal Ni{sub 2}In-type crystal structure have been prepared using arc-melting and melt spinning. All the rapidly quenched Mn{sub 1.5}X{sub 0.5}Sn alloys show moderate saturation magnetizations with the highest value of 458 emu/cm{sup 3} for Mn{sub 1.5}Fe{sub 0.5}Sn, but their Curie temperatures are less than 300 K. All samples except the Cr containing one show spin-glass-like behavior at low temperature. The magnetic anisotropy constants calculated from the high-field magnetization curves at 100 K are on the order of 1 Merg/cm{sup 3}. The vacuum annealing of the ribbons at 550 °C significantly improved theirmore » magnetic properties with the Curie temperature increasing from 206 K to 273 K for Mn{sub 1.5}Fe{sub 0.5}Sn.« less

Charge-density study on layered oxyarsenides (LaO)MAs (M = Mn, Fe, Ni, Zn)

NASA Astrophysics Data System (ADS)

Takase, Kouichi; Hiramoto, Shozo; Fukushima, Tetsuya; Sato, Kazunori; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2017-12-01

Using synchrotron X-ray powder diffraction, we investigate the charge-density distributions of the layered oxypnictides (LaO)MnAs, (LaO)FeAs, (LaO)NiAs, and (LaO)ZnAs, which are an antiferromagnetic semiconductor, a parent material of an iron-based superconductor, a low-temperature superconductor, and a non-magnetic semiconductor, respectively. For the metallic samples, clear charge densities are observed in both the transition-metal pnictide layers and the rare-earth-oxide layers. However, in the semiconducting samples, there is no finite charge density between the transition-metal element and As. These differences in charge density reflect differences in physical properties. First-principles calculations using density functional theory reproduce the experimental results reasonably well.

Density functional theory study on the structures, electronic and magnetic properties of the MFe3n‑1O4n (n = 1–3) (M=Mn, Co and Ni) clusters

NASA Astrophysics Data System (ADS)

Li, Zhi; Zhao, Zhen; Wang, Qi; Yin, Xi-tao

2018-04-01

The structures, electronic and magnetic properties of the MFe3n‑1O4n (n = 1–3) (M=Mn, Co and Ni) clusters are obtained by using the GGA-PBE functional. The results found that the CoFe3n‑1O4n (n = 1–3) clusters are more stable than the corresponding NiFe3n‑1O4n and MnFe3n‑1O4n clusters. The NiFe2O4, MnFe5O8 and CoFe5O8 clusters have higher kinetic stability than their neighbors. The average magnetic moments of MFe3n‑1O4n (n = 1–3) (M=Mn, Co and Ni) clusters are successively: NiFe3n‑1O4n > CoFe3n‑1O4n > MnFe3n‑1O4n. For NiFe3n‑1O4n and CoFe3n‑1O4n clusters, the average magnetic moments are decreased with the cluster size increasing while for MnFe3n‑1O4n, the opposite situation is occur. The difference of 3d orbital electrons of M (M=Mn, Co and Ni) atoms influence the magnetic properties of MFe3n‑1O4n clusters.

Tough cryogenic alloys from the Fe-Mn and Fe-Mn-Cr systems

NASA Technical Reports Server (NTRS)

Schanfein, M. J.; Zackay, V. F.; Morris, J. W., Jr.

1974-01-01

By adjusting composition, metastable gamma (austenite) and epsilon (hexagonal) martensite may be retained in Fe-Mn and Fe-Mn-Cr alloys and used to impact toughness through the TRIP mechanism. The resulting alloys have excellent toughness at cryogenic temperatures. The best alloys obtained to date are: Fe-20Mn, with sigma (sub y) = 79ksi and K sub IC = 275ksi square root of (in) at 77 K, and Fc-16Mn-8Cr, with sigma sub y = 85ksi and K sub IC = 72ksi square root of (in) at 77 K.

Quality of Metal Deposited Flux Cored Wire With the System Fe-C-Si-Mn-Cr-Mo-Ni-V-Co

NASA Astrophysics Data System (ADS)

Gusev, Aleksander I.; Kozyrev, Nikolay A.; Osetkovskiy, Ivan V.; Kryukov, Roman E.; Kozyreva, Olga A.

2017-10-01

Studied the effect of the introduction of vanadium and cobalt into the charge powder fused wire system Fe-C-Si-Mn-Cr-Ni-Mo-V, used in cladding assemblies and equipment parts and mechanisms operating under abrasive and abrasive shock loads. the cored wires samples were manufactured in the laboratory conditions and using appropriate powder materials and as a carbonfluoride contained material were used the dust from gas purification of aluminum production, with the following components composition, %: Al2O3 = 21-46.23; F = 18-27; Na2O = 8-15; K2O = 0.4-6; CaO = 0.7-2.3; Si2O = 0.5-2.48; Fe2O3 = 2.1-3.27; C = 12.5-30.2; MnO = 0.07-0.9; MgO = 0.06-0.9; S = 0.09-0.19; P = 0.1-0.18. Surfacing was produced on the St3 metal plates in 6 layers under the AN-26C flux by welding truck ASAW-1250. Cutting and preparation of samples for research had been implemented. The chemical composition and the hydrogen content of the weld metal were determined by modern methods. The hardness and abrasion rate of weld metal had been measured. Conducted metallographic studies of weld metal: estimated microstructure, grain size, contamination of oxide non-metallic inclusions. Metallographic studies showed that the microstructure of the surfaced layer by cored wire system Fe-C-Si-Mn-Cr-Mo-Ni-V-Co is uniform, thin dendrite branches are observed. The microstructure consists of martensite, which is formed inside the borders of the former austenite grain retained austenite present in small amounts in the form of separate islands, and thin layers of δ-ferrite, which is located on the borders of the former austenite grains. Carried out an assessment the effect of the chemical composition of the deposited metal on the hardness and wear and hydrogen content. In consequence of multivariate correlation analysis, it was determined dependence to the hardness of the deposited layer and the wear resistance of the mass fraction of the elements included in the flux-cored wires of the system Fe-C-Si-Mn-Cr-Mo-Ni

Synthesis, structural characterization, and electrochemical properties of dinuclear Ni/Mn model complexes for the active site of [NiFe]-hydrogenases.

PubMed

Song, Li-Cheng; Li, Jia-Peng; Xie, Zhao-Jun; Song, Hai-Bin

2013-10-07

Four new dinuclear Ni/Mn model complexes RN(PPh2)2Ni(μ-SEt)2(μ-Cl)Mn(CO)3 (7, R = p-MeC6H4CH2; 8, R = EtO2CCH2) and RN(PPh2)2Ni(μ-SEt)2(μ-Br)Mn(CO)3 (9, R = p-MeC6H4CH2; 10, R = EtO2CCH2) have been prepared via the four separated step-reactions involving six new precursors RN(PPh2)2 (1, R = p-MeC6H4CH2; 2, R = EtO2CCH2), RN(PPh2)2NiCl2 (3, R = p-MeC6H4CH2; 4, R = EtO2CCH2), and RN(PPh2)2Ni(SEt)2 (5, R = p-MeC6H4CH2; 6, R = EtO2CCH2). The Et3N-assisted aminolysis of Ph2PCl with p-MeC6H4CH2NH2 or EtO2CCH2NH2·HCl in CH2Cl2 gave the azadiphosphine ligands 1 and 2 in 38% and 53% yields, whereas the coordination reaction of 1 or 2 with NiCl2·6H2O in CH2Cl2/MeOH afforded the mononuclear Ni dichloride complexes 3 and 4 in 59% and 78% yields, respectively. While thiolysis of 3 or 4 with EtSH under the assistance of Et3N in CH2Cl2 produced the mononuclear Ni dithiolate complexes 5 and 6 in 64% and 68% yields, further treatment of 5 and 6 with Mn(CO)5Cl or Mn(CO)5Br resulted in formation of the dinuclear Ni/Mn model complexes 7-10 in 31-73% yields. All the new compounds 1-10 have been structurally characterized, while model complexes 7 and 9 have been found to be catalysts for HOAc proton reduction to hydrogen under CV conditions.

The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2005-01-01

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

NASA Astrophysics Data System (ADS)

Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

2018-02-01

In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

Cyclic Degradation Behavior of < 001 > -Oriented Fe-Mn-Al-Ni Single Crystals in Tension

NASA Astrophysics Data System (ADS)

Vollmer, M.; Kriegel, M. J.; Krooß, P.; Martin, S.; Klemm, V.; Weidner, A.; Chumlyakov, Y.; Biermann, H.; Rafaja, D.; Niendorf, T.

2017-12-01

In the present study, functional fatigue behavior of a near 〈001〉-oriented Fe-Mn-Al-Ni single crystal was investigated under tensile load. An incremental strain test up to 3.5% strain and cyclic tests up to 25 cycles revealed rapid pseudoelastic degradation. Progressive microstructural degradation was studied by in situ scanning electron microscopy. The results show a partially inhibited reactivation of previously formed martensite and proceeding activation of untransformed areas in subsequent cycles. The preferentially formed martensite variants were identified by means of Schmid factor calculation and the Kurdjumov-Sachs relationship. Post mortem transmission electron microscopy investigations shed light on the prevailing degradation mechanisms. Different types of dislocations were found promoting the progressive degradation during cyclic loading.

Spinel, YbFe2O4, and Yb2Fe3O7 types of structure for compounds in the In2O3 and Sc2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn) at temperatures over 1000C

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

Kimizuka, N.; Mohri, T.

In the Sc2O3-Ga2O3-CuO, Sc2O3-Ga2O3-ZnO, and Sc2O3-Al2O3-CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFeT MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAl-CuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations. 5more » references, 2 tables.« less

Modeling and Characterization of the Magnetocaloric Effect in Ni2MnGa Materials

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

Nicholson, Don M; Odbadrakh, Khorgolkhuu; Rios, Orlando

2012-01-01

Magnetic shape memory alloys have great promise as magneto-caloric effect refrigerant materials due to their combined magnetic and structural transitions. Computational and experimental research is reported on the Ni2MnGa material system. The magnetic states of this system have been explored using the Wang-Landau statistical approach in conjunction with the Locally Self-consistent Multiple-Scattering (LSMS) method to explore the magnetic states responsible for the magnet-caloric effect in this material. The effects of alloying agents on the transition temperatures of the Ni2MnGa alloy were investigated using differential scanning calorimetry (DSC) and superconducting quantum interference device (SQUID). Neutron scattering experiments were performed to observemore » the structural and magnetic phase transformations at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) on alloys of Ni-Mn-Ga and Ni-Mn-Ga-Cu-Fe. Data from the observations are discussed in comparison with the computational studies.« less

Viscosities of Fe Ni, Fe Co and Ni Co binary melts

NASA Astrophysics Data System (ADS)

Sato, Yuzuru; Sugisawa, Koji; Aoki, Daisuke; Yamamura, Tsutomu

2005-02-01

Viscosities of three binary molten alloys consisting of the iron group elements, Fe, Ni and Co, have been measured by using an oscillating cup viscometer over the entire composition range from liquidus temperatures up to 1600 °C with high precision and excellent reproducibility. The viscosities measured showed good Arrhenius linearity for all the compositions. The viscosities of Fe, Ni and Co as a function of temperature are as follows: \\eqalign{ & \\log \\eta={-}0.6074 + 2493/T\\qquad for\\quad Fe\\\\ & \\log \\eta={-}0.5695 + 2157/T\\qquad for\\quad Ni \\\\ & \\log \\eta={-}0.6620 + 2430/T\\qquad for\\quad Co.} The isothermal viscosities of Fe-Ni and Fe-Co binary melts increase monotonically with increasing Fe content. On the other hand, in Ni-Co binary melt, the isothermal viscosity decreases slightly and then increases with increasing Co. The activation energy of Fe-Co binary melt increased slightly on mixing, and those of Fe-Ni and Ni-Co melts decreased monotonically with increasing Ni content. The above behaviour is discussed based on the thermodynamic properties of the alloys.

Correlation of martensitic transformation temperatures of Ni- Mn-Ga/Al-X alloys to non-bonding electron concentration

NASA Astrophysics Data System (ADS)

Ramudu, M.; Satish Kumar, A.; Seshubai, V.; Rajasekharan, T.

2015-02-01

The martensitic transformation TM of the alloys of Ni-Mn-Ga and Ni-Mn-Al show a general trend of increase with electron per atom ratio (e/a) calculated from the total number of electrons outside the rare gas shell of the atoms. However prediction of TM fails among iron substituted Ni-Mn-Ga alloys and those with In doped for Ga, due to the absence of a useful trend. A scheme of computing modified electron concentration is presented considering only the non-bonding electrons per atom Ne/a of the compounds, based on Pauling's ideas on the electronic structure of metallic elements. Systematic variation of TM with Ne/a is reproduced for a large number of alloys of Ni-Mn-Ga and the anomaly observed for Fe containing alloys with e/a disappears. The non-bonding electron concentration is thus demonstrated to be effective in predicting TM of shape memory alloys of Ni-Mn-Ga-X system including the isoelectronic compounds of Ni-Mn-Ga-In.

Fabrication and performance of a double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O thin film detector

NASA Astrophysics Data System (ADS)

Zhou, Wei; Yin, Yiming; Yao, Niangjuan; Jiang, Lin; Qu, Yue; Wu, Jing; Gao, Y. Q.; Huang, Jingguo; Huang, Zhiming

2018-01-01

A thermal sensitive infrared and THz detector was fabricated by a double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O films. The Mn-Co-Ni-O material, as one type of transition metal oxides, has long been used as a candidate for thermal sensors or infrared detectors. The resistivity of a most important Mn-Co-Ni-O thin film, Mn1. 96Co0.96Ni0.48O4(MCN) , is about 200 Ω·cm at room temperature, which ranges about 2 orders larger than that of VOx detectors. Therefore, the thickness of a typical squared Mn-Co-Ni-O IR detector should be about 10 μm, which is too large for focal plane arrays applications. To reduce the resistivity of Mn-Co-Ni-O thin film, 1/6 of Co element was replaced by Cu. Meanwhile, a cover layer of MCN film was deposited onto the Mn-Co-Ni-Cu-O film to improve the long term stability. The detector fabricated by the double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O films showed large response to blackbody and 170 GHz radiation. The NEP of the detector was estimated to be the order of 10-8 W/Hz0. 5. By applying thermal isolation structure and additional absorption materials, the detection performance can be largely improved by 1-2 orders according to numerical estimation. The double layered Mn-Co-Ni-O film detector shows great potentials in applications in large scale IR detection arrays, and broad-band imaging.

Effect of Mn and Fe on the Formation of Fe- and Mn-Rich Intermetallics in Al–5Mg–Mn Alloys Solidified Under Near-Rapid Cooling

PubMed Central

Liu, Yulin; Huang, Gaoren; Sun, Yimeng; Zhang, Li; Huang, Zhenwei; Wang, Jijie; Liu, Chunzhong

2016-01-01

Mn was an important alloying element used in Al–Mg–Mn alloys. However, it had to be limited to a low level (<1.0 wt %) to avoid the formation of coarse intermetallics. In order to take full advantage of the benefits of Mn, research was carried out to investigate the possibility of increasing the content of Mn by studying the effect of cooling rate on the formation of Fe- and Mn-rich intermetallics at different content levels of Mn and Fe. The results indicated that in Al–5Mg–Mn alloy with low Fe content (<0.1 wt %), intermetallic Al6(Fe,Mn) was small in size and amount. With increasing Mn content, intermetallic Al6(Fe,Mn) increased, but in limited amount. In high-Fe-containing Al–5Mg–Mn alloys (0.5 wt % Fe), intermetallic Al6(Fe,Mn) became the dominant phase, even in the alloy with low Mn content (0.39 wt %). Cooling rate played a critical role in the refinement of the intermetallics. Under near-rapid cooling, intermetallic Al6(Fe,Mn) was extremely refined. Even in the high Mn and/or high-Fe-containing alloys, it still demonstrated fine Chinese script structures. However, once the alloy composition passed beyond the eutectic point, the primary intermetallic Al6(Fe,Mn) phase displayed extremely coarse platelet-like morphology. Increasing the content of Fe caused intermetallic Al6(Fe,Mn) to become the primary phase at a lower Mn content. PMID:28787888

Effect of Mn and Fe on the Formation of Fe- and Mn-Rich Intermetallics in Al-5Mg-Mn Alloys Solidified Under Near-Rapid Cooling.

PubMed

Liu, Yulin; Huang, Gaoren; Sun, Yimeng; Zhang, Li; Huang, Zhenwei; Wang, Jijie; Liu, Chunzhong

2016-01-29

Mn was an important alloying element used in Al-Mg-Mn alloys. However, it had to be limited to a low level (<1.0 wt %) to avoid the formation of coarse intermetallics. In order to take full advantage of the benefits of Mn, research was carried out to investigate the possibility of increasing the content of Mn by studying the effect of cooling rate on the formation of Fe- and Mn-rich intermetallics at different content levels of Mn and Fe. The results indicated that in Al-5Mg-Mn alloy with low Fe content (<0.1 wt %), intermetallic Al₆(Fe,Mn) was small in size and amount. With increasing Mn content, intermetallic Al₆(Fe,Mn) increased, but in limited amount. In high-Fe-containing Al-5Mg-Mn alloys (0.5 wt % Fe), intermetallic Al₆(Fe,Mn) became the dominant phase, even in the alloy with low Mn content (0.39 wt %). Cooling rate played a critical role in the refinement of the intermetallics. Under near-rapid cooling, intermetallic Al₆(Fe,Mn) was extremely refined. Even in the high Mn and/or high-Fe-containing alloys, it still demonstrated fine Chinese script structures. However, once the alloy composition passed beyond the eutectic point, the primary intermetallic Al₆(Fe,Mn) phase displayed extremely coarse platelet-like morphology. Increasing the content of Fe caused intermetallic Al₆(Fe,Mn) to become the primary phase at a lower Mn content.

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn.

PubMed

Scancar, J; Milacic, R; Strazar, M; Burica, O; Bukovec, P

2001-02-01

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.

The formation and structure of Fe-Mn-Ni-Si solute clusters and G-phase precipitates in steels

NASA Astrophysics Data System (ADS)

King, D. J. M.; Burr, P. A.; Middleburgh, S. C.; Whiting, T. M.; Burke, M. G.; Wenman, M. R.

2018-07-01

Solute clustering and G-phase precipitation cause hardening phenomena observed in some low alloy and stainless steels, respectively. Density functional theory was used to investigate the energetic driving force for the formation of these precipitates, capturing temperature effects through analysis of the system's configurational and magnetic entropies. It is shown that enrichment of Mn, Ni and Si is thermodynamically favourable compared to the dilute ferrite matrix of a typical A508 low alloy steel. We predict the ordered G-phase to form preferentially rather than a structure with B2-type ordering when the Fe content of the system falls below 10-18 at. %. The B2 → G-phase transformation is predicted to occur spontaneously when vacancies are introduced into the B2 structure in the absence of Fe.

Molten Pool Behavior and Mechanical Properties of Pulsed Current Double-Sided Synchronization GTA Welded Fe-18Cr-17Mn-Ni-N

NASA Astrophysics Data System (ADS)

Qiang, Wei; Wang, Kehong; Feng, Yuehai; Chen, Jiahe

2017-02-01

Double-sided synchronization vertical gas tungsten arc welding (DSSVW) procedure was used to weld high-nitrogen low-nickel stainless steel Fe-18Cr-17Mn-Ni-N without groove and filler wire. First, the molten pool behaviors and appearances of pulsed current DSSVW (PC-DSSVW) and constant current DSSVW (CC-DSSVW) were comparatively analyzed. The periodic variation occurs in the width of both the anode region of the arc and the molten pool tail during PC-DSSVW, while the contact angle first increases and then decreases, and both the width of the anode region and the length of arc plume increase progressively in CC-DSSVW. It is found that the weld appearance of PC-DSSVW is superior to that of CC-DSSVW. Second, the forces of the DSSVW molten pool were analyzed. The result indicates that the molten pool of the DSSVW procedure is in a state of unstable equilibrium, and it will easily lose balance after being disturbed, resulting in the asymmetrical weld or hump bead. Third, the PC-DSSVW experiments at various welding speeds were conducted to study the influence of welding speed on the weld profile, microstructure, tensile strength and impact toughness. Furthermore, the solidification mode of Fe-18Cr-17Mn-Ni-N was predicted to help determine the microstructure of the welded joint. Results indicate that the weld width, weld reinforcement and melting area all increase with decreasing welding speed, and Fe-18Cr-17Mn-Ni-N solidifies as A mode. The microstructure of the base metal (BM) and heat-affected zone (HAZ) is equiaxed austenite and that of the fusion zone (FZ) is austenite dendrite with some chromium carbides dispersed in the grain boundary; with decreasing welding speed, grains become coarse. The maximum tensile strength (UTS) and elongation of PC-DSSVW joint are 860 MPa and 8.1%, and the elongation decreases dramatically with decreasing welding speed. The impact toughness decreases substantially compared to the BM, achieving 48.2% of the BM.

Dependence of spin pumping and spin transfer torque upon Ni81Fe19 thickness in Ta/Ag /Ni 81Fe19/Ag/Co 2MnGe /Ag /Ta spin-valve structures

NASA Astrophysics Data System (ADS)

Durrant, C. J.; Shelford, L. R.; Valkass, R. A. J.; Hicken, R. J.; Figueroa, A. I.; Baker, A. A.; van der Laan, G.; Duffy, L. B.; Shafer, P.; Klewe, C.; Arenholz, E.; Cavill, S. A.; Childress, J. R.; Katine, J. A.

2017-10-01

Spin pumping has been studied within Ta / Ag / Ni81Fe19 (0-5 nm) / Ag (6 nm) / Co2MnGe (5 nm) / Ag / Ta large-area spin-valve structures, and the transverse spin current absorption of Ni81Fe19 sink layers of different thicknesses has been explored. In some circumstances, the spin current absorption can be inferred from the modification of the Co2MnGe source layer damping in vector network analyzer ferromagnetic resonance (VNA-FMR) experiments. However, the spin current absorption is more accurately determined from element-specific phase-resolved x-ray ferromagnetic resonance (XFMR) measurements that directly probe the spin transfer torque (STT) acting on the sink layer at the source layer resonance. Comparison with a macrospin model allows the real part of the effective spin mixing conductance to be extracted. We find that spin current absorption in the outer Ta layers has a significant impact, while sink layers with thicknesses of less than 0.6 nm are found to be discontinuous and superparamagnetic at room temperature, and lead to a noticeable increase of the source layer damping. For the thickest 5-nm sink layer, increased spin current absorption is found to coincide with a reduction of the zero frequency FMR linewidth that we attribute to improved interface quality. This study shows that the transverse spin current absorption does not follow a universal dependence upon sink layer thickness but instead the structural quality of the sink layer plays a crucial role.

Self-current induced spin-orbit torque in FeMn/Pt multilayers

NASA Astrophysics Data System (ADS)

Xu, Yanjun; Yang, Yumeng; Yao, Kui; Xu, Baoxi; Wu, Yihong

2016-05-01

Extensive efforts have been devoted to the study of spin-orbit torque in ferromagnetic metal/heavy metal bilayers and exploitation of it for magnetization switching using an in-plane current. As the spin-orbit torque is inversely proportional to the thickness of the ferromagnetic layer, sizable effect has only been realized in bilayers with an ultrathin ferromagnetic layer. Here we demonstrate that, by stacking ultrathin Pt and FeMn alternately, both ferromagnetic properties and current induced spin-orbit torque can be achieved in FeMn/Pt multilayers without any constraint on its total thickness. The critical behavior of these multilayers follows closely three-dimensional Heisenberg model with a finite Curie temperature distribution. The spin torque effective field is about 4 times larger than that of NiFe/Pt bilayer with a same equivalent NiFe thickness. The self-current generated spin torque is able to switch the magnetization reversibly without the need for an external field or a thick heavy metal layer. The removal of both thickness constraint and necessity of using an adjacent heavy metal layer opens new possibilities for exploiting spin-orbit torque for practical applications.

Self-current induced spin-orbit torque in FeMn/Pt multilayers

PubMed Central

Xu, Yanjun; Yang, Yumeng; Yao, Kui; Xu, Baoxi; Wu, Yihong

2016-01-01

Extensive efforts have been devoted to the study of spin-orbit torque in ferromagnetic metal/heavy metal bilayers and exploitation of it for magnetization switching using an in-plane current. As the spin-orbit torque is inversely proportional to the thickness of the ferromagnetic layer, sizable effect has only been realized in bilayers with an ultrathin ferromagnetic layer. Here we demonstrate that, by stacking ultrathin Pt and FeMn alternately, both ferromagnetic properties and current induced spin-orbit torque can be achieved in FeMn/Pt multilayers without any constraint on its total thickness. The critical behavior of these multilayers follows closely three-dimensional Heisenberg model with a finite Curie temperature distribution. The spin torque effective field is about 4 times larger than that of NiFe/Pt bilayer with a same equivalent NiFe thickness. The self-current generated spin torque is able to switch the magnetization reversibly without the need for an external field or a thick heavy metal layer. The removal of both thickness constraint and necessity of using an adjacent heavy metal layer opens new possibilities for exploiting spin-orbit torque for practical applications. PMID:27185656

Low-cost, high-strength Fe--Ni--Cr alloys for high temperature exhaust valve application

DOEpatents

Muralidharan, Govindarajan

2017-09-05

An Fe--Ni--Cr alloy is composed essentially of, in terms of wt. %: 2.4 to 3.7 Al, up to 1.05 Co, 14.8 to 15.9 Cr, 25 to 36 Fe, up to 1.2 Hf, up to 4 Mn, up to 0.6 Mo, up to 2.2 Nb, up to 1.05 Ta, 1.9 to 3.6 Ti, up to 0.08 W, up to 0.03 Zr, 0.18 to 0.27 C, up to 0.0015 N, balance Ni, wherein, in terms of atomic percent: 8.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.11.5, 0.53.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.65, and 0.16.ltoreq.Cr/(Fe+Ni+Cr+Mn).ltoreq.0.21, the alloy being essentially free of Cu, Si, and V.

A comparative study on electrochemical cycling stability of lithium rich layered cathode materials Li1.2Ni0.13M0.13Mn0.54O2 where M = Fe or Co

NASA Astrophysics Data System (ADS)

Laisa, C. P.; Nanda Kumar, A. K.; Selva Chandrasekaran, S.; Murugan, P.; Lakshminarasimhan, N.; Govindaraj, R.; Ramesha, K.

2016-08-01

In this work we compare electrochemical cycling stability of Fe containing Li rich phase Li1.2Ni0.13Fe0.13Mn0.54O2 (Fe-Li rich) with the well-known Co containing Li rich composition Li1.2Ni0.13Co0.13Mn0.54O2 (Co-Li rich). During the first charge, the activation plateau corresponding to removal of Li2O from the structure is smaller (removal of 0.6 Li) in the case of Fe-Li rich compared to Co-Li rich composition (0.8 Li removal). Consequently, the Fe compound shows better capacity retention; for example, after 100 cycles Fe-Li rich compound exhibits 20% capacity degradation where as it is about 40% in the case of Co-Li rich phase. The electrochemical and microscopy studies support the fact that compared to Co-Li rich compound, the Fe-Li rich composition display smaller voltage decay and reduced spinel conversion. XPS studies on charged/discharged Fe-Li rich samples show participation of Fe+3/Fe+4 redox during electrochemical cycling which is further supported by our first principles calculations. Also the temperature dependent magnetic studies on charge-discharged samples of Fe-Li rich compound point out that magnetic behavior is sensitive to cation oxidation states and Ni/Li disorder.

Enhanced magnetic properties in Mn0.6Zn0.4-xNixFe2O4 (x=0-0.4) nanoparticles

NASA Astrophysics Data System (ADS)

Mallesh, S.; Mandal, P.; Srinivas, V.

2018-04-01

Ni substituted MnZn ferrite fine particles were synthesized through sol-gel method. The structure, stability and magnetic properties have been investigated. Thermal stability of as-prepared (AP) particles is improved compared to that of Mn0.6Zn0.4Fe2O4 (MZF) ferrite particles. The as-prepared and samples annealed at 1200 °C exhibit pure spinel ferrite phase, while samples at intermediate temperatures (600 - 1000 °C) exhibit secondary phase of α-Fe2O3 along with ferrite phase. The Mn0.6Zn0.1Ni0.3Fe2O4 (Ni-MZF) sample shows significantly lower volume fraction of secondary phase compared to that of MZF. The observed magnetization of Ni-MZF is twice of that MZF samples. Present results suggest that a small amount (x=0.3) of Ni in place of nonmagnetic Zn in MZF significantly decreases the secondary phase fraction and improves the magnetic properties.

First-principles study of magnetoelastic effect in the difluoride compounds MF2 (M=Mn, Fe, Co, Ni)

NASA Astrophysics Data System (ADS)

Das, Hena; Kanungo, Sudipta; Saha-Dasgupta, T.

2012-08-01

Employing first-principles density-functional-theory-based calculations, we study the electronic structure and magnetoelastic effect in difluoride compounds MF2 (M=Mn, Fe, Co, Ni). The magnetoelastic-effect-driven cell-parameter changes across the series are found to exhibit nonmonotonic behavior in agreement with recent experimental reports. Our study reveals that this originates from the nonmonotonicity in the exchange striction of the bond-stretching phonon mode associated with the short M-F bond. Our study also uncovers the role of M-F covalency in driving the nonmonotonic behavior of the M-M exchange interaction across the series.

Laser photoelectron spectroscopy of MnH - 2, FeH - 2, CoH - 2, and NiH - 2: Determination of the electron affinities for the metal dihydrides

NASA Astrophysics Data System (ADS)

Miller, Amy E. S.; Feigerle, C. S.; Lineberger, W. C.

1986-04-01

The laser photoelectron spectra of MnH-2, FeH-2, CoH-2, and NiH-2 and the analogous deuterides are reported. Lack of vibrational structure in the spectra suggests that all of the dihydrides and their negative ions have linear geometries, and that the transitions observed in the spectra are due to the loss of nonbonding d electrons. The electron affinities for the metal dihydrides are determined to be 0.444±0.016 eV for MnH2, 1.049±0.014 eV for FeH2, 1.450±0.014 eV for CoH2, and 1.934±0.008 eV for NiH2. Electronic excitation energies are provided for excited states of FeH2, CoH2, and NiH2. Electron affinities and electronic excitation energies for the dideuterides are also reported. A limit on the electron affinity of CrH2 of ≥2.5 eV is determined. The electron affinities of the dihydrides directly correlate with the electron affinities of the high-spin states of the monohydrides, and with the electron affinities of the metal atoms. These results are in agreement with a qualitative model developed for bonding in the monohydrides.

Statistical theory of diffusion in concentrated bcc and fcc alloys and concentration dependencies of diffusion coefficients in bcc alloys FeCu, FeMn, FeNi, and FeCr

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

Vaks, V. G.; Khromov, K. Yu., E-mail: khromov-ky@nrcki.ru; Pankratov, I. R.

2016-07-15

The statistical theory of diffusion in concentrated bcc and fcc alloys with arbitrary pairwise interatomic interactions based on the master equation approach is developed. Vacancy–atom correlations are described using both the second-shell-jump and the nearest-neighbor-jump approximations which are shown to be usually sufficiently accurate. General expressions for Onsager coefficients in terms of microscopic interatomic interactions and some statistical averages are given. Both the analytical kinetic mean-field and the Monte Carlo methods for finding these averages are described. The theory developed is used to describe sharp concentration dependencies of diffusion coefficients in several iron-based alloy systems. For the bcc alloys FeCu,more » FeMn, and FeNi, we predict the notable increase of the iron self-diffusion coefficient with solute concentration c, up to several times, even though values of c possible for these alloys do not exceed some percent. For the bcc alloys FeCr at high temperatures T ≳ 1400 K, we show that the very strong and peculiar concentration dependencies of both tracer and chemical diffusion coefficients observed in these alloys can be naturally explained by the theory, without invoking exotic models discussed earlier.« less

Structural and magnetic transition in stainless steel Fe-21Cr-6Ni-9Mn up to 250 GPa

NASA Astrophysics Data System (ADS)

Liu, Lei; Hou, Qi-Yue; Zhang, Yi; Jing, Qiu-Min; Wang, Zhi-Gang; Bi, Yan; Xu, Ji-An; Li, Xiao-Dong; Li, Yan-Chun; Liu, Jing

2015-06-01

Stainless steel Fe-21Cr-6Ni-9Mn (SS 21-6-9), with ˜21% Cr, ˜6% Ni, and ˜9% Mn in weight percentage, has wide applications in extensive fields. In the present study, SS 21-6-9 is compressed up to 250 GPa, and its crystal structures and compressive behaviors are investigated simultaneously using the synchrotron angle-dispersive x-ray diffraction technique. The SS 21-6-9 undergoes a structural phase transition from fcc to hcp structure at ˜12.8 GPa with neglectable volume collapse within the determination error under the quasi-hydrostatic environment. The hcp structure remains stable up to the highest pressure of 250 GPa in the present experiments. The antiferromagnetic-to-nonmagnetic state transition of hcp SS 21-6-9 with the changes of inconspicuous density and structure, is discovered at ˜50 GPa, and revealed by the significant change in c/a ratio. The hcp SS-21-6-9 is compressive anisotropic: it is more compressive in the c-axis direction than in the a-axis direction. Both the equations of states (EOSs) of fcc and hcp SS 21-6-9, which are in accordance with those of fcc and hcp pure irons respectively, are also presented. Furthermore, the c/a ratio of hcp SS 21-6-9 at infinite compression, R∞, is consistent with the values of pure iron and Fe-10Ni alloy. Project supported by the National Natural Science Foundation of China (Grant Nos. U1230201, 11274281, and 11304294), the Industrial Technology Development Program, China (Grant No. 9045140509), and the Funds from the Chinese Academy of Sciences (Grant Nos. KJCX2-SW-N03 and KJCX2-SW-N20).

Edge-Cracking Behavior of CoCrFeMnNi High-Entropy Alloy During Hot Rolling

NASA Astrophysics Data System (ADS)

Won, Jong Woo; Kang, Minju; Kwon, Heoun-Jun; Lim, Ka Ram; Seo, Seong Moon; Na, Young Sang

2018-05-01

This work investigated edge-cracking behavior of equiatomic CoCrFeMnNi high-entropy alloy during hot rolling at rolling temperatures 500 ≤ T R ≤ 1000 °C. Edge cracks did not form in the material rolled at 500 °C, but widened and deepened into the inside of plate as T R increased from 500 °C. Edge cracks were most severe in the material rolled at 1000 °C. Mn-Cr-O type non-metallic inclusion and oxidation were identified as major factors that caused edge cracking. The inclusions near edge region acted as preferential sites for crack formation. Connection between inclusion cracks and surface cracks induced edge cracking. Rolling at T R ≥ 600 °C generated distinct inclusion cracks whereas they were not serious at T R = 500 °C, so noticeable edge cracks formed at T R ≥ 600 °C. At T R = 1000 °C, significant oxidation occurred at the crack surface. This accelerated edge crack penetration by embrittling the crack tip, so severe edge cracking occurred at T R = 1000 °C.

Physical Properties of NiFeCrCo-based High-Entropy Alloys

NASA Astrophysics Data System (ADS)

Zaddach, Alexander Joseph

Conventional alloy design has been based on improving the properties of a single base, or solvent, element through relatively small additions of other elements. More recently, research has been conducted on alloys that contain multiple principal elements, particularly multi-component equiatomic alloys. When such alloys form solid solution phases, they are termed "high-entropy alloys" (HEAs) due to their high configurational entropy. These alloys often have favorable properties compared to conventional dilute solution alloys, but their compositional complexity and relative novelty means that they remain difficult to design and their basic properties are often unknown. The motivation for this work is a detailed experimental exploration of some of the basic physical properties of NiFeCrCo-based alloys. NiFeCrCoMn was one of the first equiatomic HEAs developed. As the compositional space within this single system is extremely large, this work focuses primarily on equiatomic alloys and a limited subset of non-equiatomic alloys chosen for their specific properties. Several alloys are prepared using both conventional methods (arc melting) and nonequilibrium methods (mechanical alloying). Properties studied include stacking fault energy, bulk mechanical properties, single crystal elastic constants, and magnetic properties. The equiatomic NiFeCrCo and NiFeCrCoMn alloys were found to have a moderate to low stacking fault energy, 18 -- 30 mJ m-2. As they are single-phase, fcc alloys, they have high tensile ductility. Additionally, they also exhibit high work-hardening rates, resulting in high toughness. NiFeCrCo outperforms the 5-component equiatomic alloy in ductility and toughness. A 5-component alloy with higher Co content to reduce the stacking fault energy also performs well. The single crystal elastic constants were measured using nanoindentation modulus measurements of grains of known orientation. The measured elastic constants were consistent with those calculated

Dependence of spin pumping and spin transfer torque upon Ni 81 Fe 19 thickness in Ta / Ag / Ni 81 Fe 19 / Ag / Co 2 MnGe / Ag / Ta spin-valve structures

DOE PAGES

Durrant, C. J.; Shelford, L. R.; Valkass, R. A. J.; ...

2017-10-18

Spin pumping has been studied within Ta / Ag / Ni 81Fe 19 (0–5 nm) / Ag (6 nm) / Co 2MnGe (5 nm) / Ag / Ta large-area spin-valve structures, and the transverse spin current absorption of Ni 81Fe 19 sink layers of different thicknesses has been explored. In some circumstances, the spin current absorption can be inferred from the modification of the Co 2MnGe source layer damping in vector network analyzer ferromagnetic resonance (VNA-FMR) experiments. However, the spin current absorption is more accurately determined from element-specific phase-resolved x-ray ferromagnetic resonance (XFMR) measurements that directly probe the spin transfermore » torque (STT) acting on the sink layer at the source layer resonance. Comparison with a macrospin model allows the real part of the effective spin mixing conductance to be extracted. We find that spin current absorption in the outer Ta layers has a significant impact, while sink layers with thicknesses of less than 0.6 nm are found to be discontinuous and superparamagnetic at room temperature, and lead to a noticeable increase of the source layer damping. For the thickest 5-nm sink layer, increased spin current absorption is found to coincide with a reduction of the zero frequency FMR linewidth that we attribute to improved interface quality. Furthermore, this study shows that the transverse spin current absorption does not follow a universal dependence upon sink layer thickness but instead the structural quality of the sink layer plays a crucial role.« less

Dependence of spin pumping and spin transfer torque upon Ni 81 Fe 19 thickness in Ta / Ag / Ni 81 Fe 19 / Ag / Co 2 MnGe / Ag / Ta spin-valve structures

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

Durrant, C. J.; Shelford, L. R.; Valkass, R. A. J.

Spin pumping has been studied within Ta / Ag / Ni 81Fe 19 (0–5 nm) / Ag (6 nm) / Co 2MnGe (5 nm) / Ag / Ta large-area spin-valve structures, and the transverse spin current absorption of Ni 81Fe 19 sink layers of different thicknesses has been explored. In some circumstances, the spin current absorption can be inferred from the modification of the Co 2MnGe source layer damping in vector network analyzer ferromagnetic resonance (VNA-FMR) experiments. However, the spin current absorption is more accurately determined from element-specific phase-resolved x-ray ferromagnetic resonance (XFMR) measurements that directly probe the spin transfermore » torque (STT) acting on the sink layer at the source layer resonance. Comparison with a macrospin model allows the real part of the effective spin mixing conductance to be extracted. We find that spin current absorption in the outer Ta layers has a significant impact, while sink layers with thicknesses of less than 0.6 nm are found to be discontinuous and superparamagnetic at room temperature, and lead to a noticeable increase of the source layer damping. For the thickest 5-nm sink layer, increased spin current absorption is found to coincide with a reduction of the zero frequency FMR linewidth that we attribute to improved interface quality. Furthermore, this study shows that the transverse spin current absorption does not follow a universal dependence upon sink layer thickness but instead the structural quality of the sink layer plays a crucial role.« less

Molecule-based magnets formed by bimetallic three-dimensional oxalate networks and chiral tris(bipyridyl) complex cations. The series [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion).

PubMed

Coronado, E; Galán-Mascarós, J R; Gómez-García, C J; Martínez-Agudo, J M

2001-01-01

The synthesis, structure, and physical properties of the series of molecular magnets formulated as [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion) are presented. All the compounds are isostructural to the [Ru(bpy)3][ClO4][MnCr(ox)3] member whose structure (cubic space group P4(1)32 with a = 15.506(2) A, Z = 4) consists of a three-dimensional bimetallic network formed by alternating MII and CrIII ions connected by oxalate anions. The identical chirality (lambda in the solved crystal) of all the metallic centers determines the 3D chiral structure adopted by these compounds. The anionic 3D sublattice leaves some holes where the chiral [Z(bpy)3]2+ and ClO4- counterions are located. These compounds behave as soft ferromagnets with ordering temperatures up to 6.6 K and coercive fields up to 8 mT.

Hydrogen embrittlement in compositionally complex FeNiCoCrMn FCC solid solution alloy

DOE PAGES

Nygren, K. E.; Bertsch, K. M.; Wang, S.; ...

2018-02-01

The influence of internal hydrogen on the tensile properties of an equi-molar FeNiCoCrMn alloy results in a significant reduction of ductility, which is accompanied by a change in the fracture mode from ductile microvoid coalescence to intergranular failure. The introduction of 146.9 mass ppm of hydrogen reduced the plastic strain to failure from 0.67 in the uncharged case to 0.34 and 0.51 in hydrogen-charged specimens. This reduction in ductility and the transition in failure mode are clear indications that this alloy exhibits the classic signs of being susceptible to hydrogen embrittlement. The results are discussed in terms of the hydrogen-enhancedmore » plasticity mechanism and its influence on hydrogen-induced intergranular failure. Furthermore, a new additional constraint that further promotes intergranular failure is introduced for the first time.« less

Thermal conductivity, electrical resistivity, and thermopower of aerospace alloys from 4 to 300 K. 6: Fe-22Cr-13Ni-5Mn stainless steel

NASA Technical Reports Server (NTRS)

Hust, J. G.; Sparks, L. L.

1971-01-01

The equipment and techniques for determining the thermal conductivity, electrical resistivity Lorenz ratio, and thermopower characteristics of Fe-22Cr-13Ni-5Mn stainless steel are discussed. The dimensions of the specimen and its preparation are described. The experimental data are represented by arbitrary functions over the entire range and smooth tables are generated from these functions.

The reactivity of Fe/Ni colloid stabilized by carboxymethylcellulose (CMC-Fe/Ni) toward chloroform.

PubMed

Jin, Xin; Li, Qun; Yang, Qi

2018-05-16

The use of stabilizers can prevent the reactivity loss of nanoparticles due to aggregation. In this study, carboxymethylcellulose (CMC) was selected as the stabilizer to synthesize a highly stable CMC-stabilized Fe/Ni colloid (CMC-Fe/Ni) via pre-aggregation stabilization. The reactivity of CMC-Fe/Ni was evaluated via the reaction of chloroform (CF) degradation. The effect of background solution which composition was affected by the preparation of Fe/Ni (Fe/Ni precursors, NaBH 4 dosage) and the addition of solute (common ions, sulfur compounds) on the reactivity of CMC-Fe/Ni was also investigated. Additionally, the dried CMC-Fe/Ni was used for characterization in terms of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The experimental results indicated that CMC stabilization greatly improved the reactivity of Fe/Ni bimetal and CF (10 mg/L) could be completely degraded by CMC-Fe/Ni (0.1 g/L) within 45 min. The use of different Fe/Ni precursors resulting in the variations of background solution seemed to have no obvious influence on the reactivity of CMC-Fe/Ni, whereas the dosage of NaBH 4 in background solution showed a negative correlation with the reactivity of CMC-Fe/Ni. Besides, the individual addition of external solutes into background solution all had an adverse effect on the reactivity of CMC-Fe/Ni, of which the poisoning effect of sulfides (Na 2 S, Na 2 S 2 O 4 ) was significant than common ions and sulfite.

Metal elution from Ni- and Fe-based alloy reactors under hydrothermal conditions.

PubMed

Faisal, Muhammad; Quitain, Armando T; Urano, Shin-Ya; Daimon, Hiroyuki; Fujie, Koichi

2004-05-20

Elution of metals from Ni- and Fe-based alloy (i.e. Inconel 625 and SUS 316) under hydrothermal conditions was investigated. Results showed that metals could be eluted even in a short contact time. At subcritical conditions, a significant amount of Cr was extracted from SUS 316, while only traces of Ni, Fe, Mo, and Mn were eluted. In contrast, Ni was removed in significant amounts compared to Cr when Inconel 625 was tested. Several factors including temperature and contact time were found to affect elution behavior. The presence of air in the fluid even promoted elution under subcritical conditions.

H+-induced irradiation damage resistance in Fe- and Ni-based metallic glass

NASA Astrophysics Data System (ADS)

Zhang, Hongran; Mei, Xianxiu; Zhang, Xiaonan; Li, Xiaona; Wang, Yingmin; Sun, Jianrong; Wang, Younian

2016-05-01

In this study, use of 40-keV H+ ion for irradiating metallic glass Fe80Si7.43B12.57 and Ni62Ta38 as well as metallic tungsten (W) at fluences of 1 × 1018 and 3 × 1018 ions/cm2, respectively, was investigated. At the fluence of 1 × 1018 ions/cm2, a crystalline layer appeared in metallic glass Fe80Si7.43B12.57, with α-Fe as the major crystalline phase, coupled with a little Fe2B, Fe3B, and metastable β-Mn-type phase. Fe80Si7.43B12.57 exhibited good soft magnetic properties after irradiation. At the fluence of 3 × 1018 ions/cm2, Ni62Ta38 was found to be amorphous-based, with a little μ-NiTa and Ni3Ta phases. No significant irradiation damage phenomenon appeared in metallic glasses Fe80Si7.43B12.57 and Ni62Ta38. Blistering, flaking, and other damage occurred on the surface of metallic W, and the root-mean-square (RMS) roughness increased with the increase of fluence. Metallic glass Ni62Ta38 exhibited better resistance to H+ irradiation than Fe80Si7.43B12.57, both of which were superior to the metallic W.

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. 

Influence of Na+, K+, Mn2+, Fe2+ and Zn2+ ions on the electrodeposition of Ni-Co alloys: Implications for the recycling of Ni-MH batteries

NASA Astrophysics Data System (ADS)

Blanco, S.; Orta-Rodriguez, R.; Delvasto, P.

2017-01-01

A hydrometallurgical recycling procedure for the recovery of a mixed rare earths sulfate and an electrodeposited Ni-Co alloy has been described. The latter step was found to be complex, due to the presence of several ions in the battery electrode materials. Electrochemical evaluation of the influence of the ions on the Ni-Co alloy deposition was carried out by cyclic voltammetry test. It was found that ions such as K+, Fe2+ and Mn2+ improved the current efficiency for the Ni-Co deposition process on a copper surface. On the other hand, Na+ and Zn2+ ions exhibited a deleterious behaviour, minimizing the values of the reduction current. The results were used to suggest the inclusion of additional steps in the process flow diagram of the recycling operation, in order to eliminate deleterious ions from the electroplating solution.

Fe/Mn in olivine of carbonaceous meteorites

NASA Technical Reports Server (NTRS)

Steele, Ian M.

1993-01-01

Olivines in primitive meteorites show a range of Fe/Mn both within one grain and among grains suggesting that they have recorded changing conditions during or after growth. Because olivine should be an early forming phase, Fe/Mn is used here to infer these earliest conditions. Initial Fe/Mn in cores of isolated, euhedral forsterite in both C2 and C3 meteorites ranges from 25 to 35 but differs at grain edge. Murchison (C2) forsterites show Fe/Mn approaching 1.0 at the grain edge while Ornans Fe/Mn is near 60 at grain edge. These values are lower than the matrix Fe/Mn for both meteorites and the distinct difference in zoning profile indicates different processes operating during and after grain growth. The Fe/Mn of bulk samples from a particular source such as the Moon is nearly constant. Individual samples show variation suggesting that there is some fractionation of Mn from Fe. Minerals have their individual ranges of Fe/Mn which has been used to recognize different types of olivine within one meteorite. Extreme values of Fe/Mn below 1.0 occur in forsterite from some IDP's, UOC matrix, and C1 meteorites. There are apparently no detailed studies of Fe/Mn variation within single olivine grains. Forsterite grains in C2 and C3 carbonaceous chondrites show complex zoning, and the nearly pure forsterites (Fo greater than approximately 99.5) have high levels of some minor elements including Ti, Al, V, and Sc. There is disagreement on the original source of these grains and both chondrule and vapor growth have been proposed. In addition, there is clear evidence that diffusion has affected the outer margins but in some cases the whole grain. Within the cores, the FeO range is limited, and if growing under constant conditions, the Fe/Mn should be near constant as there is little fractionation of Mn from Fe by forsterite. Additionally, there are apparently no co-crystallizing phases as evidenced by a lack of common inclusions in the forsterites. These observations are now

Electrochemical studies of DNA interaction and antimicrobial activities of MnII, FeIII, CoII and NiII Schiff base tetraazamacrocyclic complexes

NASA Astrophysics Data System (ADS)

Kumar, Anuj; Vashistha, Vinod Kumar; Tevatia, Prashant; Singh, Randhir

2017-04-01

Tetraazamacrocyclic complexes of MnII, FeIII, CoII and NiII have been synthesized by template method. These tetraazamacrocycles have been analyzed with various techniques like molar conductance, IR, UV-vis, mass spectral and cyclic voltammetric studies. On the basis of all these studies, octahedral geometry has been assigned to these tetraazamacrocyclic complexes. The DNA binding properties of these macrocyclic complexes have been investigated by electronic absorption spectra, fluorescence spectra, cyclic voltammetric and differential pulse voltammetric studies. The cyclic voltammetric data showed that ipc and ipa were effectively decreased in the presence of calf thymus DNA, which is a strong evidence for the interaction of these macrocyclic complexes with the calf thymus DNA (ct-DNA). The heterogeneous electron transfer rate constant found in the order: KCoII > KNiII > KMnII which indicates that CoII macrocyclic complex has formed a strong intercalated intermediate. The Stern-Volmer quenching constant (KSV) and voltammetric binding constant were found in the order KSV(CoII) > KSV(NiII) > KSV(MnII) and K+(CoII) > K+(NiII) > K+(MnII) which shows that CoII macrocyclic complex exhibits the high interaction affinity towards ct-DNA by the intercalation binding. Biological studies of the macrocyclic complexes compared with the standard drug like Gentamycin, have shown antibacterial activities against E. coli, P. aeruginosa, B. cereus, S. aureus and antifungal activity against C. albicans.

Ageing behaviour of an Fe-20Ni-1.8Mn-1.6Ti-0.59Al (wt%) maraging alloy: clustering, precipitation and hardening

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

Pereloma, E.V.; Shekhter, A.; Miller, M.K.

2004-11-08

Changes in the solute distribution as well as the evolution of precipitation, microstructure and mechanical properties have been studied in an experimental maraging Fe-20Ni-1.8Mn-1.5Ti-0.59Al (wt%) alloy during ageing at 550 deg C. An initial hardening reaction within 5 s is reported, which is remarkable in terms of extent and rapidity. This strengthening was caused by the formation of complex multi-component atomic co-clusters containing primarily Ni-Ti-Al as well as some Mn. This cluster strengthened condition produced the optimum toughness observed throughout the ageing sequence. After 60 s ageing, the appearance of discrete precipitation of needle-shaped {eta}-Ni{sub 3}Ti particles was associated withmore » a second rise in hardness towards an eventual peak at 600 s. This precipitation hardening was accompanied by an increase in tensile strength and a decrease in ductility. A reverse transformation of martensite to austenite occurs progressively during ageing and this contributes to the initial and secondary softening.« less

Electrical transport properties and giant baroresistance effect at martensitic transformation of Ni43.7Fe5.3Mn35.4In15.6 Heusler alloy

NASA Astrophysics Data System (ADS)

Zhang, Yuanlei; He, Xijia; Li, Zhe; Xu, Kun; Liu, Changqin; Huang, Yinsheng; Jing, Chao

2018-04-01

The electrical transport properties at martensitic transformation (MT) in polycrystalline Ni43.7Fe5.3Mn35.4In15.6 have been intensively investigated under different hydrostatic pressures. For this alloy, the experimental results show that applying a higher hydrostatic pressure can convert its MT from the metamagnetic type into the paramagnetic type. It provides a unique opportunity to separate the relative contributions of electron-spin and electron-lattice scatterings across the metamagnetic MT based on the dynamical Clausius-Clapeyron equation, which delivers a deeper insight into the resistivity change of metamagnetic MT for the Mn-rich Ni-Mn based Heusler alloys. In addition, the studied alloy also reveals a giant positive baroresistance (BR) effect with a saturated value of 115% at 242 K. This performance originates from the combined effect of electron-spin and electron-lattice scatterings associated with a prominent hydrostatic pressure-induced MT, which contribute 46% and 69% to the overall BR ratio, respectively.

Magnetic properties of transition metal fluorides MF2 (M=Mn, Fe, Co, Ni) via high-energy photon diffraction

NASA Astrophysics Data System (ADS)

Strempfer, J.; Rütt, U.; Bayrakci, S.; Brückel, Th.; Jauch, W.

2004-01-01

We present an overview of recent results from nonresonant magnetic diffraction experiments on the antiferromagnetic compounds MnF2, FeF2, CoF2, and NiF2 using high-energy synchrotron radiation of photon energies above 100 keV. New results are presented on the determination of the spin and of the L/S ratio for CoF2 and NiF2. For CoF2, the saturation value of the long-range-ordered pure spin Sz component Sz=1.11(1) is considerably lower than the value Sz=3/2 for the free Co2+ ion. This is in contrast to our results for NiF2, where the full spin of the free transition-metal ion was found, Sz=0.98(1). The temperature dependence of the magnetization in the critical region as well as in the low-temperature region is also presented. For all compounds, Ising behavior is found in the critical regime, whereas the crossover to the low-temperature spin-wave behavior varies. We attribute this to different anisotropies in this series of compounds.

Electronic Topological Transitions in CuNiMnAl and CuNiMnSn under pressure from first principles study

NASA Astrophysics Data System (ADS)

Rambabu, P.; Kanchana, V.

2018-06-01

A detailed study on quaternary ordered full Heusler alloys CuNiMnAl and CuNiMnSn at ambient and under different compressions is presented using first principles electronic structure calculations. Both the compounds are found to possess ferromagnetic nature at ambient with magnetic moment of Mn being 3.14 μB and 3.35 μB respectively in CuNiMnAl and CuNiMnSn. The total magnetic moment for both the compounds is found to decrease under compression. Fermi surface (FS) topology change is observed in both compounds under pressure at V/V0 = 0.90, further leading to Electronic Topological Transitions (ETTs) and is evidenced by the anomalies visualized in density of states and elastic constants under compression.

Recent advances on Fe- and Mn-based cathode materials for lithium and sodium ion batteries

NASA Astrophysics Data System (ADS)

Zhu, Xiaobo; Lin, Tongen; Manning, Eric; Zhang, Yuancheng; Yu, Mengmeng; Zuo, Bin; Wang, Lianzhou

2018-06-01

The ever-growing market of electrochemical energy storage impels the advances on cost-effective and environmentally friendly battery chemistries. Lithium-ion batteries (LIBs) are currently the most critical energy storage devices for a variety of applications, while sodium-ion batteries (SIBs) are expected to complement LIBs in large-scale applications. In respect to their constituent components, the cathode part is the most significant sector regarding weight fraction and cost. Therefore, the development of cathode materials based on Earth's abundant elements (Fe and Mn) largely determines the prospects of the batteries. Herein, we offer a comprehensive review of the up-to-date advances on Fe- and Mn-based cathode materials for LIBs and SIBs, highlighting some promising candidates, such as Li- and Mn-rich layered oxides, LiNi0.5Mn1.5O4, LiFe1-xMnxPO4, NaxFeyMn1-yO2, Na4MnFe2(PO4)(P2O7), and Prussian blue analogs. Also, challenges and prospects are discussed to direct the possible development of cost-effective and high-performance cathode materials for future rechargeable batteries.

Microstructural Development and Ternary Interdiffusion in Ni-Mn-Ga Alloys

NASA Astrophysics Data System (ADS)

Zhou, Le; Kammerer, Catherine; Giri, Anit; Cho, Kyu; Sohn, Yongho

2015-12-01

NiMnGa alloys functioning as either ferromagnetic shape memory alloys or magnetocaloric materials have both practical applications and fundamental research value. In this study, solid-to-solid diffusion couple experiments were carried out to investigate the phase equilibria, microstructural development, and interdiffusion behavior in Ni-Mn-Ga ternary alloys. Selected diffusion couples between pure Ni, Ni25Mn75 and four ternary off-stoichiometric NiMnGa alloys ( i.e., Ni52Mn18Ga30, Ni46Mn30Ga24, Ni52Mn30Ga18, Ni58Mn18Ga24) were assembled and annealed at 1073 K, 1123 K, and 1173 K (800 °C, 850 °C, and 900 °C) for 480, 240, and 120 hours, respectively. At these high temperatures, the β NiMnGa phase has a B2 crystal structure. The microstructure of the interdiffusion zone was examined by scanning electron microscopy and transmission electron microscopy. Concentration profiles across the interdiffusion zone were determined by electron probe micro analysis. Solubility values obtained for various phases were mostly consistent with the existing isothermal phase diagrams, but the phase boundary of the γ(Mn) + β two-phase region was slightly modified. In addition, equilibrium compositions for the γ(Ni) and α' phases at 1173 K (900 °C) were also determined for the respective two-phase region. Both austenitic and martensitic phases were found at room temperature in each diffusion couple with a clear boundary. The compositions at the interfaces corresponded close to valence electron concentration (e/a) of 7.6, but trended to lower values when Mn increased to more than 35 at. pct. Average effective interdiffusion coefficients for the β phase over different compositional ranges were determined and reported in the light of temperature-dependence. Ternary interdiffusion coefficients were also determined and examined to assess the ternary diffusional interactions among Ni, Mn, and Ga. Ni was observed to interdiffuse the fastest, followed by Mn then Ga. Interdiffusion flux

Properties of metallic glasses containing actinide metals. I. Thermal properties of U--M glasses (M = V, Cr, Mn, Fe, Co, and Ni)

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

Giessen, B.C.; Elliott, R.O.

1978-01-01

The results of a preparative and calorimetric study forming part of a continuing investigation of the new actinide glasses are reported. Specifically, lower bounds for the composition limits of glass formation (G.F.) at moderate cooling rates have been obtained for the U-M (M = Mn, Fe, Co, Ni) systems and the thermal stabilities of glasses in these four systems as well as for a U-V glass and a U-Cr glass have been surveyed.

Corrosion study of single crystal Ni-Mn-Ga alloy and Tb0.27Dy0.73Fe1.95 alloy for the design of new medical microdevices.

PubMed

Pouponneau, Pierre; Savadogo, Oumarou; Napporn, Teko; Yahia, L'Hocine; Martel, Sylvain

2011-02-01

Once placed in a magnetic field, smart magnetic materials (SMM) change their shape, which could be use for the development of smaller minimally invasive surgery devices activated by magnetic field. However, the potential degradation and release of cytotoxic ions by SMM corrosion has to be determined. This paper evaluates the corrosion resistance of two SMM: a single crystal Ni-Mn-Ga alloy and Tb(0.27)Dy(0.73)Fe(1.95) alloy. Ni-Mn-Ga alloy displayed a corrosion potential (E (corr)) of -0.58 V/SCE and a corrosion current density (i (corr)) of 0.43 μA/cm(2). During the corrosion assay, Ni-Mn-Ga sample surface was partially protected; local pits were formed on 20% of the surface and nickel ions were mainly found in the electrolyte. Tb(0.27)Dy(0.73)Fe(1.95) alloy exhibited poor corrosion properties such as E (corr) of -0.87 V/SCE and i (corr) of 5.90 μA/cm(2). During the corrosion test, this alloy was continuously degraded, its surface was impaired by pits and cracks extensively and a high amount of iron ions was measured in the electrolyte. These alloys exhibited low corrosion parameters and a selective degradation in the electrolyte. They could only be used for medical applications if they are coated with high strain biocompatible materials or embedded in composites to prevent direct contact with physiological fluids.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Cation distribution of Ni-Zn-Mn ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Parvatheeswara Rao, B.; Dhanalakshmi, B.; Ramesh, S.; Subba Rao, P. S. V.

2018-06-01

Mn substituted Ni-Zn ferrite nanoparticles, Ni0.4Zn0.6-xMnxFe2O4 (x = 0.00-0.25 in steps of 0.05), using metal nitrates were prepared by sol-gel autocombustion in citric acid matrix. The samples were examined by X-ray diffraction and vibrating sample magnetometer techniques. Rietveld structural refinements using the XRD data were performed on the samples to consolidate various structural parameters like phase (spinel), crystallite size (24.86-37.43 nm), lattice constant (8.3764-8.4089 Å) etc and also to determine cation distributions based on profile matching and integrated intensity ratios. Saturation magnetization values (37.18-68.40 emu/g) were extracted from the measured M-H loops of these nanoparticles to estimate their magnetic moments. Experimental and calculated magnetic moments and lattice constants were used to confirm the derived cation distributions from Rietveld analysis. The results of these ferrite nanoparticles are discussed in terms of the compositional modifications, particle sizes and the corresponding cation distributions as a result of Mn substitutions.

MnNi-based spin valve sensors combining high thermal stability, small footprint and pTesla detectivities

NASA Astrophysics Data System (ADS)

Silva, Marília; Leitao, Diana C.; Cardoso, Susana; Freitas, Paulo

2018-05-01

Magnetoresistive sensors with high thermal robustness, low noise and high spatial resolution are the answer to a number of challenging applications. Spin valve sensors including MnNi as antiferromagnet layer provide higher exchange bias field and improved thermal stability. In this work, the influence of the buffer layer type (Ta, NiFeCr) and thickness on key sensor parameters (e.g. offset field, Hf) is investigated. A Ta buffer layer promotes a strong (111) texture which leads to a higher value of MR. In contrast, Hf is lower for NiFeCr buffer. Micrometric sensors display thermal noise levels of 1 nT/Hz1/2 and 571 pT/Hz1/2 for a sensor height (h) of 2 and 4 μm, respectively. The temperature dependence of MR and sensitivity is also addressed and compared with MnIr based spin valves. In this case, MR abruptly decreases after heating at 160°C (without magnetic field), contrary to MnNi-based spin valves, where only a 10% MR decrease (relative to the initial value) is seen at 275°C. Finally, to further decrease the noise levels and improve detectivity, MnNi spin-valves are deposited vertically, and connected in parallel and series (in-plane) to create a device with low resistance and high sensitivity. A field detection at thermal level of 346 pT/Hz1/2 is achieved for a device with a total of 300 SVs (4 vertical, 15 in series, 5 in parallel).

High power factor in thiospinels Cu2 T r Ti3S8 ( T r = Mn, Fe, Co, Ni) arising from TiS6 octahedron network

NASA Astrophysics Data System (ADS)

Hashikuni, Katsuaki; Suekuni, Koichiro; Usui, Hidetomo; Ohta, Michihiro; Kuroki, Kazuhiko; Takabatake, Toshiro

2016-10-01

Thermoelectric properties and electronic structures of n-type thiospinels Cu2T r Ti3S8 composed of CuS4 tetrahedron and (Tr/Ti)S6 octahedron network have been studied for T r = Mn, Fe, Co, and Ni. The samples with T r = Mn, Co, and Ni exhibit metallic behaviors in the electrical resistivity (ρ) and rather large and negative thermopower (S), leading to a high power factor (S2/ρ) of 0.4-0.6 mW/K2 m at 650 K. In addition to the superior electrical properties, relatively low thermal conductivity of ˜2 W/Km gives rise to a dimensionless figure of merit ZT reaching 0.16-0.18 at 650 K. The analysis of the temperature dependent magnetic susceptibility indicates that the Mn, Fe, and Ni ions are in high-spin divalent states while the Co2+ ion is in a low-spin nonmagnetic state. This electronic state for the Co2+ in Cu2CoTi3S8 is consistent with our first-principles electronic structure calculation indicating that the Fermi level lies in the conduction bands composed mainly of Ti-3d, Co-3d, and S-3p orbitals. The Ti-3d and S-3p orbitals forming the octahedron network likely results in high power factors irrespective of Tr elements. The addition of Co-3d orbitals makes a peak with steep slope in the density of states near the Fermi level, leading to the further enhanced power factor.

Development of a wear-resistant flux cored wire of Fe-C-Si-Mn-Cr-Ni-Mo-V system for deposit welding of mining equipment parts

NASA Astrophysics Data System (ADS)

Osetkovsky, I. V.; Kozyrev, N. A.; Kryukov, R. E.; Usoltsev, A. A.; Gusev, A. I.

2017-09-01

The effect of introduction of cobalt in the charge of the flux cored wire of Fe-C-Si-Mn-Cr-Ni-Mo-V system operating under abrasive and abrasive-shock loads is studied. In the laboratory conditions samples of flux cored wires were made, deposition was performed, the effect of cobalt on the hardness and the degree of wear was evaluated, metallographic studies were carried out. The influence of cobalt introduced into the charge of the flux cored wire of Fe-C-Si-Mn-Cr-Ni-Mo-V system on the structure, nature of nonmetallic inclusions, hardness and wear resistance of the weld metal was studied. In the laboratory conditions samples flux cored wire were made using appropriate powdered materials. As a carbon-fluorine-containing material dust from gas cleaning units of aluminum production was used. In the course of the study the chemical composition of the weld metal was determined, metallographic analysis was performed, mechanical properties were determined. As a result of the metallographic analysis the size of the former austenite grain, martensite dispersion in the structure of the weld metal, the level of contamination with its nonmetallic inclusions were established.

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.

Microstructural stability and mechanical behavior of FeNiMnCr high entropy alloy under ion irradiation

DOE PAGES

Leonard, Keith J.; Bei, Hongbin; Zinkle, Steven J.; ...

2016-05-13

In recent years, high entropy alloys (HEAs) have attracted significant attention due to their excellent mechanical properties and good corrosion resistance, making them potential candidates for high temperature fission and fusion structural applications. However there is very little known about their radiation resistance, particularly at elevated temperatures relevant for energy applications. In the present study, a single phase (face centered cubic) concentrated solid solution alloy of composition 27%Fe-28%Ni-27%Mn-18%Cr was irradiated with 3 or 5.8 MeV Ni ions at temperatures ranging from room temperature to 700 °C and midrange doses from 0.03 to 10 displacements per atom (dpa). Transmission electron microscopymore » (TEM), scanning transmission electron microscopy with energy dispersive x-ray spectrometry (STEM/EDS) and X-ray diffraction (XRD) were used to characterize the radiation defects and microstructural changes. Irradiation at higher temperatures showed evidence of relatively sluggish solute diffusion with limited solute depletion or enrichment at grain boundaries. The main microstructural feature at all temperatures was high-density small dislocation loops. Voids were not observed at any irradiation condition. Nano-indentation tests on specimens irradiated at room temperature showed a rapid increase in hardness ~35% and ~80% higher than the unirradiated value at 0.03 and 0.3 dpa midrange doses, respectively. The irradiation-induced hardening was less pronounced for 500 °C irradiations (<20% increase after 3 dpa). Overall, the examined HEA material exhibits superior radiation resistance compared to conventional single phase Fe-Cr-Ni austenitic alloys such as stainless steels. Furthermore, the present study provides insight on the fundamental irradiation behavior of a single phase HEA material over a broad range of irradiation temperatures.« less

Cation Distribution and Local Configuration of Fe 2+ Ions in Structurally Nonequivalent Lattice Sites of Heterometallic Fe(II)/ M(II) ( M = Mn, Co, Ni, Cu, Zn) Diaquadiformato Complexes

NASA Astrophysics Data System (ADS)

Devillers, M.; Ladrière, J.

1993-03-01

57Fe Mössbauer investigations are carried out on a wide series of heterometallic diaquadiformato Fe(II)/ M(II) complexes with M = Mn, Co, Ni, Cu, and Zn to provide a local picture of the coordination environment of the 57Fe 2+ ions as a function of (i) the nature of the host cation and (ii) the relative amounts of both metals in the matrix (between 50 and 0.25 at.% Fe). Information is obtained on the quantitative distribution of both metals between the two structurally nonequivalent lattice sites and on the local geometry around the dopant atom in each crystal site. In the mixed Fe-Cu complexes. Fe 2+ ions are preferentially incorporated in the tetrahydrated site; in Cu-rich Fe xCu 1- x(HCO 2) 2· 2H 2O, the 57Fe 2+ ions located in the hexaformato-coordinated site are surrounded by an axially compressed octahedron of formate ligands which contrasts with the elongated configuration observed in the pure iron compound and in the other mixed systems. Semiquantitative estimations of the tetragonal field splitting and of the extent of metal-ligand interactions are proposed from the temperature dependence of the quadrupole splitting values.

Room-temperature ferromagnetic transitions and the temperature dependence of magnetic behaviors in FeCoNiCr-based high-entropy alloys

NASA Astrophysics Data System (ADS)

Na, Suok-Min; Yoo, Jin-Hyeong; Lambert, Paul K.; Jones, Nicholas J.

2018-05-01

High-entropy alloys (HEAs) containing multiple principle alloying elements exhibit unique properties so they are currently receiving great attention for developing innovative alloy designs. In FeCoNi-based HEAs, magnetic behaviors strongly depend on the addition of alloying elements, usually accompanied by structural changes. In this work, the effect of non-magnetic components on the ferromagnetic transition and magnetic behaviors in equiatomic FeCoNiCrX (X=Al, Ga, Mn and Sn) HEAs was investigated. Alloy ingots of nominal compositions of HEAs were prepared by arc melting and the button ingots were cut into discs for magnetic measurements as functions of magnetic field and temperature. The HEAs of FeCoNiCrMn and FeCoNiCrSn show typical paramagnetic behaviors, composed of solid solution FCC matrix, while the additions of Ga and Al in FeCoNiCr exhibit ferromagnetic behaviors, along with the coexistence of FCC and BCC phases due to spinodal decomposition. The partial phase transition in both HEAs with the additions of Ga and Al would enhance ferromagnetic properties due to the addition of the BCC phase. The saturation magnetization for the base alloy FeCoNiCr is 0.5 emu/g at the applied field of 20 kOe (TC = 104 K). For the HEAs of FeCoNiCrGa and FeCoNiCrAl, the saturation magnetization significantly increased to 38 emu/g (TC = 703 K) and 25 emu/g (TC = 277 K), respectively. To evaluate the possibility of solid solution FCC and BCC phases in FeCoNiCr-type HEAs, we introduced a parameter of valence electron concentration (VEC). The proposed rule for solid solution formation by the VEC was matched with FeCoNiCr-type HEAs.

Structural and Magnetic Properties of Mn1.5X0.5Sn (X = Cr, Mn, Fe, Co) Melt-spun Ribbons

NASA Astrophysics Data System (ADS)

Fuglsby, R.; Kharel, P.; Zhang, W.; Valloppilly, S.; Huh, Y.; Sellmyer, D. J.

2015-03-01

Mn1.5X0.5Sn (X = Cr, Mn, Fe, Co) nanomaterials in a hexagonal Ni2In-type crystal structure have been prepared using arc-melting and melt spinning. All the samples show moderate saturation magnetization at 100 K with a highest value of 458 emu/cm3 for Mn1.5Fe0.5Sn, but their Curie temperatures (Tc) are less than 300 K. The highest Tc is 206 K for the Fe containing sample. All samples except the Cr containing one show irreversibility between the zero-field-cooled and field-cooled measurements at the low temperature, showing a spin reorientation or spin-glass-like behavior. The magnetic anisotropy constants calculated at 100 K are on the order of 1 Merg/cm3. The magnetic properties of these materials have substantially improved due to vacuum annealing, where the Tc for Mn2Sn annealed at 450 °C has increased by about 75 K from 190 K to 265 K. Research is supported by Department of Physics, SDSU. Research at UNL is supported by NSF-MRSEC Grant DMR-0820521 and DOE-BES-DMSE Grant DE-FG 02-04ER46152.

Effect of NiO spin orientation on the magnetic anisotropy of the Fe film in epitaxially grown Fe/NiO/Ag(001) and Fe/NiO/MgO(001)

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

Kim, W.; Jin, E.; Wu, J.

Single crystalline Fe/NiO bilayers were epitaxially grown on Ag(001) and on MgO(001), and investigated by Low Energy Electron Diffraction (LEED), Magneto-Optic Kerr Effect (MOKE), and X-ray Magnetic Linear Dichroism (XMLD). We find that while the Fe film has an in-plane magnetization in both Fe/NiO/Ag(001) and Fe/NiO/MgO(001) systems, the NiO spin orientation changes from in-plane direction in Fe/NiO/Ag(001) to out-of-plane direction in Fe/NiO/MgO(001). These two different NiO spin orientations generate remarkable different effects that the NiO induced magnetic anisotropy in the Fe film is much greater in Fe/NiO/Ag(001) than in Fe/NiO/MgO(001). XMLD measurement shows that the much greater magnetic anisotropy inmore » Fe/NiO/Ag(001) is due to a 90{sup o}-coupling between the in-plane NiO spins and the in-plane Fe spins.« less

Magnetostructural phase transitions and magnetocaloric effects in MnNiGe1-xAlx

NASA Astrophysics Data System (ADS)

Samanta, Tapas; Dubenko, Igor; Quetz, Abdiel; Temple, Samuel; Stadler, Shane; Ali, Naushad

2012-01-01

The thermomagnetic and magnetocaloric properties of the MnNiGe1-xAlx system have been investigated by magnetization and differential scanning calorimetry (DSC) measurements. The presence of first-order magnetostructural transitions (MSTs) from hexagonal ferromagnetic to orthorhombic antiferromagnetic phases has been detected for x = 0.085 and 0.09 at 193 K and 186 K, respectively. The values of latent heat (L = 6.6 J/g) and corresponding total entropy changes (ΔST = 35 J/kg K) have been evaluated for the MST (x = 0.09) from DSC measurements. The magnetic entropy change for x = 0.09 (ΔSM = 17.6 J/kg K for 5 T) was found to be comparable with well-known giant magnetocaloric materials, such as Gd5Si2Ge2, MnFeP0.45As0.55, and Ni50Mn37Sn13.

Dissimilatory Fe(III) and Mn(IV) reduction.

PubMed Central

Lovley, D R

1991-01-01

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process. PMID:1886521

UV Spectra of Tris(2,2'-bipyridine)-M(II) Complex Ions in Vacuo (M = Mn, Fe, Co, Ni, Cu, Zn).

PubMed

Xu, Shuang; Smith, James E T; Weber, J Mathias

2016-11-21

We present electronic spectra in the π-π* region of a series of tris(bpy)-M(II) complex ions (bpy = 2,2'-bipyridine; M = Mn, Fe, Co, Ni, Cu, Zn) in vacuo for the first time. By applying photodissociation spectroscopy to cryogenically cooled and mass selected [M II (bpy) 3 ] 2+ ions, we obtain the intrinsic spectra of these ions at low temperature without perturbation by solvent interaction or crystal lattice shifts. This allows spectroscopic analysis of these complex ions in greater detail than possible in the condensed phase. We interpret our experimental data by comparison with time-dependent density functional theory.

Formation of Fe-Mn crusts within a continental margin environment

USGS Publications Warehouse

Conrad, Tracey A.; Hein, James R.; Paytan, Adina; Clague, David A.

2017-01-01

This study examines Fe-Mn crusts that form on seamounts along the California continental-margin (CCM), within the United States 200 nautical mile exclusive economic zone. The study area extends from approximately 30° to 38° North latitudes and from 117° to 126° West longitudes. The area of study is a tectonically active northeast Pacific plate boundary region and is also part of the North Pacific Subtropical Gyre with currents dominated by the California Current System. Upwelling of nutrient-rich water results in high primary productivity that produces a pronounced oxygen minimum zone. Hydrogenetic Fe-Mn crusts forming along the CCM show distinct chemical and mineral compositions compared to open-ocean crusts. On average, CCM crusts contain more Fe relative to Mn than open-ocean Pacific crusts. The continental shelf and slope release both Fe and Mn under low-oxygen conditions. Silica is also enriched relative to Al compared to open-ocean crusts. This is due to the North Pacific silica plume and enrichment of Si along the path of deep-water circulation, resulting in Si enrichment in bottom and intermediate waters of the eastern Pacific.The CCM Fe-Mn crusts have a higher percentage of birnessite than open-ocean crusts, reflecting lower dissolved seawater oxygen that results from the intense coastal upwelling and proximity to zones of continental slope pore-water anoxia. Carbonate fluorapatite (CFA) is not present and CCM crusts do not show evidence of phosphatization, even in the older sections. The mineralogy indicates a suboxic environment under which birnessite forms, but in which pH is not high enough to facilitate CFA deposition. Growth rates of CCM crusts generally increase with increasing water depth, likely due to deep-water Fe sources mobilized from reduced shelf and slope sediments.Many elements of economic interest including Mn, Co, Ni, Cu, W, and Te have slightly or significantly lower concentrations in CCM crusts relative to crusts from the Pacific

Magnetic interactions in BiFe0.5Mn0.5O3 films and BiFeO3/BiMnO3 superlattices

NASA Astrophysics Data System (ADS)

Xu, Qingyu; Sheng, Yan; Khalid, M.; Cao, Yanqiang; Wang, Yutian; Qiu, Xiangbiao; Zhang, Wen; He, Maocheng; Wang, Shuangbao; Zhou, Shengqiang; Li, Qi; Wu, Di; Zhai, Ya; Liu, Wenqing; Wang, Peng; Xu, Y. B.; Du, Jun

2015-03-01

The clear understanding of exchange interactions between magnetic ions in substituted BiFeO3 is the prerequisite for the comprehensive studies on magnetic properties. BiFe0.5Mn0.5O3 films and BiFeO3/BiMnO3 superlattices have been fabricated by pulsed laser deposition on (001) SrTiO3 substrates. Using piezoresponse force microscopy (PFM), the ferroelectricity at room temperature has been inferred from the observation of PFM hysteresis loops and electrical writing of ferroelectric domains for both samples. Spin glass behavior has been observed in both samples by temperature dependent magnetization curves and decay of thermo-remnant magnetization with time. The magnetic ordering has been studied by X-ray magnetic circular dichroism measurements, and Fe-O-Mn interaction has been confirmed to be antiferromagnetic (AF). The observed spin glass in BiFe0.5Mn0.5O3 films has been attributed to cluster spin glass due to Mn-rich ferromagnetic (FM) clusters in AF matrix, while spin glass in BiFeO3/BiMnO3 superlattices is due to competition between AF Fe-O-Fe, AF Fe-O-Mn and FM Mn-O-Mn interactions in the well ordered square lattice with two Fe ions in BiFeO3 layer and two Mn ions in BiMnO3 layer at interfaces.

Hydrometallurgical recovery of metals: Ce, La, Co, Fe, Mn, Ni and Zn from the stream of used Ni-MH cells.

PubMed

Sobianowska-Turek, Agnieszka

2018-04-11

The utilization of the stream of waste secondary nickel-metal hydride (Ni-MH) and lithium-ion (Li-ion) cells, representing annually about 33% of all consumer batteries and accumulators placed on the Polish market, will soon become a big challenge for both legislators and plants dealing with the recycling of this type of hazardous waste. It is due to the fact that no company in Poland operating on the market has a complete technology for the processing of a full stream of waste chemical energy sources produced in this country. Until now, the most commonly used techniques of processing this type of waste were pyrometallurgical process. In this paper, the quantitative and qualitative characteristics of the stream of waste batteries and accumulators collected at separate collection points are presented. The results of metal recovery: caesium, lanthanum, cobalt, iron, manganese, nickel and zinc from the stream of waste Ni-MH cells, type R6 (AA), using hydrometallurgical methods are also offered. The paper demonstrates that one-stage leaching at an initial temperature of 25.0 °C, with 3 M H 2 SO 4 and at the solid to liquid ratio of s/l = 1/10, within 75 min, at a mixing speed of 500 rpm and in a strongly acidic environment should be adopted as optimal parameters for acid leaching of the paramagnetic fraction created after mechanical machining of Ni-MH battery, for which the leaching rates of individual metals were as follows: Ce - 97.7%, La - 88.7%, Co - 79.4%, Fe - 68.5%, Mn - 91.9%, Ni - 66.2% and Zn - 100%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Strength of "Light" Ferritic and Austenitic Steels Based on the Fe - Mn - Al - C System

NASA Astrophysics Data System (ADS)

Kaputkina, L. M.; Svyazhin, A. G.; Smarygina, I. V.; Kindop, V. E.

2017-01-01

The phase composition, the hardness, the mechanical properties at room temperature, and the resistance to hot (950 - 1000°C) and warm (550°C) deformation are studied for cast deformable "light" ferritic and austenitic steels of the Fe - (12 - 25)% Mn - (0 - 15)% Al - (0 - 2)% C system alloyed additionally with about 5% Ni. The high-aluminum high-manganese low-carbon and carbonless ferritic steels at a temperature of about 0.5 T melt have a specific strength close to that of the austenitic steels and may be used as weldable scale-resistant and wear-resistant materials. The high-carbon Fe - (20 - 24)% Mn - (5 - 9)% Al - 5% Ni - 1.5% C austenitic steels may be applied as light high-strength materials operating at cryogenic temperatures after a solution treatment and as scale- and heat-resistant materials in an aged condition.

Surface chemistry, friction, and wear of Ni-Zn and Mn-Zn ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

X-ray photoelectron and Auger electron spectroscopy analysis were used in sliding friction experiments. These experiments were conducted with hot-pressed polycrystalline Ni-Zn and Mn-Zn ferrites, and single-crystal Mn-Zn ferrite in contact with various transition metals at room temperature in both vacuum and argon. The results indicate that Ni2O3 and Fe3O4 were present on the Ni-Zn ferrite surface in addition to the nominal bulk constituents, while MnO2 and Fe3O4 were present on the Mn-Zn ferrite surface in addition to the nominal bulk constituents. The coefficients of friction for the ferrites in contact with metals were related to the relative chemical activity of these metals. The more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites were correlated with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite does strengthen the metal-ferrite contact and increase the friction. The ferrites exhibit local cracking and fracture with sliding under adhesive conditions. All the metals transferred to the surfaces of the ferrites in sliding. Previously announced in STAR as N83-19901

Surface chemistry, friction and wear of Ni-Zn and Mn-Zn ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron and Auger electron spectroscopy analysis were used in sliding friction experiments. These experiments were conducted with hot-pressed polycrystalline Ni-Zn and Mn-Zn ferrites, and single-crystal Mn-Zn ferrite in contact with various transition metals at room temperature in both vacuum and argon. The results indicate that Ni2O3 and Fe3O4 were present on the Ni-Zn ferrite surface in addition to the nominal bulk constituents, while MnO2 and Fe3O4 were present on the Mn-Zn ferrite surface in addition to the nominal bulk constituents. The coefficients of friction for the ferrites in contact with metals were related to the relative chemical activity of these metals. The more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites were correlated with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite does strengthen the metal-ferrite contact and increase the friction. The ferrites exhibit local cracking and fracture with sliding under adhesive conditions. All the metals transferred to he surfaces of the ferrites in sliding.

Co and Fe doping effect on negative temperature coefficient characteristics of nano-grained NiMn2O4 thick films fabricated by aerosol-deposition.

PubMed

Ryu, Jungho; Han, Guifang; Lee, Jong-Pil; Lim, Dong-Soo; Park, Yun-Soo; Jeong, Dae-Yong

2013-05-01

Spinel structured highly dense NiMn2O4-based (NMO) negative temperature coefficient (NTC) thermistor thick films were fabricated by aerosol-deposition at room temperature. To enhance the thermistor B constant, which represents the temperature sensitivity of the NMO thermistor material, Co and Co-Fe doping was applied. In the case of single element doping of Co, 5 mol% doped NMO showed a high B constant of over 5000 K, while undoped NMO showed -4000 K. By doping Fe to the 5 mol% Co doped NMO, the B constant was more enhanced at over 5600 K. The aging effect on the NTC characteristics of Co doped and Fe-Co co-doped NMO thick film showed very stable resistivity-time characteristics because of the highly dense microstructure.

Effect of H2O on metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe: Implications for the oxidation state of the Earth and Mars

NASA Astrophysics Data System (ADS)

Clesi, V.; Bouhifd, M. A.; Bolfan-Casanova, N.; Manthilake, G.; Fabbrizio, A.; Andrault, D.

2016-11-01

This study investigates the metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe during core mantle differentiation of terrestrial planets under hydrous conditions. For this, we equilibrated a molten hydrous CI chondrite model composition with various Fe-rich alloys in the system Fe-C-Ni-Co-Si-S in a multi-anvil over a range of P, T, fO2 and water content (5-20 GPa, 2073-2500 K, from 1 to 5 log units below the iron-wüstite (IW) buffer and for XH2O varying from 500 ppm to 1.5 wt%). By comparing the present experiments with the available data sets on dry systems, we observes that the effect of water on the partition coefficients of moderately siderophile elements is only moderate. For example, for iron we observed a decrease in the partition coefficient of Fe (Dmet/silFe) from 9.5 to 4.3, with increasing water content of the silicate melt, from 0 to 1.44 wt%, respectively. The evolution of metal-silicate partition coefficients of Ni, Co, V, Cr, Mn and Fe are modelled based on sets of empirical parameters. These empirical models are then used to refine the process of core segregation during accretion of Mars and the Earth. It appears that the likely presence of 3.5 wt% water on Mars during the core-mantle segregation could account for ∼74% of the FeO content of the Martian mantle. In contrast, water does not play such an important role for the Earth; only 4-6% of the FeO content of its mantle could be due to the water-induced Fe-oxidation, for a likely initial water concentration of 1.8 wt%. Thus, in order to reproduce the present-day FeO content of 8 wt% in the mantle, the Earth could initially have been accreted from a large fraction (between 85% and 90%) of reducing bodies (similar to EH chondrites), with 10-15% of the Earth's mass likely made of more oxidized components that introduced the major part of water and FeO to the Earth. This high proportion of enstatite chondrites in the original constitution of the Earth is consistent with the 17O,48Ca,50Ti,62Ni

Influence of thermal history on the electrochemical properties of Li[Ni0.5Mn1.5]O4

NASA Astrophysics Data System (ADS)

Liu, Guoqiang; Park, Kyu-Sung; Song, Jie; Goodenough, John B.

2013-12-01

The oxygen-stoichiometric spinel Li[Ni0.5Mn1.5]O4 is an insulator with ordered Ni(II) and Mn(IV). Although it delivers 4.7 V versus Li, the ordered phase gives poor performance as the cathode of a Li-ion battery. Here we demonstrate control of the degree of cation order by adjusting the oxygen stoichiometry with thermal history of the synthesis rather than by doping 2M(III) for Ni(II) + Mn(IV) (M = Cr, Mn, Fe, Co, Al, Ga). We report retention of capacity near 100 mAh g-1 at room temperature at 10C/10C charge/discharge rate with little capacity fade; at 55 °C, a capacity fade occurs as a result of reaction with the electrolyte, but it is reduced to a level comparable to that obtained by doping.

The Structure and Mechanical Properties of Ni-Mo PM Steels with Addition of Mn And Cu

NASA Astrophysics Data System (ADS)

Lichańska, E.; Kulecki, P.; Pańcikiewicz, K.

2017-12-01

The aim of the study was to evaluate the effect of chemical composition on the structure and mechanical properties of Mn-Ni-Mo and Ni-Mo-Cu PM steels. Pre-alloyed powder Astaloy 85Mo, diffusion alloyed powders Distaloy AQ and Distaloy AB produced by Höganäs, low carbon ferromanganese, carbonyl nickel powder T255 with three-dimensional filamentary structure and graphite CU-F have been used as the basic powders. Three mixtures with compositions of Fe-1%Mn-(0.5/1.75)%Ni-(0.5/0.85)%Mo-0.8%C and Fe-1.75%Ni-0.5%Mo-1.5%Cu-0.8%C were prepared in a Turbula mixer. Green compacts were single pressed in a steel die at 660 MPa according to PN-EN ISO 2740 standard. Sinterhardening was carried out at 1250°C in a mixture of 95% N2+5% H2 for 60 minutes. Mechanical tests (tensile, bend, hardness) and microstructural investigations were performed. Additionally, XRD and EDS analysis, fractographic investigations were carried out. The microstructures of steels investigated were mainly bainitic or bainitic-martensitic. Addition 1% Mn to Distaloy AQ based steel caused increase of tensile properties (YS from 422 to 489 MPa, UTS from 522 to 638 MPa, TRS from 901 to 1096 MPa) and decrease of plasticity (elongation from 3.65 to 2.84%).

Investigation of the mineralogy and the sorption mechanism of Ni, Cu, Co and Mo by turbostratic phyllomanganates of Mn-nodules from the eastern equatorial Pacific Ocean using XAS

NASA Astrophysics Data System (ADS)

Wegorzewski, A.; Webb, S.; Grangeon, S.; Kuhn, T.

2016-12-01

Mn-nodules are Mn-Fe (oxy)hydroxides bearing high amounts of economically important metals such as Ni, Cu, Co, Mo, as well as high field strength elements. According to that nodules are interesting for science and industry. Especially the sorption sites of metals (Ni, Cu, Mo) by the mineral phases are important to understand their coordination environment and further to tailor a specific metallurgical treatment in order to optimize the metal extraction procedure. Nodules used for this study were sampled from the German license area within the Clarion Clipperton Zone in the Pacific. These nodules grow on the seafloor in 4200 m depth by metal precipitation from oxic (hydrogenetic growth) and/or suboxic waters (suboxic diagenetic growth; Halbach et al., 1988). They show a complex texture characterized by irregular, concentrically banded nm- to µm-thick layered growth structures (LGS). Electronmicroprobe and X-ray diffraction analyses reveal: suboxic diagenetic LGS have high Mn/Fe ratios (9-826; Mn ≈ 40 wt. %; Fe ≈ 0.5 wt %), high Ni (0.3-2.6 wt %) and Cu (0.5-3.0 wt %) contents but low Co content (0.02±0.01 wt %). Mineralogically those LGS are turbostratic phyllomanganates (vernadite), which consist of [MnO6]-octahedral layers, separated from each other by cations (e.g., Na, Mg) and water in the interlayer, forming 7 and 10 Å phyllomanganates (Bode et al., 2007). In contrast hydrogenetic LGS show low Mn/Fe ratios (<5), low Ni+Cu content (<1 wt%) but enrichment in Co (≤0.5 wt%). Those LGS are of δ-MnO2, which is epitaxially intergrown with an amorphous FeOOH phase. In general, phyllomanganates have a high opportunity to incorporate metals due to their negative layer charge deficit cause by abundant isomorphic substitution of Mn4+ by Mn3+ and vacancies within MnO2 sheets. The negative charge deficit can be balanced by hydrated interlayer cations (e.g., Na, Mg) or due to metals adsorption at cation vacancy sites, incorporation into the MnO2 sheet and

The design of an Fe-12Mn-O.2Ti alloy steel for low temperature use

NASA Technical Reports Server (NTRS)

Hwang, S. K.; Morris, J. W., Jr.

1977-01-01

An investigation was made to improve the low temperature mechanical properties of Fe-8 approximately 12% Mn-O 2Ti alloy steels. A two-phase(alpha + gamma) tempering in combination with cold working or hot working was identified as an effective treatment. A potential application as a Ni-free cryogenic steel was shown for this alloy. It was also shown that an Fe-8Mn steel could be grain-refined by a purely thermal treatment because of its dislocated martensitic structure and absence of epsilon phase. A significant reduction of the ductile-brittle transition temperature was obtained in this alloy. The nature and origin of brittle fracture in Fe-Mn alloys were also investigated. Two embrittling regions were found in a cooling curve of an Fe-12Mn-O 2Ti steel which was shown to be responsible for intergranular fracture. Auger electron spectroscopy identified no segregation during solution-annealing treatment. Avoiding the embrittling zones by controlled cooling led to a high cryogenic toughness in a solution-annealed condition.

Structural features of [NiFeSe] and [NiFe] hydrogenases determining their different properties: a computational approach.

PubMed

Baltazar, Carla S A; Teixeira, Vitor H; Soares, Cláudio M

2012-04-01

Hydrogenases are metalloenzymes that catalyze the reversible reaction H(2)<->2H(+) + 2e(-), being potentially useful in H(2) production or oxidation. [NiFeSe] hydrogenases are a particularly interesting subgroup of the [NiFe] class that exhibit tolerance to O(2) inhibition and produce more H(2) than standard [NiFe] hydrogenases. However, the molecular determinants responsible for these properties remain unknown. Hydrophobic pathways for H(2) diffusion have been identified in [NiFe] hydrogenases, as have proton transfer pathways, but they have never been studied in [NiFeSe] hydrogenases. Our aim was, for the first time, to characterize the H(2) and proton pathways in a [NiFeSe] hydrogenase and compare them with those in a standard [NiFe] hydrogenase. We performed molecular dynamics simulations of H(2) diffusion in the [NiFeSe] hydrogenase from Desulfomicrobium baculatum and extended previous simulations of the [NiFe] hydrogenase from Desulfovibrio gigas (Teixeira et al. in Biophys J 91:2035-2045, 2006). The comparison showed that H(2) density near the active site is much higher in [NiFeSe] hydrogenase, which appears to have an alternative route for the access of H(2) to the active site. We have also determined a possible proton transfer pathway in the [NiFeSe] hydrogenase from D. baculatum using continuum electrostatics and Monte Carlo simulation and compared it with the proton pathway we found in the [NiFe] hydrogenase from D. gigas (Teixeira et al. in Proteins 70:1010-1022, 2008). The residues constituting both proton transfer pathways are considerably different, although in the same region of the protein. These results support the hypothesis that some of the special properties of [NiFeSe] hydrogenases could be related to differences in the H(2) and proton pathways. © SBIC 2012

Studies on the efficient dual performance of Mn1-xNixFe2O4 spinel nanoparticles in photodegradation and antibacterial activity.

PubMed

Jesudoss, S K; Vijaya, J Judith; Kennedy, L John; Rajan, P Iyyappa; Al-Lohedan, Hamad A; Ramalingam, R Jothi; Kaviyarasu, K; Bououdina, M

2016-12-01

The present work describes the successful synthesize of spinel magnetic ferrite Mn 1-x Ni x Fe 2 O 4 (x=0.0, 0.1, 0.2, 0.3, 0.4 & 0.5) nanoparticles via a simple microwave combustion method which was then evaluated for its photocatalytic activity in the degradation of indigo carmine (IC) synthetic dye, a major water pollutant. Our results reveal that the synthesized of Ni 2+ doped MnFe 2 O 4 nanoparticles possess well-crystalline pure cubic spinel phase, exhibit excellent optical and magnetic properties. Further, the photocatalytic performance of the synthesized nanoparticles at different concentration ratios of Ni 2+ ions was monitored by photocatalytic degradation of indigo carmine synthetic dye under UV (λ=365nm) light irradiation. In order to get maximum photocatalytic degradation (PCD) efficiency, we have optimized various parameters, which include catalyst dosage, initial dye concentration, pH and Ni 2+ dopant content. It was found that the reaction was facilitated with optimum catalyst dose of 50mg/100mL, high dye concentrations of 150mg/L and acidic pH and among all the synthesized samples, Mn 0·5 Ni 0.5 Fe 2 O 4 exhibit superior performance of photocatalytic activity on the degradation of indigo carmine synthetic dye. These results highlighted the potential use of effective, low-cost and easily available photocatalysts for the promotion of wastewater treatment and environmental remediation. In addition, the antibacterial activity of spinel magnetic Mn 1-x Ni x Fe 2 O 4 nanoparticles against two Gram positive bacteria (Staphylococcus aureus and Bacillus subtilis) and two Gram negative bacteria (Pseudomonas aeruginosa and Escherichia coli) was also examined. Our antibacterial activity results are comparable with the results obtained using the antibiotic, streptomycin. Copyright © 2016 Elsevier B.V. All rights reserved.

Using complimentary microscopy methods to examine Ni-Mn-Si-precipitates in highly-irradiated reactor pressure vessel steels

DOE PAGES

Edmondson, P. D.; Parish, C. M.; Nanstad, R. K.

2017-05-29

Nano-scale Ni-Mn-Si-rich precipitates formed in a reactor pressure vessel steel under high neutron fluence have been characterized using highly complimentary atom probe tomography (APT) and scanning transmission electron microscopy with energy dispersive spectroscopy (STEM-EDS) combined with STEM-EDS modeling. Using these techniques in a synergistic manner to overcome the well-known trajectory aberrations in APT data, the average upper limit Fe concentration within the precipitates was found to be ~6 at.%. Using this knowledge, accurate compositions of the precipitates was determined and it was found that the spread of precipitate compositions was large, but mostly centered around the Γ2-and G-phases. The usemore » of STEM-EDS also allowed for larger areas to be examined, and segregation of minor solutes was observed to occur on grain boundaries, along with Ni-Mn-Si-rich precipitates that were smaller in size than those in the matrix. Solute segregation at the grain boundaries is proposed to occur through a radiation induced segregation or radiation enhanced diffusion mechanism due to the presence of a denuded zone about the grain boundary. It is also proposed that the reduced precipitate size at the grain boundaries is due to the structure of the grain boundary. The lack of Ni-Mn-Si precipitates observed in larger Mo-rich precipitates is also discussed, and the absence of the minor solutes required to form the Ni-Mn-Si precipitates results in the lack of nucleation. This is in contrast to cementite phases in which Ni-Mn-Si precipitates have been seen to be formed. It was also determined through this work that the exclusion of all the Fe ions during atom probe analysis is a reasonable approximation.« less

Magnetocaloric effect and negative thermal expansion in hexagonal Fe doped MnNiGe compounds with a magnetoelastic AFM-FM-like transition

PubMed Central

Xu, Kun; Li, Zhe; Liu, Enke; Zhou, Haichun; Zhang, Yuanlei; Jing, Chao

2017-01-01

We report a detailed study of two successive first-order transitions, including a martensitic transition (MT) and an antiferromagnetic (AFM)-ferromagnetic (FM)-like transition, in Mn1-xFexNiGe (x = 0, 0.06, 0.11) alloys by X-ray diffraction, differential scanning calorimetry, magnetization and linear thermal expansion measurements. Such an AFM-FM-like transition occurring in the martensitic state has seldom been observed in the M(T) curves. The results of Arrott plot and linear relationship of the critical temperature with M2 provide explicit evidence of its first-order magnetoelastic nature. On the other hand, their performances as magnetocaloric and negative thermal expansion materials were characterized. The isothermal entropy change for a field change of 30 kOe reaches an impressive value of −25.8 J/kg K at 203 K for x = 0.11 compared to the other two samples. It demonstrates that the magneto-responsive ability has been significantly promoted since an appropriate amount of Fe doping can break the local Ni-6Mn AFM configuration. Moreover, the Fe-doped samples reveal both the giant negative thermal expansion and near-zero thermal expansion for different temperature ranges. For instance, the average thermal expansion coefficient ā of x = 0.06 reaches −60.7 × 10−6/K over T = 231–338 K and 0.6 × 10−6/K over T = 175–231 K during cooling. PMID:28134355

Study of the preparation of NI-Mn-Zn ferrite using spent NI-MH and alkaline Zn-Mn batteries

NASA Astrophysics Data System (ADS)

Xi, Guoxi; Xi, Yuebin; Xu, Huidao; Wang, Lu

2016-01-01

Magnetic nanoparticles of Ni-Mn-Zn ferrite have been prepared by a sol-gel method making use of spent Ni-MH and Zn-Mn batteries as source materials. Characterization by X-ray diffraction was carried out to study the particle size. The presence of functional groups was identified by Fourier transform infrared spectroscopy. From studies by thermogravimetry and differential scanning calorimetry, crystallization occurred at temperatures above 560 °C. The magnetic properties of the final products were found to be directly influenced by the average particle size of the product. The Ms values increase and the Hc values decrease as the size of the Ni-Mn-Zn ferrite particles increases.

Effect of Quenching Process on Microstructures and Mechanical Properties of Fe-0.9Mn-0.5Cr-2.4Ni-0.5Mo-C Steel

NASA Astrophysics Data System (ADS)

Chen, Jie; Li, Changsheng; Jin, Xin; Chen, Liqing; Fang, Lei

2018-03-01

To develop an appropriate quenching process to produce Fe-0.9Mn-0.5Cr-2.4Ni-0.5Mo-C steel, the microstructures and mechanical properties of this steel were investigated under the direct quenching and tempering (DQT) and the direct quenching, reheated quenching and tempering (DQQT) heat treatment processes. The microstructure of the DQQT specimen was basically tempered sorbite with spherical precipitates, while quite a bit of tempered martensite was in the DQT specimen with dispersive nanoscaled precipitates. The yield strengths of the DQT and DQQT specimens were 1154 and 955 MPa, respectively. The yield strength of the DQT specimen was higher than that of the DQQT specimen because of its finer grain size, higher density of dislocations and dispersed precipitates. The DQQT specimen had spherical precipitates, which hindered the propagation of the crack. Moreover, the high-angle grain boundaries in the DQQT specimen took a higher proportion. Therefore, the Charpy impact values of DQT and DQQT specimens at - 60 °C were 38 and 75 J, respectively. Consequently, the mechanical properties of the Fe-0.9Mn-0.5Cr-2.4Ni-0.5Mo-C steel, which met the standard of 1000 MPa grade steel plate for hydropower station, were acquired by the DQQT process.

Advanced Na[Ni0.25Fe0.5Mn0.25]O2/C-Fe3O4 sodium-ion batteries using EMS electrolyte for energy storage.

PubMed

Oh, Seung-Min; Myung, Seung-Taek; Yoon, Chong Seung; Lu, Jun; Hassoun, Jusef; Scrosati, Bruno; Amine, Khalil; Sun, Yang-Kook

2014-03-12

While much research effort has been devoted to the development of advanced lithium-ion batteries for renewal energy storage applications, the sodium-ion battery is also of considerable interest because sodium is one of the most abundant elements in the Earth's crust. In this work, we report a sodium-ion battery based on a carbon-coated Fe3O4 anode, Na[Ni0.25Fe0.5Mn0.25]O2 layered cathode, and NaClO4 in fluoroethylene carbonate and ethyl methanesulfonate electrolyte. This unique battery system combines an intercalation cathode and a conversion anode, resulting in high capacity, high rate capability, thermal stability, and much improved cycle life. This performance suggests that our sodium-ion system is potentially promising power sources for promoting the substantial use of low-cost energy storage systems in the near future.

Thermal stability of spin valves based on a synthetic antiferromagnet and Fe50Mn50 alloy

NASA Astrophysics Data System (ADS)

Milyaev, M. A.; Naumova, L. I.; Proglyado, V. V.; Chernyshova, T. A.; Blagodatkov, D. V.; Kamenskii, I. Yu.; Ustinov, V. V.

2015-11-01

Magnetron sputtering was used to prepare spin valves with the Ta/Ni80Fe20/Co90Fe10/Cu/Co90Fe10/Ru/Co90Fe10/Fe50Mn50/Ta composition. Changes in the functional characteristics of the spin valves were studied in a temperature range of-180 to +160°C. The maximum temperature at which the functional characteristics of spin valve remain unchanged was shown to depend on the relationship of thicknesses of Co90Fe10 layers separated by the Ru interlayer.

Phase diagram and magnetocaloric effects in aluminum doped MnNiGe alloys

NASA Astrophysics Data System (ADS)

Quetz, Abdiel; Samanta, Tapas; Dubenko, Igor; Kangas, Michael J.; Chan, Julia Y.; Stadler, Shane; Ali, Naushad

2013-10-01

The magnetocaloric and thermomagnetic properties of the MnNiGe1-xAlx system have been studied by temperature-dependent x-ray diffraction, differential scanning calorimetry (DSC), and magnetization measurements. The partial substitution of Al for Ge in MnNiGe1-xAlx results in a first order magnetostructural transition (MST) from a hexagonal ferromagnetic to an orthorhombic antiferromagnetic phase at 186 K (for x = 0.09). A large magnetic entropy change of ΔSM = -17.6 J/kg K for ΔH = 5 T was observed in the vicinity of TM = 186 K for x = 0.09. The value is comparable to those of giant magnetocaloric materials such as Gd5Si2Ge2, MnFeP0.45As0.55, and Ni50Mn37Sn13. The values of the latent heat (L = 6.6 J/g) and corresponding total entropy changes (ΔST = 35 J/kg K) have been evaluated for the MST using DSC measurements. Large negative values of ΔSM of -5.8 and -4.8 J/kg K for ΔH = 5 T in the vicinity of TC were observed for x = 0.09 and 0.085, respectively. A concentration-dependent phase diagram of transition temperatures (magnetic, structural, and magnetostructural) has been generated using magnetic, XRD, and DSC data. The role of magnetic and structural changes on transition temperatures is discussed.

Heterobimetallic [NiFe] Complexes Containing Mixed CO/CN- Ligands: Analogs of the Active Site of the [NiFe] Hydrogenases.

PubMed

Perotto, Carlo U; Sodipo, Charlene L; Jones, Graham J; Tidey, Jeremiah P; Blake, Alexander J; Lewis, William; Davies, E Stephen; McMaster, Jonathan; Schröder, Martin

2018-03-05

The development of synthetic analogs of the active sites of [NiFe] hydrogenases remains challenging, and, in spite of the number of complexes featuring a [NiFe] center, those featuring CO and CN - ligands at the Fe center are under-represented. We report herein the synthesis of three bimetallic [NiFe] complexes [Ni( N 2 S 2 )Fe(CO) 2 (CN) 2 ], [Ni( S 4 )Fe(CO) 2 (CN) 2 ], and [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] that each contain a Ni center that bridges through two thiolato S donors to a {Fe(CO) 2 (CN) 2 } unit. X-ray crystallographic studies on [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ], supported by DFT calculations, are consistent with a solid-state structure containing distinct molecules in the singlet ( S = 0) and triplet ( S = 1) states. Each cluster exhibits irreversible reduction processes between -1.45 and -1.67 V vs Fc + /Fc and [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] possesses a reversible oxidation process at 0.17 V vs Fc + /Fc. Spectroelectrochemical infrared (IR) and electron paramagnetic resonance (EPR) studies, supported by density functional theory (DFT) calculations, are consistent with a Ni III Fe II formulation for [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + . The singly occupied molecular orbital (SOMO) in [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + is based on Ni 3d z 2 and 3p S with the S contributions deriving principally from the apical S-donor. The nature of the SOMO corresponds to that proposed for the Ni-C state of the [NiFe] hydrogenases for which a Ni III Fe II formulation has also been proposed. A comparison of the experimental structures, and the electrochemical and spectroscopic properties of [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] and its [Ni( N 2 S 3 )] precursor, together with calculations on the oxidized [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + and [Ni( N 2 S 3 )] + forms suggests that the binding of the {Fe(CO)(CN) 2 } unit to the {Ni(CysS) 4 } center at the active site of the [NiFe] hydrogenases suppresses thiolate-based oxidative chemistry involving the bridging thiolate S donors

Low-cost Fe--Ni--Cr alloys for high temperature valve applications

DOEpatents

Muralidharan, Govindarajan

2017-03-28

An Fe--Ni--Cr alloy is composed essentially of, in terms of weight percent: 1 to 3.5 Al, up to 2 Co, 15 to 19.5 Cr, up to 2 Cu, 23 to 40 Fe, up to 0.3 Hf, up to 4 Mn, 0.15 to 2 Mo, up to 0.15 Si, up to 1.05 Ta, 2.8 to 4.3 Ti, up to 0.5 W, up to 0.06 Zr, 0.02 to 0.15 C, 0.0001 to 0.007 N, balance Ni, wherein, in terms of atomic percent: 6.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.10, 0.33.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.065, 4.ltoreq.(Fe+Cr)/(Al+Ti+Zr+Hf+Ta).ltoreq.10, the alloy being essentially free of Nb and V.

3D Computer Models of T- x- y Diagrams, Forming the Fe-Ni-Co-FeS-NiS-CoS Subsystem

NASA Astrophysics Data System (ADS)

Lutsyk, V. I.; Vorob'eva, V. P.

2017-12-01

3D computer models of Fe-Ni-Co, Fe-Ni-FeS-NiS, Fe-Co-FeS-CoS, Ni-Co-NiS-CoS T- x- y diagrams have been designed. The geometric structure (35 surfaces, two-phase surface of the reaction type change, 17 phase regions) of the Fe-Ni-FeS-NiS T- x- y diagram is investigated in detail. The liquidus hypersurfaces prediction of the Fe-Ni-Co-FeS-NiS-CoS subsystem is represented.

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.

Magnetocaloric effect in Heusler alloys Ni50Mn34In16 and Ni50Mn34Sn16

NASA Astrophysics Data System (ADS)

Sharma, V. K.; Chattopadhyay, M. K.; Kumar, Ravi; Ganguli, Tapas; Tiwari, Pragya; Roy, S. B.

2007-12-01

We present results of detailed ac susceptibility, magnetization and specific heat measurements in Heusler alloys Ni50Mn34In16 and Ni50Mn34Sn16. These alloys undergo a paramagnetic to ferromagnetic transition around 305 K, which is followed by a martensitic transition in the temperature regime around 220 K. Inside the martensite phase both the alloys show signatures of field-induced transition from martensite to austenite phase. Both field- and temperature-induced martensite-austenite transitions are relatively sharp in Ni50Mn34In16. We estimate the isothermal magnetic entropy change and adiabatic temperature change across the various phase transitions in these alloys and investigate the possible influence of these transitions on the estimated magnetocaloric effect. The sharp martensitic transition in Ni50Mn34In16 gives rise to a comparatively large inverse magnetocaloric effect across this transition. On the other hand the magnitudes of the conventional magnetocaloric effect associated with the paramagnetic to ferromagnetic transition are quite comparable in these alloys.

Novel reactions of homodinuclear Ni2 complexes [Ni(RNPyS4)]2 with Fe3(CO)12 to give heterotrinuclear NiFe2 and mononuclear Fe complexes relevant to [NiFe]- and [Fe]-hydrogenases.

PubMed

Song, Li-Cheng; Cao, Meng; Wang, Yong-Xiang

2015-04-21

The homodinuclear complexes [Ni(RNPyS4)]2 (; RNPyS4 = 2,6-bis(2-mercaptophenylthiomethyl)-4-R-pyridine; R = H, MeO, Cl, Br, i-Pr) were found to be prepared by reactions of the in situ generated Li2[Ni(1,2-S2C6H4)2] with 2,6-bis[(tosyloxy)methyl]pyridine and its substituted derivatives 2,6-bis[(tosyloxy)methyl]-4-R-pyridine. Further reactions of with Fe3(CO)12 gave both heterotrinuclear complexes NiFe2(RNPyS4)(CO)5 () and mononuclear complexes Fe(RNPyS4)(CO) (), unexpectedly. Interestingly, complexes and could be regarded as models for the active sites of [NiFe]- and [Fe]-hydrogenases, respectively. All the prepared complexes were characterized by elemental analysis, spectroscopy, and particularly for some of them, by X-ray crystallography. In addition, the electrochemical properties of and as well as the electrocatalytic H2 production catalyzed by and were investigated by CV techniques.

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.

A dithiolate-bridged (CN)2(CO)Fe-Ni complex reproducing the IR bands of [NiFe] hydrogenase.

PubMed

Tanino, Soichiro; Li, Zilong; Ohki, Yasuhiro; Tatsumi, Kazuyuki

2009-03-16

A dithiolate-bridged dinuclear Fe-Ni complex, which has the desired fac-(CN)(2)(CO) ligand set at iron, has been synthesized. Its CN/CO bands in the IR spectrum reproduce those of the Ni-A, Ni-B, and Ni-SU states, which indicate that these octahedral Fe(II) centers have similar electronic properties. This result verifies the assignment of a (CN)(2)(CO)Fe(II) moiety in the active site of [NiFe] hydrogenase.

Fast Timing Study of the β- Decay of 63Mn to 63Fe

NASA Astrophysics Data System (ADS)

Olaizola, B.; Fraile, L. M.; Mach, H.; Briz, J. A.; Cal-González, J.; Ghita, D.; Köster, U.; Kurcewicz, W.; Lesher, S. R.; Pauwels, D.; Picado, E.; Poves, A.; Radulov, D.; Simpson, G. S.; Udias, J. M.

The β- decay of 63Mn to 63Fe has been studied in an experiment at ISOLDE, CERN. The previously known 63Fe level scheme has been confirmed and greatly expanded, to a total of 31 levels and 73 γ lines. The energy of the 9/2+ isomer state has been measured for the first time at 475.0 keV, completing the systematics of such states in odd-Fe isotopes below 68Ni. In addition, the lifetimes of the low-lying states have been measured, allowing the tentative assignment of the spin-parity sequence for those levels.

Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

NASA Astrophysics Data System (ADS)

de P. R. Moreira, Ibério; Dovesi, Roberto; Roetti, Carla; Saunders, Victor R.; Orlando, Roberto

2000-09-01

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

Structural, dielectric and gas sensing behavior of Mn substituted spinel MFe2O4 (M=Zn, Cu, Ni, and Co) ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ranjith Kumar, E.; Siva Prasada Reddy, P.; Sarala Devi, G.; Sathiyaraj, S.

2016-01-01

Spinel ferrite (MnZnFe2O4, MnCuFe2O4, MnNiFe2O4 and MnCoFe2O4) nanoparticles have been prepared by evaporation method. The annealing temperature plays an important role on changing particle size of the spinel ferrite nanoparticles was found out by X-ray diffraction and transmission electron microscopy. The role of manganese substitution in the spinel ferrite nanoparticles were also analyzed for different annealing temperature. The substitution of Mn also creates a vital change in dielectric properties have been measured in the frequency range of 100 kHz to 5 MHz. These spinel ferrites are decomposed to α-Fe2O3 after annealing above 550 °C in air. Through the characterization of the prepared powder, the effect of annealing temperature, chemical composition and preparation technique on the microstructure, particle size and dielectric properties of the Mn substituted spinel ferrite nanoparticles are discussed. Furthermore, Conductance response of Mn substituted MFe2O4 ferrite nanoparticles were measured by exposing the materials to reducing gas like liquefied petroleum gas (LPG).

Revisiting Mn and Fe removal in humic rich estuaries

NASA Astrophysics Data System (ADS)

Oldham, Véronique E.; Miller, Megan T.; Jensen, Laramie T.; Luther, George W.

2017-07-01

Metal removal by estuarine mixing has been studied for several decades, but few studies emphasize dissolved metal speciation and organic ligand complexation. Findings from the last decade indicate that metal-humic complexation can be significant for dissolved metals including Cu(II), Al(III) and Fe(III), but little consideration is given to the precipitation of these complexes with humic material at pH < 2. Given that total soluble metal analysis involves an acidification step for sample preservation, we show that Mn and other metal concentrations may have been underestimated in estuaries, especially when humic substance concentrations are high. A competitive ligand assay of selected samples from our study site, a coastal waterway bordered by wetlands (Broadkill River, DE), showed that Mn(III)-humic complexation is significant, and that some Mn(III)-L complexes precipitate during acidification. In the oxygenated surface waters of the Broadkill River, total dissolved Mn (dMnT) was up to 100% complexed to ambient ligands as Mn(III)-L, and we present evidence for humic-type Mn(III)-L complexes. The Mn(III) complexes were kinetically stabilized against Fe(II) reduction, even when [Fe(II)] was 17 times higher than [dMnT]. Unlike typical oceanic surface waters, [Fe(II)] > [Fe(III)-L] in surface waters, which may be attributed to high rates of photoreduction of Fe(III)-L complexes. Total [Mn(III)-L] ranged from 0.22 to 8.4 μM, in excess of solid MnOx (below 0.28 μM in all samples). Filtration of samples through 0.02 μm filters indicated that all Mn(III)-L complexes pass through the filters and were not colloidal species in contrast to dissolved Fe. Incubation experiments indicated that the reductive dissolution of solid MnOx by ambient ligands may be responsible for Mn(III) formation in this system. Unlike previous studies of estuarine mixing, which demonstrated metal removal during mixing, we show significant export of dMn and dissolved Fe (dFe) in the summer and fall

Magneto Caloric Effect in Ni-Mn-Ga alloys: First Principles and Experimental studies

NASA Astrophysics Data System (ADS)

Odbadrakh, Khorgolkhuu; Nicholson, Don; Brown, Gregory; Rusanu, Aurelian; Rios, Orlando; Hodges, Jason; Safa-Sefat, Athena; Ludtka, Gerard; Eisenbach, Markus; Evans, Boyd

2012-02-01

Understanding the Magneto-Caloric Effect (MCE) in alloys with real technological potential is important to the development of viable MCE based products. We report results of computational and experimental investigation of a candidate MCE materials Ni-Mn-Ga alloys. The Wang-Landau statistical method is used in tandem with Locally Self-consistent Multiple Scattering (LSMS) method to explore magnetic states of the system. A classical Heisenberg Hamiltonian is parametrized based on these states and used in obtaining the density of magnetic states. The Currie temperature, isothermal entropy change, and adiabatic temperature change are then calculated from the density of states. Experiments to observe the structural and magnetic phase transformations were performed at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) on alloys of Ni-Mn-Ga and Fe-Ni-Mn-Ga-Cu. Data from the observations are discussed in comparison with the computational studies. This work was sponsored by the Laboratory Directed Research and Development Program (ORNL), by the Mathematical, Information, and Computational Sciences Division; Office of Advanced Scientific Computing Research (US DOE), and by the Materials Sciences and Engineering Division; Office of Basic Energy Sciences (US DOE).

Cu-Mn-Fe alloys and Mn-rich amphiboles in ancient copper slags from the Jabal Samran area, Saudi Arabia: With synopsis on chemistry of Fe-Mn(III) oxyhydroxides in alteration zones

NASA Astrophysics Data System (ADS)

Surour, Adel A.

2015-01-01

In the Jabal Samran area (western Saudi Arabia), secondary copper mineralization in a NE-trending shear zone in which the arc metavolcanic host rocks (dacite-rhyodacite) show conjugate fractures and extensive hydrothermal alteration and bleaching. The zones contain frequent Fe-Mn(III) oxyhydroxides (FeOH-MnOH) that resulted from oxidation of pyrite and Mn-bearing silicates. In the bleached part, the groundmass is represented by Fe-bearing interstratified illite-smectite with up to 4.02 wt% FeOt. FeOH-MnOH are pre-weathering phases formed by hydrothermal alteration in a submarine environment prior to uplifting. Five varieties of FeOH are distinguished, four of them are exclusively hydrothermal with ∼20 wt% H2O whereas the fifth contains ∼31-33 wt% H2O and might represent reworking of earlier hydrothermal FeOH phases by weathering. FeOH fills thin fractures in the form of veinlets and crenulated laminae or as a pseudomorph for pyrite, goethite and finally ferrihydrite, and this oxyhydroxide is characterized by positive correlation of Fe2O3 with SiO2 and Al2O3. On the other hand, MOH shows positive correlation between MnO2 and Al2O3 whereas it is negative between Fe2O3 and SiO2. Paratacamite is the most common secondary copper mineral that fills fractures and post-dates FeOH and MnOH. It is believed that Cl- in the structure of paratacamite represents inherited marine storage rather than from surfacial evaporates or meteoric water. The mineralogy of slags suggests a complicated mineral assemblage that includes native Cu prills, synthetic spinifixed Mn-rich amphiboles with 16.73 wt% MnO, brown glass and Ca-Mn-Fe phase close to the olivine structure. EMPA indicate that the some Cu prills have either grey discontinuous boarder zone of S-rich Mn-Cu alloy (with up to 21.95 wt% S and 19.45 wt% Mn) or grey Cu-Mn-Fe alloy (with up to 15.9 wt% Cu, 39. 12 wt% Mn and 61.64 wt% Fe). Mn in the Cu prills is expelled inward as Cu-Mn-Fe alloy inclusions whereas S is expelled

Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe-Mn binary oxides: influence of Mn/Fe ratio, pH, Ca2+, and humic acid.

PubMed

Zhang, Gaosheng; Liu, Huijuan; Qu, Jiuhui; Jefferson, William

2012-01-15

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe-Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe-Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe-Mn binary oxides. To create Fe-Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe-Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO(2) at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO(2) in the binary oxides. The presence of Ca(2+) enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe-Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe-Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater. Copyright © 2011 Elsevier Inc. All rights reserved.

Boric acid flux synthesis, structure and magnetic property of MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn)

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

Yang, Dingfeng; Cong, Rihong; Gao, Wenliang, E-mail: gaowl@cqu.edu.cn

2013-05-01

Three new borates MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) have been synthesized by boric acid flux methods, which are isotypic to NiB₁₂O₁₄(OH)₁₀. Single-crystal XRD was performed to determine the crystal structures in detail. They all crystallize in the monoclinic space group P2₁/c. The size of MO{sub 6} (M=Mg, Mn, Fe, Co, Ni, Zn) octahedron shows a good agreement with the Shannon effective ionic radii of M²⁺. Magnetic measurements indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. The values of its magnetic superexchange constants were evaluated by DFT calculations, which explain the observed magnetic behavior. The UV–vis diffuse reflectancemore » spectrum of ZnB₁₂O₁₄(OH)₁₀ suggests a band gap ~4.6 eV. DFT calculations indicate it has a direct band gap 4.9 eV. The optical band gap is contributed by charge transfers from the occupied O 2p to the unoccupied Zn 4s states. - Graphical abstract: Experimental and theoretical studies indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering. DFT calculations show ZnB₁₂O₁₄(OH)₁₀ has a direct band gap of 4.9 eV. Highlights: • MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) are synthesized by two-step boric acid flux method. • Single-crystal XRD was performed to determine the crystal structures in detail. • Size of MO₆ (M=Mg, Mn, Fe, Co, Ni, Zn) agrees with the effective ionic radii. • MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. • DFT calculations indicate ZnB₁₂O₁₄(OH)₁₀ has a direct band gap 4.9 eV.« less

Synthesis and characterization of T[Ni(CN){sub 4}].2pyz with T=Fe, Ni; pyz=pyrazine: Formation of T-pyz-Ni bridges

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

Lemus-Santana, A.A.; Rodriguez-Hernandez, J.; Institute of Materials Science and Technology, University of Havana

2011-08-15

The formation of T-pyz-Ni bridges (pyz=pyrazine) in the T[Ni(CN){sub 4}].2pyz series is known for T=Mn, Zn, Cd and Co but not with T=Fe, Ni. In this contribution the existence of such bridges also for T=Fe, Ni is discussed. The obtained pillared solids, T[Ni(CN){sub 4}].2pyz, were characterized from XRD, TG, UV-Vis, IR, Raman, Moessbauer and magnetic data. Their crystal structures were refined in the orthorhombic Pmna space group from XRD powder patterns. The structural behavior of these solids on cooling down to 77 K was also studied. In the 180-200 K temperature range the occurrence of a structural transition to amore » monoclinic structure (P2{sub 1}/c space group) was observed. No temperature induced spin transition was observed for Fe[Ni(CN){sub 4}].2pyz. The iron (II) was found to be in high spin electronic state and this configuration is preserved on cooling down to 2 K. The magnetic data indicate the occurrence of a low temperature weak anti-ferromagnetic interaction between T metal centers within the T[Ni(CN){sub 4}] layer. In the paramagnetic region for Ni[Ni(CN){sub 4}].2pyz, a reversible temperature induced spin transition for the inner Ni atom was detected. - Graphical abstract: Rippled sheets structure for the pillared solids T[Ni(CN){sub 4}].2pyz. The pyrazine molecule is found forming T-pyz-Ni bridges between neighboring layers. Highlights: > Pillared 2D solids. > Inorganic-organic solids. > Assembling of molecular blocks. > From 1D and 2D building blocks to 3D solids.« less

Twinning-mediated work hardening and texture evolution in CrCoFeMnNi high entropy alloys at cryogenic temperature

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

Liu, T. K.; Wu, Z.; Stoica, A. D.

The cryogenic plastic deformation of CrCoFeMnNi high entropy alloy is characterized by three distinct stages based on the change of the work hardening rate. Microstructure and bulk texture at different strain levels were studied by electron backscatter diffraction (EBSD) and neutron diffraction. Our findings indicate that the deformation twins led to the constant work hardening rate at Stage II and resulted in the appearance of <115 >//TA texture component, while the dislocation slip was involved all though the entire plastic deformation. As a result, the twinning-mediated tensile plastic deformation at cryogenic temperature finally induced the strong {111}- < 112 >more » texture component and minor {001} < 110 > texture component accompanied with twinning-induced {115}< 552 > texture component.« less

Twinning-mediated work hardening and texture evolution in CrCoFeMnNi high entropy alloys at cryogenic temperature

DOE PAGES

Liu, T. K.; Wu, Z.; Stoica, A. D.; ...

2017-06-17

The cryogenic plastic deformation of CrCoFeMnNi high entropy alloy is characterized by three distinct stages based on the change of the work hardening rate. Microstructure and bulk texture at different strain levels were studied by electron backscatter diffraction (EBSD) and neutron diffraction. Our findings indicate that the deformation twins led to the constant work hardening rate at Stage II and resulted in the appearance of <115 >//TA texture component, while the dislocation slip was involved all though the entire plastic deformation. As a result, the twinning-mediated tensile plastic deformation at cryogenic temperature finally induced the strong {111}- < 112 >more » texture component and minor {001} < 110 > texture component accompanied with twinning-induced {115}< 552 > texture component.« less

Structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds

NASA Astrophysics Data System (ADS)

Liu, Yangzhen; Xing, Jiandong; Fu, Hanguang; Li, Yefei; Sun, Liang; Lv, Zheng

2017-08-01

The properties of sulfides are important in the design of new iron-steel materials. In this study, first-principles calculations were used to estimate the structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds. The results reveal that these XS binary compounds are thermodynamically stable, because their formation enthalpy is negative. The elastic constants, Cij, and moduli (B, G, E) were investigated using stress-strain and Voigt-Reuss-Hill approximation, respectively. The sulfide anisotropy was discussed from an anisotropic index and three-dimensional surface contours. The electronic structures reveal that the bonding characteristics of the XS compounds are a mixture of metallic and covalent bonds. Using a quasi-harmonic Debye approximation, the heat capacity at constant pressure and constant volume was estimated. NiS possesses the largest CP and CV of the sulfides.

Room temperature ferromagnetism in Mn-doped NiO nanoparticles

NASA Astrophysics Data System (ADS)

Layek, Samar; Verma, H. C.

2016-01-01

Mn-doped NiO nanoparticles of the series Ni1-xMnxO (x=0.00, 0.02, 0.04 and 0.06) are successfully synthesized using a low temperature hydrothermal method. Samples up to 6% Mn-doping are single phase in nature as observed from powder x-ray diffraction (XRD) studies. Rietveld refinement of the XRD data shows that all the single phase samples crystallize in the NaCl like fcc structure with space group Fm-3m. Unit cell volume decreases with increasing Mn-doping. Pure NiO nanoparticles show weak ferromagnetism, may be due to nanosize nature. Introduction of Mn within NiO lattice improves the magnetic properties significantly. Room temperature ferromagnetism is found in all the doped samples whereas the magnetization is highest for 2% Mn-doping and then decreases with further doping. The ZFC and FC branches in the temperature dependent magnetization separate well above 350 K indicating transition temperature well above room temperature for 2% Mn-doped NiO Nanoparticle. The ferromagnetic Curie temperature is found to be 653 K for the same sample as measured by temperature dependent magnetization study using vibrating sample magnetometer (VSM) in high vacuum.

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.

[FeFe]- and [NiFe]-hydrogenase diversity, mechanism, and maturation.

PubMed

Peters, John W; Schut, Gerrit J; Boyd, Eric S; Mulder, David W; Shepard, Eric M; Broderick, Joan B; King, Paul W; Adams, Michael W W

2015-06-01

The [FeFe]- and [NiFe]-hydrogenases catalyze the formal interconversion between hydrogen and protons and electrons, possess characteristic non-protein ligands at their catalytic sites and thus share common mechanistic features. Despite the similarities between these two types of hydrogenases, they clearly have distinct evolutionary origins and likely emerged from different selective pressures. [FeFe]-hydrogenases are widely distributed in fermentative anaerobic microorganisms and likely evolved under selective pressure to couple hydrogen production to the recycling of electron carriers that accumulate during anaerobic metabolism. In contrast, many [NiFe]-hydrogenases catalyze hydrogen oxidation as part of energy metabolism and were likely key enzymes in early life and arguably represent the predecessors of modern respiratory metabolism. Although the reversible combination of protons and electrons to generate hydrogen gas is the simplest of chemical reactions, the [FeFe]- and [NiFe]-hydrogenases have distinct mechanisms and differ in the fundamental chemistry associated with proton transfer and control of electron flow that also help to define catalytic bias. A unifying feature of these enzymes is that hydrogen activation itself has been restricted to one solution involving diatomic ligands (carbon monoxide and cyanide) bound to an Fe ion. On the other hand, and quite remarkably, the biosynthetic mechanisms to produce these ligands are exclusive to each type of enzyme. Furthermore, these mechanisms represent two independent solutions to the formation of complex bioinorganic active sites for catalyzing the simplest of chemical reactions, reversible hydrogen oxidation. As such, the [FeFe]- and [NiFe]-hydrogenases are arguably the most profound case of convergent evolution. This article is part of a Special Issue entitled: Fe/S proteins: Analysis, structure, function, biogenesis and diseases. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

A New CuO-Fe2 O3 -Mesocarbon Microbeads Conversion Anode in a High-Performance Lithium-Ion Battery with a Li1.35 Ni0.48 Fe0.1 Mn1.72 O4 Spinel Cathode.

PubMed

Di Lecce, Daniele; Verrelli, Roberta; Campanella, Daniele; Marangon, Vittorio; Hassoun, Jusef

2017-04-10

A ternary CuO-Fe 2 O 3 -mesocarbon microbeads (MCMB) conversion anode was characterized and combined with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 spinel cathode in a lithium-ion battery of relevant performance in terms of cycling stability and rate capability. The CuO-Fe 2 O 3 -MCMB composite was prepared by using high-energy milling, a low-cost pathway that leads to a crystalline structure and homogeneous submicrometrical morphology as revealed by XRD and electron microscopy. The anode reversibly exchanges lithium ions through the conversion reactions of CuO and Fe 2 O 3 and by insertion into the MCMB carbon. Electrochemical tests, including impedance spectroscopy, revealed a conductive electrode/electrolyte interface that enabled the anode to achieve a reversible capacity value higher than 500 mAh g -1 when cycled at a current of 120 mA g -1 . The remarkable stability of the CuO-Fe 2 O 3 -MCMB electrode and the suitable characteristics in terms of delivered capacity and voltage-profile retention allowed its use in an efficient full lithium-ion cell with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 cathode. The cell had a working voltage of 3.6 V and delivered a capacity of 110 mAh g cathode -1 with a Coulombic efficiency above 99 % after 100 cycles at 148 mA g cathode -1 . This relevant performances, rarely achieved by lithium-ion systems that use the conversion reaction, are the result of an excellent cell balance in terms of negative-to-positive ratio, favored by the anode composition and electrochemical features. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controllable synthesis and enhanced microwave absorbing properties of Fe3O4/NiFe2O4/Ni heterostructure porous rods

NASA Astrophysics Data System (ADS)

Li, Yana; Wu, Tong; Jin, Keying; Qian, Yao; Qian, Naxin; Jiang, Kedan; Wu, Wenhua; Tong, Guoxiu

2016-11-01

We developed a coordinated self-assembly/precipitate transfer/sintering method that allows the controllable synthesis of Fe3O4/NiFe2O4/Ni heterostructure porous rods (HPRs). A series of characterizations confirms that changing [Ni2+] can effectively control the crystal size, internal strain, composition, textural characteristics, and properties of HPRs. Molar percentages of Ni and NiFe2O4 in HPRs increase with [Ni2+] in various Boltzmann function modes. Saturation magnetization Ms and coercivity Hc show U-shaped change trends because of crystal size, composition, and interface magnetic coupling. High magnetic loss is maintained after decorating NiFe2O4 and Ni on the surface of Fe3O4 PRs. Controlling the NiFe2O4 interface layers and Ni content can improve impedance matching and dielectric losses, thereby leading to lighter weight, stronger absorption, and broader absorption band of Fe3O4/NiFe2O4/Ni HPRs than Fe3O4 PRs. An optimum EM wave absorbing property was exhibited by Fe3O4/NiFe2O4/Ni HPRs formed at [Ni2+] = 0.05 M. The maximum reflection loss (RL) reaches -58.4 dB at 13.68 GHz, which corresponds to a 2.1 mm matching thickness. The absorbing bandwidth (RL ≤ -20 dB) reaches 14.4 GHz with the sample thickness at 1.6-2.4 and 2.8-10.0 mm. These excellent properties verify that Fe3O4/NiFe2O4/Ni HPRs are promising candidates for new and effective absorptive materials.

Critical Evaluations and Thermodynamic Optimizations of the MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 Systems

NASA Astrophysics Data System (ADS)

Kang, Youn-Bae; Jung, In-Ho

2017-06-01

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe-Mn-Si-O system (MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 systems) are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25°C) to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Slag (molten oxide) was modeled using the modified quasichemical model in the pair approximation. Olivine (Fe2SiO4-Mn2SiO4) was modeled using two-sublattice model in the framework of the compound energy formalism (CEF), while rhodonite (MnSiO3-FeSiO3) and braunite (Mn7SiO_{12} with excess Mn2O3) were modeled as simple Henrian solutions. It is shown that the already developed models and databases of two spinel phases (cubic- and tetragonal-(Fe, Mn)3O4) using CEF [Kang and Jung, J. Phys. Chem. Solids (2016), vol. 98, pp. 237-246] can successfully be integrated into a larger thermodynamic database to be used in practically important higher order system such as silicate. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.

(Bi,Sr) (Fe1−x,Mx)O3−δ (M = Co, Ni and Mn) Cathode Materials with Mixed Electro-Ionic Conductivity

PubMed Central

Wei, Wen-Cheng J.; Huang, Der-Rong; Wang, Dan

2016-01-01

(Bi,Sr)FeO3−δ (BSF) cathode materials doped with either Co, Ni or Mn are synthesized by an ethylene diamine tetra-acetic acid (EDTA)-citrate complexing method, and the effects of the doping level on the mixed electronic-ionic conductivity at various temperatures are studied up to 800 °C. The phase purity and solid solution limit are investigated by X-ray diffraction (XRD). The ionic conductivity is measured by the four-probe direct current (DC) method, the valence state of Fe and Mn by X-ray photoelectron spectroscopy (XPS), and the oxygen non-stoichiometry by differential thermo-gravimetric analysis (TGA). The doped ferrites show interesting electronic conductivity dependent on the testing temperature, implying two conductive mechanisms, either controlled by double exchange at lower temperatures or small polaron (electron-oxygen vacancy) conduction at temperatures greater than 400 °C. The results of Co-doped BSF (S50C20) show the best mixed conductivity among the ferrites, and this is used to assemble cells. The cell with a S50C20 cathode in the region of 600–800 °C is improved by 15% in maximum power density greater than the cell with La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) due to the balanced contribution from oxygen ions, vacancies and electrons. PMID:28774043

The Mn-Fe negative correlation in olivines in ALHA 77257 ureilite

NASA Technical Reports Server (NTRS)

Miyamoto, M.; Furuta, T.; Fujii, N.; Mckay, D. S.; Lofgren, G. E.; Duke, M. B.

1993-01-01

An electron probe microanalyzer is used to measure the Mn, Fe, and oxygen zoning profiles of olivines in the ALHA 77257 ureilite. This is done to study the effects of reduction on the Mn-Fe value, as ureilite olivines exhibit thin reduced rims. Since the Mn content gradually increases toward the rim of ureilite olivines, while the Fa (= 100 x Fe/(Mg + Fe), mol percent) component decreases, the Mn-Fe content of olivine is likely related to redox conditions. The results of melting experiments suggest that the Mn-Fe positive correlation is related to temperature and that the negative correlation of Mn-Fe in olivine and low-Ca pyroxene is related to reduction.

[NiFeSe]-hydrogenase chemistry.

PubMed

Wombwell, Claire; Caputo, Christine A; Reisner, Erwin

2015-11-17

The development of technology for the inexpensive generation of the renewable energy vector H2 through water splitting is of immediate economic, ecological, and humanitarian interest. Recent interest in hydrogenases has been fueled by their exceptionally high catalytic rates for H2 production at a marginal overpotential, which is presently only matched by the nonscalable noble metal platinum. The mechanistic understanding of hydrogenase function guides the design of synthetic catalysts, and selection of a suitable hydrogenase enables direct applications in electro- and photocatalysis. [FeFe]-hydrogenases display excellent H2 evolution activity, but they are irreversibly damaged upon exposure to O2, which currently prevents their use in full water splitting systems. O2-tolerant [NiFe]-hydrogenases are known, but they are typically strongly biased toward H2 oxidation, while H2 production by [NiFe]-hydrogenases is often product (H2) inhibited. [NiFeSe]-hydrogenases are a subclass of [NiFe]-hydrogenases with a selenocysteine residue coordinated to the active site nickel center in place of a cysteine. They exhibit a combination of unique properties that are highly advantageous for applications in water splitting compared with other hydrogenases. They display a high H2 evolution rate with marginal inhibition by H2 and tolerance to O2. [NiFeSe]-hydrogenases are therefore one of the most active molecular H2 evolution catalysts applicable in water splitting. Herein, we summarize our recent progress in exploring the unique chemistry of [NiFeSe]-hydrogenases through biomimetic model chemistry and the chemistry with [NiFeSe]-hydrogenases in semiartificial photosynthetic systems. We gain perspective from the structural, spectroscopic, and electrochemical properties of the [NiFeSe]-hydrogenases and compare them with the chemistry of synthetic models of this hydrogenase active site. Our synthetic models give insight into the effects on the electronic properties and reactivity of

Temperature dependence of exchange bias in (NiFe/IrMn)n multilayer films studied through static and dynamic techniques

NASA Astrophysics Data System (ADS)

Adams, Daniel J.; Khanal, Shankar; Khan, Mohammad Asif; Maksymov, Artur; Spinu, Leonard

2018-05-01

The in-plane temperature dependence of exchange bias was studied through both dc magnetometry and ferromagnetic resonance spectroscopy in a series of [NiFe/IrMn]n multilayer films, where n is the number of layer repetitions. Major hysteresis loops were recorded in the temperature range of 300 K to 2 K to reveal the effect of temperature on the exchange bias in the static regime while temperature-dependent continuous-wave ferromagnetic resonance for frequencies from 3 to 16 GHz was used to determine the exchange bias dynamically. Strong divergence between the values of exchange bias determined using the two different types of measurements as well as a peak in temperature dependence of the resonance linewidth were observed. These results are explained in terms of the slow-relaxer mechanism.

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

PubMed

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

2018-06-01

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

Magnetic anisotropy of Fe{sub 1−y}X{sub y}Pt-L1{sub 0} [X = Cr, Mn, Co, Ni, Cu] bulk alloys

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

Cuadrado, R.; Chantrell, R. W.; Klemmer, Timothy J.

2014-10-13

We demonstrate by means of fully relativistic first principles calculations that, by substitution of Fe by Cr, Mn, Co, Ni, or Cu in FePt-L1{sub 0} bulk alloys, with fixed Pt content, it is possible to tune the magnetocrystalline anisotropy energy by adjusting the content of the non-magnetic species in the material. The changes in the geometry due to the inclusion of each element induces different values of the tetragonality and hence changes in the magnetic anisotropy and in the net magnetic moment. The site resolved magnetic moments of Fe increase with the X content while those of Pt and Xmore » are simultaneously reduced. The calculations are in good quantitative agreement with experimental data and demonstrate that models with fixed band structure but varying numbers of electrons per unit cell are insufficient to describe the experimental data for doped FePt-L1{sub 0} alloys.« less

Damping behavior of polymer composites with high volume fraction of NiMnGa powders

NASA Astrophysics Data System (ADS)

Sun, Xiaogang; Song, Jie; Jiang, Hong; Zhang, Xiaoning; Xie, Chaoying

2011-03-01

Polymer composites inserted with high volume fraction (up to 70 Vol%) of NiMnGa powders were fabricated and their damping behavior was investigated by dynamic mechanical analysis. It is found that the polymer matrix has little influence on the transformation temperatures of NiMnGa powders. A damping peak appears for NiMnGa/epoxy resin (EP) composites accompanying with the martensitic transformation or reverse martensitic transformation of NiMnGa powders during cooling or heating. The damping capacity for NiMnGa/EP composites increases linearly with the increase of volume fraction of NiMnGa powders and, decreases dramatically as the test frequency increases. The fracture strain of NiMnGa/EP composites decrease with the increase of NiMnGa powders.

Synthesis, electrochemical investigation and structural analysis of doped Li[Ni0.6Mn0.2Co0.2-xMx]O2 (x = 0, 0.05; M = Al, Fe, Sn) cathode materials

NASA Astrophysics Data System (ADS)

Eilers-Rethwisch, Matthias; Winter, Martin; Schappacher, Falko Mark

2018-05-01

Layered Ni-rich Li[Ni0.6Mn0.2Co0.2-xMx]O2 cathode materials (x = 0, 0.05; M = Al, Fe, Sn) are synthesized via a co-precipitation synthesis route and the effect of dopants on the structure and electrochemical performance is investigated. All synthesized materials show a well-defined layered structure of the hexagonal α-NaFeO2 phase investigated by X-ray diffraction (XRD). Undoped LiNi0.6Mn0.2Co0.2O2 exhibits a discharge capacity of 170 mAh g-1 in Li-metal 2032 coin-type cells. Doped materials reach lower capacities between 145 mAh g-1 for Al and 160 mAh g-1 for Sn. However, all doped materials prolong the cycle life by up to 20%. Changes of the lattice parameter before and after delithiation yield information about structural stability. A smaller repulsion of the transition metal layer during delithiation in the Sn-doped material leads to a smaller expansion of the unit cell, which results in enhanced structural stability of the material. The improved structural stability of Sn-doped NMC cathode active material is proven by thermal investigations with the help of Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA).

The improvement of cryogenic mechanical properties of Fe-12 Mn and Fe-8 Mn alloy steels through thermal/mechanical treatments

NASA Technical Reports Server (NTRS)

Hwang, S. K.; Morris, J. W., Jr.

1979-01-01

An investigation has been made to improve the low temperature mechanical properties of Fe-8Mn and Fe-12Mn-0.2 Ti alloy steels. A reversion annealing heat treatment in the two-phase (alpha + gamma) region following cold working has been identified as an effective treatment. In an Fe-12Mn-0.2Ti alloy a promising combination of low temperature (-196 C) fracture toughness and yield strength was obtained by this method. The improvement of properties was attributed to the refinement of grain size and to the introduction of a uniform distribution of retained austenite (gamma). It was also shown that an Fe-8Mn steel could be grain-refined by a purely thermal treatment because of its dislocated alpha-prime martensitic structure and absence of epsilon martensite. As a result, a significant reduction of ductile to brittle transition temperature was obtained.

Evolution of phase transformation and magnetic properties with Fe content in Ni55-x Fe x Mn20Ga25 Heusler alloys

NASA Astrophysics Data System (ADS)

Zhang, Yuanlei; Li, Zhe; He, Xijia; Huang, Yinsheng; Xu, Kun; Jing, Chao

2018-02-01

A series of Ni55-x Fe x Mn20Ga25 (0  ⩽  x  ⩽  5) Heusler alloys was prepared to investigate their phase transitions and magnetic properties. At room temperature, these alloys present various crystal structures, and the unit cell volume enlarges with increase of Fe content in both austenite and martensite. Multiple magneto-structural transformations were observed in the parent alloy (x  =  0). In the process of cooling, it undergoes martensitic transformation (MT) from L21-type paramagnetic austenite to L10-type ferromagnetic martensite, accompanying an intermartensitic transformation (IMT, 7M  →  L10). By establishing a detailed phase diagram, we found that both MT and IMT shift to lower temperature simultaneously, while the ferromagnetic (FM) transition of austenite moves to higher temperature as Fe increases. With the further increase of Fe content beyond a critical value, both the IMT and the FM transitions split off from MT, and the former follows with the transforming sequence of 7M  →  5M. Based on the experimental data, some key magnetic parameters have been obtained in this system. The calculated magnetocrystalline anisotropy constant ({{K}1} ) of martensite quickly increases as Fe increases, and then it almost reaches a saturated value (~5.5  ×  105 J m-3) for the alloys with x  >  3. However, the spontaneous magnetic moment ({μs} ) attains a peak value of about 4.2 μ B/f.u. in the alloy with x  =  4, which is not consistent with the linear increasing of effective magnetic moment ({μef f} ). Further magnetic measurements with hydrostatic pressure indicate that such a discrepancy could be ascribed to the competition between the magnetic exchange interaction and the volume change of unit cell governed by the dopant Fe content.

V-insertion in Li(Fe,Mn)FePO4

NASA Astrophysics Data System (ADS)

Wu, T.; Liu, J.; Sun, L.; Cong, L.; Xie, H.; Abdel-Ghany, A.; Mauger, A.; Julien, C. M.

2018-04-01

Insertion of 3% vanadium in LiMn1-yFeyPO4 has been investigated, with y = 0.2 corresponding to the highest manganese concentration before the stress/strain field degrades the electrochemical performance. V substitutes for Fe2+ in the trivalent state V3+. This substitution is accompanied with the formation of Fe vacancies while Mn remains in the Mn2+ valence state, leading to a composition LiMn0.8Fe0.2-0.045V0.03□0.015PO4 where □ is a Fe vacancy. The comparison between electrochemical properties of a pristine sample and a sample with 3 mol.% vanadium made of particles with the same morphology (spherical particles with the same dispersion 100-150 nm in size) and same carbon coating (same conductivity of the carbon layer) is reported. Although the vanadium is in the V3+ state at open circuit voltage (2.6 V) before cycling, a reversible V3+/V2+ is observed when the potential of the half-cell is lowered below the redox potential of 1.8 V vs Li+/Li, due to Li-vacancies. The V-insertion improves the electrochemical properties, due to a synergetic effect of an increase of the lithium diffusion coefficient by a factor two and an increase of the electric conductivity at any Li-concentration during the cycling process, in contradiction with prior claims that attributed the increase of conductivity to V-based impurities.

Euhedral metallic-Fe-Ni grains in extraterrestrial samples

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

1993-01-01

Metallic Fe-Ni is rare in terrestrial rocks, being largely restricted to serpentinized peridotites and volcanic rocks that assimilated carbonaceous material. In contrast, metallic Fe-Ni is nearly ubiquitous among extraterrestrial samples (i.e., meteorites, lunar rocks, and interplanetary dust particles). Anhedral grains are common. For example, in eucrites and lunar basalts, most of the metallic Fe-Ni occurs interstitially between silicate grains and thus tends to have irregular morphologies. In many porphyritic chondrules, metallic Fe-Ni and troilite form rounded blebs in the mesostasis because their precursors were immiscible droplets. In metamorphosed ordinary chondrites, metallic Fe-Ni and troilite form coarse anhedral grains. Some of the metallic Fe-Ni and troilite grains has also been mobilized and injected into fractures in adjacent silicate grains where local shock-reheating temperatures reached the Fe-FeS eutectic (988 C). In interplanetary dust particles metallic Fe-Ni most commonly occurs along with sulfide as spheroids and fragments. Euhedral metallic Fe-Ni grains are extremely rare. Several conditions must be met before such grains can form: (1) grain growth must occur at free surfaces, restricting euhedral metallic Fe-Ni grains to systems that are igneous or undergoing vapor-deposition; (2) the metal (+/-) sulfide assemblage must have an appropriate bulk composition so that taenite is the liquidus phase in igneous systems or the stable condensate phase in vapor-deposition systems; and (3) metallic Fe-Ni grains must remain underformed during subsequent compaction, thermal metamorphism, and shock. Because of these restrictions, the occurrence of euhedral metallic Fe-Ni grains in an object can potentially provide important petrogenetic information. Despite its rarity, euhedral metallic Fe-Ni occurs in a wide variety of extraterrestrial materials. Some of these materials formed in the solar nebula; others formed on parent body surfaces by meteoroid

Cyclic and isothermal oxidation behavior at 1100 and 1200 C of Ni-20Cr, Ni-20Cr-3Mn, Ni-20Cr-3Si, and Ni-40Cr alloys

NASA Technical Reports Server (NTRS)

Lowell, C. E.

1973-01-01

Alloys of Ni-20Cr, Ni-20Cr-3Mn, Ni-20Cr-3Si, and Ni-40Cr were cyclically oxidized at 1100 and 1200 C for up to 100 hours. Oxidation behavior was judged by sample thickness and weight change, metallography, diffraction, and microprobe analysis. The least attacked were Ni-40Cr and Ni-20Cr-3Si. The alloy Ni-20Cr-3Mn was much less attacked than Ni-20Cr, but more than the other alloys. The formation of Cr2O3 accounted for the increased resistance of Ni-Cr and Ni-20Cr-3Si, and the formation of MnCr2O4 accounts for the improvement in Ni-20Cr-3mn over Ni-20Cr.

Nanoscale origins of the damage tolerance of the high-entropy alloy CrMnFeCoNi

DOE PAGES

Zhang, ZiJiao; Mao, M. M.; Wang, Jiangwei; ...

2015-12-09

Damage tolerance can be an elusive characteristic of structural materials requiring both high strength and ductility, properties that are often mutually exclusive. High-entropy alloys are of interest in this regard. Specifically, the single-phase CrMnFeCoNi alloy displays tensile strength levels of ~1 GPa, excellent ductility (~60–70%) and exceptional fracture toughness (KJIc>200M Pa√m). Here through the use of in situ straining in an aberration-corrected transmission electron microscope, we report on the salient atomistic to micro-scale mechanisms underlying the origin of these properties. We identify a synergy of multiple deformation mechanisms, rarely achieved in metallic alloys, which generates high strength, work hardening andmore » ductility, including the easy motion of Shockley partials, their interactions to form stacking-fault parallelepipeds, and arrest at planar slip bands of undissociated dislocations. In conclusion, we further show that crack propagation is impeded by twinned, nanoscale bridges that form between the near-tip crack faces and delay fracture by shielding the crack tip.« less

Nanoscale origins of the damage tolerance of the high-entropy alloy CrMnFeCoNi

PubMed Central

Zhang, ZiJiao; Mao, M. M.; Wang, Jiangwei; Gludovatz, Bernd; Zhang, Ze; Mao, Scott X.; George, Easo P.; Yu, Qian; Ritchie, Robert O.

2015-01-01

Damage tolerance can be an elusive characteristic of structural materials requiring both high strength and ductility, properties that are often mutually exclusive. High-entropy alloys are of interest in this regard. Specifically, the single-phase CrMnFeCoNi alloy displays tensile strength levels of ∼1 GPa, excellent ductility (∼60–70%) and exceptional fracture toughness (KJIc>200 MPa√m). Here through the use of in situ straining in an aberration-corrected transmission electron microscope, we report on the salient atomistic to micro-scale mechanisms underlying the origin of these properties. We identify a synergy of multiple deformation mechanisms, rarely achieved in metallic alloys, which generates high strength, work hardening and ductility, including the easy motion of Shockley partials, their interactions to form stacking-fault parallelepipeds, and arrest at planar slip bands of undissociated dislocations. We further show that crack propagation is impeded by twinned, nanoscale bridges that form between the near-tip crack faces and delay fracture by shielding the crack tip. PMID:26647978

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5Mn 1.5O 4 Electrodes

DOE PAGES

Qiao, Ruimin; Wray, L. Andrew; Kim, Jung -Hyun; ...

2015-11-11

The LiNi 0.5Mn 1.5O 4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs Li/Li +). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi 0.5Mn 1.5O 4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi 0.5Mnmore » 1.5O 4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni 2+ and Mn 2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi 0.5Mn 1.5O 4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.« less

MWCNT-MnFe2O4 nanocomposite for efficient hyperthermia applications

NASA Astrophysics Data System (ADS)

Seal, Papori; Hazarika, Monalisa; Paul, Nibedita; Borah, J. P.

2018-04-01

In this work we present synthesis of multi-walled carbon nanotube (MWCNT)-Manganese ferrite (MnFe2O4) nanocomposite and its probable application in hyperthermia. MnFe2O4 nanoparticles were synthesized by co-precipitation method. X ray diffractogram (XRD) confirms the formation of cubic phase of MnFe2O4 with preferred crystallographic orientation along (311) plane. High resolution electron microscope (HRTEM) image of the composites confirms the presence of MnFe2O4 spherical nanoparticles on the surface of CNT which are bound strongly to the surface. MWCNT-MnFe2O4 nanocomposite were prepared after acid functionalization of MWCNT. Vibrational features of the synthesized samples were confirmed through Fourier transformed infra-red spectroscopy (FTIR). FTIR spectra of acid functionalized MWCNT shows a peak positioned at ˜1620cm-1 which corresponds to C=O functional group of carboxylic acid. Prepared MnFe2O4 nanoparticles and MWCNT-MnFe2O4 nanocomposites were subjected to hyperthermia studies.

Fluorescence x-ray absorption fine structure studies of Fe-Ni-S and Fe-Ni-Si melts to 1600 K

NASA Astrophysics Data System (ADS)

Manghnani, M. H.; Hong, X.; Balogh, J.; Amulele, G.; Sekar, M.; Newville, M.

2008-04-01

We report NiK -edge fluorescence x-ray absorption fine structure spectra (XAFS) for Fe0.75Ni0.05S0.20 and Fe0.75Ni0.05Si0.20 ternary alloys from room temperature up to 1600 K. A high-temperature furnace designed for these studies incorporates two x-ray transparent windows and enables both a vertical orientation of the molten sample and a wide opening angle, so that XAFS can be measured in the fluorescence mode with a detector at 90° with respect to the incident x-ray beam. An analysis of the Ni XAFS data for these two alloys indicates different local structural environments for Ni in Fe0.75Ni0.05S0.20 and Fe0.75Ni0.05Si0.20 melts, with more Ni-Si coordination than Ni-S coordination persisting from room temperature through melting. These results suggest that light elements such as S and Si may impact the structural and chemical properties of Fe-Ni alloys with a composition similar to the earth’s core.

Effect of Ti content on the microstructure and mechanical behavior of (Fe 36Ni 18Mn 33Al 13) 100–xTi x high entropy alloys

DOE PAGES

Wang, Zhangwei; Wu, Margaret; Cai, Zhonghou; ...

2016-06-13

The microstructure and mechanical properties studies of a series of two-phase f.c.c./B2 (ordered b.c.c.) lamellar-structured, high entropy alloys (HEA) Fe 36Ni 18Mn 33Al 13Ti x with x up to 6 at. % Ti have been investigated. X-ray microanalysis in a TEM showed that the Ti resided mostly in the B2 phase. The lamellar spacing decreased significantly with increasing Ti content from 1.56 μm for the undoped alloy to 155 nm with an addition of 4 at. % Ti, leading to a sharp increase in room-temperature yield strength,σ y, from 270 MPa to 953 MPa, but with a concomitant decrease inmore » ductility from 22% elongation to 2.3%. Annealing at 1173 K for 20 h greatly increased the lamellar spacing of Fe 36Ni 18Mn 33Al 13Ti 4 to 577 nm, producing a corresponding decrease in σy to 511 MPa. The yield strengths of all the doped alloys decreased significantly when tensile tested at 973 K with a concomitant increase in ductility due to softening of the B2 phase. The fracture mode changed from cleavage at room temperature to a ductile dimple-type rupture at 973 K. Lastly, the results are discussed in terms of the Hall-Petch-type relationship.« less

Effect of Ti content on the microstructure and mechanical behavior of (Fe 36Ni 18Mn 33Al 13) 100–xTi x high entropy alloys

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

Wang, Zhangwei; Wu, Margaret; Cai, Zhonghou

The microstructure and mechanical properties studies of a series of two-phase f.c.c./B2 (ordered b.c.c.) lamellar-structured, high entropy alloys (HEA) Fe 36Ni 18Mn 33Al 13Ti x with x up to 6 at. % Ti have been investigated. X-ray microanalysis in a TEM showed that the Ti resided mostly in the B2 phase. The lamellar spacing decreased significantly with increasing Ti content from 1.56 μm for the undoped alloy to 155 nm with an addition of 4 at. % Ti, leading to a sharp increase in room-temperature yield strength,σ y, from 270 MPa to 953 MPa, but with a concomitant decrease inmore » ductility from 22% elongation to 2.3%. Annealing at 1173 K for 20 h greatly increased the lamellar spacing of Fe 36Ni 18Mn 33Al 13Ti 4 to 577 nm, producing a corresponding decrease in σy to 511 MPa. The yield strengths of all the doped alloys decreased significantly when tensile tested at 973 K with a concomitant increase in ductility due to softening of the B2 phase. The fracture mode changed from cleavage at room temperature to a ductile dimple-type rupture at 973 K. Lastly, the results are discussed in terms of the Hall-Petch-type relationship.« less

Anomalous magnetotransport behavior in Fe-doped MnNiGe alloys

NASA Astrophysics Data System (ADS)

Dutta, P.; Pramanick, S.; Singh, Vijay; Major, Dan Thomas; Das, D.; Chatterjee, S.

2016-04-01

The electrical dc transport properties of hexagonal magnetic equiatomic alloys of nominal composition Mn1 -xFexNiGe (x =0.2 and0.25 ) have been investigated experimentally as well as theoretically using first-principles electronic structure calculations. Thermal hysteresis in the magnetization data indicates that the alloys undergo a first-order martensitic transition. Both the alloys show unusual nonmetallic resistivity behavior and a noticeable amount of training effect in resistivity when thermally cycled through the first-order martensitic transition. We observe moderate negative magnetoresistance (˜-11.5 % for 150 kOe) at 5 K (well below the martensitic transition temperature) associated with clear virgin line effect for both the alloys. We have adapted different flavors of density functional theory approach to understand the experimentally observed nonmetallic transport behavior.

Ring head recording on perpendicular media: Output spectra for CoCr and CoCr/NiFe media

NASA Astrophysics Data System (ADS)

Stubbs, D. P.; Whisler, J. W.; Moe, C. D.; Skorjanec, J.

1985-04-01

The recording density response for sputtered CoCr (thickness=0.5 μm) and CoCr/NiFe (t=0.25 μm/0.5 μm) as well as evaporated CoNi (t=0.12 μm) and Co surface-doped iron oxide particulate media has been measured by reading and writing with Mn-Zn ferrite heads (gap length=0.375 μm, track width=37 μm) in contact with the media. Measurements to 200 kfc/i (thousand flux changes per inch) show a gap null around 115 kfc/i. The data have been normalized by dividing out the head sensitivity to obtain the value of spacing plus transition width (d+a) for the various media. For the CoCr media this value varied from 0.075-0.088 μm; for CoNi, 0.100 μm, and for the particulate medium, 0.163 μm. In addition, testing with a larger gapped Mn-Zn ferrite head (g=2.43 μm) shows that the head fields are distorted by the soft magnetic underlayer in dual layer CoCr/NiFe samples when the gap length is large compared to the distance to the underlayer.

Bimetallic NiFe2O4 synthesized via confined carburization in NiFe-MOFs for efficient oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Fang, Zhiqiang; Hao, Zhaomin; Dong, Qingsong; Cui, Yong

2018-04-01

Transition metal oxides that derived from metal-organic framework (MOF) precursor have intensively received attention because of their numerous electrochemical applications. Bimetallic Ni-Fe oxides have been rarely reported on the basis of MOF-related strategy. Herein, a bimetallic NiFe2O4 was successfully synthesized via confined carburization in NiFe-MOF precursors and characterized by XRD, XPS, SEM, and TEM. After conducting an investigation of oxygen evolution reaction (OER), the as-synthesized NiFe2O4 material exhibited good catalytic efficiency and high stability and durability in alkaline media. The as-synthesized NiFe2O4 material would promote the development of MOFs in non-noble-metal OER catalyst.

Effect of Ni on Fe FeS phase relations at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Zhang, Li; Fei, Yingwei

2008-04-01

A series of melting experiments in the Fe-rich portion of the Fe-Ni-S system have been conducted at 19-23 GPa and 800-1100 °C. The solubility of S in the Fe-Ni solid alloy and the eutectic melting in the Fe-Ni-S system were determined as a function of Ni content. The maximum S solubility in the Fe-Ni alloy is 2.7 wt.% at 20 GPa and the eutectic temperature. The eutectic melting temperature in the Fe-Ni(5wt.%)-S system is ~ 1000 °C lower than the melting point of pure Fe at 20 GPa. We also found that Ni can substitute Fe in the Fe 3S structure to form (Fe,Ni) 3S solid solutions up to at least a Fe/Ni atomic ratio of 0.5. Similar to melting behavior in the Fe-FeS system, the eutectic melting relations in the Fe-Ni-S system could produce inner and outer cores with the right light element balance to account for the density difference between the solid inner core and the liquid outer core.

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.

Study of certain features of the electronic structure of the ternary alloys Ni2(Mn, Fe) and Ni3(Mn, Co)

NASA Technical Reports Server (NTRS)

Zhukova, V. M.; Fadin, V. P.

1981-01-01

The changes in electronic structure related to transport processes occurring during the alloying of he alloy Ni3Mn with iron and cobalt, and the ordering of the ternary alloys thus formed are presented. The Hall effect, the absolute thermal emf, the internal saturation induction, the Nernst-Ettingshausen constant, and the electrical resistivity were measured. Results show a decrease in the contribution of hole sections of the Fermi surface to the transport process occurs together with a considerable increase in the contribution of electron sections. In this case, the mobility of 3 dimensional holes decreases and the mobility of 4s electrons increases considerably.

Structural alteration of hexagonal birnessite by aqueous Mn(II): Impacts on Ni(II) sorption

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

Lefkowitz, Joshua P.; Elzinga, Evert J.

We studied the impacts of aqueous Mn(II) (1 mM) on the sorption of Ni(II) (200 μM) by hexagonal birnessite (0.1 g L- 1) at pH 6.5 and 7.5 with batch experiments and XRD, ATR-FTIR and Ni K-edge EXAFS analyses. In the absence of Mn(II)aq, sorbed Ni(II) was coordinated predominantly as triple corner-sharing complexes at layer vacancies at both pH values. Introduction of Mn(II)aq into Ni(II)-birnessite suspensions at pH 6.5 caused Ni(II) desorption and led to the formation of edge-sharing Ni(II) complexes. This was attributed to competitive displacement of Ni(II) from layer vacancies by either Mn(II) or by Mn(III) formed throughmore » interfacial Mn(II)-Mn(IV) comproportionation, and/or incorporation of Ni(II) into the birnessite lattice promoted by Mn(II)-catalyzed recrystallization of the sorbent. Similar to Mn(II)aq, the presence of HEPES or MES caused the formation of edge-sharing Ni(II) sorption complexes in Ni(II)-birnessite suspensions, which was attributed to partial reduction of the sorbent by the buffers. At pH 7.5, interaction with aqueous Mn(II) caused reductive transformation of birnessite into secondary feitknechtite that incorporated Ni(II), enhancing removal of Ni(II) from solution. These results demonstrate that reductive alteration of phyllomanganates may significantly affect the speciation and solubility of Ni(II) in anoxic and suboxic environments.« 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.

Exact ab initio transport coefficients in bcc Fe-X (X=Cr, Cu, Mn, Ni, P, Si) dilute alloys

NASA Astrophysics Data System (ADS)

Messina, Luca; Nastar, Maylise; Garnier, Thomas; Domain, Christophe; Olsson, Pär

2014-09-01

Defect-driven diffusion of impurities is the major phenomenon leading to formation of embrittling nanoscopic precipitates in irradiated reactor pressure vessel (RPV) steels. Diffusion depends strongly on the kinetic correlations that may lead to flux coupling between solute atoms and point defects. In this work, flux coupling phenomena such as solute drag by vacancies and radiation-induced segregation at defect sinks are systematically investigated for six bcc iron-based dilute binary alloys, containing Cr, Cu, Mn, Ni, P, and Si impurities, respectively. First, solute-vacancy interactions and migration energies are obtained by means of ab initio calculations; subsequently, self-consistent mean field theory is employed in order to determine the exact Onsager matrix of the alloys. This innovative multiscale approach provides a more complete treatment of the solute-defect interaction than previous multifrequency models. Solute drag is found to be a widespread phenomenon that occurs systematically in ferritic alloys and is enhanced at low temperatures (as for instance RPV operational temperature), as long as an attractive solute-vacancy interaction is present, and that the kinetic modeling of bcc alloys requires the extension of the interaction shell to the second-nearest neighbors. Drag occurs in all alloys except Fe(Cr); the transition from dragging to nondragging regime takes place for the other alloys around (Cu, Mn, Ni) or above (P, Si) the Curie temperature. As far as only the vacancy-mediated solute migration is concerned, Cr depletion at sinks is foreseen by the model, as opposed to the other impurities which are expected to enrich up to no less than 1000 K. The results of this study confirm the current interpretation of the hardening processes in ferritic-martensitic steels under irradiation.

Geochemical Constraints on Core-Mantle Interaction from Fe/Mn Ratios

NASA Astrophysics Data System (ADS)

Humayun, M.; Qin, L.

2003-12-01

The greater density of liquid iron alloy, and its immiscibility with silicate, maintains the physical separation of the core from the mantle. There are no a priori reasons, however, why the Earth's mantle should be chemically isolated from the core. Osmium isotopic variations in mantle plumes have been interpreted in terms of interaction between outer core and the source regions of deep mantle plumes. If chemical transport occurs across the core-mantle boundary its mechanism remains to be established. The Os isotope evidence has also been interpreted as the signatures of subducted Mn-sediments, which are known to have relatively high Pt/Os. In the mantle, Fe occurs mainly as the divalent ferrous ion, and Mn occurs solely as a divalent ion, and both behave in a geochemically coherent manner because of similarity in ionic charge and radius. Thus, the Fe/Mn ratio is a planetary constant insensitive to processes of mantle differentiation by partial melting. Two processes may perturb the ambient mantle Fe/Mn of 60: a) the subduction of Mn-sediments should decrease the Fe/Mn ratio in plume sources, while b) chemical transport from the outer core may increase the Fe/Mn ratio. The differentiation of the liquid outer core to form the solid inner core may increase abundances of the light element constituents (FeS, FeO, etc.) to the point of exsolution from the core at the CMB. The exact rate of this process is determined by the rate of inner core growth. Two end-member models include 1) inner core formation mainly prior to 3.5 Ga with heat release dominated by radioactive sources, or 2) inner core formation occurring mainly in the last 1.5 Ga with heat release dominated by latent heat. This latter model would imply large fluxes of Fe into the sources of modern mantle plumes. Existing Fe/Mn data for Gorgona and Hawaiian samples place limits on both these processes. We describe a new procedure for the precise determination of the Fe/Mn ratio in magmatic rocks by ICP-MS. This

Site occupancy trend of Co in Ni{sub 2}MnIn: Ab initio approach

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

Pal, Soumyadipta, E-mail: soumyadipta.pal@gmail.com; Mahadevan, Priya; Biswas, C.

2015-06-24

The trend of site occupation of Co at Ni sites of Ni{sub 2}MnIn system is studied in austenitic phase having L2{sub 1} structure by ab initio density functional theory (DFT) calculation. The Co atoms prefer to be at Ni sites rather than Mn site and are ferromagetically coupled with Ni and Mn. The ground state has tetragonal structure for Ni{sub 1.5}Co{sub 0.5}MnIn and Ni{sub 1.25}Co{sub 0.75}MnIn. The Co tends to form cluster.

Control of the transition between Ni-C and Ni-SI(a) states by the redox state of the proximal Fe-S cluster in the catalytic cycle of [NiFe] hydrogenase.

PubMed

Tai, Hulin; Nishikawa, Koji; Suzuki, Masayuki; Higuchi, Yoshiki; Hirota, Shun

2014-12-08

[NiFe] hydrogenase catalyzes the reversible cleavage of H2. The electrons produced by the H2 cleavage pass through three Fe-S clusters in [NiFe] hydrogenase to its redox partner. It has been reported that the Ni-SI(a), Ni-C, and Ni-R states of [NiFe] hydrogenase are involved in the catalytic cycle, although the mechanism and regulation of the transition between the Ni-C and Ni-SI(a) states remain unrevealed. In this study, the FT-IR spectra under light irradiation at 138-198 K show that the Ni-L state of [NiFe] hydrogenase is an intermediate between the transition of the Ni-C and Ni-SI(a) states. The transition of the Ni-C state to the Ni-SI(a) state occurred when the proximal [Fe4S4]p(2+/+) cluster was oxidized, but not when it was reduced. These results show that the catalytic cycle of [NiFe] hydrogenase is controlled by the redox state of its [Fe4S4]p(2+/+) cluster, which may function as a gate for the electron flow from the NiFe active site to the redox partner. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kineococcus radiotolerans Dps forms a heteronuclear Mn-Fe ferroxidase center that may explain the Mn-dependent protection against oxidative stress.

PubMed

Ardini, Matteo; Fiorillo, Annarita; Fittipaldi, Maria; Stefanini, Simonetta; Gatteschi, Dante; Ilari, Andrea; Chiancone, Emilia

2013-06-01

The ferroxidase center of DNA-binding protein from starved cells (Dps) is a major player in the iron oxidation/detoxification process that leads to a decreased reactive oxygen species production. The possible Mn(II) participation in this process has been studied in Dps from Kineococcus radiotolerans, a radiation-resistant bacterium with a high cytosolic Mn/Fe ratio and a high capacity to survive ionizing and stress conditions. The X-ray structure of recombinant K. radiotolerans Dps loaded with Mn(II) has been solved at 2.0Å resolution. Mn(II) binding to K. radiotolerans Dps and its effect on Fe(II) oxidation have been characterized in spectroscopic measurements. In K. radiotolerans Dps, the Fe-Fe ferroxidase center can have a Mn-Fe composition. Mn(II) binds only at the high affinity, so-called A site, whereas Fe(II) binds also at the low affinity, so-called B site. The Mn-Fe and Fe-Fe centers behave distinctly upon iron oxidation by O2. A site-bound Mn(II) or Fe(II) plays a catalytic role, while B site-bound Fe(II) behaves like a substrate and can be replaced by another Fe(II) after oxidation. When H2O2 is the Fe(II) oxidant, single electrons are transferred to aromatic residues near the ferroxidase center and give rise to intra-protein radicals thereby limiting OH release in solution. The presence of the Mn-Fe center results in significant differences in the development of such intra-protein radicals. Mn(II) bound at the Dps ferroxidase center A site undergoes redox cycling provided the B site contains Fe. The results provide a likely molecular mechanism for the protective role of Mn(II) under oxidative stress conditions as it participates in redox cycling in the hetero-binuclear ferroxidase center. Copyright © 2013 Elsevier B.V. All rights reserved.

Hierachical Ni@Fe2O3 superparticles through epitaxial growth of γ-Fe2O3 nanorods on in situ formed Ni nanoplates

NASA Astrophysics Data System (ADS)

Tahir, Muhammad Nawaz; Herzberger, Jana; Natalio, Filipe; Köhler, Oskar; Branscheid, Robert; Mugnaioli, Enrico; Ksenofontov, Vadim; Panthöfer, Martin; Kolb, Ute; Frey, Holger; Tremel, Wolfgang

2016-05-01

One endeavour of nanochemistry is the bottom-up synthesis of functional mesoscale structures from basic building blocks. We report a one-pot wet chemical synthesis of Ni@γ-Fe2O3 superparticles containing Ni cores densely covered with highly oriented γ-Fe2O3 (maghemite) nanorods (NRs) by controlled reduction/decomposition of nickel acetate (Ni(ac)2) and Fe(CO)5. Automated diffraction tomography (ADT) of the Ni-Fe2O3 interface in combination with Mössbauer spectroscopy showed that selective and oriented growth of the γ-Fe2O3 nanorods on the Ni core is facilitated through the formation of a Fe0.05Ni0.95 alloy and the appearance of superstructure features that may reduce strain at the Ni-Fe2O3 interface. The common orientation of the maghemite nanorods on the Ni core of the superparticles leads to a greatly enhanced magnetization. After functionalization with a catechol-functional polyethylene glycol (C-PEG) ligand the Ni@γ-Fe2O3 superparticles were dispersible in water.One endeavour of nanochemistry is the bottom-up synthesis of functional mesoscale structures from basic building blocks. We report a one-pot wet chemical synthesis of Ni@γ-Fe2O3 superparticles containing Ni cores densely covered with highly oriented γ-Fe2O3 (maghemite) nanorods (NRs) by controlled reduction/decomposition of nickel acetate (Ni(ac)2) and Fe(CO)5. Automated diffraction tomography (ADT) of the Ni-Fe2O3 interface in combination with Mössbauer spectroscopy showed that selective and oriented growth of the γ-Fe2O3 nanorods on the Ni core is facilitated through the formation of a Fe0.05Ni0.95 alloy and the appearance of superstructure features that may reduce strain at the Ni-Fe2O3 interface. The common orientation of the maghemite nanorods on the Ni core of the superparticles leads to a greatly enhanced magnetization. After functionalization with a catechol-functional polyethylene glycol (C-PEG) ligand the Ni@γ-Fe2O3 superparticles were dispersible in water. Electronic supplementary

The effect of Fe2NiO4 and Fe4NiO4Zn magnetic nanoparticles on anaerobic digestion activity.

PubMed

Chen, Jian Lin; Steele, Terry W J; Stuckey, David C

2018-06-11

Two types of magnetic nanoparticles (MNPs), i.e. Ni ferrite nanoparticles (Fe 2 NiO 4 ) and Ni Zn ferrite nanoparticles (Fe 4 NiO 4 Zn) containing the trace metals Ni and Fe, were added to the anaerobic digestion of synthetic municipal wastewater at concentrations between 1 and 100 mg Ni L -1 in order to compare their effects on biogas (methane) production and sludge activity. Using the production of methane over time as a measure, the assays revealed that anaerobic digestion was stimulated by the addition of 100 mg Ni L -1 in Fe 2 NiO 4 NPs, while it was inhibited by the addition of 1-100 mg Ni L -1 in Fe 4 NiO 4 Zn NPs. Especially at 100 mg Ni L -1 , Fe 4 NiO 4 Zn NPs resulted in a total inhibition of anaerobic digestion. The metabolic activity of the anaerobic sludge was tested using the resazurin reduction assay, and the assay clearly revealed the negative effect of Fe 4 NiO 4 Zn NPs and the positive effect of Fe 2 NiO 4 NPs. Re-feeding fresh synthetic medium reactivated the NPs added to the anaerobic sludge, except for the experiment with 100 mg Ni L -1 addition of Fe 4 NiO 4 Zn NPs. The findings in this present study indicate a possible new strategy for NPs design to enhance anaerobic digestion. Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.

Synthesis and characterization of mesoporous and hollow-mesoporous MxFe3-xO4 (M=Mg, Mn, Fe, Co, Ni, Cu, Zn) microspheres for microwave-triggered controllable drug delivery

NASA Astrophysics Data System (ADS)

Chen, Ping; Cui, Bin; Bu, Yumei; Yang, Zhenfeng; Wang, Yaoyu

2017-12-01

Spinel ferrites can be used in magnetic targeting and microwave heating and can therefore be used for targeted and controllable drug delivery. We used the cetyltrimethylammonium bromide-assisted solvothermal method to synthesize a series of spinel ferrites (MxFe3-xO4, M=Mg, Mn, Fe, Co, Ni, Cu, Zn) with a mesoporous or hollow-mesoporous structure suitable for direct drug loading and the particle diameters ranging from 200 to 350 nm. We investigated the effects of M2+ cation on the morphology and properties of these products by analyzing their transmission electron microscopy images, mesoporous properties, magnetic properties, and microwave responses. We chose hollow-mesoporous MxFe3-xO4 (M=Fe, Co, Zn) nanoparticles, which had better overall properties, for the drug VP16 (etoposide) loading and microwave-controlled release. The CoxFe3-xO4 and Fe3O4 particles trapped 61.5 and 64.8%, respectively, of the VP16, which were higher than that (60.4%) of ZnxFe3-xO4. Controllable drug release by these simple magnetic nanocarriers can be achieved by microwave irradiation, and VP16-loaded CoxFe3-xO4 released the most VP16 molecules (more than 50% after 1 h and 69.1% after 6 h) under microwave irradiation. Our results confirm the favorable drug loading and microwave-controlled delivery by these ferrites, and lay a theoretical foundation to promote clinical application of the targeted controllable drug delivery system. [Figure not available: see fulltext.

Solid-state reactions during mechanical alloying of ternary Fe-Al-X (X=Ni, Mn, Cu, Ti, Cr, B, Si) systems: A review

NASA Astrophysics Data System (ADS)

Hadef, Fatma

2016-12-01

The last decade has witnessed an intensive research in the field of nanocrystalline materials due to their enhanced properties. A lot of processing techniques were developed in order to synthesis these novel materials, among them mechanical alloying or high-energy ball milling. In fact, mechanical alloying is one of the most common operations in the processing of solids. It can be used to quickly and easily synthesize a variety of technologically useful materials which are very difficult to manufacture by other techniques. One advantage of MA over many other techniques is that is a solid state technique and consequently problems associated with melting and solidification are bypassed. Special attention is being paid to the synthesis of alloys through reactions mainly occurring in solid state in many metallic ternary Fe-Al-X systems, in order to improve mainly Fe-Al structural and mechanical properties. The results show that nanocrystallization is the common result occurring in all systems during MA process. The aim of this work is to illustrate the uniqueness of MA process to induce phase transformation in metallic Fe-Al-X (X=Ni, Mn, Cu, Ti, Cr, B, Si) systems.

Comparative study on the physical properties of transition metal-doped (Co, Ni, Fe, and Mn) ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Azab, A. A.; Ateia, Ebtesam E.; Esmail, S. A.

2018-07-01

Nano-crystalline of TM-doped ZnO with general formula Zn0.97TM0.03O (TM: Mn, Fe, Co, and Ni) was prepared using sol-gel method. The dependence of crystal structure, morphology, and optical and magnetic properties on the type of transition metals was investigated. The XRD investigation of pure and TM-doped ZnO nanoparticles samples confirms the formation of single-phase hexagonal wurtzite structure. The estimated crystallite sizes are found in the range of 17 and 38 nm for the doped and pure samples, respectively. The obtained data suggest that the dopant type plays a vital role in the physical properties of the investigated samples. The optical band-gap energy Eg has been calculated from near infrared (NIR) and visible (VIS) reflectance spectra using the Kubelka-Munk function. Minimum value of 2.398 eV and maximum one of 3.29 eV were obtained for Manganese-doped ZnO and pure ZnO, respectively. The analysis of XRD and VSM of the samples confirms that the observed room-temperature (RT) ferromagnetism can be attributed to an intrinsic property of doped material sample and not due to formation of any secondary phase. The magnetic results show that Mn is the most effective dopant for producing ferromagnetism in nanoparticles of ZnO.

Characterization of Ni-Mn-Ga alloy with Gd addition

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

Zhang, Z.Y.; Du, Z.W.; Shao, B.L.

2008-08-15

The effect of rare earth element Gd additions in an Ni-Mn-Ga alloy on magnetocaloric effect has previously been investigated. In this paper, the microstructure of Ni{sub 53.4}Mn{sub 20}Ga{sub 25.6}Gd{sub 1} was studied by TEM. The results show that Gd partly dissolves in the matrix and partly occurs as precipitates such as Gd and Ni-rich Ni-Mn-Ga-Gd quaternary phases. At room temperature, the alloy is mainly composed of non-modulated martensite with a small amount of seven-layered and ten-layered modulated martensite. The high-resolution electron microscopy (HREM) images also reveal that some layered structures in certain zones are microtwins in nature with a thicknessmore » of a few atomic planes as the stacking sequence is not periodic.« less

Tuning static and dynamic properties of FeGa/NiFe heterostructures

NASA Astrophysics Data System (ADS)

Rementer, Colin R.; Fitzell, Kevin; Xu, Qiang; Nordeen, Paul; Carman, Gregory P.; Wang, Yuanxun E.; Chang, Jane P.

2017-06-01

In this work, the frequency-dependent magnetic properties of sputtered Galfenol/Permalloy (Fe85Ga15/Ni81Fe19 or FeGa/NiFe) magnetic multilayers were examined to tailor their magnetic softness, loss at microwave frequencies, permeability, and magnetoelasticity, leveraging the magnetic softness and low loss of NiFe and the high saturation magnetostriction (λs) and magnetization (MS) of FeGa. The total volume of each material and their ratio were kept constant, and the number of alternating layers was increased (with decreasing individual layer thickness) to assess the role of increasing interfaces in these magnetic heterostructures. A systematic change was observed as the number of bilayers or interfaces increases: a seven-bilayer structure results in an 88% reduction in coercivity and a 55% reduction in ferromagnetic resonance linewidth at the X-band compared to a single phase FeGa film, while maintaining a high relative permeability of 700. The magnetostriction was slightly reduced by the addition of NiFe but was still maintained at up to 67% that of single phase FeGa. The tunability of these magnetic heterostructures makes them excellent candidates for RF magnetic applications requiring strong magnetoelastic coupling and low loss.

Engineering of high performance supercapacitor electrode based on Fe-Ni/Fe{sub 2}O{sub 3}-NiO core/shell hybrid nanostructures

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

Singh, Ashutosh K., E-mail: ashuvishen@gmail.com, E-mail: aksingh@bose.res.in; Mandal, Kalyan

The present work reports on fabrication and supercapacitor applications of a core/shell Fe-Ni/Fe{sub 2}O{sub 3}-NiO hybrid nanostructures (HNs) electrode. The core/shell Fe-Ni/Fe{sub 2}O{sub 3}-NiO hybrid nanostructures have been fabricated through a two step method (nanowire fabrication and their controlled oxidation). The 1D hybrid nanostructure consists of highly porous shell layer (redox active materials NiO and Fe{sub 2}O{sub 3}) and the conductive core (FeNi nanowire). Thus, the highly porous shell layer allows facile electrolyte diffusion as well as faster redox reaction kinetics; whereas the conductive FeNi nanowire core provides the proficient express way for electrons to travel to the current collector,more » which helps in the superior electrochemical performance. The core/shell Fe-Ni/Fe{sub 2}O{sub 3}-NiO hybrid nanostructures electrode based supercapacitor shows very good electrochemical performances in terms of high specific capacitance nearly 1415 F g{sup −1} at a current density of 2.5 A g{sup −1}, excellent cycling stability and rate capability. The high quality electrochemical performance of core/shell hybrid nanostructures electrode shows its potential as an alternative electrode for forthcoming supercapacitor devices.« less

Connecting [NiFe]- and [FeFe]-Hydrogenases: Mixed-Valence Nickel-Iron Dithiolates With Rotated Structures

PubMed Central

Schilter, David; Rauchfuss, Thomas B.; Stein, Matthias

2012-01-01

A series of mixed-valence iron-nickel dithiolates is described that exhibits structures similar to those of mixed-valence diiron dithiolates. Interaction of tricarbonyl salt [(dppe)Ni(pdt)Fe(CO)3]BF4 ([1]BF4, dppe = Ph2PCH2CH2PPh2, pdtH2 = HSCH2CH2CH2SH) with P-donor ligands (L) afforded the substituted derivatives [(dppe)Ni(pdt)Fe(CO)2L]BF4 incorporating L = PHCy2 ([1a]BF4), PPh(NEt2)2 ([1b]BF4), P(NMe2)3 ([1c]BF4), P(i-Pr)3 ([1d]BF4) and PCy3 ([1e]BF4). The related precursor [(dcpe)Ni(pdt)Fe(CO)3]BF4 ([2]BF4, dcpe = Cy2PCH2CH2PCy2) gave the more electron-rich family of compounds [(dcpe)Ni(pdt)Fe(CO)2L]BF4 for L = PPh2(2-pyridyl) ([2a]BF4), PPh3 ([2b]BF4) and PCy3 ([2c]BF4). For bulky and strongly basic monophosphorus ligands, the salts feature distorted Fe coordination geometries: crystallographic analyses of [1e]BF4 and [2c]BF4 showed they adopt ‘rotated’ Fe(I) centers, in which PCy3 occupies a basal site and one CO ligand partially bridges the Ni and Fe centers. Like the undistorted mixed-valence derivatives, the new class of complexes are described as Ni(II)Fe(I) (S = ½) systems according to EPR spectroscopy, although with attenuated 31P hyperfine interactions. DFT calculations using the BP86, B3LYP, and PBE0 exchange-correlation functionals agree with the structural and spectroscopic data, suggesting that the spin for [1e]+ is localized in a Fe(I)-centered d(z2) orbital, orthogonal to the Fe-P bond. The PCy3 complexes, rare examples of species featuring ‘rotated’ Fe centers, both structurally and spectroscopically resemble mixed-valence diiron dithiolates. Also reproducing the NiS2Fe core of the [NiFe]-H2ase active site, the hybrid models incorporate key features of the two major classes of H2ase. Furthermore, cyclic voltammetry experiments suggest that the highly basic phosphine ligands enable a second oxidation corresponding to the couple [(dxpe)Ni(pdt)Fe(CO)2L]+/2+. The resulting unsaturated 32e− dications represent the closest approach to

Mechanical properties, microstructure and thermal stability of a nanocrystalline CoCrFeMnNi high-entropy alloy after severe plastic deformation

DOE PAGES

Schuh, B.; Mendez-Martin, F.; Völker, B.; ...

2015-06-24

An equiatomic CoCrFeMnNi high-entropy alloy (HEA), produced by arc melting and drop casting, was subjected to severe plastic deformation (SPD) using high-pressure torsion. This process induced substantial grain refinement in the coarse-grained casting leading to a grain size of approximately 50 nm. As a result, strength increased significantly to 1950 MPa, and hardness to similar to 520 MV. Analyses using transmission electron microscopy (TEM) and 3-dimensional atom probe tomography (3D-APT) showed that, after SPD, the alloy remained a true single-phase solid solution down to the atomic scale. Subsequent investigations characterized the evolution of mechanical properties and microstructure of this nanocrystallinemore » HEA upon annealing. Isochronal (for 1 h) and isothermal heat treatments were performed followed by microhardness and tensile tests. The isochronal anneals led to a marked hardness increase with a maximum hardness of similar to 630 HV at about 450 degrees C before softening set in at higher temperatures. The isothermal anneals, performed at this peak hardness temperature, revealed an additional hardness rise to a maximum of about 910 MV after 100 h. To clarify this unexpected annealing response, comprehensive microstructural analyses were performed using TEM and 3D-APT. New nano-scale phases were observed to form in the originally single-phase HEA. After times as short as 5 min at 450 degrees C, a NiMn phase and Cr-rich phase formed. With increasing annealing time, their volume fractions increased and a third phase, FeCo, also formed. It appears that the surfeit of grain boundaries in the nanocrystalline HEA offer many fast diffusion pathways and nucleation sites to facilitate this phase decomposition. The hardness increase, especially for the longer annealing times, can be attributed to these nano-scaled phases embedded in the HEA matrix. The present results give new valuable insights into the phase stability of single-phase high-entropy alloys as

Galvanostatically deposited Fe: MnO2 electrodes for supercapacitor application

NASA Astrophysics Data System (ADS)

Dubal, D. P.; Kim, W. B.; Lokhande, C. D.

2012-01-01

The present investigation describes the addition of iron (Fe) in order to improve the supercapacitive properties of MnO2 electrodes using galvanostatic mode. These amorphous worm like Fe: MnO2 electrodes are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR) and wettability test. The supercapacitive properties of MnO2 and Fe: MnO2 electrodes are investigated using cyclic voltammetry, chronopotentiometry and impedance techniques. It is seen that the supercapacitance increases with increase in Fe doping concentration and achieved a maximum of 173 F g-1 at 2 at% Fe doping. The maximum supercapacitance obtained is 218 F g-1 for 2 at% Fe: MnO2 electrode. This hydrous binary oxide exhibited ideal capacitive behavior with high reversibility and high pulse charge-discharge property between -0.1 and +0.9 V/SCE in 1 M Na2SO4 electrolyte indicating a promising electrode material for electrochemical supercapacitors.

Soft x-ray absorption spectroscopy study of the electronic structures of the MnFe Prussian blue analogs (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] H2O

NASA Astrophysics Data System (ADS)

Lee, Eunsook; Seong, Seungho; Kim, Hyun Woo; Kim, D. H.; Thakur, Nidhi; Yusuf, S. M.; Kim, Bongjae; Min, B. I.; Kim, Younghak; Kim, J.-Y.; de Groot, F. M. F.; Kang, J.-S.

2017-11-01

The electronic structures of Prussian blue analog (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] cyanides have been investigated by employing soft x-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) at the Fe and Mn L (2 p ) edges. The measured XAS spectra have been analyzed with the configuration-interaction (CI) cluster model calculations. The valence states of the Fe and Mn ions are found to be Fe2 +-Fe3 + mixed valent, with an average valency of v (Fe )˜2.8 and nearly divalent (Mn2 +), respectively. Our Mn/Fe 2 p XMCD study supports that Mn2 + ions are in the high-spin states while Fe2 +-Fe3 + ions are in the low-spin states. The Fe and Mn 2 p XAS spectra are found to be essentially the same for 80 ≤T ≤ 300 K, suggesting that a simple charge transfer upon cooling from Fe3 +-CN -Mn2 + to Fe2 +-CN -Mn3 + does not occur in (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] . According to the CI cluster model analysis, it is necessary to take into account both the ligand-to-metal charge transfer and the metal-to-ligand charge transfer in describing Fe 2 p XAS, while the effect of charge transfer is negligible in describing Mn 2 p XAS. The CI cluster model analysis also shows that the trivalent Fe3 + ions have a strong covalent bonding with the C ≡N ligands and are under a large crystal-field energy of 10 D q ˜3 eV, in contrast to the weak covalency effect and a small 10 D q ˜0.6 eV for the divalent Mn2 + ions.

Giant magnetic coercivity in CaCu{sub 5}-type SmNi{sub 3}TSi (T=Mn–Cu) solid solutions

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

Yao, Jinlei; Yan, Xu; Morozkin, A.V., E-mail: morozkin@tech.chem.msu.ru

The effects of transition metal substitution for Ni on the magnetic properties of the CaCu{sub 5}-type SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) solid solutions have been investigated. SmNi{sub 3}MnSi, SmNi{sub 3}FeSi, SmNi{sub 3}CoSi and SmNi{sub 3}CuSi show ferromagnetic ordering at 125 K, 190 K, 46 K and 12 K and field induced transitions at 65 K, 110 K, 30 K and 6 K, respectively. The magnetocaloric effects of SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) were calculated in terms of isothermal magnetic entropy change (ΔS{sub m}). The magnetic entropy ΔS{sub m} reaches value of −1.1 J/kg K at 130 K formore » SmNi{sub 3}MnSi, −0.4 J/kg K at 180 K for SmNi{sub 3}FeSi, −0.37 J/kg K at 45 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 12 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the ferromagnetic ordering temperature. They show positive ΔS{sub m} of +2.4 J/kg K at 30 K for SmNi{sub 3}MnSi, −2.6 J/kg K at 65 K for SmNi{sub 3}FeSi, +0.73 J/kg K at 15 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 6 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the metamagnetic-like transition temperature. Below the field induced transition temperature, SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) exhibits giant magnetic coercivity of 80 kOe at 20 K for SmNi{sub 3}MnSi, 87 kOe at 40 K for SmNi{sub 3}FeSi, 27 kOe at 20 K for SmNi{sub 3}CoSi and 54 kOe at 5 K for SmNi{sub 3}CuSi. - Graphical abstract: CaCu{sub 5}-type SmNi{sub 3}MnSi, SmNi{sub 3}FeSi, SmNi{sub 3}CoSi and SmNi{sub 3}CuSi show ferromagnetic ordering at 125 K, 190 K, 46 K and 12 K and field induced transitions at 65 K, 110 K, 30 K and 6 K, respectively. The magnetic entropy ΔS{sub m} reaches value of −1.1 J/kg K at 130 K for SmNi{sub 3}MnSi, −0.4 J/kg K at 180 K for SmNi{sub 3}FeSi, −0.37 J/kg K at 45 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 12 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the ferromagnetic ordering temperature. They show positive ΔS{sub m} of +2.4 J/kg K at 30 K for SmNi{sub 3}Mn

The 3D Distribution of Dissolved and Colloidal Fe, Mn, Zn, Cu, Ni, Cd and Pb in the Western Antarctic Peninsula Shelf Region; Implications for Natural Fe Fertilization

NASA Astrophysics Data System (ADS)

Sherrell, R. M.; Fitzsimmons, J. N.; Roccanova, J.; Schofield, O.; Meredith, M. P.

2016-02-01

The Western Antarctic Peninsula (WAP) shelf region is is a natural Fe fertilization zone where primary production exceeds that of the adjacent open Southern Ocean. Until recently, however, distributions of Fe and of other bioactive metals were completely lacking for the WAP, and the sources and delivery mechanisms of Fe to the euphotic zone were only speculated upon. We have previously presented surface water (2m) dissolved (dTM, <0.2µm) and particulate (pTM, >0.45µm) distributions for Fe and a suite of other bioactive metals over the WAP shelf, covering the Palmer LTER sampling grid for Jan. 2010, 2011 and 2012. We now report the first complete 3D distribution of dissolved and colloidal Fe (and Mn, Zn, Cu, Ni, Cd and Pb) over the LTER grid in Jan. 2015, allowing assessment of dFe size speciation, sources and transport pathways in this dynamic shelf system. Dissolved metals were analyzed by automated offline preconcentration (seaFAST-pico, ESI) followed by sector-field ICP-MS. We confirm previous findings of low ( 0.1nM) dFe in surface waters on the mid-outer shelf in the northern portion of the grid, and now find that concentrations at this level or below persist through the euphotic zone. However, dFe increases rapidly with depth, with low surface values underlain by substantially higher concentrations even at 50m. Inner shelf surface waters are generally substantially > 0.1nM, suggesting Fe replete conditions in this region. Vertical profiles reveal that dFe generally increases with depth, much moreso in the inner shelf (dFe up to 5.0nM) than the outer shelf. A general N-S gradient in dFe is also evident, with concentrations higher in the southern WAP, especially in Marguerite Bay. In addition, shelf stations often show a dFe maximum suggesting remineralization from sinking biogenic particles. These findings for dFe and for the other metals, will be used to help unravel the biogeochemical workings of natural Fe fertilization in this region.

Microbially-induced Fe and Mn oxides in condensed pelagic sediments (Middle-Upper Jurassic, Western Sicily)

NASA Astrophysics Data System (ADS)

Préat, A.; Mamet, B.; Di Stefano, P.; Martire, L.; Kolo, K.

2011-06-01

This article presents a petrographic comparison of the Rosso Ammonitico facies of Western Sicily and the original Rosso Ammonitico Veronese of Northern Italy based on a total of 27 sections. The Rosso Ammonitico has been the subject of numerous controversies that range from bathyal to shallow-water platform sedimentation. Therefore it seemed interesting to verify if the term Rosso Ammonitico has the same geologic connotation from region to region. The Middle-Upper Jurassic Rosso Ammonitico of Western Sicily is a condensed succession formed during a period of extensional synsedimentary tectonics related to the spreading of the Ionian Ocean. Slope-to-basin or pelagic carbonate deposits characterize the sedimentation which consists of reddish mudstones and wackestones. The abundant fauna is composed of radiolarians, protoglobigerinids, Saccocoma, Bositra associated with ammonites. A few ferruginous hardgrounds, Fe-Mn oxide crusts and Mn-coated condensation horizons are also present. The red matrices contain abundant Fe-Mn encrusted, microbored and bioeroded bioclasts. Sporadic Fe-Mn oncolites composed of amorphous Mn-minerals and goethite are also conspicuous. The matrix, as well as the shells and the fillings of the complex associated veinlets, are frequently altered into calcite microsparite. Submicronic iron bacterial and fungal filaments associated with mineralized extracellular polymeric substances (EPS) are observed in the matrix. They record dysaerobic microenvironments at or near the sediment-water interfaces. Early mineralized discontinuities enhanced by subsequent pressure dissolution are reported in the succession. Mn-(Ni) bacterial filaments are exceptionally observed in the cortex of the Fe-Mn oncolites. As a consequence of an early lithification, the Mn filaments are poorly preserved. The pigmentation of the rock is due to the dispersion of submicronic oxyhydroxides (now goethite and amorphous iron) formed by bacterial mediation during early diagenesis

Anomalous magnetic configuration of Mn{sub 2}NiAl ribbon and the role of hybridization in the martensitic transformation of Mn{sub 50}Ni{sub 50−x}Al{sub x} ribbons

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

Zhao, R. B.; Department of Physics, Hebei Medical University, Shijiazhuang 050017; Zhao, D. W.

2014-12-08

The magnetic configuration of Mn{sub 2}NiAl ribbon has been investigated. In contrast to Ni{sub 2}MnAl, the compound Mn{sub 2}NiAl with considerable disorder does exhibit ferromagnetism and, due to exchange interaction competition, both ferromagnetic and antiferromagnetic moment orientations can coexist between nearest neighbor Mn atoms. This is unexpected in Heusler alloys. Regarding the mechanism of the martensitic transformation in Mn{sub 50}Ni{sub 50−x}Al{sub x}, it is found that increasing the Al content results in an unusual change in the lattice constant, a decrease of the transformation entropy change, and enhancement of the calculated electron localization. These results indicate that the p-d covalentmore » hybridization between Mn (or Ni) and Al atoms gradually increases at the expense of the d-d hybridization between Ni and Mn atoms. This leads to an increased stability of the austenite phase and a decrease of the martensitic transformation temperature. For 11 ≤ x ≤ 14, Mn{sub 50}Ni{sub 50−x}Al{sub x} ferromagnetic shape memory alloys are obtained.« less

High-Strength Ultra-Fine-Grained Hypereutectic Al-Si-Fe-X (X = Cr, Mn) Alloys Prepared by Short-Term Mechanical Alloying and Spark Plasma Sintering.

PubMed

Průša, Filip; Bláhová, Markéta; Vojtěch, Dalibor; Kučera, Vojtěch; Bernatiková, Adriana; Kubatík, Tomáš František; Michalcová, Alena

2016-11-30

In this work, Al-20Si-10Fe-6Cr and Al-20Si-10Fe-6Mn (wt %) alloys were prepared by a combination of short-term mechanical alloying and spark plasma sintering. The microstructure was composed of homogeneously dispersed intermetallic particles forming composite-like structures. X-ray diffraction analysis and TEM + EDS analysis determined that the α-Al along with α-Al 15 (Fe,Cr)₃Si₂ or α-Al 15 (Fe,Mn)₃Si₂ phases were present, with dimensions below 130 nm. The highest hardness of 380 ± 7 HV5 was observed for the Al-20Si-10Fe-6Mn alloy, exceeding the hardness of the reference as-cast Al-12Si-1Cu-1 Mg-1Ni alloy (121 ± 2 HV5) by nearly a factor of three. Both of the prepared alloys showed exceptional thermal stability with the hardness remaining almost the same even after 100 h of annealing at 400 °C. Additionally, the compressive strengths of the Al-20Si-10Fe-6Cr and Al-20Si-10Fe-6Mn alloys reached 869 MPa and 887 MPa, respectively, and had virtually the same values of 870 MPa and 865 MPa, respectively, even after 100 h of annealing. More importantly, the alloys showed an increase in ductility at 400 °C, reaching several tens of percent. Thus, both of the investigated alloys showed better mechanical properties, including superior hardness, compressive strength and thermal stability, as compared to the reference Al-10Si-1Cu-1Mg-1Ni alloy, which softened remarkably, reducing its hardness by almost 50% to 63 ± 8 HV5.

High-Strength Ultra-Fine-Grained Hypereutectic Al-Si-Fe-X (X = Cr, Mn) Alloys Prepared by Short-Term Mechanical Alloying and Spark Plasma Sintering

PubMed Central

Průša, Filip; Bláhová, Markéta; Vojtěch, Dalibor; Kučera, Vojtěch; Bernatiková, Adriana; Kubatík, Tomáš František; Michalcová, Alena

2016-01-01

In this work, Al-20Si-10Fe-6Cr and Al-20Si-10Fe-6Mn (wt %) alloys were prepared by a combination of short-term mechanical alloying and spark plasma sintering. The microstructure was composed of homogeneously dispersed intermetallic particles forming composite-like structures. X-ray diffraction analysis and TEM + EDS analysis determined that the α-Al along with α-Al15(Fe,Cr)3Si2 or α-Al15(Fe,Mn)3Si2 phases were present, with dimensions below 130 nm. The highest hardness of 380 ± 7 HV5 was observed for the Al-20Si-10Fe-6Mn alloy, exceeding the hardness of the reference as-cast Al-12Si-1Cu-1 Mg-1Ni alloy (121 ± 2 HV5) by nearly a factor of three. Both of the prepared alloys showed exceptional thermal stability with the hardness remaining almost the same even after 100 h of annealing at 400 °C. Additionally, the compressive strengths of the Al-20Si-10Fe-6Cr and Al-20Si-10Fe-6Mn alloys reached 869 MPa and 887 MPa, respectively, and had virtually the same values of 870 MPa and 865 MPa, respectively, even after 100 h of annealing. More importantly, the alloys showed an increase in ductility at 400 °C, reaching several tens of percent. Thus, both of the investigated alloys showed better mechanical properties, including superior hardness, compressive strength and thermal stability, as compared to the reference Al-10Si-1Cu-1Mg-1Ni alloy, which softened remarkably, reducing its hardness by almost 50% to 63 ± 8 HV5. PMID:28774094

An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

PubMed

Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

2013-01-30

The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

Tuning Surface Electronic Configuration of NiFe LDHs Nanosheets by Introducing Cation Vacancies (Fe or Ni) as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction.

PubMed

Wang, Yanyong; Qiao, Man; Li, Yafei; Wang, Shuangyin

2018-04-01

Intrinsically inferior electrocatalytic activity of NiFe layered double hydroxides (LDHs) nanosheets is considered as a limiting factor to inhibit the electrocatalytic properties for oxygen evolution reaction (OER). Proper defect engineering to tune the surface electronic configuration of electrocatalysts may significantly improve the intrinsic activity. In this work, the selective formation of cation vacancies in NiFe LDHs nanosheets is successfully realized. The as-synthesized NiFe LDHs-V Fe and NiFe LDHs-V Ni electrocatalysts show excellent activity for OER, mainly attributed to the introduction of rich iron or nickel vacancies in NiFe LDHs nanosheets, which efficiently tune the surface electronic structure increasing the adsorbing capacity of OER intermediates. Density functional theory (DFT) computational results also further indicate that the OER catalytic performance of NiFe LDHs can be pronouncedly improved by introducing Fe or Ni vacancies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Enhanced magneto-caloric effect upon Co substitution in Ni-Mn-Sn thin films

NASA Astrophysics Data System (ADS)

Modak, Rajkumar; Raja, M. Manivel; Srinivasan, A.

2018-02-01

Mn rich Ni-Mn-Sn and Ni-Mn-Co-Sn alloy films were deposited on Si (1 0 0) substrate by dc magnetron sputtering from Ni50Mn37Sn13 alloy target at 1.8 Pa Ar pressure with 70 W dc power. Co was introduced by placing Co chips on the Ni-Mn-Sn target. As-deposited films were vacuum annealed at 823 K for 1 h. X-ray diffraction patterns of the films revealed modulated 14 M structure of the martensite phase at room temperature. Magnetic entropy change (ΔSm) across the Curie temperature of the ferromagnetic films was estimated from initial isothermal magnetization curves using Maxwell's equation. ΔSm and refrigeration capacity (RC) of Ni-Mn-Sn and Ni-Mn-Co-Sn films increased with increasing film thickness. Upon Co substitution in Mn/Sn site(s), ΔSm and RC increased more remarkably. The change is more prominent in the case of 360 nm films, wherein a 3.8-fold increase in ΔSM and 8.9-fold increase in RC was observed. Introduction of Co increased the magnetic moment and broadened the magnetic transition. These factors increased ΔSm and RC in Co substituted Ni-Mn-Sn alloy. Since TC shifted to higher temperatures with Co substitution, operating temperature of these magnetic refrigerants also shifted to higher temperature. This study indicates the possibility of developing high temperature cooling devices and waste energy harvesters using these films.

Investigation of spin-dependent transports and microstructure in NiMnSb-based magnetoresistive devices

NASA Astrophysics Data System (ADS)

Qu, Guanxiong; Cheng, P.-H.; Du, Ye; Sakuraba, Yuya; Kasai, Shinya; Hono, Kazuhiro

2017-11-01

We have fabricated fully epitaxial current-perpendicular-to-plane giant magnetoresistance (CPP-GMR) devices using C1b-half Heusler compound NiMnSb, the first candidate of the half-metallic material, as the electrode with a Ag spacer. The device shows magnetoresistance ratios of 25% at 4.2 K and 9.6% at 290 K, which are one of the highest values for the CPP-GMR with half-Heusler compounds. However, these values are much lower compared to those reported for CPP-GMR devices with L21-full Heusler compounds. Careful analysis of the microstructure using scanning transmission electron microscopy and energy dispersive spectroscopy through the upper NiMnSb/Ag interface indicates the heterogeneous formation of Ag-rich solid solution or the island growth of Ag on top of NiMnSb, which clarified a difficulty in evaluating an intrinsic spin-polarization in NiMnSb from CPP-GMR devices. Thus, to evaluate a spin-polarization of a NiMnSb thin film, we fabricated non-local spin valve (NLSV) devices using NiMnSb with Cu channel wires, which is free from the diffusion of Cu to NiMnSb because of no annealing proccess after deposition of Cu. Finally, intrinsic spin polarization of the NiMnSb single layer was extrapolated to be around 50% from NLSV, suggesting a difficulty in obtaining half-metallic nature in the NiMnSb epitaxial thin film.

Multiple resonance peaks of FeCo thin films with NiFe underlayer

NASA Astrophysics Data System (ADS)

Zhong, Xiaoxi; Soh, Wee Tee; Phuoc, Nguyen N.; Liu, Ying; Ong, C. K.

2015-01-01

Under zero external magnetic fields, single-layer FeCo thin films exhibit no ferromagnetic resonance (FMR) peaks, while multiple FMR peaks were obtained by growing FeCo thin films on NiFe underlayers with various thicknesses up to 50 nm. Comprehensive investigations of the dynamic magnetic properties and origin of the peaks were conducted through measurements of microwave permeability via a shorted microstrip perturbation technique. Through fitted values of saturation magnetization Ms, uniaxial anisotropy HKsta, and rotatable anisotropy HKrot extracted from the FMR experiments, it was found that two of the three resonance peaks originate from FeCo, and the third from NiFe. The two magnetic phases of FeCo grains are found to have different values of HKrot and explained by the exchange interaction between FeCo and NiFe grains.

A novel sandwich Fe-Mn damping alloy with ferrite shell prepared by vacuum annealing

NASA Astrophysics Data System (ADS)

Qian, Bingnan; Peng, Huabei; Wen, Yuhua

2018-04-01

To improve the corrosion resistance of high strength Fe-Mn damping alloys, we fabricated a novel sandwich Fe-17.5Mn damping alloy with Mn-depleted ferrite shell by vacuum annealing at 1100 °C. The formation behavior of the ferrite shell obeys the parabolic law for the vacuum annealed Fe-17.5Mn alloy at 1100 °C. The sandwich Fe-17.5Mn alloy with ferrite shell exhibits not only better corrosion resistance but also higher damping capacity than the conventional annealed Fe-17.5Mn alloy under argon atmosphere. The existence of only ferrite shell on the surface accounts for the better corrosion in the sandwich Fe-17.5Mn alloy. The better damping capacity in the sandwich Fe-17.5Mn alloy is owed to more stacking faults inside both ɛ martensite and γ austenite induced by the stress from ferrite shell. Vacuum annealing is a new way to improve the corrosion resistance and damping capacity of Fe-Mn damping alloys.

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.

Exchange bias of Ni nanoparticles embedded in an antiferromagnetic IrMn matrix.

PubMed

Kuerbanjiang, Balati; Wiedwald, Ulf; Haering, Felix; Biskupek, Johannes; Kaiser, Ute; Ziemann, Paul; Herr, Ulrich

2013-11-15

The magnetic properties of Ni nanoparticles (Ni-NPs) embedded in an antiferromagnetic IrMn matrix were investigated. The Ni-NPs of 8.4 nm mean diameter were synthesized by inert gas aggregation. In a second processing step, the Ni-NPs were in situ embedded in IrMn films or SiOx films under ultrahigh vacuum (UHV) conditions. Findings showed that Ni-NPs embedded in IrMn have an exchange bias field HEB = 821 Oe at 10 K, and 50 Oe at 300 K. The extracted value of the exchange energy density is 0.06 mJ m(-2) at 10 K, which is in good accordance with the results from multilayered thin film systems. The Ni-NPs embedded in SiOx did not show exchange bias. As expected for this particle size, they are superparamagnetic at T = 300 K. A direct comparison of the Ni-NPs embedded in IrMn or SiOx reveals an increase of the blocking temperature from 210 K to around 400 K. The coercivity of the Ni-NPs exchange coupled to the IrMn matrix at 10 K is 8 times larger than the value for Ni-NPs embedded in SiOx. We studied time-dependent remanent magnetization at different temperatures. The relaxation behavior is described by a magnetic viscosity model which reflects a rather flat distribution of energy barriers. Furthermore, we investigated the effects of different field cooling processes on the magnetic properties of the embedded Ni-NPs. Exchange bias values fit to model calculations which correlate the contribution of the antiferromagnetic IrMn matrix to its grain size.

Positron Annihilation Spectroscopy and Small Angle Neutron Scattering Characterization of Nanostructural Features in Irradiated Fe-Cu-Mn Alloys

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

Wirth, B D; Asoka-Kumar, P; Howell, R H

2001-01-01

Radiation embrittlement of nuclear reactor pressure vessel steels results from a high number density of nanometer sized Cu-Mn-Ni rich precipitates (CRPs) and sub-nanometer matrix features, thought to be vacancy-solute cluster complexes (VSC). However, questions exist regarding both the composition of the precipitates and the defect character and composition of the matrix features. We present results of positron annihilation spectroscopy (PAS) and small angle neutron scattering (SANS) characterization of irradiated and thermally aged Fe-Cu and Fe-Cu-Mn alloys. These complementary techniques provide insight into the composition and character of both types of nanoscale features. The SANS measurements indicate populations of CRPs andmore » VSCs in both alloys. The CRPs are coarser in the Fe-Cu alloy and the number densities of CRP and VSC increase with the addition of Mn. The PAS involved measuring both the positron lifetimes and the Doppler broadened annihilation spectra in the high momentum region to provide elemental sensitivity at the annihilation site. The spectra in Fe-Cu-Mn specimens thermally aged to peak hardness at 450 C and irradiated at 288 C are nearly identical to elemental Cu. Positron lifetime and spectrum measurements in Fe-Cu specimens irradiated at 288 C clearly show the existence of long lifetime ({approx}500 ps) open volume defects, which also contain Cu. Thus the SANS and PAS provide a self-consistent picture of nanostructures composed of CRPs and VSCs and tend to discount high Fe concentrations in the CRPs.« less

Unique coordination of pyrazine in T[Ni(CN){sub 4}].2pyz with T=Mn, Zn, Cd

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

Lemus-Santana, A.A.; Rodriguez-Hernandez, J.; Castillo, L.F. del, E-mail: lfelipe@servidor.unam.m

2009-04-15

The materials under study, T[Ni(CN){sub 4}].2pyz with T=Mn, Zn, Cd, were prepared by separation of T[Ni(CN){sub 4}] layers in citrate aqueous solution to allow the intercalation of the pyrazine molecules. The obtained solids were characterized from chemical analyses, X-ray diffraction, infrared, Raman, thermogravimetry, UV-Vis, magnetic and adsorption data. Their crystal structure was solved from ab initio using direct methods and then refined by the Rietveld method. A unique coordination for pyrazine to metal centers at neighboring layers was observed. The pyrazine molecule is found forming a bridge between Ni and T atoms, quite different from the proposed structures for T=Fe,more » Ni where it remains coordinated to two T atoms to form a vertical pillar between neighboring layers. The coordination of pyrazine to both Ni and T atoms minimizes the material free volume and leads to form a hydrophobic framework. On heating the solids remain stable up to 140 deg. C. No CO{sub 2} and H{sub 2} adsorption was observed in the small free spaces of their frameworks. - Graphical abstract: Framework for T[Ni(CN){sub 4}].2pyz with T=Mn, Zn, Cd.« less

Magnetic properties of Mn0.1Mg0.2TM0.7Fe2O4 (TM = Zn, Co, or Ni) prepared by hydrothermal processes: The effects of crystal size and chemical composition

NASA Astrophysics Data System (ADS)

Nhlapo, T. A.; Msomi, J. Z.; Moyo, T.

2018-02-01

Nano-crystalline Zn-, Co-, and Ni-substituted Mn-Mg ferrites were prepared by hydrothermal process and annealed at 1100 °C. Annealing conditions are critical on the crystalline phase. TEM and XRD data reveal particle sizes between 8 nm and 15 nm for the as-prepared fine powders, which increase to about 73 nm after sintering at 1100 °C. Mӧssbauer spectra show well resolved magnetic splitting in bulk samples. The as-prepared fine powders show weak hyperfine splitting and broad central doublets associated with fine particles. Magnetization data reveal a high coercive field at about 300 K of about 945 Oe in the Co-based nanosized oxide, which reduces to about 360 Oe after thermal annealing at 1100 °C. The magnetization curves of Zn- and Ni-based samples show much lower coercive fields indicative of superparamagnetic nanoparticles. The crystallite size and chemical composition have significant effects on the properties of Mn0.1Mg0.2(Zn,Co,Ni)0.7Fe2O4 investigated.

Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

DOE PAGES

Liu, Yifei; Göeltl, Florian; Ro, Insoo; ...

2017-06-13

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivitymore » toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to

An Effective Electrodeposition Mode for Porous MnO₂/Ni Foam Composite for Asymmetric Supercapacitors.

PubMed

Tsai, Yi-Chiun; Yang, Wein-Duo; Lee, Kuan-Ching; Huang, Chao-Ming

2016-03-30

Three kinds of MnO₂/Ni foam composite electrode with hierarchical meso-macroporous structures were prepared using potentiodynamic (PD), potentiostatic (PS), and a combination of PS and PD(PS + PD) modes of electrodeposition. The electrodeposition mode markedly influenced the surface morphological, textural, and supercapacitive properties of the MnO₂/Ni electrodes. The supercapacitive performance of the MnO₂/Ni electrode obtained via PS + PD(PS + PD(MnO₂/Ni)) was found to be superior to those of MnO₂/Ni electrodes obtained via PD and PS, respectively. Moreover, an asymmetric supercapacitor device, activated carbon (AC)/PS + PD(MnO₂/Ni), utilizing PS + PD(MnO₂/Ni) as a positive electrode and AC as a negative electrode, was fabricated. The device exhibited an energy density of 7.7 Wh·kg -1 at a power density of 600 W·kg -1 and superior cycling stability, retaining 98% of its initial capacity after 10,000 cycles. The good supercapacitive performance and excellent stability of the AC/PS + PD(MnO₂/Ni) device can be ascribed to its high surface area, hierarchical structure, and interconnected three-dimensional reticular configuration of the nickel metal support, which facilitates electrolyte ion intercalation and deintercalation at the electrode/electrolyte interface and mitigates volume change during repeated charge/discharge cycling. These results demonstrate the great potential of the combination of PS and PD modes for MnO₂ electrodeposition for the development of high-performance electrodes for supercapacitors.

Structure, reactivity and electronic properties of Mn doped Ni13 clusters

NASA Astrophysics Data System (ADS)

Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

2013-06-01

In this work we have studied the structural and magnetic properties of Ni13 cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H2 molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni12Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni12MnH2. Our analysis of the stability and HOMO-LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H2 absorption in the doped NiMnm alloy clusters. This has been reported earlier for smaller Nin clusters [1].

Effect of chitosan coating on the structural and magnetic properties of MnFe2O4 and Mn0.5Co0.5Fe2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Mdlalose, W. B.; Mokhosi, S. R.; Dlamini, S.; Moyo, T.; Singh, M.

2018-05-01

We report the influence of polymer coatings on structural and magnetic properties of MnFe2O4 and Mn0.5Co0.5Fe2O4 nanoferrites synthesized by glycol thermal technique and then coated with chitosan viz. CHI-MnFe2O4 and CHI-Mn0.5Co0.5Fe2O4. The compounds were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), high-resolution scanning electron microscopy (HRSEM), Mössbauer spectroscopy and magnetization measurements. The powder XRD patterns of naked nanoferrites confirmed single-phase spinel cubic structure with an average crystallite size of 13 nm, while the coated samples exhibited an average particle size of 15 nm. We observed a reduction in lattice parameters with coating. HRTEM results correlated well with XRD results. 57Fe Mössbauer spectra showed ordered magnetic spin states in both nanoferrites. This study shows that coatings have significant effects on the structural and magnetic properties of Mn-nanoferrites. Magnetization studies performed at room temperature in fields up to 14 kOe revealed the superparamagnetic nature of both naked and coated nanoparticles with spontaneous magnetizations at room temperature of 49.2 emu/g for MnFe2O4, 23.6 emu/g for coated CHI-MnFe2O4 nanoparticles, 63.2 emu/g for Mn0.5Co0.5Fe2O4 and 33.2 emu/g for coated CHI-Mn0.5Co0.5Fe2O4 nanoparticles. We observed reduction in coercive fields due to coating. Overall, chitosan-coated manganese and manganese-cobalt nanoferrites present as suitable candidates for biomedical applications owing to physicochemical, and magnetic properties exhibited.

Structural evolution of the double perovskites Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) upon reduction: Magnetic behavior of the uranium cations

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

Pinacca, R.M., E-mail: rmp@unsl.edu.ar; Viola, M.C.; Pedregosa, J.C.

2011-11-15

Highlights: {yields} Evolution of the double perovskites Sr{sub 2}B'UO{sub 6} upon reduction were studied by XRPD. {yields} Orthorhombic (Pnma) disordered perovskites SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} were obtained at 900 {sup o}C. {yields} U{sup 5+/4+} and Zn{sup 2+} cations are distributed at random over the octahedral positions. {yields} AFM ordering for the perovskite with B' = Zn appears below 30 K. -- Abstract: We describe the preparation of five perovskite oxides obtained upon reduction of Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) with H{sub 2}/N{sub 2} (5%/95%) at 900 {sup o}C during 8 h, and their structural characterizationmore » by X-ray powder diffraction (XRPD). During the reduction process there is a partial segregation of the elemental metal when B' = Co, Ni, Fe, and the corresponding B'O oxide when B' = Mn, Zn. Whereas the parent, oxygen stoichiometric double perovskites Sr{sub 2}B'UO{sub 6} are long-range ordered concerning B' and U cations. The crystal structures of the reduced phases, SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} with 0.37 < x < 0.27, correspond to simple, disordered perovskites; they are orthorhombic, space group Pnma (No. 62), with a full cationic disorder at the B site. Magnetic measurements performed on the phase with B' = Zn, indicate uncompensated antiferromagnetic ordering of the U{sup 5+}/U{sup 4+} sublattice below 30 K.« less

Comparing magnetostructural transitions in Ni50Mn18.75Cu6.25Ga25 and Ni49.80Mn34.66In15.54 Heusler alloys

NASA Astrophysics Data System (ADS)

Dubenko, Igor; Granovsky, Alexander; Lahderanta, Erkki; Kashirin, Maxim; Makagonov, Vladimir; Aryal, Anil; Quetz, Abdiel; Pandey, Sudip; Rodionov, Igor; Samanta, Tapas; Stadler, Shane; Mazumdar, Dipanjan; Ali, Naushad

2016-03-01

The crystal structure, magnetic and transport properties, including resistivity and thermopower, of Ni50Mn18.75Cu6.25Ga25 and Ni49.80Mn34.66In15.54 Heusler alloys were studied in the (10-400) K temperature interval. We show that their physical properties are remarkably different, thereby pointing to different origin of their magnetostructural transition (MST). A Seebeck coefficient (S) was found to pass minimum of about -20 μV/K in respect of temperature for both compounds. It was shown that MST observed for both compounds results in jump-like changes in S for Ga-based compound and jump in resistivity of about 20 and 200 μΩ cm for Ga and In -based compounds, respectively. The combined analyzes of the present results with that from literature show that the density of states at the Fermi level does not change strongly at the MST in the case of Ni-Mn-In alloys as compared to that of Ni-Mn-Ga.

The polarization of Sb overlayers on NiMnSb(100)

NASA Astrophysics Data System (ADS)

Komesu, Takashi; Borca, C. N.; Jeong, Hae-Kyung; Dowben, P. A.; Ristoiu, Delia; Nozières, J. P.; Stadler, Shane; Idzerda, Y. U.

2000-08-01

We have investigated the induced polarization of paramagnetic Sb overlayers on the Heusler alloy NiMnSb. From combined X-ray absorption spectroscopy (XAS) and spin-polarized inverse photoemission spectroscopy (SPIPES), we can assign some of the unoccupied states of the Heusler alloy NiMnSb. With increasing thickness of the Sb overlayer, there is a decline in the density of states near the Fermi energy, as expected for a semimetal overlayer on a metallic substrate. While the Sb is polarized by the ferromagnetic NiMnSb substrate, consistent with the expectations of mean field theory, the polarization at the center of the surface/overlayer Brillouin zone cannot be easily related to the induced magnetization.

Structural and electrochemical properties of iron- and nickel-substituted Li2MnO3 cathodes in charged and discharged states

NASA Astrophysics Data System (ADS)

Yuge, Ryota; Kuroshima, Sadanori; Toda, Akio; Miyazaki, Takashi; Tabuchi, Mitsuharu; Doumae, Kyosuke; Shibuya, Hideka; Tamura, Noriyuki

2017-10-01

Structural change and the charge compensation mechanism of lithium-rich layered cathode (Li1.23Fe0.15Ni0.15Mn0.46O2) in charged and discharged states were investigated. Selected area electron diffraction analysis revealed that in discharged state, an initial structure composed of a single phase of monoclinic layered rock-salt changed to a mixture of hexagonal layered rock-salt and spinel-like structures. In charged state, the spinel-like phase became dominant as transition-metal ions migrate. 57Fe Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), and Soft-XAS showed that the valence of Fe and Ni ions approximately changed from Fe3+ to Fe3.2+ and Ni2+ to Ni3.5+ during charge-discharge, although Mn ions remained as Mn4+. Various oxidation states of oxide ions such as superoxide, peroxide, and hole states have also been detected in charged state. Considering that actual discharge capacity was 255 mAh/g, the contribution to charge compensation from the valence change of Fe and Ni ions was extremely small, and it only contributed to about one-third of total capacity. Therefore, the mechanism to yield high capacity of the Li1.23Fe0.15Ni0.15Mn0.46O2 cathode relates strongly to the redox reaction of oxide ions. Moreover, the decrease in capacity during charge-discharge cycling was mainly due to the irreversible redox reaction of Mn, Fe, and oxide ions.

Compositional instability of {beta}-phase in Ni-Mn-Ga alloys

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

Chernenko, V.A.

1999-02-05

The ferromagnetic Heusler alloys of stoichiometric Ni{sub 2}MnGa and nonstoichiometric Ni-Mn-Ga chemical compositions though not containing a noble-metal, indeed, belong to {beta}-alloys which lattice stability is decided by the Hume-Rothery mechanism: electron concentration e/a measuring the decrease of the electron energy due to the pseudogap formation and size factor. The intriguing feature of Ni-Mn-Ga alloys similarly to Ti-Ni, Cu-Al-Be and Ni-Al alloys arises that transformation temperature, M{sub s}, is dramatically dependent on concentration reflecting an extremely high sensitivity of the lattice stability toward the content variation. The main purpose of present paper is an analysis of previous data concerning themore » compositional dependence of M{sub s} from the viewpoint of searching for empirical correlation between the electron concentration and stability of {beta}-phase in Ni-Mn-Ga system. This analysis will provide a confirmation of the feasibility of a reasonable explanation of seemingly random collection of alloys grouped with respect to their M{sub s} values as well as other features. The alloys of compositional range studied previously are added here to a few alloys including ones doped with V and Ge to ensure the decisive role of e/a ratio on M{sub s}. Original results about the temperature dependent resistance behavior are presented as well.« less

Porous Ni-Co-Mn oxides prisms for high performance electrochemical energy storage

NASA Astrophysics Data System (ADS)

Zhao, Jianbo; Li, Man; Li, Junru; Wei, Chengzhen; He, Yuyue; Huang, Yixuan; Li, Qiaoling

2017-12-01

Porous Ni-Co-Mn oxides prisms have been successfully synthesized via a facile route. The process involves the preparation of nickel-cobalt-manganese acetate hydroxide by a simple co-precipitation method and subsequently the thermal treatment. The as-synthesized Ni-Co-Mn oxides prisms had a large surface area (96.53 m2 g-1) and porous structure. As electrode materials for supercapacitors, porous Ni-Co-Mn oxides prisms showed a high specific capacitance of 1623.5 F g-1 at 1.0 A g-1. Moreover, the porous Ni-Co-Mn oxides prisms were also employed as positive electrode materials to assemble flexible solid-state asymmetric supercapacitors. The resulting flexible device had a maximum volumetric energy density (0.885 mW h cm-3) and power density (48.9 mW cm-3). Encouragingly, the flexible device exhibited good cycling stability with only about 2.2% loss after 5000 charge-discharge cycles and excellent mechanical stability. These results indicate that porous Ni-Co-Mn oxides prisms have the promising application in high performance electrochemical energy storage.

Insight into Ca-Substitution Effects on O3-Type NaNi1/3 Fe1/3 Mn1/3 O2 Cathode Materials for Sodium-Ion Batteries Application.

PubMed

Sun, Liqi; Xie, Yingying; Liao, Xiao-Zhen; Wang, Hong; Tan, Guoqiang; Chen, Zonghai; Ren, Yang; Gim, Jihyeon; Tang, Wan; He, Yu-Shi; Amine, Khalil; Ma, Zi-Feng

2018-04-18

O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NaNFM) is well investigated as a promising cathode material for sodium-ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali-layer distance inside the layer structure of NaNFM may benefit Na + diffusion. Herein, the effect of Ca-substitution is reported in Na sites on the structural and electrochemical properties of Na 1- x Ca x /2 NFM (x = 0, 0.05, 0.1). X-ray diffraction (XRD) patterns of the prepared Na 1- x Ca x /2 NFM samples show single α-NaFeO 2 type phase with slightly increased alkali-layer distance as Ca content increases. The cycling stabilities of Ca-substituted samples are remarkably improved. The Na 0.9 Ca 0.05 Ni 1/3 Fe 1/3 Mn 1/3 O 2 (Na 0.9 Ca 0.05 NFM) cathode delivers a capacity of 116.3 mAh g -1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3-P3-P3-O3 sequence of Na 0.9 Ca 0.05 NFM cathode during cycling. Compared to NaNMF, the Na 0.9 Ca 0.05 NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na 0.9 Ca 0.05 NFM makes it a promising material for practical applications in sodium-ion batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic properties and magnetocaloric effect in Pt doped Ni-Mn-Ga

NASA Astrophysics Data System (ADS)

Singh, Sanjay; D'Souza, S. W.; Mukherjee, K.; Kushwaha, P.; Barman, S. R.; Agarwal, Sandeep; Mukhopadhyay, P. K.; Chakrabarti, Aparna; Sampathkumaran, E. V.

2014-06-01

Large magnetocaloric effect is observed in Ni1.8Pt0.2MnGa close to room temperature. The entropy change shows a crossover from positive to negative sign at the martensite transition. It is negative above 1.6 T and its magnitude increases linearly with magnetic field. An increase in the saturation magnetic moment is observed with Pt doping in Ni2MnGa. Ab initio theoretical calculations show that the increase in magnetic moment with Pt doping in Ni2MnGa is associated with increase in the Mn and Pt local moments in the ferromagnetic ground state. The Curie temperature calculated from the exchange interaction parameters is in good agreement with experiment, showing the absence of any antiferromagnetic correlation due to Pt doping.

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

Giant magnetic-field-induced strains in polycrystalline Ni-Mn-Ga foams.

PubMed

Chmielus, M; Zhang, X X; Witherspoon, C; Dunand, D C; Müllner, P

2009-11-01

The magnetic shape-memory alloy Ni-Mn-Ga shows, in monocrystalline form, a reversible magnetic-field-induced strain (MFIS) up to 10%. This strain, which is produced by twin boundaries moving solely by internal stresses generated by magnetic anisotropy energy, can be used in actuators, sensors and energy-harvesting devices. Compared with monocrystalline Ni-Mn-Ga, fine-grained Ni-Mn-Ga is much easier to process but shows near-zero MFIS because twin boundary motion is inhibited by constraints imposed by grain boundaries. Recently, we showed that partial removal of these constraints, by introducing pores with sizes similar to grains, resulted in MFIS values of 0.12% in polycrystalline Ni-Mn-Ga foams, close to those of the best commercial magnetostrictive materials. Here, we demonstrate that introducing pores smaller than the grain size further reduces constraints and markedly increases MFIS to 2.0-8.7%. These strains, which remain stable over >200,000 cycles, are much larger than those of any polycrystalline, active material.

Coercivity scaling in antidot lattices in Fe, Ni, and NiFe thin films

NASA Astrophysics Data System (ADS)

Gräfe, Joachim; Schütz, Gisela; Goering, Eberhard J.

2016-12-01

Antidot lattices can be used to artificially engineer magnetic properties in thin films, however, a conclusive model that describes the coercivity enhancement in this class of magnetic nano-structures has so far not been found. We prepared Fe, Ni, and NiFe thin films and patterned each with 21 square antidot lattices with different geometric parameters and measured their hysteretic behavior. On the basis of this extensive dataset we are able to provide a model that can describe both the coercivity scaling over a wide range of geometric lattice parameters and the influence of different materials.

Quaternary M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4} (M = Ni, Zn, Co, Mn) ferrite oxides: Synthesis, characterization and magnetic properties

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

Ciocarlan, Radu George; Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen; Pui, Aurel, E-mail: aurel@uaic.ro

2016-09-15

Highlights: • Superparamagnetic quaternary nanoferrite (M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4,} where M = Mn, Zn, Co, Ni) were obtained. • C, O, H and metals were observed by XPS analysis. • Phases purity were confirmed by XRD diffraction and crystallite size (3–10 nm) were determind. - Abstract: We report the synthesis of M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4} (where M = Mn, Zn, Co, Ni) nanoparticles using the coprecipitation method in the presence of carboxymethyl cellulose (CMC) as the in-situ surfactant. The crystalline structure and surface morphology were examined by means of X-ray diffraction (XRD) and scanning electron microscopymore » (SEM) and it was established that the average diameter of the magnetic nanoparticles (MNPs) is in the range of 3–10 nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) show that the MNPs are activated by the hydrophilic groups of the surfactant, which coat them and enhance their stability. The vibrating sample magnetometry measurements show the superparamagnetic behavior of the nanoparticles. Due to their small crystallite size, which implies large surface area, and their functionalization with organic groups, the obtained nanoparticles could have medical and catalytic applications.« less

Thermoelastic properties of γ-Fe and γ- Fe64Ni36 alloys

NASA Astrophysics Data System (ADS)

Tsujino, N.; Nishihara, Y.; Nakajima, Y.; Takahashi, E.; Funakoshi, K.

2009-12-01

The Earth’s core consists mainly of Fe-Ni alloy. Therefore the physical property of Fe-Ni alloy is a key issue to understand the planetary core. At 1 bar, γ-Fe is known as Anti-Invar alloy which shows anomalously high thermal expansivity, while γ-Fe64Ni36 is as a typical Inver-alloy. In addition, previous studies on γ-Fe-Ni Invar-alloys reported an anomalous pressure dependence of compression behavior (e.g., Dubrovinsky et al., 2001, Nataf et al., 2006, Matsushita et al., 2008). However, these studies were conducted at limited pressure range (> 6 GPa) or low temperature (30-300 K) conditions to identify physical properties of those alloys in the planetary interior. Therefore, we performed pressure-volume-temperature (P-V-T) measurements on γ-Fe and γ-Fe-Ni alloys at a wide P-T range of 0-23 GPa and 773-1873 K using the SPEED- Mk.II kawai-type multi-anvil apparatus at the SPring-8 synchrotron facility. On the basis of 2-γ state model by Weiss (1963), the thermal expansivity of γ-Fe can be decreased significantly with pressure. Our data, however, show no anomalous variation in the thermal expansion coefficient relative to pressure up to 23 GPa. In addition, anomalous pressure dependence on volume of γ-Fe64Ni36 reported by Matsushita et al. (2008) was not observed. Fitting 3rd order Birch-Murnaghan EOS and Mie-Grüneisen-Debye EOS to the P-V-T data of γ-Fe yielded V 0 = 49.028 ± 0.027 Å 3 , K T 0 = 111.2 ± 1.8 GPa, K ’ T = 5.2 ± 0.2, γ 0 = 2.30 ± 0.04 and q = -0.09 ± 0.21 with the fixed value of θ 0 = 340 K. The P-V data of γ- Fe64Ni36 was fittied using the 3rd order Birch-Marnagan, which yields V 0 = 48.85 ± 0.06 Å 3 , K T 0 = 88.1 ± 3.4 GPa, and K ’ 0 = 8.6± 0.5 at 1273 K.

A dedicated AMS setup for 53Mn/60Fe at the Cologne FN tandem accelerator

NASA Astrophysics Data System (ADS)

Schiffer, M.; Dewald, A.; Feuerstein, C.; Altenkirch, R.; Stolz, A.; Heinze, S.

2015-10-01

Following demands for AMS measurements of medium mass isotopes, especially for 53Mn and 60Fe, we started to build a dedicated AMS setup at the Cologne FN tandem accelerator. This accelerator with a maximum terminal voltage of 10 MV can be reliably operated at a terminal voltage of 9.5 MV which corresponds to energies of 93-102 MeV for 60Fe or 53Mn beams using the 9+ or 10+ charge state. These charge states can be obtained by foil stripping with efficiencies of 30% and 20%, respectively. Energies around 100 MeV are sufficient to effectively suppress the stable isobars 60Ni and 53Cr by (dE/dx) techniques using combinations of energy degrader foils and dispersive elements like electrostatic analyzers and time of flight (TOF) systems as well as (dE/dx)E ion detectors. In this contribution we report on the actual status of the AMS setup and discuss details and expected features.

Synthesis of FeCoNi nanoparticles by galvanostatic technique

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

Budi, Setia, E-mail: setiabudi@unj.ac.id; Department of Chemistry, Faculty of Mathematics and Sciences, Universitas Negeri Jakarta, Jl. Pemuda No.10, Rawamangun, Jakarta 13220; Hafizah, Masayu Elita

Soft magnetic nanoparticles of FeCoNi have been becoming interesting objects for many researchers due to its potential application in electronic devices. One of the most promising methods for material preparation is the electrodeposition which capable of growing nanoparticles alloy directly onto the substrate. In this paper, we report our electrodeposition studies on nanoparticles synthesis using galvanostatic electrodeposition technique. Chemical composition of the synthesized FeCoNi was successfully controlled through the adjustment of the applied currents. It is revealed that the content of each element, obtained from quantitative analysis using atomic absorption spectrometer (AAS), could be modified by the adjustment of currentmore » in which Fe and Co content decreased at larger applied currents, while Ni content increased. The nanoparticles of Co-rich FeCoNi and Ni-rich FeCoNi were obtained from sulphate electrolyte at the range of applied current investigated in this work. Broad diffracted peaks in the X-ray diffractograms indicated typical nanostructures of the solid solution of FeCoNi.« less

MnFe2O4: Synthesis, morphology and electrochemical properties

NASA Astrophysics Data System (ADS)

Kulkarni, Shrikant; Thombare, Balu; Patil, Shankar

2017-05-01

MnFe2O4 has been synthesized by simple ammonia assisted co-precipitation method to obtain nanocrystalline powder. X-ray diffraction studies confirmed its crystallinity and phase purity. The MnFe2O4 calcined at 1000°C for 4 h has spinel crystal structure with Fd3m space group and lattice constant 8.511 Å. The electrode was prepared by dip coating method on stainless steel substrate and fired at 600°C for 2 h. Random shape grains of 0.2 to 1.5 micron with pores of 1-2 micron dimensions were observed in SEM images. The electrochemical studies of MnFe2O4 were carried out with 1 mole Na2SO4 electrolyte. The MnFe2O4 electrode shows highest specific capacitance of 27.53 F.g-1 and interfacial capacitance of 0.83 F.cm-2.

Internal Friction of Austenitic Fe-Mn-C-Al Alloys

NASA Astrophysics Data System (ADS)

Lee, Young-Kook; Jeong, Sohee; Kang, Jee-Hyun; Lee, Sang-Min

2017-12-01

The internal friction (IF) spectra of Fe-Mn-C-Al alloys with a face-centered-cubic (fcc) austenitic phase were measured at a wide range of temperature and frequency ( f) to understand the mechanisms of anelastic relaxations occurring particularly in Fe-Mn-C twinning-induced plasticity steels. Four IF peaks were observed at 346 K (73 °C) (P1), 389 K (116 °C) (P2), 511 K (238 °C) (P3), and 634 K (361 °C) (P4) when f was 0.1 Hz. However, when f increased to 100 Hz, whereas P1, P2, and P4 disappeared, only P3 remained without the change in peak height, but with the increased peak temperature. P3 matches well with the IF peak of Fe-high Mn-C alloys reported in the literature. The effects of chemical composition and vacancy (v) on the four IF peaks were also investigated using various alloys with different concentrations of C, Mn, Al, and vacancy. As a result, the defect pair responsible for each IF peak was found as follows: a v-v pair for P1, a C-v pair for P2, a C-C pair for P3, and a C-C-v complex (major effect) + a Mn-C pair (minor effect) for P4. These results showed that the IF peaks of Fe-Mn-C-Al alloys reported previously were caused by the reorientation of C in C-C pairs, not by the reorientation of C in Mn-C pairs.

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.

Study of the aging of LaNi 3.55Mn 0.4Al 0.3(Co 1-xFe x) 0.75 (0⩽ x⩽1) compounds in Ni-MH batteries by SEM and magnetic measurements

NASA Astrophysics Data System (ADS)

Ayari, M.; Paul-Boncour, V.; Lamloumi, J.; Percheron-Guégan, A.; Guillot, M.

2005-03-01

The study of LaNi 3.55Mn 0.4Al 0.3(Co 1-xFe x) 0.75 (0⩽ x⩽1) alloys as material for negative electrodes in Ni-MH batteries has shown that the electrochemical cycle life is strongly dependent on the amount of substituted iron. The samples have been characterized before and after 2 to 50 electrochemical cycles by scanning electron microscopy (SEM) and magnetization measurements in order to follow the decrepitation and the decomposition of the alloys. The bulk magnetic properties of the alloy show an evolution from a spin glass behaviour dominated by antiferromagnetic interactions towards a ferromagnetic behaviour as the Fe content increases. After electrochemical cycling, the alloys are partially decomposed into La hydroxide and small metallic and oxidized transition metal particles. A correlation has been established between the loss of electrochemical capacity and the alloy decomposition which reaches 45% after 50 cycles for x=1, whereas it remains limited to 10-15% for x=0 and 0.47. A model combining both SEM and magnetic results has been used to estimate the average thickness of the corrosion layer.

Photocatalytic degradation of methylene blue dye and magneto-optical studies of magnetically recyclable spinel NixMn1-xFe2O4 (x = 0.0-1.0) nanoparticles

NASA Astrophysics Data System (ADS)

Mathubala, G.; Manikandan, A.; Arul Antony, S.; Ramar, P.

2016-06-01

Nickel doped spinel manganese ferrite (NixMn1-xFe2O4: x = 0.0-1.0) nanoparticles were prepared successfully by a superficial microwave irradiation technique using urea as the fuel. Powder X-ray diffraction (XRD) analysis was recognized the configuration of single phase spinel structure of NixMn1-xFe2O4. Debye Sherrer's formula was used to calculate the average crystallite size of the samples, which were found in the range of 15-20 nm. High resolution scanning electron microscopy (HR-SEM) was used to analyze the surface morphology of the samples, which showed the particle like-morphology with smaller agglomeration, and it was also confirmed by high resolution transmission electron microscopy (HR-TEM). Energy dispersive X-ray (EDX) analysis confirmed the elemental composition, which also evidence for the formation of single pure phase. Microwave heating method produced well crystalline nature of the products, which was confirmed by selected area electron diffraction (SAED) analysis. UV-Visible diffuse reflectance spectra (DRS) were used to calculate the energy band gap and the observed values are increased slightly from 2.05 eV to 2.44 eV with increasing the Ni-dapant. Magnetic characterization of the samples were analyzed by room temperature vibrating sample magnetometer (VSM) technique and the observed magnetization (Ms) values are decreased with increasing Ni content, due to the different magnetic moments of Mn2+ and Ni2+ cations. Photocatalytic degradation (PCD) of methylene blue dye was carried out by self designed photo-catalytic reactor. It was observed that PCD efficiency is increased with increase in concentration of Ni and the sample Ni0.6Mn0.4Fe2O4 shows better photocatalytic activity (96.73%) than other samples.

Hierarchically structured MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Sun, Zhipeng; Firdoz, Shaik; Ying-Xuan Yap, Esther; Li, Lan; Lu, Xianmao

2013-05-01

We report a hierarchical Ni@MnO2 structure consisting of MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors. The Ni@MnO2 structure, which was prepared via a facile electrodeposition method, is highly porous and appears like a forest of pine trees grown vertically on a substrate. At a MnO2 mass loading of 0.35 mg cm-2, the Ni@MnO2 electrode demonstrated a specific capacitance of 1125 F g-1 that is close to the theoretical value. In addition, a remarkable high-rate performance (766 F g-1 at a discharge current density of 100 A g-1) was achieved. Electrochemical tests in a two-electrode configuration for the Ni@MnO2 structure with a high MnO2 loading of 3.6 mg cm-2 showed a low equivalent series resistance (ESR) of 1 Ω and a high specific power of 72 kW kg-1. This superior performance can be attributed to the highly porous and hierarchical structure of Ni@MnO2 that favors rapid diffusion of an electrolyte, highly conductive pathway for electron transport, and efficient material utilization.We report a hierarchical Ni@MnO2 structure consisting of MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors. The Ni@MnO2 structure, which was prepared via a facile electrodeposition method, is highly porous and appears like a forest of pine trees grown vertically on a substrate. At a MnO2 mass loading of 0.35 mg cm-2, the Ni@MnO2 electrode demonstrated a specific capacitance of 1125 F g-1 that is close to the theoretical value. In addition, a remarkable high-rate performance (766 F g-1 at a discharge current density of 100 A g-1) was achieved. Electrochemical tests in a two-electrode configuration for the Ni@MnO2 structure with a high MnO2 loading of 3.6 mg cm-2 showed a low equivalent series resistance (ESR) of 1 Ω and a high specific power of 72 kW kg-1. This superior performance can be attributed to the highly porous and hierarchical structure of Ni@MnO2 that favors rapid diffusion of an electrolyte, highly

Transition metal redox and Mn disproportional reaction in LiMn0.5Fe0.5PO4 electrodes cycled with aqueous electrolyte

NASA Astrophysics Data System (ADS)

Zhuo, Zengqing; Hu, Jiangtao; Duan, Yandong; Yang, Wanli; Pan, Feng

2016-07-01

We performed soft x-ray absorption spectroscopy (sXAS) and a quantitative analysis of the transition metal redox in the LiMn0.5Fe0.5PO4 electrodes upon electrochemical cycling. In order to circumvent the complication of the surface reactions with organic electrolyte at high potential, the LiMn0.5Fe0.5PO4 electrodes are cycled with aqueous electrolyte. The analysis of the transitional metal L-edge spectra allows a quantitative determination of the redox evolution of Mn and Fe during the electrochemical cycling. The sXAS analysis reveals the evolving Mn oxidation states in LiMn0.5Fe0.5PO4. We found that electrochemically inactive Mn2+ is formed on the electrode surface during cycling. Additionally, the signal indicates about 20% concentration of Mn4+ at the charged state, providing a strong experimental evidence of the disproportional reaction of Mn3+ to Mn2+ and Mn4+ on the surface of the charged LiMn0.5Fe0.5PO4 electrodes.

NiFe nanoparticles: a soft magnetic material?

PubMed

Margeat, Olivier; Ciuculescu, Diana; Lecante, Pierre; Respaud, Marc; Amiens, Catherine; Chaudret, Bruno

2007-03-01

Polytetrahedral NiFe nanoparticles with diameters of (2.8+/-0.3) nm have been obtained by hydrogenation of Ni[(COD)(2)] (COD=1,5-cyclooctadiene) and Fe[{N(SiMe(3))(2)}(2)] at 150 degrees C using stearic acid and hexadecylamine as stabilizing ligands. The nanoparticles are superparamagnetic at room temperature and display a blocking temperature of 17.6 K. Their anisotropy (2.7x10(5)J m(-3)) is determined to be more than two orders of magnitude higher than that of the bulk NiFe alloy (10(3)J m(-3)) and is close to that determined for Fe nanoparticles of the same size. Still, they display a magnetization of (1.69+/-0.05) mu(B) per metallic atom, identical to that of the bulk NiFe alloy. Combining the results from X-ray absorption and Mössbauer studies, we evidence a progressive enrichment in iron atoms from the core to the surface of the nanoparticles. These results are discussed in relation to both size and chemical effects. They show the main role played by the enriched Fe surface on the magnetic properties and address the feasibility of soft magnetic materials at the nanoscale.

Monte Carlo and Ab-initio calculation of TM (Ti, V, Cr, Mn, Fe, Co, Ni) doped MgH2 hydride: GGA and SIC approximation

NASA Astrophysics Data System (ADS)

Salmani, E.; Laghrissi, A.; Laamouri, R.; Benchafia, E.; Ez-Zahraouy, H.; Benyoussef, A.

2017-02-01

MgH2: TM (TM: V, Cr, Mn, Fe, Co, Ni) based dilute magnetic semiconductors (DMS) are investigated using first principle calculations. Our results show that the ferromagnetic state is stable when TM introduces magnetic moments as well as intrinsic carriers in TM: Co, V, Cr, Ti; Mg0.95TM0.05H2. Some of the DMS Ferro magnets under study exhibit a half-metallic behavior, which make them suitable for spintronic applications. The double exchange is shown to be the underlying mechanism responsible for the magnetism of such materials. The exchange interactions obtained from first principle calculations and used in a classical Ising model by a Monte Carlo approach resulted in ferromagnetic states with Curie temperatures within the ambient conditions.

MnNiO3 revisited with modern theoretical and experimental methods

NASA Astrophysics Data System (ADS)

Dzubak, Allison L.; Mitra, Chandrima; Chance, Michael; Kuhn, Stephen; Jellison, Gerald E.; Sefat, Athena S.; Krogel, Jaron T.; Reboredo, Fernando A.

2017-11-01

MnNiO3 is a strongly correlated transition metal oxide that has recently been investigated theoretically for its potential application as an oxygen-evolution photocatalyst. However, there is no experimental report on critical quantities such as the band gap or bulk modulus. Recent theoretical predictions with standard functionals such as LDA+U and HSE show large discrepancies in the band gaps (about 1.23 eV), depending on the nature of the functional used. Hence there is clearly a need for an accurate quantitative prediction of the band gap to gauge its utility as a photocatalyst. In this work, we present a diffusion quantum Monte Carlo study of the bulk properties of MnNiO3 and revisit the synthesis and experimental properties of the compound. We predict quasiparticle band gaps of 2.0(5) eV and 3.8(6) eV for the majority and minority spin channels, respectively, and an equilibrium volume of 92.8 Å3, which compares well to the experimental value of 94.4 Å3. A bulk modulus of 217 GPa is predicted for MnNiO3. We rationalize the difficulty for the formation of ordered ilmenite-type structure with specific sites for Ni and Mn to be potentially due to the formation of antisite defects that form during synthesis, which ultimately affects the physical properties of MnNiO3.

Fe-Ni-bearing serpentines from the saprolite horizon of Caribbean Ni-laterite deposits: new insights from thermodynamic calculations

NASA Astrophysics Data System (ADS)

Villanova-de-Benavent, Cristina; Domènech, Cristina; Tauler, Esperança; Galí, Salvador; Tassara, Santiago; Proenza, Joaquín A.

2017-10-01

Fe-Ni-bearing serpentine from the saprolite horizon is the main Ni ores in hydrous silicate-type Ni laterites and formed by chemical weathering of partially serpentinized ultramafic rocks under tropical conditions. During lateritization, Mg, Si, and Ni are leached from the surface and transported downwards. Fe2+ is oxidized to Fe3+ and fixed as insoluble Fe-oxyhydroxides (mostly goethite) that incorporate Ni. This Ni is later leached from goethite and incorporated in secondary serpentine and garnierite. As a result, a serpentine-dominated saprolite horizon forms over the ultramafic protolith, overlapped by a Fe-oxyhydroxide-dominated limonite horizon. The serpentine from the protolith (serpentine I) is of hydrothermal origin and yields similar Ni (0.10-0.62 wt.% NiO) and lower Fe (mostly 1.37-5.81 wt.% FeO) concentrations than the primary olivine. In contrast, Fe-Ni-bearing serpentine from the saprolite (serpentine II) shows significantly higher and variable Fe and Ni contents, typically ranging from 2.23 to 15.59 wt.% Fe2O3 and from 1.30 to 7.67 wt.% NiO, suggesting that serpentine get enriched in Fe and Ni under supergene conditions. This study presents detailed mineralogical, textural, and chemical data on this serpentine II, as well as new insights by thermodynamic calculations assuming ideal solution between Fe-, Ni- and Mg-pure serpentines. The aim is to assess if at atmospheric pressure and temperature Fe-Ni-bearing serpentine can be formed by precipitation. Results indicate that the formation of serpentine II under atmospheric pressure and temperature is thermodynamically supported, and pH, Eh, and the equilibrium constant of the reaction are the parameters that affect the results more significantly.

Eutectic equilibria in the quaternary system Fe-Cr-Mn-C

NASA Technical Reports Server (NTRS)

Nowotny, H.; Wayne, S.; Schuster, J. C.

1982-01-01

The constitution of the quaternary system, Fe-Cr-Mn-C and to a lesser extent of the quinary system, Fe-Cr-Mn-Al-C were examined for in situ composite alloy candidates. Multivariant eutectic compositions were determined from phase equilibria studies wherein M7C3 carbides (approximately 30% by volume) formed from the melt within gamma iron. An extended field of the hexagonal carbide, (Cr, Fe, Mn)7 C3, was found without undergoing transformation to the orthorhombic structure. Increasing stability for this carbide was found for higher ratios of Cr/Fe(+) Cr + Mn. Aluminum additions promoted a ferritic matrix while manganese favored the desired gamma austenitic matrix. In coexistence with the matrix phase, chromium enters preferentially the carbide phase while manganese distributes equally between the gamma matrix and the M7C3 carbide. The composition and lattice parameters of the carbide and matrix phases were determined to establish their respective stabilities.

Effect of anti-site disorder on magnetism in La2NiMnO6

NASA Astrophysics Data System (ADS)

Pal, Somnath; Sharada Govinda, Goyal, Manik; Mukherjee, Soham; Pal, Banabir; Saha, Rana; Sundaresan, A.; Jana, Somnath; Karis, Olof; Freeland, John W.; Sarma, D. D.

2018-04-01

La2NiMnO6 has been reported to exhibit a paramagnetic to ferromagnetic transition with a transition temperature of ˜260 K. However, most of its magnetic properties, such as the saturation magnetization and even the transition temperature, appear to vary considerably among different reports. This is possibly because the crystallographic structure as well as the extent of the anti-site disorder (ASD) at the Ni/Mn sites are strongly influenced by the choice of synthesis routes. There are diverse reports connecting the extent of ASD to the valencies of Ni and Mn ions, such as Ni2 +-Mn4 + and Ni3 +-Mn3 + , including suggestions of thermally induced valence transitions. Consequently, these reports arrive at very different conclusions on the mechanism behind the magnetic properties of La2NiMnO6 . To address the correlation between ASD and valency, we have carried out a comparative study of two monoclinic La2NiMnO6 polycrystals with different degrees of ASD. Using a combination of x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and magnetometry, we conclude that the valency of the transition metal ions, and the transition temperature, are insensitive to the extent of ASD. However, we find the magnetic moment decreases strongly with an increasing ASD. We attribute this effect to the introduction of antiferromagnetic interactions in the anti-site disordered regions.

Wire-type MnO2/Multilayer graphene/Ni electrode for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Hu, Minglei; Liu, Yuhao; Zhang, Min; Wei, Helin; Gao, Yihua

2016-12-01

Commercially available wearable energy storage devices need a wire-type electrode with high strength, conductivity and electrochemical performance, as well as stable structure under deformation. Herein, we report a novel wire-type electrode of hierarchically structure MnO2 on Ni wire with multilayer graphene (MGr) as a buffer layer to enhance the electrical conductivity of the MnO2 and interface contact between the MnO2 and Ni wire. Thus, the wire-type MnO2/MGr/Ni electrode has a stable and high quality interface. The wire-type supercapacitor (WSC) based on wire-type MnO2/MGr/Ni electrode exhibits good electrochemical performance, high rate capability, extraordinary flexibility, and superior cycle lifetime. Length (area, volumetric) specific capacitance of the WSC reaches 6.9 mF cm-1 (73.2 mF cm-2, 9.8 F cm-3). Maximum length (volumetric) energy density of the WSC based on MnO2/MGr/Ni reaches 0.62 μWh cm-1 (0.88 mWh cm-3). Furthermore, the WSC has a short time constant (0.5-400 ms) and exhibits minimal change in capacitance under different bending shapes.

Martensitic Transformations and Mechanical and Corrosion Properties of Fe-Mn-Si Alloys for Biodegradable Medical Implants

NASA Astrophysics Data System (ADS)

Drevet, Richard; Zhukova, Yulia; Malikova, Polina; Dubinskiy, Sergey; Korotitskiy, Andrey; Pustov, Yury; Prokoshkin, Sergey

2018-03-01

The Fe-Mn-Si alloys are promising materials for biodegradable metallic implants for temporary healing process in the human body. In this study, three different compositions are considered (Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si, all in wt pct). The phase composition analysis by XRD reveals ɛ-martensite, α-martensite, and γ-austenite in various proportions depending on the manganese amount. The DSC study shows that the starting temperature of the martensitic transformation ( M s) of the alloys decreases when the manganese content increases (416 K, 401 K, and 323 K (143 °C, 128 °C, and 50 °C) for the Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si alloys, respectively). Moreover, mechanical compression tests indicate that these alloys have a much lower Young's modulus ( E) than pure iron (220 GPa), i.e., 145, 133, and 118 GPa for the Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si alloys, respectively. The corrosion behavior of the alloys is studied in Hank's solution at 310 K (37 °C) using electrochemical experiments and weight loss measurements. The corrosion kinetics of the Fe-Mn-Si increases with the manganese content (0.48, 0.59, and 0.80 mm/year for the Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si alloys, respectively). The alloy with the highest manganese content shows the most promising properties for biomedical applications as a biodegradable and biomechanically compatible implant material.

Interfacial Ferromagnetism in LaNiO3/CaMnO3 Superlattices

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

Grutter, Alexander J.; Yang, Hao; Kirby, B. J.

2013-08-01

We observe interfacial ferromagnetism in superlattices of the paramagnetic metal LaNiO3 and the antiferromagnetic insulator CaMnO3. LaNiO3 exhibits a thickness dependent metal-insulator transition and we find the emergence of ferromagnetism to be coincident with the conducting state of LaNiO3. That is, only superlattices in which the LaNiO3 layers are metallic exhibit ferromagnetism. Using several magnetic probes, we have determined that the ferromagnetism arises in a single unit cell of CaMnO3 at the interface. Together these results suggest that ferromagnetism can be attributed to a double exchange interaction among Mn ions mediated by the adjacent itinerant metal.

Nickel recovery from electronic waste II electrodeposition of Ni and Ni-Fe alloys from diluted sulfate solutions.

PubMed

Robotin, B; Ispas, A; Coman, V; Bund, A; Ilea, P

2013-11-01

This study focuses on the electrodeposition of Ni and Ni-Fe alloys from synthetic solutions similar to those obtained by the dissolution of electron gun (an electrical component of cathode ray tubes) waste. The influence of various parameters (pH, electrolyte composition, Ni(2+)/Fe(2+) ratio, current density) on the electrodeposition process was investigated. Scanning electron microscopy (SEM) and X-ray fluorescence analysis (XRFA) were used to provide information about the obtained deposits' thickness, morphology, and elemental composition. By controlling the experimental parameters, the composition of the Ni-Fe alloys can be tailored towards specific applications. Complementarily, the differences in the nucleation mechanisms for Ni, Fe and Ni-Fe deposition from sulfate solutions have been evaluated and discussed using cyclic voltammetry and potential step chronoamperometry. The obtained results suggest a progressive nucleation mechanism for Ni, while for Fe and Ni-Fe, the obtained data points are best fitted to an instantaneous nucleation model. Copyright © 2013 Elsevier Ltd. All rights reserved.

Reverse Shape Memory Effect Related to α → γ Transformation in a Fe-Mn-Al-Ni Shape Memory Alloy

NASA Astrophysics Data System (ADS)

Peng, Huabei; Huang, Pan; Zhou, Tiannan; Wang, Shanling; Wen, Yuhua

2017-05-01

In this study, we investigated the shape memory behavior and phase transformations of solution-treated Fe43.61Mn34.74Al13.38Ni8.27 alloy between room temperature and 1173 K (900 °C). This alloy exhibits the reverse shape memory effect resulting from the phase transformation of α (bcc) → γ (fcc) between 673 K and 1073 K (400 °C and 800 °C) in addition to the shape memory effect resulting from the martensitic reverse transformation of γ' (fcc) → α (bcc) below 673 K (400 °C). There is a high density of hairpin-shaped dislocations in the α phase undergoing the martensitic reverse transformation of γ' → α. The lath γ phase, which preferentially nucleates and grows in the reversed α phase, has the same crystal orientation with the reverse-transformed γ' martensite. However, the vermiculate γ phase, which is precipitated in the α phase between lath γ phase, has different crystal orientations. The lath γ phase is beneficial to attaining better reverse shape memory effect than the vermiculate γ phase.

Exchange bias properties of 140 nm-sized dipolarly interacting circular dots with ultrafine IrMn and NiFe layers

NASA Astrophysics Data System (ADS)

Spizzo, F.; Tamisari, M.; Chinni, F.; Bonfiglioli, E.; Gerardino, A.; Barucca, G.; Bisero, D.; Fin, S.; Del Bianco, L.

2016-02-01

We studied the exchange bias effect in an array of IrMn(3 nm)/NiFe(3 nm) circular dots (size 140 nm and center-to-center distance 200 nm, as revealed by microscopy analyses), prepared on a large area (3×3 mm2) by electron beam lithography and lift-off, using dc sputtering deposition. Hysteresis loops were measured by SQUID magnetometer at increasing values of temperature T (in the 5-300 K range) after cooling from 300 K down to 5 K in zero field (ZFC mode) and in a saturating magnetic field (FC mode). The exchange bias effect disappears above T 200 K and, at each temperature, the exchange field HEX measured in ZFC is substantially lower than the FC one. Micromagnetic calculations indicate that, at room temperature, each dot is in high-remanence ground state, but magnetic dipolar interactions establish a low-remanence configuration of the array as a whole. Hence, at low temperature, following the ZFC procedure, the exchange anisotropy in the dot array is averaged out, tending to zero. However, even the FC values of HEX and of the coercivity HC are definitely smaller compared to those measured in a reference continuous film with the same stack configuration (at T=5 K, HEX 90 Oe and HC 180 Oe in the dots and HEX 1270 Oe and HC 860 Oe in the film). Our explanation is based on the proven glassy magnetic nature of the ultrathin IrMn layer, implying the existence of magnetic correlations among the spins, culminating in a collective freezing below T 100 K. We propose, also by the light of micromagnetic simulations, that the small dot size imposes a spatial constraint on the magnetic correlation length among the IrMn spins so that, even at the lowest temperature, their thermal stability, especially at the dot border, is compromised.

Template-grown NiFe/Cu/NiFe nanowires for spin transfer devices.

PubMed

Piraux, Luc; Renard, Krystel; Guillemet, Raphael; Matéfi-Tempfli, Stefan; Matéfi-Tempfli, Maria; Antohe, Vlad Andrei; Fusil, Stéphane; Bouzehouane, Karim; Cros, Vincent

2007-09-01

We have developed a new reliable method combining template synthesis and nanolithography-based contacting technique to elaborate current perpendicular-to-plane giant magnetoresistance spin valve nanowires, which are very promising for the exploration of electrical spin transfer phenomena. The method allows the electrical connection of one single nanowire in a large assembly of wires embedded in anodic porous alumina supported on Si substrate with diameters and periodicities to be controllable to a large extent. Both magnetic excitations and switching phenomena driven by a spin-polarized current were clearly demonstrated in our electrodeposited NiFe/Cu/ NiFe trilayer nanowires. This novel approach promises to be of strong interest for subsequent fabrication of phase-locked arrays of spin transfer nano-oscillators with increased output power for microwave applications.

Realization of magnetostructural coupling by modifying structural transitions in MnNiSi-CoNiGe system with a wide Curie-temperature window.

PubMed

Liu, Jun; Gong, Yuanyuan; Xu, Guizhou; Peng, Guo; Shah, Ishfaq Ahmad; Ul Hassan, Najam; Xu, Feng

2016-03-16

The magnetostructural coupling between structural and magnetic transitions leads to magneto-multifunctionalities of phase-transition alloys. Due to the increasing demands of multifunctional applications, to search for the new materials with tunable magnetostructural transformations in a large operating temperature range is important. In this work, we demonstrate that by chemically alloying MnNiSi with CoNiGe, the structural transformation temperature of MnNiSi (1200 K) is remarkably decreased by almost 1000 K. A tunable magnetostructural transformation between the paramagnetic hexagonal and ferromagnetic orthorhombic phase over a wide temperature window from 425 to 125 K is realized in (MnNiSi)1-x(CoNiGe)x system. The magnetic-field-induced magnetostructural transformation is accompanied by the high-performance magnetocaloric effect, proving that MnNiSi-CoNiGe system is a promising candidate for magnetic cooling refrigerant.

Substituting Fe for two of the four Mn ions in photosystem II-effects on water-oxidation.

PubMed

Semin, Boris K; Seibert, Michael

2016-06-01

We have investigated the interaction of Fe(II) cations with Ca-depleted PSII membranes (PSII[-Ca,4Mn]) in the dark and found that Fe(II) incubation removes 2 of 4 Mn ions from the tetranuclear Mn cluster of the photosynthetic O2-evolving complex (OEC). The reduction of Mn ions in PSII(-Ca,4Mn) by Fe(II) and the concomitant release of two Mn(II) cations is accompanied by the binding of newly generated Fe(III) in at least one vacated Mn site. Flash-induced chlorophyll (Chl) fluorescence yield measurements of this new 2Mn/nFe cluster (PSII[-Ca,2Mn,nFe]) show that charge recombination in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) occurs between Qa (-) and the remaining Mn/Fe cluster (but not YZ (●)) in the OEC, and extraction of 2 Mn occurs uniformly in all PSII complexes. No O2 evolution is observed, but the heteronuclear metal cluster in PSII(-Ca,2Mn,nFe) samples is still able to supply electrons for reduction of the exogenous electron acceptor, 2,6-dichlorophrenolindophenol, by photooxidizing water and producing H2O2 in the absence of an exogenous donor as seen previously with PSII(-Ca,4Mn). Selective extraction of Mn or Fe cations from the 2Mn/nFe heteronuclear cluster demonstrates that the high-affinity Mn-binding site is occupied by one of the iron cations. It is notable that partial water-oxidation function still occurs when only two Mn cations are present in the PSII OEC.

An Effective Electrodeposition Mode for Porous MnO2/Ni Foam Composite for Asymmetric Supercapacitors

PubMed Central

Tsai, Yi-Chiun; Yang, Wein-Duo; Lee, Kuan-Ching; Huang, Chao-Ming

2016-01-01

Three kinds of MnO2/Ni foam composite electrode with hierarchical meso-macroporous structures were prepared using potentiodynamic (PD), potentiostatic (PS), and a combination of PS and PD(PS + PD) modes of electrodeposition. The electrodeposition mode markedly influenced the surface morphological, textural, and supercapacitive properties of the MnO2/Ni electrodes. The supercapacitive performance of the MnO2/Ni electrode obtained via PS + PD(PS + PD(MnO2/Ni)) was found to be superior to those of MnO2/Ni electrodes obtained via PD and PS, respectively. Moreover, an asymmetric supercapacitor device, activated carbon (AC)/PS + PD(MnO2/Ni), utilizing PS + PD(MnO2/Ni) as a positive electrode and AC as a negative electrode, was fabricated. The device exhibited an energy density of 7.7 Wh·kg−1 at a power density of 600 W·kg−1 and superior cycling stability, retaining 98% of its initial capacity after 10,000 cycles. The good supercapacitive performance and excellent stability of the AC/PS + PD(MnO2/Ni) device can be ascribed to its high surface area, hierarchical structure, and interconnected three-dimensional reticular configuration of the nickel metal support, which facilitates electrolyte ion intercalation and deintercalation at the electrode/electrolyte interface and mitigates volume change during repeated charge/discharge cycling. These results demonstrate the great potential of the combination of PS and PD modes for MnO2 electrodeposition for the development of high-performance electrodes for supercapacitors. PMID:28773371

Effect of a CoFeB layer on the anisotropic magnetoresistance of Ta/CoFeB/MgO/NiFe/MgO/CoFeB/Ta films

NASA Astrophysics Data System (ADS)

Li, Minghua; Shi, Hui; Dong, Yuegang; Ding, Lei; Han, Gang; Zhang, Yao; Liu, Ye; Yu, Guanghua

2017-10-01

The anisotropic magnetoresistance (AMR) and magnetic properties of NiFe films can be remarkably enhanced via CoFeB layer. In the case of an ultrathin NiFe film having a Ta/CoFeB/MgO/NiFe/MgO/CoFeB/Ta structure, the CoFeB/MgO layers suppressed the formation of magnetic dead layers and the interdiffusions and interface reactions between the NiFe and Ta layers. The AMR reached a maximum value of 3.56% at 450 °C. More importantly, a single NiFe (1 1 1) peak can be formed resulting in higher AMR values for films having CoFeB layer. This enhanced AMR also originated from the significant specular reflection of electrons owing to the crystalline MgO layer, together with the sharp interfaces with the NiFe layer. These factors together resulted in higher AMR and improved magnetic properties.

Synthesis and characterization of Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO nanocomposites from waste batteries for photocatalytic, electrochemical and thermal studies

NASA Astrophysics Data System (ADS)

Mylarappa, M.; Venkata Lakshmi, V.; Vishnu Mahesh, K. R.; Nagaswarupa, H. P.; Raghavendra, N.

2017-11-01

In the present paper, Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO composites recovered from waste batteries using acid dissolution and ferrite processing were studied. The recovered Mn-ZnFe2O4 nanocomposites were decorated onto rGO using the facile hydrothermal method. The recovered material was characterized using x-ray powder diffraction to study the particle size and crystallinity. The morphology of the composites was analyzed using scanning electron microscopy, and elements present in the materials were studied using energy dispersive x-ray analysis. The functional groups attached were observed using a Fourier transform infrared spectrometer. Furthermore, the recovered composites were evaluated in thermal studies using thermal gravimetric analysis, differential scanning calorimetry and dynamic thermal analysis. The material was used as a photocatalyst for the removal of acid orange 88 dye, and as an electrocatalyst. The decreased band gap energy for the Mn-ZnFe2O4/rGO composite was displayed in better photocatalytic activity for a given reaction. The electrochemical properties of Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO have been investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with a paste-type electrode. The CV indicated the reversibility of the electrode reaction, and the EIS revealed that a decrease in the charge transfer resistance increases the double layer capacitance of the rGO/Mn-ZnFe2O4 electrode.

Structural, magnetic and dielectric properties of polyaniline/MnCoFe2O4 nanocomposites

NASA Astrophysics Data System (ADS)

Chitra, Palanisamy; Muthusamy, Athianna; Jayaprakash, Rajan

2015-12-01

Ferromagnetic PANI containing MnCoFe2O4 nanocomposites were synthesized by in-situ chemical polymerization of aniline incorporated MnCoFe2O4 nanoparticles (20%, 10% w/w of fine powders) with and without ultrasonic treatment. The MnCoFe2O4 nanoparticles were synthesized by auto combustion method. The PANI/MnCoFe2O4 nanocomposites were characterized with Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The average particle size of the resulting PANI/MnCoFe2O4 nanocomposites was confirmed from the TEM and XRD analysis. The structure and morphology of the composites were confirmed by FT-IR spectroscopy, XRD and SEM. In addition, the electrical and magnetic properties of the nanocomposites were investigated. The PANI/MnCoFe2O4 nanocomposites under applied magnetic field exhibited the hysteresis loops of ferromagnetic nature at room temperature. The variation of Dielectric constant, Dielectric loss, and AC conductivity of PANI/MnCoFe2O4 nanocomposites at room temperature as a function of frequency in the range 50 Hz-5 MHz has been studied. Effect of ultrasonication on the PANI/MnCoFe2O4 nanocomposites was also investigated.

Failure Mechanisms of SAC/Fe-Ni Solder Joints During Thermal Cycling

NASA Astrophysics Data System (ADS)

Gao, Li-Yin; Liu, Zhi-Quan; Li, Cai-Fu

2017-08-01

Thermal cycling tests have been conducted on Sn-Ag-Cu/Fe- xNi ( x = 73 wt.% or 45 wt.%) and Sn-Ag-Cu/Cu solder joints according to the Joint Electron Device Engineering Council industrial standard to study their interfacial reliability under thermal stress. The interfacial intermetallic compounds formed for solder joints on Cu, Fe-73Ni, and Fe-45Ni were 4.5 μm, 1.7 μm, and 1.4 μm thick, respectively, after 3000 cycles, demonstrating excellent diffusion barrier effect of Fe-Ni under bump metallization (UBM). Also, two deformation modes, viz. solder extrusion and fatigue crack formation, were observed by scanning electron microscopy and three-dimensional x-ray microscopy. Solder extrusion dominated for solder joints on Cu, while fatigue cracks dominated for solder joints on Fe-45Ni and both modes were detected for those on Fe-73Ni. Solder joints on Fe-Ni presented inferior reliability during thermal cycling compared with those on Cu, with characteristic lifetime of 3441 h, 3190 h, and 1247 h for Cu, Fe-73Ni, and Fe-45Ni UBM, respectively. This degradation of the interfacial reliability for solder joints on Fe-Ni is attributed to the mismatch in coefficient of thermal expansion (CTE) at interconnection level. The CTE mismatch at microstructure level was also analyzed by electron backscatter diffraction for clearer identification of recrystallization-related deformation mechanisms.

Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

DOE PAGES

Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; ...

2015-08-10

The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique ‘wagging’ mode involving H- motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe–CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)57Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)57Fe(CO)3]+ and DFT calculations, which collectively indicate amore » low-spin Ni(II)(μ-H)Fe(II) core for Ni-R, with H- binding Ni more tightly than Fe. Lastly, the present methodology is also relevant to characterizing Fe–H moieties in other important natural and synthetic catalysts.« less

Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

PubMed Central

Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; Schilter, David; Pelmenschikov, Vladimir; van Gastel, Maurice; Neese, Frank; Rauchfuss, Thomas B.; Gee, Leland B.; Scott, Aubrey D.; Yoda, Yoshitaka; Tanaka, Yoshihito; Lubitz, Wolfgang; Cramer, Stephen P.

2015-01-01

The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique ‘wagging' mode involving H− motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe–CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)57Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)57Fe(CO)3]+ and DFT calculations, which collectively indicate a low-spin Ni(II)(μ-H)Fe(II) core for Ni-R, with H− binding Ni more tightly than Fe. The present methodology is also relevant to characterizing Fe–H moieties in other important natural and synthetic catalysts. PMID:26259066

Unoccupied electronic structure of Ni2MnGa ferromagnetic shape memory alloy

NASA Astrophysics Data System (ADS)

Maniraj, M.; D`Souza, S. W.; Rai, Abhishek; Schlagel, D. L.; Lograsso, T. A.; Chakrabarti, Aparna; Barman, S. R.

2015-11-01

Momentum resolved inverse photoemission spectroscopy measurements show that the dispersion of the unoccupied bands of Ni2MnGa is significant in the austenite phase. In the martensite phase, it is markedly reduced, which is possibly related to the structural transition to an incommensurate modulated state in the martensite phase. Based on the first principle calculations of the electronic structure of Ni-Mn-Ga, we show that the modification of the spectral shape with surface composition is related to change in the hybridization between the Mn 3d and Ni 3d-like states that dominate the unoccupied conduction band.

Understanding the physical metallurgy of the CoCrFeMnNi high-entropy alloy: an atomistic simulation study

NASA Astrophysics Data System (ADS)

Choi, Won-Mi; Jo, Yong Hee; Sohn, Seok Su; Lee, Sunghak; Lee, Byeong-Joo

2018-01-01

Although high-entropy alloys (HEAs) are attracting interest, the physical metallurgical mechanisms related to their properties have mostly not been clarified, and this limits wider industrial applications, in addition to the high alloy costs. We clarify the physical metallurgical reasons for the materials phenomena (sluggish diffusion and micro-twining at cryogenic temperatures) and investigate the effect of individual elements on solid solution hardening for the equiatomic CoCrFeMnNi HEA based on atomistic simulations (Monte Carlo, molecular dynamics and molecular statics). A significant number of stable vacant lattice sites with high migration energy barriers exists and is thought to cause the sluggish diffusion. We predict that the hexagonal close-packed (hcp) structure is more stable than the face-centered cubic (fcc) structure at 0 K, which we propose as the fundamental reason for the micro-twinning at cryogenic temperatures. The alloying effect on the critical resolved shear stress (CRSS) is well predicted by the atomistic simulation, used for a design of non-equiatomic fcc HEAs with improved strength, and is experimentally verified. This study demonstrates the applicability of the proposed atomistic approach combined with a thermodynamic calculation technique to a computational design of advanced HEAs.

Sulfur evolution in chemical looping combustion of coal with MnFe2O4 oxygen carrier.

PubMed

Wang, Baowen; Gao, Chuchang; Wang, Weishu; Zhao, Haibo; Zheng, Chuguang

2014-05-01

Chemical looping combustion (CLC) of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier (OC) was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi (LZ) bituminous coal, was performed in a thermogravimetric analyzer (TGA)-Fourier transform infrared (FT-IR) spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFe2O4 OC was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn3O4 or Fe2O3, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe3O4 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Serrated Flow and Dynamic Strain Aging in Fe-Mn-C TWIP Steel

NASA Astrophysics Data System (ADS)

Lan, Peng; Zhang, Jiaquan

2018-01-01

The tensile behavior, serrated flow, and dynamic strain aging of Fe-(20 to 24)Mn-(0.4 to 0.6)C twinning-induced plasticity (TWIP) steel have been investigated. A mathematical approach to analyze the DSA and PLC band parameters has been developed. For Fe-(20 to 24)Mn-(0.4 to 0.6)C TWIP steel with a theoretical ordering index (TOI) between 0.1 and 0.3, DSA can occur at the very beginning of plastic deformation and provide serrations during work hardening, while for TOI less than 0.1 the occurrence of DSA is delayed and twinning-dominant work hardening remains relatively smooth. The critical strain for the onset of DSA and PLC bands in Fe-Mn-C TWIP steels decreases as C content increases, while the numbers of serrations and bands increase. As Mn content increases, the critical strain for DSA and PLC band varies irregularly, but the numbers of serrations and bands increase. For Fe-(20 to 24)Mn-(0.4 to 0.6)C TWIP steel with grain size of about 10 to 20 μm, the twinning-induced work hardening rate is about 2.5 to 3.0 GPa, while the DSA-dominant hardening rate is about 2.0 GPa on average. With increasing engineering strain from 0.01 to 0.55 at an applied strain rate of 0.001s-1, the cycle time for PLC bands in Fe-Mn-C TWIP steel increases from 6.5 to 162 seconds, while the band velocity decreases from 4.5 to 0.5 mm s-1, and the band strain increases from 0.005 to 0.08. Increasing applied strain rate leads to a linear increase of band velocity despite composition differences. In addition, the influence of the Mn and C content on the tensile properties of Fe-Mn-C TWIP steel has been also studied. As C content increases, the yield strength and tensile strength of Fe-Mn-C TWIP steel increase, but the total elongation variation against C content is dependent on Mn content. As Mn content increases, the yield strength and tensile strength decrease, while the total elongation increases, despite C content. Taking both tensile properties and serrated flow behavior into

Binder-jetting 3D printing and alloy development of new biodegradable Fe-Mn-Ca/Mg alloys.

PubMed

Hong, Daeho; Chou, Da-Tren; Velikokhatnyi, Oleg I; Roy, Abhijit; Lee, Boeun; Swink, Isaac; Issaev, Ilona; Kuhn, Howard A; Kumta, Prashant N

2016-11-01

3D printing of various biomaterials including titanium and stainless steel has been studied for treating patients with cranio-maxillofacial bone defect. The potential long term complications with use of inert biometals have opened the opportunities for use of biodegradable metals in the clinical arena. The authors previously reported that binder-jet 3D printing technique enhanced the degradation rates of biodegradable Fe-Mn alloy by creating engineered micropores rendering the system attractive as biodegradable implantable devices. In the present study, the authors employed CALPHAD modeling to systematically study and modify the Fe-Mn alloy composition to achieve enhanced degradation rates. Accordingly, Ca and Mg addition to Fe-35wt% Mn solid solution predicted increase in degradation rates. In order to validate the CALPHAD results, Fe - (35-y)wt% Mn - ywt% X (X=Ca, Mg, and y=0, 1, 2) were synthesized by using high energy mechanical alloying (HEMA). Sintered pellets of Fe-Mn-Ca and Fe-Mn-Mg were then subjected to potentiodynamic polarization (PDP) and live/dead cell viability tests. Sintered pellets of Fe-Mn, Fe-Mn-Ca, and Fe-Mn-Mg also exhibited MC3T3 murine pre-osteoblast cells viability in the live/dead assay results. Fe-Mn and Fe-Mn-1Ca were thus accordingly selected for 3D printing and the results further confirmed enhanced degradation of Ca addition to 3D printed constructs validating the theoretical and alloy development studies. Live/dead and MTT cell viability results also confirmed good cytocompatibility of the 3D-printed Fe-Mn and Fe-Mn-1Ca constructs. Bone grafting is widely used for the treatment of cranio-maxillofacial bone injuries. 3D printing of biodegradable Fe alloy is anticipated to be advantageous over current bone grafting techniques. 3D printing offers the fabrication of precise and tailored bone grafts to fit the patient specific bone defect needs. Biodegradable Fe alloy is a good candidate for 3D printing synthetic grafts to regenerate bone

Structural, Transport and Electrochemical Properties of LiFePO4 Substituted in Lithium and Iron Sublattices (Al, Zr, W, Mn, Co and Ni)

PubMed Central

Molenda, Janina; Kulka, Andrzej; Milewska, Anna; Zając, Wojciech; Świerczek, Konrad

2013-01-01

LiFePO4 is considered to be one of the most promising cathode materials for lithium ion batteries for electric vehicle (EV) application. However, there are still a number of unsolved issues regarding the influence of Li and Fe-site substitution on the physicochemical properties of LiFePO4. This is a review-type article, presenting results of our group, related to the possibility of the chemical modification of phosphoolivine by introduction of cation dopants in Li and Fe sublattices. Along with a synthetic review of previous papers, a large number of new results are included. The possibility of substitution of Li+ by Al3+, Zr4+, W6+ and its influence on the physicochemical properties of LiFePO4 was investigated by means of XRD, SEM/EDS, electrical conductivity and Seebeck coefficient measurements. The range of solid solution formation in Li1−3xAlxFePO4, Li1−4xZrxFePO4 and Li1−6xWxFePO4 materials was found to be very narrow. Transport properties of the synthesized materials were found to be rather weakly dependent on the chemical composition. The battery performance of selected olivines was tested by cyclic voltammetry (CV). In the case of LiFe1−yMyPO4 (M = Mn, Co and Ni), solid solution formation was observed over a large range of y (0 < y ≤ 1). An increase of electrical conductivity for the substitution level y = 0.25 was observed. Electrons of 3d metals other than iron do not contribute to the electrical properties of LiFe1−yMyPO4, and substitution level y > 0.25 leads to considerably lower values of σ. The activated character of electrical conductivity with a rather weak temperature dependence of the Seebeck coefficient suggests a small polaron-type conduction mechanism. The electrochemical properties of LiFe1−yMyPO4 strongly depend on the Fe substitution level. PMID:28809235

MnNiO 3 revisited with modern theoretical and experimental methods

DOE PAGES

Dzubak, Allison L.; Mitra, Chandrima; Chance, Michael; ...

2017-11-03

MnNiO 3 is a strongly correlated transition metal oxide that has recently been investigated theoretically for its potential application as an oxygen-evolution photocatalyst. However, there is no experimental report on critical quantities such as the band gap or bulk modulus. Recent theoretical predictions with standard functionals such as LDA+U and HSE show large discrepancies in the band gaps (about 1.23 eV), depending on the nature of the functional used. Hence there is clearly a need for an accurate quantitative prediction of the band gap to gauge its utility as a photocatalyst. In this work, we present a diffusion quantum Montemore » Carlo study of the bulk properties of MnNiO 3 and revisit the synthesis and experimental properties of the compound. We predict quasiparticle band gaps of 2.0(5) eV and 3.8(6) eV for the majority and minority spin channels, respectively, and an equilibrium volume of 92.8 Å 3, which compares well to the experimental value of 94.4 Å 3. A bulk modulus of 217 GPa is predicted for MnNiO 3. As a result, we rationalize the difficulty for the formation of ordered ilmenite-type structure with specific sites for Ni and Mn to be potentially due to the formation of antisite defects that form during synthesis, which ultimately affects the physical properties of MnNiO 3.« less

MnNiO 3 revisited with modern theoretical and experimental methods

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

Dzubak, Allison L.; Mitra, Chandrima; Chance, Michael

MnNiO 3 is a strongly correlated transition metal oxide that has recently been investigated theoretically for its potential application as an oxygen-evolution photocatalyst. However, there is no experimental report on critical quantities such as the band gap or bulk modulus. Recent theoretical predictions with standard functionals such as LDA+U and HSE show large discrepancies in the band gaps (about 1.23 eV), depending on the nature of the functional used. Hence there is clearly a need for an accurate quantitative prediction of the band gap to gauge its utility as a photocatalyst. In this work, we present a diffusion quantum Montemore » Carlo study of the bulk properties of MnNiO 3 and revisit the synthesis and experimental properties of the compound. We predict quasiparticle band gaps of 2.0(5) eV and 3.8(6) eV for the majority and minority spin channels, respectively, and an equilibrium volume of 92.8 Å 3, which compares well to the experimental value of 94.4 Å 3. A bulk modulus of 217 GPa is predicted for MnNiO 3. As a result, we rationalize the difficulty for the formation of ordered ilmenite-type structure with specific sites for Ni and Mn to be potentially due to the formation of antisite defects that form during synthesis, which ultimately affects the physical properties of MnNiO 3.« less

Nucleation and Growth of Tetrataenite (FeNi) in Meteorites

NASA Astrophysics Data System (ADS)

Goldstein, J. I.; Williams, D. B.; Zhang, J.

1992-07-01

The mineral tetrataenite (ordered FeNi) has been observed in chondrites, stony irons, and iron meteorites (1). FeNi is an equilibrium phase in the Fe-Ni phase diagram (Figure 1) and orders to tetrataenite at ~320 degrees C (2). The phase forms at temperatures at or below the eutectoid temperature (~400 degrees C) where taenite (gamma) transforms to kamacite (alpha) plus FeNi (gamma"). An understanding of the formation of tetrataenite can lead to a new method for determining cooling rates at low temperatures (<400 degrees C) for all types of meteorites. In a recent study of plessite in iron meteorites (3), two transformation sequences for the formation of tetrataenite were observed. In either sequence, during the cooling process, the taenite (gamma) phase initially undergoes a diffusionless transformation to a martensite (alpha, bcc) phase without a composition change. The martensite then decomposes either above or below the eutectoid temperature (~400 degrees C) during cooling or upon subsequent reheating. During martensite decomposition above the eutectoid, the taenite (gamma) phase nucleates by the reaction alpha(sub)2 ---> alpha + gamma and grows under volume diffusion control. The Ni composition of the taenite increases continuously following the equilibrium gamma/alpha + gamma boundary while the Ni composition of the kamacite matrix decreases following the alpha/alpha + gamma phase boundary (2), see Figure 1. Below the eutectoid temperature, the precipitate composition follows the equilibrium gamma"/alpha + gamma" boundary and reaches ~52 wt% Ni, the composition of FeNi, gamma". The kamacite (alpha) matrix composition approaches ~4 to 5 wt% Ni. The ordering transformation starts at ~320 degrees C forming the tetrataenite phase. During martensite decomposition below the eutectoid temperature, FeNi should form directly by the reaction alpha2 --> alpha + gamma" (FeNi). If this transformation sequence occurs, then the composition of kamacite and tetrataenite

Dinuclear complexes containing linear M-F-M [M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)] bridges: trends in structures, antiferromagnetic superexchange interactions, and spectroscopic properties.

PubMed

Reger, Daniel L; Pascui, Andrea E; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

2012-11-05

The reaction of M(BF(4))(2)·xH(2)O, where M is Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II), with the new ditopic ligand m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (L(m)*) leads to the formation of monofluoride-bridged dinuclear metallacycles of the formula [M(2)(μ-F)(μ-L(m)*)(2)](BF(4))(3). The analogous manganese(II) species, [Mn(2)(μ-F)(μ-L(m)*)(2)](ClO(4))(3), was isolated starting with Mn(ClO(4))(2)·6H(2)O using NaBF(4) as the source of the bridging fluoride. In all of these complexes, the geometry around the metal centers is trigonal bipyramidal, and the fluoride bridges are linear. The (1)H, (13)C, and (19)F NMR spectra of the zinc(II) and cadmium(II) compounds and the (113)Cd NMR of the cadmium(II) compound indicate that the metallacycles retain their structure in acetonitrile and acetone solution. The compounds with M = Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) are antiferromagnetically coupled, although the magnitude of the coupling increases dramatically with the metal as one moves to the right across the periodic table: Mn(II) (-6.7 cm(-1)) < Fe(II) (-16.3 cm(-1)) < Co(II) (-24.1 cm(-1)) < Ni(II) (-39.0 cm(-1)) ≪ Cu(II) (-322 cm(-1)). High-field EPR spectra of the copper(II) complexes were interpreted using the coupled-spin Hamiltonian with g(x) = 2.150, g(y) = 2.329, g(z) = 2.010, D = 0.173 cm(-1), and E = 0.089 cm(-1). Interpretation of the EPR spectra of the iron(II) and manganese(II) complexes required the spin Hamiltonian using the noncoupled spin operators of two metal ions. The values g(x) = 2.26, g(y) = 2.29, g(z) = 1.99, J = -16.0 cm(-1), D(1) = -9.89 cm(-1), and D(12) = -0.065 cm(-1) were obtained for the iron(II) complex and g(x) = g(y) = g(z) = 2.00, D(1) = -0.3254 cm(-1), E(1) = -0.0153, J = -6.7 cm(-1), and D(12) = 0.0302 cm(-1) were found for the manganese(II) complex. Density functional theory (DFT) calculations of the exchange integrals and the zero-field splitting on manganese(II) and iron(II) ions were performed

Synthetic Active Site Model of the [NiFeSe] Hydrogenase

PubMed Central

Wombwell, Claire; Reisner, Erwin

2015-01-01

A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe(‘S2Se2’)(CO)3] (H2‘S2Se2’=1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni(‘S2Se2’)] with [Fe(CO)3bda] (bda=benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe(‘S2Se2’)(CO)3] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe(‘S2Se2’)(CO)3] with the previously reported thiolate analogue [NiFe(‘S4’)(CO)3] (H2‘S4’=H2xbsms=1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe(‘S2Se2’)(CO)3] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe(‘S2Se2’)(CO)3] and [NiFe(‘S4’)(CO)3] demonstrated that both complexes do not operate as homogenous H2 evolution catalysts, but are precursors to a solid deposit on an electrode surface for H2 evolution catalysis in organic and aqueous solution. PMID:25847470

Biocorrosion investigation of two shape memory nickel based alloys: Ni-Mn-Ga and thin film NiTi.

PubMed

Stepan, L L; Levi, D S; Gans, E; Mohanchandra, K P; Ujihara, M; Carman, G P

2007-09-01

Thin film nitinol and single crystal Ni-Mn-Ga represent two new shape memory materials with potential to be used as percutaneously placed implant devices. However, the biocompatibility of these materials has not been adequately assessed. Immersion tests were conducted on both thin film nitinol and single crystal Ni-Mn-Ga in Hank's balanced salt solution at 37 degrees C and pH 7.4. After 12 h, large pits were found on the Ni-Mn-Ga samples while thin film nitinol displayed no signs of corrosion. Further electrochemical tests on thin film nitinol samples revealed breakdown potentials superior to a mechanically polished nitinol disc. These results suggest that passivation or electropolishing of thin film nitinol maybe unnecessary to promote corrosion resistance.

Degradable and porous Fe-Mn-C alloy for biomaterials candidate

NASA Astrophysics Data System (ADS)

Pratesa, Yudha; Harjanto, Sri; Larasati, Almira; Suharno, Bambang; Ariati, Myrna

2018-02-01

Nowadays, degradable implants attract attention to be developed because it can improve the quality of life of patients. The degradable implant is expected to degrade easily in the body until the bone healing process already achieved. However, there is limited material that could be used as a degradable implant, polymer, magnesium, and iron. In the previous study, Fe-Mn-C alloys had succesfully produced austenitic phase. However, the weakness of the alloy is degradation rate of materials was considered below the expectation. This study aimed to produce porous Fe-Mn-C materials to improve degradation rate and reduce the density of alloy without losing it non-magnetic properties. Potassium carbonate (K2CO3) were chosen as filler material to produce foam structure by sintering and dissolution process. Multisteps sintering process under argon gas environment was performed to generate austenite phase. The product showed an increment of the degradation rate of the foamed Fe-Mn-C alloy compared with the solid Fe-Mn-C alloy without losing the Austenitic Structure

Microstructure and degradation behavior of forged Fe-Mn-Si alloys

NASA Astrophysics Data System (ADS)

Xu, Zhigang; Hodgson, Michael A.; Cao, Peng

2015-03-01

This work presents a comparative study of a series of Fe-Mn-Si alloys proposed as degradable biomaterials for medical applications. Five Fe-28wt.%Mn-xSi (where x = 0 to 8 wt.%) alloys were fabricated by an arc-melting method. All the as-cast alloys were subsequently subjected to homogenization treatment and hot forging. The microstructure and phase constituents were investigated. It is found that the grain size of the as-forged alloys ranged approximately from 30 to 50 μm. The as-forged Fe-Mn-Si alloys containing Si from 2 to 6 wt.% was comprised of duplex martensitic ɛ and austenitic γ phases; however, the Si-free and 8 wt.% Si alloys only consisted of a single γ phase. After 30 days of static immersion test in a simulated body fluid (SBF) medium, it is found that pitting and general corrosion occur on the sample surfaces. Potentiodynamic analysis reveals that the degradation rate of the Fe-Mn-Si alloys increased gradually with Si content up to 6 wt.%, beyond which the degradation slows down.

Chemical Separation of Fe-Ni Particles after Impact

NASA Astrophysics Data System (ADS)

Miura, Y.; Fukuyama, S.; Kedves, M. A.; Yamori, A.; Okamoto, M.; Gucsik, A.

Tiny grains of Fe-Ni system originated from planetesimals or meteoroids can remain under solid (or melt)-solid impact reactions even after impact process, probably together with high pressure form of Fe phase. Impact fragment with major Fe-Si (-Ni) system can be formed under vapor condition of impact reaction from terrestrial and artificial impact craters and spherules, and those with Ni-Cl (-S) system in composi- tion are formed under vapor condition of artificial impact experiments on the Barringer iron meteorite. These impact grains of Fe-bearing composition or high pressure form of iron-rich phases will be found probably on the asteroids in future exploration

Ferromagnetic phase in partially oxidized FeMn films

NASA Astrophysics Data System (ADS)

Svalov, A. V.; Savin, P. A.; Lepalovskij, V. N.; Vas'kovskiy, V. O.; Larrañaga, A.; Kurlyandskaya, G. V.

2018-04-01

The structure, magnetic and magnetoresistive properties of ferromagnetic phase in partially oxidized FeMn films was studied. The oxidation was performed by annealing of the samples under atmospheric pressure in a gas mixture (nitrogen with 0.5% oxygen) at the temperature of 300 °C. The resulting ferromagnetic phase was isotropic in the film plane. The value of the anisotropic magnetoresistance was similar to the value of the anisotropic magnetoresistance usually observed in films of pure iron. The oxidation of antiferromagnetic FeMn films resulted in the appearance of an exchange bias.

Atomic-scale dynamics of edge dislocations in Ni and concentrated solid solution NiFe alloys

DOE PAGES

Zhao, Shijun; Osetsky, Yuri N.; Zhang, Yanwen; ...

2017-01-19

Single-phase concentrated solid solution alloys (CSAs), including high entropy alloys, exhibit excellent mechanical properties compared to conventional dilute alloys. However, the origin of this observation is not clear yet because the dislocation properties in CSAs are poorly understood. In this work, the mobility of a <110>{111} edge dislocation in pure Ni and equiatomic solid solution Ni 0.5Fe 0.5 (NiFe) is studied using molecular dynamics simulations with different empirical potentials. The threshold stress to initiate dislocation movement in NiFe is found to be much higher compared to pure Ni. The drag coefficient of the dislocation motion calculated from the linear regimemore » of dislocation velocities versus applied stress suggests that the movement of dislocations in NiFe is strongly damped compared to that in Ni. The present results indicate that the mobility of edge dislocations in fcc CSAs are controlled by the fluctuations in local stacking fault energy caused by the local variation of alloy composition.« less

Increasing magnetoplasticity in polycrystalline Ni-Mn-Ga by reducing internal constraints through porosity.

PubMed

Boonyongmaneerat, Yuttanant; Chmielus, Markus; Dunand, David C; Müllner, Peter

2007-12-14

Foams with 55% and 76% open porosity were produced from a Ni-Mn-Ga magnetic shape-memory alloy by replication casting. These polycrystalline martensitic foams display a fully reversible magnetic-field-induced strain of up to 0.115% without bias stress, which is about 50 times larger than nonporous, fine-grained Ni-Mn-Ga. This very large improvement is attributed to the bamboolike structure of grains in the foam struts which, due to reduced internal constraints, deform by magnetic-field-induced twinning more easily than equiaxed grains in nonporous Ni-Mn-Ga.

Band structure of the quaternary Heusler alloys ScMnFeSn and ScFeCoAl

NASA Astrophysics Data System (ADS)

Shanthi, N.; Teja, Y. N.; Shaji, Shephine M.; Hosamani, Shashikala; Divya, H. S.

2018-04-01

In our quest for materials with specific applications, a theoretical study plays an important role in predicting the properties of compounds. Heusler alloys or compounds are the most studied in this context. More recently, a lot of quaternary Heusler compounds are investigated for potential applications in fields like Spintronics. We report here our preliminary study of the alloys ScMnFeSn and ScFeCoAl, using the ab-initio linear muffin-tin orbital method within the atomic sphere approximation (LMTO-ASA). The alloy ScMnFeSn shows perfect half-metallicity, namely, one of the spins shows a metallic behaviour and the other spin shows semi-conducting behaviour. Such materials find application in devices such as the spin-transfer torque random access memory (STT-MRAM). In addition, the alloy ScMnFeSn is found to have an integral magnetic moment of 4 µB, as predicted by the Slater-Pauling rule. The alloy ScFeCoAl does not show half-metallicity.

Synthetic Active Site Model of the [NiFeSe] Hydrogenase.

PubMed

Wombwell, Claire; Reisner, Erwin

2015-05-26

A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe('S2Se2')(CO)3] (H2'S2Se2' = 1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni('S2Se2')] with [Fe(CO)3bda] (bda = benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe('S2Se2')(CO)3] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe('S2Se2')(CO)3] with the previously reported thiolate analogue [NiFe('S4')(CO)3] (H2'S4' = H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe('S2Se2')(CO)3] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe('S2Se2')(CO)3] and [NiFe('S4')(CO)3] demonstrated that both complexes do not operate as homogenous H2 evolution catalysts, but are precursors to a solid deposit on an electrode surface for H2 evolution catalysis in organic and aqueous solution. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Modulation of the electronic structure and the Ni–Fe distance in heterobimetallic models for the active site in [NiFe]hydrogenase

PubMed Central

Zhu, Wenfeng; Marr, Andrew C.; Wang, Qiang; Neese, Frank; Spencer, Douglas J. E.; Blake, Alexander J.; Cooke, Paul A.; Wilson, Claire; Schröder, Martin

2005-01-01

Reaction of the mononuclear Ni(II) thiolate complexes [Ni(L)] [L, L1, H2L1, bis(2-mercaptoethyl)-1,2-dimercaptoethane; L2, H2L2, N,N′-dimethyl-N,N′-bis(2-mercaptoethyl)-bis(aminoethyl)sulfide] with [FeCp(CO)2I] gives the dithiolate-bridged heterobimetallic species, [Ni(L1)FeCp(CO)]PF6, 1, and [Ni(L2)FeCp]I, 2, respectively. Binding of a Fe(CO)3 fragment via reaction of square-planar [Ni(pdt)(dppe)] (dppe, 1,2-diphenylphosphinoethane; pdt2–, 1,3-propanedithiolate) with Fe3(CO)12 or [Fe(CO)3(BDA)] (BDA, benzylidene acetone) affords diamagnetic [(dppe)Ni(μ-pdt)Fe(CO)3], 3, in which the Ni(II) center is bound tetrahedrally to two thiolate S-donors and to two P-donors. The complex [(dppe)Ni(μ-pdt)Fe(CO)3], 3, reacts in solution via rearrangement to afford [(OC)Ni(μ-dppe)(μ-pdt)Fe(CO)2], 4, in which one P-donor of dppe is bound to Ni and the other to Fe, and a CO ligand has transferred from Fe to Ni. Additionally, the syntheses of 3 and 4 afford the side products [(dppe)Ni(CO)2] and [(OC)3Fe(pdt)Fe(CO)3] together with the trinuclear species [(dppe)(CO)Fe(μ-CO)(μ-pdt)Fe(μ-pdt)Fe(CO)3], 5. Reaction of [Ni(pdt)(dppe)] with [FeCp(CO)2I] in CH2Cl2 affords two products [(dppe)Ni(μ-pdt)FeCp(CO)]PF6, 6, and [(dppe)Ni(pdt)(μ-I)Ni(dppe)]PF6, 7. The complexes 2, 3, and 4 show Ni–Fe distances of 2.539(4), 2.4666(6), and 2.4777(7) Å, respectively, with relatively acute dihedral angles of 79.5–81.8° for the Ni–S2-Fe bridge, thus mimicking the shortened Ni...Fe distance (2.5 Å) and the acute dihedral angle of the Ni–S2–Fe moiety observed in certain active forms of [NiFe]hydrogenase. The role of direct Ni–Fe bonding in these complexes is discussed and linked to electronic structure calculations on [(dppe)Ni(pdt)Fe(CO)3], 3, which confirm the presence of a bent Ni(dz2)-Fe(dz2) σ-bond in a singlet ground state. PMID:16352727

Characteristics of 5M modulated martensite in Ni-Mn-Ga magnetic shape memory alloys

NASA Astrophysics Data System (ADS)

Ćakır, A.; Acet, M.; Righi, L.; Albertini, F.; Farle, M.

2015-09-01

The applicability of the magnetic shape memory effect in Ni-Mn-based martensitic Heusler alloys is closely related to the nature of the crystallographically modulated martensite phase in these materials. We study the properties of modulated phases as a function of temperature and composition in three magnetic shape memory alloys Ni49.8Mn25.0Ga25.2, Ni49.8Mn27.1Ga23.1 and Ni49.5Mn28.6Ga21.9. The effect of substituting Ga for Mn leads to an anisotropic expansion of the lattice, where the b-parameter of the 5M modulated structure increases and the a and c-parameters decrease with increasing Ga concentration. The modulation vector is found to be both temperature and composition dependent. The size of the modulation vector corresponds to an incommensurate structure for Ni49.8Mn25.0Ga25.2 at all temperatures. For the other samples the modulation is incommensurate at low temperatures but reaches a commensurate value of q ≈ 0.400 close to room temperature. The results show that commensurateness of the 5M modulated structure is a special case of incommensurate 5M at a particular temperature.

MnO2/multiwall carbon nanotube/Ni-foam hybrid electrode for electrochemical capacitor

NASA Astrophysics Data System (ADS)

Chen, L. H.; Li, L.; Qian, W. J.; Dong, C. K.

2018-01-01

The ternary composites of manganese dioxide/multiwall carbon nanotube/Ni-foam (MnO2/MWNT/Ni-foam) for supercapacitors were fabricated via a hydrothermal method after direct growth of MWNTs on the Ni-foam. The structural properties of the electrodes were characterized by SEM and TEM. The electrode exhibited excellent electrochemical properties from the investigation based on the three-electrode setup. Low contact resistance Rs of about 0.291 Ω between MnO2/MWNT and Ni-foam was reached benefited from the direct growth structure. High capacitance of 355.1 F/g at the current density of 2 A/g was achieved, with good capacitive response at high current density. The MnO2/MWNT/Ni-foam electrode exhibits good stability performance after 2000 cycles at a current of 40 mA.

Charge ordering and multiferroicity in Fe{sub 3}BO{sub 5} and Fe{sub 2}MnBO{sub 5} oxyborates

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

Maignan, A., E-mail: antoine.maignan@ensicaen.fr; Lainé, F.; Guesdon, A.

2017-02-15

The comparison of Fe{sub 3}BO{sub 5} and Fe{sub 2}MnBO{sub 5} reveals that the 2Fe{sup 2+}: Fe{sup 3+} charge ordering of the former is suppressed in the latter. Spin dynamics probed by ac susceptibility are strongly affected by the substitution, inducing superparamagnetism at low temperature in Fe{sub 2}MnBO{sub 5}. Interestingly, for both oxyborates, glassiness is observed in the dielectric properties at low temperature, but only Fe{sub 3}BO{sub 5} shows a magnetodielectric effect close to its lower magnetic transition. A change in the electrical polarization, measured by pyroelectric current integration, is observed in Fe{sub 3}BO{sub 5} and is even more pronounced inmore » Fe{sub 2}MnBO{sub 5}. Such results suggest that these oxyborates behave like antiferromagnetic relaxor ferroelectrics. These features are proposed to be related to the distribution of the species (Fe{sup 3+}, Fe{sup 2+} and Mn{sup 2+}) over the four transition metal sites forming the ludwigite structure. - Graphical abstract: 90 K [010] electron diffraction patterns of Fe{sub 3}BO{sub 5}. The yellow arrows in the pattern indicate the extra-spots corresponding to the superstructure induced by the charge ordering. - Highlights: • The TEM (ED) study of the Fe{sub 3}BO{sub 5} oxyborate at 90 K reveals a superstructure related to a Fe{sup 2+}/Fe{sup 3+} ordering. • The Fe{sub 2}MnBO{sub 5}, Mn-substituted counterpart, does not show such ordering. • Our magnetic and electric measurements demonstrate that these magnetic ferrites exhibit glassiness in their charges (relaxor-type) with additional superparamagnetism at low T for Fe{sub 2}MnBO{sub 5} and magnetodielectric coupling near T{sub N2}=72 K in Fe{sub 3}BO{sub 5}. • The pyroelectric measurements confirm the existence of a ferroelectric behavior in these antiferromagnets. Accordingly, our results open the route to the study of other large class of the M{sub 2}{sup 2+}M’{sup 3+}BO{sub 5} ludwigites and to their complex magnetism and